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NanoManufacturing

Michael De Volder, Engineering Department - IfM

Studying at Cambridge

Nanoscience News

Copper‐Catalyzed ortho‐Functionalization of Quinoline N‐Oxides with Vinyl Arenes

By Hui Hu, Xiaoping Hu, Yuanhong Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

An efficient copper‐catalyzed regioselective C‐H alkenylation and borylative alkylation of quinoline N ‐oxides with vinyl arenes in the presence of pinacol diborane has been developed. The reaction proceeds through the borylcupration of the vinyl arenes followed by nucleophilic attack of the resulting alkyl copper species to the quinoline N ‐oxides. Benzoquinone and KO t Bu were identified as the necessary additives at the second step of the reaction that are crucial for the success of the reaction. A wide range of C2‐functionalizaed quinolines were obtained with good functional group tolerance, which may find utilities in pharmaceuticals and synthetic chemistry.

Exploitation of the New Reactivity of Vinylcyclopropanes for Palladium‐Catalyzed, Asymmetric [5+2] Dipolar Cycloadditions

By Liang-Qiu Lu, Miao-Miao Li, Qin Xiong, Bao-Le Qu, Yu Lan, Wen-Jing Xiao, Yu-Qing Xiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Vinylcyclopropanes (VCPs) are commonly used in transition metal‐catalyzed cycloadditions, and the exploitation of their recently realized reactivities to construct new cyclic architectures is of great significance in modern synthetic chemistry. Herein, a palladium‐catalyzed, visible light‐driven, asymmetric [5+2] cycloaddition of VCPs with α‐diazoketones was first accomplished by switching the reactivity of the Pd‐containing dipolar intermediates from all‐carbon 1,3‐dipoles to oxo‐1,5‐dipoles. Enantioenriched 7‐membered lactones were produced with good reaction efficiency and selectivity (23 examples, 52‐92% yields with up to 99:1 er and 12.5:1 dr). In addition, computational investigations were performed to rationalize the observed high chemo‐ and periselectivities.

Ligand Regulated Regiodivergent Hydrosilylation of Isoprene under Iron Catalysis

By Chang-Sheng Kuai, Ding-Wei Ji, Chao-Yang Zhao, Heng Liu, Yan-Cheng Hu, Qing-An Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

A regiodivergent and stereoselective hydrosilylation of basic industrial feedstock isoprene with unactivated silanes has been developed using earth‐abundant iron catalyst. The manipulation of regioselectivity relies on fine modification of the coordination geometry of iron center. While a bidentate pyridine imine ligand promotes the formation of allylic silanes via a 4,1‐addition, the selectivity toward 3,4‐adduct homoallylic silanes was achieved by switching to tridentate nitrogen ligand. Experimental studies and analysis have been performed to interpret the mechanism and the regioselective manipulation. This work contributes to the art of regioselective control in alkene hydrofunctionalization.

Mon 20 Jul 11:30: Understanding regulatory systems and mechanisms of genetic interactions: from yeast to pediatric cancer Please email anna.toporska@cruk.cam.ac.uk by Friday 17th July to receive a ZOOM registration link

From All Talks (aka the CURE list). Published on Jul 03, 2020.

Understanding regulatory systems and mechanisms of genetic interactions: from yeast to pediatric cancer

To understand regulatory systems, it is useful to systematically determine how individual genes contribute to the expression of all other genes. We have therefore monitored genome-wide mRNA expression for individual deletions of one-quarter of yeast genes. By including gene expression profiles of double deletions, we could also investigate genetic interactions, a phenomenon where combinations of mutations lead to unexpected effects. Understanding mechanisms of genetic interactions is important for deciphering pathway architecture as well as understanding the relationship between genetic variation and disease. To decipher potential mechanisms we have employed modelling approaches using Boolean networks and Petri Net modelling where genes are represented as nodes and relationships between genes as edges. This allowed over 9 million possible models to be enumerated and exposed that a quantitative edge difference is a strict requirement to explain inversion, a previously uncharacterized genetic interaction pattern. Genetic interactions between mutated genes likely play an important role in cancer onset and progression. Little is however known about the genetic interactions within pediatric cancer. To create an initial map of potential genetic interactions within cancer and further study their underlying mechanisms, we have analysed close to 2,600 childhood tumours for mutually exclusive or co-occurring interactions between the different cancer types. This map also provides a solid starting point to select candidates for experimental validation as well as extending the analyses to investigate the contribution of genetic interactions towards structural variants, genetic predisposition and cellular pathways.

Please email anna.toporska@cruk.cam.ac.uk by Friday 17th July to receive a ZOOM registration link

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Formyl MIDA Boronate: a C1 Building Block Enabling Straightforward Access to α‐Functionalized Organoboron Derivatives

By Yevhen M. Ivon, Ivan V. Mazurenko, Yuliya O. Kuchkovska, Zoya V. Voitenko, Oleksandr O Grygorenko from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Formyl MIDA boronate has been known to be an elusive instance of acylboronate derivatives which could not be obtained to date. In this work, an approach to one‐pot preparation and chemical transformations of formyl MIDA boronate was developed to provide new structural types of α‐functionalized organoboron compounds. Among them are acylboronate reagents which present boron‐substituted analogues of ynones and β‐dicarbonyl compounds. The developed synthetic procedures utilizing formyl MIDA boronate were demonstrated to be tolerant to diverse functional groups, which makes this reagent an advantageous C 1 building block for extending the scope of organoboron chemistry.

A Modular Approach to Dibenzo‐fused ε‐Lactams: Palladium Carbene Bridging C‐H Activation and Its Synthetic Application

By Yinghua Yu, Liyao Ma, Jiajin Xia, Luoting Xin, Lei Zhu, Xueliang Huang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Tricyclic ring systems possessing a dibenzo structure joined to a seven‐membered heterocyclic ring frequently show important biological activities. However, a modular approach to these molecules based on efficient intermolecular reaction of readily available chemicals is lacking. Herein, an unprecedented palladium‐catalyzed formal [4+3] annulation for modular construction of these tricyclic systems is described. This reaction features easily accessible reactants ( o ‐haloarylaldehydes and N ‐tosylhydrazones), broad substrate scope, and excellent functional group compatibility. The synthetic potential is demonstrated by the easy scale‐up reactions, late‐stage modification of complex molecules, and collective synthesis of bioactive molecules and approved drugs.

Tailoring Optical Properties of Luminescent Semiconducting Nanocrystals via Hydrostatic, Anisotropic Static, and Dynamic Pressures

By Gill V. Biesold-McGee, Shuang Liang, Blair Brettmann, Naresh Thadhani, Zhitao Kang, Zhiqun Lin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Luminescent semiconductor nanocrystals are a fascinating class of materials because of their size‐dependent emission. Multitudes of past studies have demonstrated that semiconductor nanoparticles with radii smaller than their Bohr radius experience quantum confinement and thus size‐dependent emission. Exerting pressure to these nanoparticles represents an additional, more dynamic, strategy to alter their size and shift their emission. Upon the application of pressure, lattices are strained, and electronic structure is altered. In this review, colloidal semiconductor nanocrystals are first introduced. The effects of uniform hydrostatic pressure on the optical properties of metal halide perovskite (ABX 3 ), II‐VI, III‐V, and IV‐VI semiconductor nanocrystals are then examined. The optical properties of semiconductor nanocrystals under both static and dynamic anisotropic pressure are then summarized. Finally, future research directions and applications utilizing the pressure‐dependent optical properties of semiconductor nanocrystals are discussed.

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

By Szymon Chorazy, Tomasz Charytanowicz, Dawid Pinkowicz, Junhao Wang, Koji Nakabayashi, Stephen Klimke, Franz Renz, Shin‐ichi Ohkoshi, Barbara Sieklucka from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Perfect rhenium mediator: Octacyanidorhenate(V) ion is presented as a promising molecular precursor for the construction of an advanced spin‐crossover material linking a multistep spin transition with strong cooperativity. An anionic layered FeII‐ReV cyanido‐bridged framework non‐covalently bonded to Cs+ counterions is reported. It exhibits a two‐step hysteretic FeII spin‐crossover effect controlled by temperature, light irradiation, and pressure. Abstract A two‐step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3‐CNpy)2][Re(CN)8]}⋅H2O (1) (3‐CNpy=3‐cyanopyridine) assembly consisting of cyanido‐bridged FeII‐ReV square grid sheets bonded by Cs+ ions. The presence of two non‐equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non‐covalent interlayer interactions involving Cs+, [ReV(CN)8]3− ions, and 3‐CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin‐transition phenomenon could be tuned by an external pressure giving the room‐temperature range of SCO, as well as by visible‐light irradiation, inducing an efficient recovery of the high‐spin FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.

Direct Catalytic Conversion of Ethanol to C5+ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

By Senthil Subramaniam, Mond F. Guo, Tanmayi Bathena, Michel Gray, Xiao Zhang, Abraham Martinez, Libor Kovarik, Konstantinos A. Goulas, Karthikeyan K. Ramasamy from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

The formation of Pd–Zn alloy on a Pd‐ZnO‐ZrO2 results in the modification of the Pd electronic structure and enables the highly selective formation of C5+ ketones from renewable ethanol (>70 %yield) for extended catalysts lifetimes above 2000 hours. Abstract Ethanol can be used as a platform molecule for synthesizing valuable chemicals and fuel precursors. Direct synthesis of C5+ ketones, building blocks for lubricants and hydrocarbon fuels, from ethanol was achieved over a stable Pd‐promoted ZnO‐ZrO2 catalyst. The sequence of reaction steps involved in the C5+ ketone formation from ethanol was determined. The key reaction steps were found to be the in situ generation of the acetone intermediate and the cross‐aldol condensation between the reaction intermediates acetaldehyde and acetone. The formation of a Pd–Zn alloy in situ was identified to be the critical factor in maintaining high yield to the C5+ ketones and the stability of the catalyst. A yield of >70 % to C5+ ketones was achieved over a 0.1 % Pd‐ZnO‐ZrO2 mixed oxide catalyst, and the catalyst was demonstrated to be stable beyond 2000 hours on stream without any catalyst deactivation.

Understanding the Role of Parallel Pathways via In‐Situ Switching of Quantum Interference in Molecular Tunneling Junctions

By Saurabh Soni, Gang Ye, Jueting Zheng, Yanxi Zhang, Andika Asyuda, Michael Zharnikov, Wenjing Hong, Ryan C. Chiechi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Manipulating conductance in parallel molecular pathways is a crucial element in molecular electronics. We explore intramolecular parallel pathways with different bond topology, in form of a quantum circuit, in tunneling junctions comprising self‐assembled monolayers. We employ quantum‐interference switching/gating with an acid, without any structural changes, in single‐molecular junctions. Abstract This study describes the modulation of tunneling probabilities in molecular junctions by switching one of two parallel intramolecular pathways. A linearly conjugated molecular wire provides a rigid framework that allows a second, cross‐conjugated pathway to be effectively switched on and off by protonation, affecting the total conductance of the junction. This approach works because a traversing electron interacts with the entire quantum‐mechanical circuit simultaneously; Kirchhoff's rules do not apply. We confirm this concept by comparing the conductances of a series of compounds with single or parallel pathways in large‐area junctions using EGaIn contacts and single‐molecule break junctions using gold contacts. We affect switching selectively in one of two parallel pathways by converting a cross‐conjugated carbonyl carbon into a trivalent carbocation, which replaces destructive quantum interference with a symmetrical resonance, causing an increase in transmission in the bias window.

Dinickelaferrocene: A Ferrocene Analogue with Two Aromatic Nickeloles Realized by Electron Back‐Donation from Iron

By Zhe Huang, Yu Zheng, Wen‐Xiong Zhang, Shengfa Ye, Liang Deng, Zhenfeng Xi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

A different origin of aromaticity: Dinickelaferrocene was realized as the first example of a transition‐metal dimetallaferrocene. The nickelole ligands act as non‐innocent ligands and accept electron density from Fe via back‐donation to achieve aromaticity. Abstract The first example of ferrocene analogues with two transition‐metal metallole ligands of the general formula (η5‐C4R4M)2Fe in a sandwich structure are reported. Specifically, dinickelaferrocene 2, a type of dimetallametallocene, is efficiently synthesized from the reaction of dilithionickelole 1 with FeBr2 or FeCl2, presumably via a redox process, and is subjected to detailed experimental (single‐crystal X‐ray structural analysis, ICP‐OES, magnetometry, 57Fe Mössbauer, XPS) and theoretical (MOs, CDA, NICS, ICSS, and AICD) characterizations. Unlike ferrocene and its Cp ligands, the aromaticity of dinickelaferrocene and its nickelole ligands is accomplished by electron back‐donation from the Fe 3d orbitals to the π* orbitals of nickelole. Taken together, this work describes a new class of metallaferrocene sandwich complexes and provides a novel approach to effect aromaticity that will contribute to further development of metallocene chemistry.

Size‐ and Halide‐Dependent Auger Recombination in Lead Halide Perovskite Nanocrystals

By Yulu Li, Xiao Luo, Tao Ding, Xin Lu, Kaifeng Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Lawful behavior: A wide range of monodisperse lead perovskite nanocrystals with different cation and anion compositions and varying sizes were synthesized and their biexciton Auger recombination lifetimes measured by ultrafast spectroscopy (see picture). Volume scaling laws for the Auger lifetime of the nanocrystals were determined, thus enabling facile estimation of Auger rates, which are key parameters for perovskite‐nanocrystal‐based devices. Abstract Lead halide perovskite nanocrystals (NCs) hold strong promise for a variety of light‐harvesting, emitting, and detecting applications, all of which, however, could be complicated by multicarrier Auger recombination. Therefore, complete documentation of the size‐ and composition‐dependent Auger recombination rates of these NCs is highly desirable, as it can guide system design in many applications. Herein we report the synthesis and Auger measurements of monodisperse APbX3 (A=Cs and FA; X=Cl, Br, and I) NCs in an extensive size range (ca. 3–9 nm). The biexciton Auger lifetime of all the NCs scales linearly with the NC volume. The scaling coefficient is virtually independent of the cation but rather depends sensitively on the anion, and is 0.035, 0.085, and 0.142 ps nm−3 for Cl, Br, and I, respectively. In all of these nanocrystals the Auger recombination is much faster than in standard CdSe and PbSe NCs (ca. 1 ps nm−3).

Counterion‐Dictated Self‐Cleaning Behavior of Polycation Coating upon Water Action: Macroscopic Dissection of Hydration of Anions

By Qi Tao, Shu Huang, Xu Li, Xue‐Feng Chu, Xiaolin Lu, Dayang Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Polydiallyldimethylammonium surfaces with surface counterions with a positive Jones–Dole viscosity coefficient (Bη) exhibit excellent self‐cleaning function upon water action. Those with surface counterions with negative Bη reasonably adhere to oil under water. This ion‐specific effect enables the guidance of the oil flow on ionic surfaces upon water action according to the nature of surface (counter)ions. Abstract The counterions of polydiallyldimethylammonium (PDADMA) coatings were altered by incubation in aqueous solutions of different electrolytes. Oil de‐wetting on the resulting polycationic surfaces upon water action exhibited a straightforward connection with the Jones–Dole viscosity B‐coefficient (Bη) sign of surface counteranions. Upon water action, surface counteranions with negative Bη render PDADMA coatings oil‐adhering, but those with positive Bη furnish PDADMA coatings with excellent self‐cleaning. The oil‐adhering PDADMA surfaces can become self‐cleaning upon water action in response to the Bη of surface counteranions sign‐switching with increasing water temperature. Courtesy of surface counter‐anions with Bη>0, self‐cleaning PDADMA coatings enable not only conversion of conventional meshes into self‐cleaning membranes for oil/water separation, but also regioselective maneuver of oil flow on polycationic surfaces according to the Bη sign of surface counteranions patterned atop.

Natural Soft/Rigid Superlattice as Anodes for High Performance Lithium‐ion Batteries

By Yi Xie, Wei Bai, Jingyu Gao, Kun Li, Gongrui Wang, Tengfei Zhou, Pengju Li, Shengyong Qin, Genqiang Zhang, Zaiping Guo, Chong Xiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

The volume expansion and poor conductivity are two major obstacles that hinder the pursuing for the lithium‐ion batteries with long cycling life and high power density. Herein, we highlight a misfit compound PbNbS 3 with soft/rigid superlattice structure, which was unambiguously confirmed by scanning tunneling microscopy and electrochemical characterization, as a promising anode material for high performance lithium‐ion batteries with simultaneously optimized capacity, stability and conductivity. In this model, the soft PbS sublayers primarily react with lithium, endow the capacity and prevent the decompositon of the superlattice structure, while the rigid NbS 2 sublayers support the skeleton and enhances the migration of electrons and lithium ions, as a result synergistically leading to a specific capacity of 710 mAh g −1 at 100 mA g −1 which is 1.6 times of NbS 2 and 3.9 times of PbS. Our finding reveals the competitive strategy of soft/rigid structure in lithium‐ion battery and broadens the horizons in designing new single‐phase anode materials.

A Dipeptide‐Based Hierarchical Nanoarchitecture with Enhanced Catalytic Activity

By Junbai Li, Chenlei Wang, Jinbo Fei, Keqing Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Achieving synthetic architectures with simple structures and robust biomimetic catalytic activities remains a great challenge. Herein, we explore a facile supramolecular assembly approach to construct a dipeptide‐based hierarchical nanoarchitecture with enhanced enzyme‐like catalytic activity. In this nanoarchitecture, nanospheres are with chain‐like arrangement through coordination‐driven directional self‐assembly. The reversible transformation of anisotropic nanochains to isotropic nanospheres switches biomimetic activity. Notably, such assembled nanoarchitecture exhibits high enzyme‐like activity and remarkable long‐term stability to promote hydroquinone oxidation, superior to the natural counterpart. This work will pave the way to develop reversible and reusable supramolecular biocatalysts with ordered hierarchical structures for accelerating chemical transformations.

NiMn‐Based Bimetal‐Organic Framework Nanosheets Supported on Multi‐Channel Carbon Fibers for Efficient Oxygen Electrocatalysis

By Xiong-Wen (David) Lou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 03, 2020.

Developing noble‐metal‐free bifunctional oxygen electrocatalysts is of great significance for several key energy conversion and storage systems, yet remains as a grand challenge. Herein, we have developed a transformation method for growing NiMn‐based bimetal‐organic framework (NiMn‐MOF) nanosheets on multi‐channel carbon fibers (MCCF) as a promising bifunctional oxygen electrocatalyst. Owing to the active NiMn‐MOF nanosheets and their tight connection with the highly conductive MCCF support, the obtained MCCF/NiMn‐MOFs manifest comparable electrocatalytic performance towards oxygen reduction reaction (ORR) with the commercial Pt/C electrocatalyst and superior performance towards oxygen evolution reaction (OER) to the benchmark RuO 2 electrocatalyst. X‐ray absorption fine structure (XAFS) spectroscopy and density‐functional theory (DFT) calculations reveal that the strong synergetic effect of adjacent Ni and Mn nodes within MCCF/NiMn‐MOFs effectively promotes the thermodynamic formation of key *O and *OOH intermediates over active NiO 6 centers towards fast ORR and OER kinetics.

[ASAP] HIOx–IONO2 Dynamics at the Air–Water Interface: Revealing the Existence of a Halogen Bond at the Atmospheric Aerosol Surface

By Manoj Kumar†, Tarek Trabelsi†, Juan Carlos Go´mez Marti´n‡, Alfonso Saiz-Lopez§, and Joseph S. Francisco*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 03, 2020.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05232

Monolayer 2D ZrTe2 transition metal dichalcogenide as nanoscatter for random laser action

By Anderson S. L. Gomes from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03152F, Paper
Pablo I. R. Pincheira, Manoel Leonardo Silva Neto, Melissa Maldonado, Cid Bartolomeu de Araújo, Ali Jawaid, Robert Busch, Allyson Ritter, Richard A. Vaia, Anderson S. L. Gomes
We demonstrate random laser emission from Rhodamine 6G with ZrTe2 transition metal dichalcogenide (TMD) as nanoscatters, both in powder and 2D nanoflakes liquid suspension. The 2D semimetal ZrTe2 was synthesized...
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Assembling well-arranged covalent organic frameworks on MOF-derived graphitic carbon for remarkable formaldehyde sensing

By Yusuke Yamauchi from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03041D, Communication
Shuaihua Zhang, Qian Yang, Xingtao Xu, Xiaohong Liu, Qian Li, Jingru Guo, Nagy L. Torad, Saad M. Alshehri, Tansir Ahamad, Md. Shahriar A. Hossain, Yusuf Kaneti, Yusuke Yamauchi
Constructing heterostructures with advanced architectures is an effective strategy for enhancing the crystallinity and functional performance of covalent organic frameworks (COFs) for promising applications. Herein, a novel core-shell heterostructure integrating...
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Dynamics of chiral state transitions and relaxations in an FeGe nanoplate via in situ Lorentz microscopy

By Jianqi Li from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03278F, Paper
Ke Chai, Zi-An Li, Ruibin Liu, Bingsuo Zou, Michael Farle, Jianqi Li
Studying the magnetic transition between different topological spin textures in noncentrosymmetric magnets under external stimuli is an important topic in chiral magnetism. Here, using in situ Lorentz transmission electron microscopy...
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Nano-lateral heterojunction of selenium-coated tellurium for infrared-band soliton fiber lasers

By Han Zhang from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR02548H, Paper
Yufeng Song, Kaixi You, Jinlai Zhao, Dazhou Huang, Yunxiang Chen, Chenyang Xing, Han Zhang
In this work, ultrafast fiber lasers based on 2D selenium-coated tellurium nanosheets at infrared band is reported. 2D selenium-coated tellurium as a mode locker is shown with broadband saturable absorption...
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Universal relation between the density and the viscosity of dispersions of nanoparticles and stabilized emulsions

By Hatim Machrafi from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03130E, Paper
Hatim Machrafi
The effective viscosity of nanoparticle dispersions has been investigated experimentally quite a lot and various behaviours have been observed. Many models have been proposed to predict the effective viscosity, but...
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Correction: A rapid hemostatic sponge based on large, mesoporous silica nanoparticles and N-alkylated chitosan

By Feng Tian from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR90129F, Correction
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Zihao Chen, Lei Han, Changjun Liu, Yu Du, Xiao Hu, Ge Du, Chao Shan, Kun Yang, Chunlai Wang, Minggao Li, Fan Li, Feng Tian
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Simple Spectroscopic Determination of the Hard Protein Corona Composition in AuNPs: Albumin at the 75 %

By victor puntes from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR02379E, Paper
Michele Vitali, Eudald Casals, Francesc Canals, Nuria Colomé, victor puntes
We analysed the different spectroscopic profiles of the nanoparticle hard protein corona formation using two model proteins, albumin and immunoglobulin. When compared to serum, this served for the analysis of...
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Nonlinear Optical ASnX (A = Na, H; X = N, P) Nanosheets with Divalent Tin Lone Electron Pair Effect by First-Principles Design

By Zheshuai Lin from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03778H, Paper
Shengzi Zhang, Lei Kang, Zheshuai Lin
We propose a series of novel ASnX (A = Na, H; X = N, P) layered structures based on first-principles modeling and simulation. These nanosheet materials are all derived from...
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Solid-state thiolate-stabilized copper nanoclusters with ultrahigh photoluminescence quantum yield for white light-emitting devices

By Wei Chen from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03640D, Paper
Hao-Hua Deng, Qiong-Qiong Zhuang, Kai-Yuan Huang, Paramasivam Balasubramanian, Zhen Lin, Hua-Ping Peng, Xing-Hua Xia, Wei Chen
As a new emerging candidate for solid-state phosphor, copper nanoclusters (CuNCs) have gained tremendous interest in the field of white light-emitting devices (WLEDs). However, their further applications are impeded by...
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Mechanically robust, UV screener core double shell nanostructures provides enhanced shielding for EM radiations over wide angle of incidence

By Suryasarathi Bose from RSC - Nanoscale latest articles. Published on Jul 03, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR02654A, Paper
Yudhajit Bhattacharjee, Sambit B, Suryasarathi Bose
Herein, we have designed and synthesized first of its kind core-double shell nano heterostructure materials where primitive ferrite (Fe3O4) acts as a diffused shell around an amorphous conducting core (carbon...
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SnO2 Quantum Dots: Rational Design to Achieve Highly Reversible Conversion Reaction and Stable Capacities for Lithium and Sodium Storage

By Yong Cheng, Shaohua Wang, Lin Zhou, Limin Chang, Wanqiang Liu, Dongming Yin, Zheng Yi, Limin Wang from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

SnO2 quantum dots (≈5 nm) embedded in porous N‐doped carbon matrix (SnO2/NC) are developed via a hydrothermal step combined with a self‐polymerization process at room temperature. The ultrasmall size in quantum dots greatly shortens the ion diffusion distance and lowers the internal strain, significantly improving the conversion reaction efficiency and initial coulombic efficiency in lithium and sodium storage. Abstract SnO2 has been considered as a promising anode material for lithium‐ion batteries (LIBs) and sodium ion batteries (SIBs), but challenging as well for the low‐reversible conversion reaction and coulombic efficiency. To address these issues, herein, SnO2 quantum dots (≈5 nm) embedded in porous N‐doped carbon matrix (SnO2/NC) are developed via a hydrothermal step combined with a self‐polymerization process at room temperature. The ultrasmall size in quantum dots can greatly shorten the ion diffusion distance and lower the internal strain, improving the conversion reaction efficiency and coulombic efficiency. The rich mesopores/micropores and highly conductive N‐doped carbon matrix can further enhance the overall conductivity and buffer effect of the composite. As a result, the optimized SnO2/NC‐2 composite for LIBs exhibits a high coulombic efficiency of 72.9%, a high discharge capacity of 1255.2 mAh g−1 at 0.1 A g−1 after 100 cycles and a long life‐span with a capacity of 753 mAh g−1 after 1500 cycles at 1 A g−1. The SnO2/NC‐2 composite also displays excellent performance for SIBs, delivering a superior discharge capacity of 212.6 mAh g−1 at 1 A g−1 after 3000 cycles. These excellent results can be of visible significance for the size effect of the uniform quantum dots.

From Molecular Reconstruction of Mesoscopic Functional Conductive Silk Fibrous Materials to Remote Respiration Monitoring

By Liyun Ma, Qiang Liu, Ronghui Wu, Zhaohui Meng, Aniruddha Patil, Rui Yu, Yun Yang, Shuihong Zhu, Xuwei Fan, Chen Hou, Yanran Li, Wu Qiu, Lianfen Huang, Jun Wang, Naibo Lin, Yizao Wan, Jian Hu, Xiang Yang Liu from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

A new conceptual silk meso‐fibrous material for biocompatible electronic applications is developed by carbon nanotubes meso reconstruction. It can be adopted to fabricate various fibrous sensors, i.e., electronic humidity sensors. In combination with internet of things (IoTs) and artificial intelligence technologies, a remote respiratory condition monitoring and diagnosis can be achieved. Abstract Turning insulating silk fibroin materials into conductive ones turns out to be the essential step toward achieving active silk flexible electronics. This work aims to acquire electrically conductive biocompatible fibers of regenerated Bombyx mori silk fibroin (SF) materials based on carbon nanotubes (CNTs) templated nucleation reconstruction of silk fibroin networks. The electronical conductivity of the reconstructed mesoscopic functional fibers can be tuned by the density of the incorporated CNTs. It follows that the hybrid fibers experience an abrupt increase in conductivity when exceeding the percolation threshold of CNTs >35 wt%, which leads to the highest conductivity of 638.9 S m−1 among organic‐carbon‐based hybrid fibers, and 8 times higher than the best available materials of the similar types. In addition, the silk‐CNT mesoscopic hybrid materials achieve some new functionalities, i.e., humidity‐responsive conductivity, which is attributed to the coupling of the humidity inducing cyclic contraction of SFs and the conductivity of CNTs. The silk‐CNT materials, as a type of biocompatible electronic functional fibrous material for pressure and electric response humidity sensing, are further fabricated into a smart facial mask to implement respiration condition monitoring for remote diagnosis and medication.

X‐Ray‐Induced Growth Dynamics of Luminescent Silver Clusters in Zeolites

By Oliver Fenwick, Eduardo Coutiño‐Gonzalez, Fanny Richard, Sara Bonacchi, Wouter Baekelant, Dirk Vos, Maarten B. J. Roeffaers, Johan Hofkens, Paolo Samorì from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Luminescent silver clusters can be formed in zeolite frameworks by X‐ray irradiation, but they have a broader size distribution. Cluster growth dynamics is framework‐dependent and is also dependent on degree of silver loading in the framework. Growth from cations to luminescent clusters then non‐luminescent metallic nanoparticles is observed. Abstract Herein, AlKα X‐rays are used to drive the growth of luminescent silver clusters in zeolites. The growth of the silver species is tracked using Auger spectroscopy and fluorescence microscopy, by monitoring the evolution from their ions to luminescent clusters and then metallic, dark nanoparticles. It is shown that the growth rate in different zeolites is determined by the mobility of the silver ions in the framework and that the growth dynamics in calcined samples obeys the Hill–Langmuir equation for noncooperative binding. Comparison of the optical properties of X‐ray‐grown silver clusters with silver clusters formed by standard heat treatment indicates that the latter have a higher specificity toward the formation of luminescent clusters of a specific (small) nuclearity, whereas the former produce a wide distribution of cluster species as well as larger nanoparticles.

Remarkable Piezophoto Coupling Catalysis Behavior of BiOX/BaTiO3 (X = Cl, Br, Cl0.166Br0.834) Piezoelectric Composites

By Xiaofeng Zhou, Fei Yan, Shuanghao Wu, Bo Shen, Huarong Zeng, Jiwei Zhai from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Under coirradiation of light and ultrasound, BiOX/BTO (X = Cl, Br, Cl0.166Br0.834) piezoelectric composites create a depolarization field induced by polarization charges of piezoelectric effect, which can be used as a driving force to promote the separation of photoinduced charge carriers, thus resulting in more excited electrons participating in photocatalytic reactions through reduction products •O2− and •OH radicals. Abstract Polarization field engineering of piezoelectric materials is considered as an advisable strategy in fine‐tuning photocatalytic performance which has drawn much attention recently. However, the efficient charge separation that determines the photocatalytic reactivities of these materials is quite restricted. Herein, a judicious combination of piezoelectric and photocatalytic performances of BiOX/BaTiO3 (X = Cl, Br, Cl0.166Br0.834) to enable a high piezophotocatalytic activity is demonstrated. Under the synergic advantages of chemical potential difference and piezoelectric potential difference in BiOX/BaTiO3 composites, the photoinduced carriers recombination is largely halted, which directly contributes to the significantly promoted piezophotocatalytic activity of piezoelectric composites. Inspiringly, the BiOBr/BaTiO3 composites under light irradiation with auxiliary ultrasonic activation result in an ultrahigh and stable photocatalytic performance, which is much higher than the total of those by isolated photocatalysis and piezocatalysis, and can rival current excellent photocatalytic system. In fact, the theoretical piezoelectric potential difference of BiOBr/BaTiO3 composites reaches 100 mV, which far exceeds the pure BaTiO3 of 31.21 mV and BiOBr of 30 mV, respectively. First, fabrication of BiOX/BaTiO3 piezoelectric composites and its remarkable piezophoto coupling catalysis behavior lays new ground for developing high‐efficiency piezoelectric photocatalysts in purifying wastewater, killing bacteria, and other piezophototronic processes.

Enhanced Photocatalytic H2‐Production Activity of CdS Quantum Dots Using Sn2+ as Cocatalyst under Visible Light Irradiation

By Xianglin Xiang, Bicheng Zhu, Bei Cheng, Jiaguo Yu, Hongjin Lv from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Sn2+ greatly enhances the H2‐production activity of water‐soluble CdS quantum dots (QDs). Sn2+ ions are reduced to Sn atoms by the electrons generated from the conduction band of CdS quantum dots under visible light irradiation. Sn atoms not only serve as photocatalytic cocatalyst for hydrogen generation, but also participate in forming CdS/Sn Schottky heterojunction. Abstract Herein, oil‐soluble CdS quantum dots (QDs) are first prepared through a solvent‐thermal process. Then, oil‐soluble CdS QDs are changed into water‐soluble QDs via ligand exchange using mercaptopropionic acid as capping agent at pH 13. The photocatalytic performance is investigated under the visible light irradiation using glycerol as sacrificial agent and Sn2+ as cocatalyst. No H2‐production activity is observed for oil‐soluble CdS QDs. Water‐soluble CdS QDs exhibit significantly enhanced hydrogen evolution rate. When the concentration of cocatalyst Sn2+ increases to 0.2 × 10−3 m, the rate of hydrogen evolution reaches 1.61 mmol g−1 h−1, which is 24 times higher than that of the pristine water‐soluble CdS QDs. The enhanced H2‐production efficiency is attributed to the adsorption of Sn2+ ions on the surface of CdS QDs that are further reduced to Sn atoms by photogenerated electrons. The in situ generated Sn atoms serve as photocatalytic cocatalyst for efficient hydrogen generation.

Temporal Sampling of Enzymes from Live Cells by Localized Electroporation and Quantification of Activity by SAMDI Mass Spectrometry

By Prithvijit Mukherjee, Eric J. Berns, Cesar A. Patino, Elamar Hakim Moully, Lingqian Chang, S. Shiva P. Nathamgari, John A. Kessler, Milan Mrksich, Horacio D. Espinosa from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

A microfluidic device for the nondestructive sampling of enzymes from cells and measuring their activity is presented. Cytoplasmic enzymes are extracted from small cell populations by localized electroporation. The enzymes modify a substrate immobilized on a self‐assembled monolayer and their activity is quantified using mass spectrometry. Activity change in cell populations is monitored by repeating the process at multiple timepoints. Abstract Measuring changes in enzymatic activity over time from small numbers of cells remains a significant technical challenge. In this work, a method for sampling the cytoplasm of cells is introduced to extract enzymes and measure their activity at multiple time points. A microfluidic device, termed the live cell analysis device (LCAD), is designed, where cells are cultured in microwell arrays fabricated on polymer membranes containing nanochannels. Localized electroporation of the cells opens transient pores in the cell membrane at the interface with the nanochannels, enabling extraction of enzymes into nanoliter‐volume chambers. In the extraction chambers, the enzymes modify immobilized substrates, and their activity is quantified by self‐assembled monolayers for matrix‐assisted laser desorption/ionization (SAMDI) mass spectrometry. By employing the LCAD‐SAMDI platform, protein delivery into cells is demonstrated. Next, it is shown that enzymes can be extracted, and their activity measured without a loss in viability. Lastly, cells are sampled at multiple time points to study changes in phosphatase activity in response to oxidation by hydrogen peroxide. With this unique sampling device and label‐free assay format, the LCAD with SAMDI enables a powerful new method for monitoring the dynamics of cellular activity from small populations of cells.

Ultrathin 2D Mesoporous TiO2/rGO Heterostructure for High‐Performance Lithium Storage

By Yaru Liang, Xiang Xiong, Zhuijun Xu, Qingbing Xia, Liyang Wan, Rutie Liu, Guoxin Chen, Shu‐Lei Chou from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

2D ultrathin mesoporous TiO2/rGO heterostructure is fabricated after heat treatment of the coprecipitated single‐layered Ti3O72−/GO nanosheet. Owing to the ultrathin mesoporous characteristics and the enhanced ionic and electron conductivity, the resulting 2D ultrathin mesoporous heterostructures can deliver an extremely high lithium storage capacity and excellent cycling stability at high current density. Abstract Lithium‐ion batteries (LIBs) have been widely applied and studied as an effective energy supplement for a variety of electronic devices. Titanium dioxide (TiO2), with a high theoretical capacity (335 mAh g−1) and low volume expansion ratio upon lithiation, has been considered as one of the most promising anode materials for LIBs. However, the application of TiO2 is hindered by its low electrical conductivity and slow ionic diffusion rate. Herein, a 2D ultrathin mesoporous TiO2/reduced graphene (rGO) heterostructure is fabricated via a layer‐by‐layer assembly process. The synergistic effect of ultrathin mesoporous TiO2 and the rGO nanosheets significantly enhances the ionic diffusion and electron conductivity of the composite. The introduced 2D mesoporous heterostructure delivers a significantly improved capacity of 350 mAh g−1 at a current density of 200 mA g−1 and excellent cycling stability, with a capacity of 245 mAh g−1 maintained over 1000 cycles at a high current density of 1 A g−1. The in situ transmission electron microscopy analysis indicates that the volume of the as‐prepared 2D heterostructures changes slightly upon the insertion and extraction of Li+, thus contributing to the enhanced long‐cycle performance.

Bath Electrospinning of Continuous and Scalable Multifunctional MXene‐Infiltrated Nanoyarns

By Ariana Levitt, Shayan Seyedin, Jizhen Zhang, Xuehang Wang, Joselito M. Razal, Genevieve Dion, Yury Gogotsi from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Continuous and electroactive MXene‐based nanofiber yarns (nanoyarns) are fabricated using a bath electrospinning method, which captures MXene flakes throughout the entire cross‐section of a nanoyarn, maximizing interactions between nanofibers and flakes. The high stretchability of polymeric nanofibers and the electrical and electrochemical properties of MXene offer a platform for storing energy and sensing body movements in wearable textiles. Abstract Electroactive yarns that are stretchable are desired for many electronic textile applications, including energy storage, soft robotics, and sensing. However, using current methods to produce these yarns, achieving high loadings of electroactive materials and simultaneously demonstrating stretchability is a critical challenge. Here, a one‐step bath electrospinning technique is developed to effectively capture Ti3C2Tx MXene flakes throughout continuous nylon and polyurethane (PU) nanofiber yarns (nanoyarns). With up to ≈90 wt% MXene loading, the resulting MXene/nylon nanoyarns demonstrate high electrical conductivity (up to 1195 S cm−1). By varying the flake size and MXene concentration, nanoyarns achieve stretchability of up to 43% (MXene/nylon) and 263% (MXene/PU). MXene/nylon nanoyarn electrodes offer high specific capacitance in saturated LiClO4 electrolyte (440 F cm−3 at 5 mV s−1), with a wide voltage window of 1.25 V and high rate capability (72% between 5 and 500 mV s−1). As strain sensors, MXene/PU yarns demonstrate a wide sensing range (60% under cyclic stretching), high sensitivity (gauge factor of ≈17 in the range of 20–50% strain), and low drift. Utilizing the stretchability of polymer nanofibers and the electrical and electrochemical properties of MXene, MXene‐based nanoyarns demonstrate potential in a wide range of applications, including stretchable electronics and body movement monitoring.

Urchin‐Like Fe3Se4 Hierarchitectures: A Novel Pseudocapacitive Sodium‐Ion Storage Anode with Prominent Rate and Cycling Properties

By Jian Zhang, Yongchang Liu, Hui Liu, Yuzhu Song, Shengdong Sun, Qiang Li, Xianran Xing, Jun Chen from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

A Fe3Se4 anode featuring urchin‐like hierarchitectures presents ultrahigh rate capability and outstanding cyclic stability in sodium‐ion batteries. As revealed by electrochemical analyses and in situ XRD, the phase transformation from monoclinic to amorphous structure accompanied by the pseudocapacitive Na+ storage behavior accounts for the superior electrochemical performance. Abstract Transition metal chalcogenides have received great attention as promising anode candidates for sodium‐ion batteries (SIBs). However, the undesirable cyclic life and inferior rate capability still restrict their practical applications. The design of micro–nano hierarchitectures is considered as a possible strategy to facilitate the electrochemical reaction kinetics and strengthen the electrode structure stability upon repeated Na+ insertion/extraction. Herein, urchin‐like Fe3Se4 hierarchitectures are successfully prepared and developed as a novel anode material for SIBs. Impressively, the as‐prepared urchin‐like Fe3Se4 can present an ultrahigh rate capacity of 200.2 mAh g‐1 at 30 A g‐1 and a prominent capacity retention of 99.9% over 1000 cycles at 1 A g‐1, meanwhile, a respectable initial coulombic efficiency of ≈100% is achieved. Through the conjunct study of in situ X‐ray diffraction, ex situ X‐ray absorption near‐edge structure spectroscopy, as well as cyclic voltammetry curves, it is intriguing to reveal that the phase transformation from monoclinic to amorphous structure accompanied by the pseudocapacitive Na+ storage behavior accounts for the superior electrochemical performance. When paired with the Na3V2(PO4)3 cathode materials, the assembled full cell enables high energy density and decent cyclic stability, demonstrating potential practical feasibility of the present urchin‐like Fe3Se4 anode.

One‐Step Preparation of Highly Durable Superhydrophobic Carbon Nanothorn Arrays

By Xiaodong Li, Ning Wang, Jianjiang He, Ze Yang, Fuhua Zhao, Kun Wang, Changshui Huang from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Novel methyl‐substituted graphdiyne nanothorn arrays (MGDY NTAs) are prepared on various substrates using a one‐step method. These are similar to hedgehog thorns, whereas methyls are similar to the flowers on thorns, which have a protective role. In contrast, the MGDY NTA morphology is similar to grass, while porous substrates are similar to soil, which can be used for oil–water separation. Abstract This study proposes a one‐step method for growing superhydrophobic carbon nanothorn arrays (NTAs) directly on various substrates. The fabricated carbon material (named methyl‐substituted graphdiyne (MGDY)) comprises sp and sp2 carbons in a conjugated‐backbone form, as well as methyl groups introduced into the framework as hydrophobic‐enhanced functional groups. MGDY NTAs exhibit excellent hydrophobicity (contact angle ≥152°), substantial long‐period hydrophobic durability (the contact angle decreased by only 3.2% over 800 days), and acid/alkali tolerance. Owing to the enhanced durability and specific stability of carbon, a superhydrophobic interface can easily be constructed using MGDY NTAs, which can be applied to achieve successful long‐term metal‐corrosion protection and efficient oil–water separation.

In Vivo Repeatedly Activated Persistent Luminescence Nanoparticles by Radiopharmaceuticals for Long‐Lasting Tumor Optical Imaging

By Nian Liu, Junpeng Shi, Qiang Wang, Jingru Guo, Zhenyu Hou, Xinhui Su, Hongwu Zhang, Xiaolian Sun from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Radiopharmaceuticals (18F‐FDG) with a short decay half‐life are used as the internal light source to in vivo excite Cr3+‐doped zinc gallate (ZGCs) for long‐lasting luminescence for multiple times. This strategy can provide tumor luminescence imaging with high sensitivity, high contrast, and long decay time at desired time, greatly benefiting image‐guided surgery in the future. Abstract Persistent luminescence nanoparticles (PLNPs) with rechargeable near‐infrared afterglow properties attract much attention for tumor diagnosis in living animals since they can avoid tissue autofluorescence and greatly improve the signal‐to‐background ratio. Using UV, visible light, or X‐ray as excitation sources to power up persistent luminescence (PL) faces the challenges such as limited tissue penetration, inefficient charging capability, or tissue damage caused by irradiation. Here, it is proved that radiopharmaceuticals can efficiently excite ZnGa2O4:Cr3+ nanoparticles (ZGCs) for both fluorescence and afterglow luminescence via Cerenkov resonance energy transfer as well as ionizing radiation. 18F‐FDG, a clinically approved tumor‐imaging radiopharmaceutical with a short decay half‐life around 110 min, is successfully used as the internal light source to in vivo excite intravenously injected ZGCs for tumor luminescence imaging over 3 h. The luminescence with similar decay time can be re‐obtained for multiple times upon injection of 18F‐FDG at any time needed with no health concern. It is believed this strategy can not only provide tumor luminescence imaging with high sensitivity, high contrast, and long decay time at desired time, but also guarantee the patients much less radiation exposure, greatly benefiting image‐guided surgery in the future.

Adsorption‐Free Growth of Ultra‐Thin Molybdenum Membranes with a Low‐Symmetry Rectangular Lattice Structure

By Jingjing Si, Mengqi Zeng, Huy Q. Ta, Shuting Zheng, Jihai Liao, Xiaobao Yang, Mark H. Rümmeli, Lei Fu from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Ultra‐thin body‐centered‐cubic phase molybdenum membranes with a low‐symmetry rectangular (110) crystal face are synthesized via an adsorption free reaction. This work provides new insight for the preparation of well‐defined two‐dimensional transition metals with (110) faces and also is beneficial for the exploration and development of low‐symmetry rectangular lattice structured materials with unique properties. Abstract Although low‐symmetry lattice structure of 2D transition metals is highly anticipated for both fundamental research and potentially distinctive application, it still has not been experimentally realized, which greatly hinders the exploration of the unique properties. Here, ultra‐thin body‐centered‐cubic (bcc) phase molybdenum (Mo) membranes are successfully synthesized with a low‐symmetry rectangular (110) crystal face via an adsorption‐free reaction. Through experimental and density functional theory studies, no foreign atoms being adsorbed is shown to be a key factor for the successful preparation of the bcc phase 2D transition metal with (110) faces. The realization of 2D Mo(110) with a low‐symmetric rectangular lattice structure extends the scope of 2D structures and is also beneficial for the exploration and development of low‐symmetry rectangular lattice‐structured materials with unique properties.

Confinement Growth of Layered WS2 in Hollow Beaded Carbon Nanofibers with Synergistic Anchoring Effect to Reinforce Li+/Na+ Storage Performance

By Huayu Wu, Xing Chen, Chen Qian, Hui Yan, Chenyi Yan, Nuo Xu, Yuanzhe Piao, Guowang Diao, Ming Chen from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Tungsten disulfide (WS2) nanosheets are anchored on the surface and inside of hollow beaded carbon nanofibers (HB CNFs) via a confined growth strategy to construct hierarchical structure HB WS2@CNFs. The conversion mechanism of Li+/Na+ storage is analyzed by an ex situ method. This special structure can effectively restrain the volume effect and improve the storage performance of lithium‐ion batteries and sodium‐ion batteries. Abstract Novel nitrogen doped (N‐doped) hollow beaded structural composite carbon nanofibers are successfully applied for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). Tungsten disulfide (WS2) nanosheets are confined, through synergistic anchoring, on the surface and inside of hollow beaded carbon nanofibers (HB CNFs) via a hydrothermal reaction method to construct the hierarchical structure HB WS2@CNFs. Benefiting from this unique advantage, HB WS2@CNFs exhibits remarkable lithium‐storage performance in terms of high rate capability (≈351 mAh g−1 at 2 A g−1) and stable long‐term cycle (≈446 mAh g−1 at 1 A g−1 after 100 cycles). Moreover, as an anode material for SIBs, HB WS2@CNFs obtains excellent long cycle life and rate performance. During the charging/discharging process, the evolution of morphology and composition of the composite are analyzed by a set of ex situ methods. This synergistic anchoring effect between WS2 nanosheets and HB CNFs is capable of effectively restraining volume expansion from the metal ions intercalation/deintercalation process and improving the cycling stability and rate performance in LIBs and SIBs.

Sensitive and Stable Tin–Lead Hybrid Perovskite Photodetectors Enabled by Double‐Sided Surface Passivation for Infrared Upconversion Detection

By Yan Zhao, Chenglong Li, Jizhong Jiang, Boming Wang, Liang Shen from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

The double‐sided surface passivation engineering is the use of phenethylammonium iodide to effectively passivate the top and bottom defects of Sn‐based perovskite films. The increase of grain size, the decrease in density of trap states, and the surface hydrophobicity effectively improve the sensitivity and stability of Sn‐based perovskite photodetectors. Finally, the photodetectors realize the infrared upconversion application. Abstract Tin(Sn)‐based perovskite is currently considered one of the most promising materials due to extending the absorption spectrum and reducing the use of lead (Pb). However, Sn2+ is easily oxidized to Sn4+ in atmosphere, causing more defects and degradation of perovskite materials. Herein, double‐sided interface engineering is proposed, that is, Sn‐Pb perovskite films are sandwiched between the phenethylammonium iodide (PEAI) in both the bottom and top sides. The larger organic cations of PEA+ are arranged into a perovskite surface lattice to form a 2D capping layer, which can effectively prevent the water and oxygen to destroy bulk perovskite. Meanwhile, the PEA+ can also passivate defects of iodide anions at the bottom of perovskite films, which is always present but rarely considered previously. Compared to one sided passivation, Sn‐Pb hybrid perovskite photodetectors contribute a significant enhancement of performance and stability, yielding a broadband response of 300–1050 nm, a low dark current density of 1.25 × 10–3 mA cm–2 at –0.1 V, fast response speed of 35 ns, and stability beyond 240 h. Furthermore, the Sn‐Pb broadband photodetectors are integrated in an infrared up‐conversion system, converting near‐infrared light into visible light. It is believed that a double‐sided passivation method can provide new strategies to achieving high‐performance perovskite photodetectors.

A High‐Energy and Long‐Life Aqueous Zn/Birnessite Battery via Reversible Water and Zn2+ Coinsertion

By Zhiguo Hou, Mengfei Dong, Yali Xiong, Xueqian Zhang, Huaisheng Ao, Mengke Liu, Yongchun Zhu, Yitai Qian from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

A mechanism of aqueous rechargeable zinc ion batteries is demonstrated. Through engineering Zn2+ primary solvation sheath in aqueous electrolyte, highly reversible [Zn(H2O)2]2+ intercalation/extraction into/from birnessite cathode is obtained and cathode–electrolyte interfaces are in‐situ formed suppressing the Mn dissolution. In addition, the Zn metal anode also shows high reversibility without formation of “death‐zinc” and detrimental dendrite. Abstract Aqueous rechargeable Zn/birnessite batteries have recently attracted extensive attention for energy storage system because of their low cost and high safety. However, the reaction mechanism of the birnessite cathode in aqueous electrolytes and the cathode structure degradation mechanics still remain elusive and controversial. In this work, it is found that solvation water molecules coordinated to Zn2+ are coinserted into birnessite lattice structure contributing to Zn2+ diffusion. However, the birnessite will suffer from hydroxylation and Mn dissolution with too much solvated water coinsertion. Through engineering Zn2+ primary solvation sheath with strong‐field ligand in aqueous electrolyte, highly reversible [Zn(H2O)2]2+ complex intercalation/extraction into/from birnessite cathode is obtained. Cathode–electrolyte interface suppressing the Mn dissolution also forms. The Zn metal anode also shows high reversibility without formation of “death‐zinc” and detrimental dendrite. A full cell coupled with birnessite cathode and Zn metal anode delivers a discharge capacity of 270 mAh g−1, a high energy density of 280 Wh kg−1 (based on total mass of cathode and anode active materials), and capacity retention of 90% over 5000 cycles.

Hyperboloid‐Drum Microdisk Laser Biosensors for Ultrasensitive Detection of Human IgG

By Zhihe Guo, Yingchun Qin, Peizong Chen, Jinliang Hu, Yi Zhou, Xuyang Zhao, Zhiran Liu, Yiyan Fei, Xiaoshun Jiang, Xiang Wu from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

The new kind of microdisk lasers in a hyperboloid‐drum (HD) shape is a combination of a dye‐doped photoresist and a silica microdisk. Such HD microdisk laser biosensors can achieve specific detection of human immunoglobulin G in phosphate‐buffered saline and artificial serum. The results from this study are approximately four orders of magnitude more sensitive than previous reports. Abstract Whispering gallery mode (WGM) microresonators have been used as optical sensors in fundamental research and practical applications. The majority of WGM sensors are passive resonators that require complex systems, thereby limiting their practicality. Active resonators enable the remote excitation and collection of WGM‐modulated fluorescence spectra, without requiring complex systems, and can be used as alternatives to passive microresonators. This paper demonstrates an active microresonator, which is a microdisk laser in a hyperboloid‐drum (HD) shape. The HD microdisk lasers are a combination of a rhodamine B‐doped photoresist and a silica microdisk. These HD microdisk lasers can be utilized for the detection of label‐free biomolecules. The biomolecule concentration can be as low as 1 ag mL−1, whereas the theoretical detection limit of the biosensor for human IgG in phosphate buffer saline is 9 ag mL−1 (0.06 aM). Additionally, the biosensors are able to detect biomolecules in an artificial serum, with a theoretical detection limit of 9 ag mL−1 (0.06 aM). These results are approximately four orders of magnitude more sensitive than those for the typical active WGM biosensors. The proposed HD microdisk laser biosensors show enormous detection potential for biomarkers in protein secretions or body fluids.

Engineering Supramolecular Polymer Conformation for Efficient Carbon Nanotube Sorting

By Theodore Z. Gao, Zehao Sun, Xuzhou Yan, Hung‐Chin Wu, Hongping Yan, Zhenan Bao from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

The addition of chain stoppers significantly improves carbon nanotube (CNT) sorting with an H‐bonding supramolecular polymer. In‐depth characterization reveals that this supramolecular polymer exhibits ring–chain equilibrium, and that stoppers skew the distribution toward chains, which can wrap CNTs more effectively. Careful selection of the stopper–monomer ratio results in doubling of the sorting yield without compromising the purity or properties of sorted CNTs. Abstract Supramolecular polymer sorting is a promising approach to separating single‐walled carbon nanotubes (CNTs) by electronic type. Unlike conjugated polymers, they can be easily removed from the CNTs after sorting by breaking the supramolecular bonds, allowing for isolation of electronically pristine CNTs as well as facile recycling of the sorting polymer. However, little is understood about how supramolecular polymer properties affect CNT sorting. Herein, chain stoppers are used to engineer the conformation of a supramolecular sorting polymer, thereby elucidating the relationship between sorting efficacy and polymer conformation. Through NMR and UV–vis spectroscopy, small‐angle X‐ray scattering (SAXS), and thermodynamic modeling, it is shown that this supramolecular polymer exhibits ring–chain equilibrium, and that this equilibrium can be skewed toward chains by the addition of chain stoppers. Furthermore, by controlling the stopper–monomer ratio, the sorting yield can be doubled from 7% to 14% without compromising the semiconducting purity (>99%) or properties of sorted CNTs.

Is GSH Chelated Pt Molecule Inactive in Anti‐Cancer Treatment? A Case Study of Pt6GS4

By Chunyu Zhang, Liang Gao, Qing Yuan, Lina Zhao, Wenchao Niu, Pengju Cai, Jiaojiao Li, Xu Han, Zhesheng He, Fuping Gao, Yaling Wang, Huaidong Jiang, Zhifang Chai, Xueyun Gao from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Previous reports have advocated that cancer cells could utilize endogenous GSH to chelate Pt drugs to produce inactive GSH‐Pt adduct. Herein, a GSH chelated Pt molecule is precisely synthesized, which exhibits efficient cancer therapy without systemic toxicity in vivo. This work opens a route to explore polynuclear Pt compounds with accurate architectures as promising anti‐tumor agents. Abstract Platinum (Pt) drugs are widely used in anti‐cancer treatment although many reports advocated that tumor cells could inactivate Pt drugs via glutathione‐Pt (GSH‐Pt) adducts formation. To date, GSH chelated Pt molecules have not been assessed in cancer treatment because GSH‐Pt adducts are not capable of killing cancer cells, which is widely accepted and well followed. In this report, endogenous biothiol is utilized to precisely synthesize a GSH chelated Pt molecule (Pt6GS4). This Pt6GS4 molecule can be well taken up by aggressive triple negative breast cancer (TNBC) cells. Subsequently, its metabolites could enter nuclei to interact with DNA, finally the DNA‐Pt complex triggers TNBC cell apoptosis via the p53 pathway. Impressively, high efficacy for anti‐cancer treatment is achieved by Pt6GS4 both in vitro and in vivo when compared with traditional first‐line carboplatin in the same dosage. Compared with carboplatin, Pt6GS4 keeps tumor bearing mice alive for a longer time and is non‐toxic for the liver and kidneys. This work opens a route to explore polynuclear Pt compound with accurate architecture for enhancing therapeutic effects and reducing systemic toxicity.

Masthead: (Small 26/2020)

By from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Carbon Nanothorn Arrays: One‐Step Preparation of Highly Durable Superhydrophobic Carbon Nanothorn Arrays (Small 26/2020)

By Xiaodong Li, Ning Wang, Jianjiang He, Ze Yang, Fuhua Zhao, Kun Wang, Changshui Huang from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

In article number 1907013, Changshui Huang and co‐workers directly prepare the methyl substituted graphdiyne nanothorn arrays (MGDY NTAs) on a variety of substrates by a one‐step method, which shows superhydrophobic properties, and high durability. The MGDY NTAs can be applied in the fields of metal corrosion protection and oil–water separation.

Enzyme Sampling: Temporal Sampling of Enzymes from Live Cells by Localized Electroporation and Quantification of Activity by SAMDI Mass Spectrometry (Small 26/2020)

By Prithvijit Mukherjee, Eric J. Berns, Cesar A. Patino, Elamar Hakim Moully, Lingqian Chang, S. Shiva P. Nathamgari, John A. Kessler, Milan Mrksich, Horacio D. Espinosa from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

In article number 2000584, Milan Mrksich, Horacio D. Espinosa, and co‐workers report on a method for non‐destructively sampling enzymes multiple times from small populations of cells, using localized electroporation in microfluidic live cell analysis devices. The enzymes are captured in extraction chambers, where they modify immobilized substrates on a self‐assembled monolayer, and their activity is quantified using self‐assembled monolayers for matrix‐assisted laser desorption/ionization (SAMDI) mass spectrometry.

Perovskite Photodetectors: Sensitive and Stable Tin–Lead Hybrid Perovskite Photodetectors Enabled by Double‐Sided Surface Passivation for Infrared Upconversion Detection (Small 26/2020)

By Yan Zhao, Chenglong Li, Jizhong Jiang, Boming Wang, Liang Shen from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

In article number 2001534, Liang Shen and co‐workers demonstrate a sensitive and stable Sn‐Pb perovskite photodetector, employing phenethylammonium iodide to complete defects passivation aiming the top and bottom of films. The double‐sided surface passivation engineering can promote the grain growth, reduce the density of trap states and improve surface hydrophobicity. Finally, it realizes infrared up‐conversion application for visualization.

Respiration Monitoring: From Molecular Reconstruction of Mesoscopic Functional Conductive Silk Fibrous Materials to Remote Respiration Monitoring (Small 26/2020)

By Liyun Ma, Qiang Liu, Ronghui Wu, Zhaohui Meng, Aniruddha Patil, Rui Yu, Yun Yang, Shuihong Zhu, Xuwei Fan, Chen Hou, Yanran Li, Wu Qiu, Lianfen Huang, Jun Wang, Naibo Lin, Yizao Wan, Jian Hu, Xiang Yang Liu from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

In article number 2000203, Xiang Yang Liu and co‐workers meso‐reconstruct silkworm silk fibrous materials based on carbon nanotubes which give rise to conductive silk fibers, for the fabrication of silk flexible electronics. They have humidity dependent conductivity and can be developed into biocompatible electronic humidity sensors. The combination with cloud computation and big data leads to remote monitoring and diagnosis of respiration and other physiological conditions.

Progress on Lithium Dendrite Suppression Strategies from the Interior to Exterior by Hierarchical Structure Designs

By Lu Shen, Peiran Shi, Xiaoge Hao, Qiang Zhao, Jiabin Ma, Yan‐Bing He, Feiyu Kang from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

The strategy of suppressing Li dendrite growth and accommodating volume expansion is put forward from a new perspective of hierarchical structure designs of the Li anode from the interior (3D porous current collector and host matrix) to exterior (artificial solid electrolyte interphase (SEI), protective layer, separator, and solid‐state electrolyte). The Li dendrite growth mechanisms and suppression strategies are also concluded. Abstract Lithium (Li) metal is promising for high energy density batteries due to its low electrochemical potential (−3.04 V) and high specific capacity (3860 mAh g−1). However, the safety issues impede the commercialization of Li anode batteries. In this work, research of hierarchical structure designs for Li anodes to suppress Li dendrite growth and alleviate volume expansion from the interior (by the 3D current collector and host matrix) to the exterior (by the artificial solid electrolyte interphase (SEI), protective layer, separator, and solid state electrolyte) is concluded. The basic principles for achieving Li dendrite and volume expansion free Li anode are summarized. Following these principles, 3D porous current collector and host matrix are designed to suppress the Li dendrite growth from the interior. Second, artificial SEI, the protective layer, and separator as well as solid‐state electrolyte are constructed to regulate the distribution of current and control the Li nucleation and deposition homogeneously for suppressing the Li dendrite growth from exterior of Li anode. Ultimately, this work puts forward that it is significant to combine the Li dendrite suppression strategies from the interior to exterior by 3D hierarchical structure designs and Li metal modification to achieve excellent cycling and safety performance of Li metal batteries.

Improving the Quality and Luminescence Performance of All‐Inorganic Perovskite Nanomaterials for Light‐Emitting Devices by Surface Engineering

By Zhaohui Shen, Suling Zhao, Dandan Song, Zheng Xu, Bo Qiao, Pengjie Song, Qiongyu Bai, Jingyue Cao, Gaoqian Zhang, Wageh Swelm from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Surface engineering could influence the performance of inorganic perovskite nanomaterials and devices. Herein, common synthesis methods of perovskite nanomaterials and the working principles and effects of common ligands are reviewed, and the surface treatment methods used to improve the performance of perovskite quantum dot light emitting diodes are introduced . Abstract Lead halide perovskites and their applications in the optoelectronic field have garnered intensive interest over the years. Inorganic perovskites (IHP), though a novel class of material, are considered as one of the most promising optoelectronic materials. These materials are widely used in detectors, solar cells, and other devices, owing to their excellent charge‐transport properties, high defect tolerance, composition‐ and size‐dependent luminescence, narrow emission, and high photoluminescence quantum yield. In recent years, numerous encouraging achievements have been realized, especially in the research of CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) and surface engineering. Therefore, it is necessary to summarize the principles and effects of these surface engineering optimization methods. It is also important to scientifically guide the applications and promote the development of perovskites more efficiently. Herein, the principles of surface ligands are reviewed, and various surface treatment methods used in CsPbX3 NCs as well as quantum‐dot light‐emitting diodes are presented. Finally, a brief outlook on CsPbX3 NC surface engineering is offered, illustrating the present challenges and the direction in which future investigations are intended to obtain high‐quality CsPbX3 NCs that can be utilized in more applications.

In Situ Grazing‐Incidence Wide‐Angle Scattering Reveals Mechanisms for Phase Distribution and Disorientation in 2D Halide Perovskite Films

By Justin M. Hoffman, Joseph Strzalka, Nathan C. Flanders, Ido Hadar, Shelby A. Cuthriell, Qingteng Zhang, Richard D. Schaller, William R. Dichtel, Lin X. Chen, Mercouri G. Kanatzidis from Wiley: Advanced Materials: Table of Contents. Published on Jul 02, 2020.

The mechanism of 2D halide perovskite film formation is resolved using in situ grazing‐incidence wide‐angle scattering (GIWAXS). The film begins as a sol–gel precursor before first forming a 3D MAPbI3‐like phase at the air/liquid interface. This acts as the template for the highly textured 2D phase with the layers perpendicular to the substrate, which grows closer to the substrate. Abstract 2D hybrid halide perovskites with the formula (A′)2(A)n‐1PbnI3n+1 have remarkable stability and promising efficiency in photovoltaic and optoelectronic devices, yet fundamental understanding of film formation, key to optimizing these devices, is lacking. Here, in situ grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) is used to monitor film formation during spin‐coating. This elucidates the general film formation mechanism of 2D halide perovskites during one‐step spin‐coating. There are three stages of film formation: sol–gel, oriented 3D, and 2D. Three precursor phases form during the sol–gel stage and transform to perovskite, first giving a highly oriented 3D‐like phase at the air/liquid interface followed by subsequent nucleations forming slightly less oriented 2D perovskite. Furthermore, heating before crystallization leads to fewer nucleations and faster removal of the precursors, improving orientation. This outlines the primary causes of phase distribution and perpendicular orientation in 2D perovskite films and paves the way for rationally designed film fabrication techniques.

Multifunctional Active‐Center‐Transferable Platinum/Lithium Cobalt Oxide Heterostructured Electrocatalysts towards Superior Water Splitting

By Xiaobo Zheng, Peixin Cui, Yumin Qian, Guoqiang Zhao, Xusheng Zheng, Xun Xu, Zhenxiang Cheng, Yuanyue Liu, Shi Xue Dou, Wenping Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Center of attention: Multifunctional platinum/lithium cobalt oxide (Pt/LiCoO2) heterostructures are prepared that allow the active center to be switched between Pt species for the hydrogen evolution reaction (HER) and LiCoO2 species for the oxygen evolution reaction (OER). Abstract Designing cost‐effective and efficient electrocatalysts plays a pivotal role in advancing the development of electrochemical water splitting for hydrogen generation. Herein, multifunctional active‐center‐transferable heterostructured electrocatalysts, platinum/lithium cobalt oxide (Pt/LiCoO2) composites with Pt nanoparticles (Pt NPs) anchored on LiCoO2 nanosheets, are designed towards highly efficient water splitting. In this electrocatalyst system, the active center can be alternatively switched between Pt species and LiCoO2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Specifically, Pt species are the active centers and LiCoO2 acts as the co‐catalyst for HER, whereas the active center transfers to LiCoO2 and Pt turns into the co‐catalyst for OER. The unique architecture of Pt/LiCoO2 heterostructure provides abundant interfaces with favorable electronic structure and coordination environment towards optimal adsorption behavior of reaction intermediates. The 30 % Pt/LiCoO2 heterostructured electrocatalyst delivers low overpotentials of 61 and 285 mV to achieve 10 mA cm−2 for HER and OER in alkaline medium, respectively.

Fast and Stable N‐Terminal Cysteine Modification through Thiazolidino Boronate Mediated Acyl Transfer

By Kaicheng Li, Wenjian Wang, Jianmin Gao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Fast and dynamic thiazolidine boronate (TzB) formation followed by an acyl‐transfer reaction enables facile N‐terminal cysteine modification with single‐digit micromolar concentrations of labeling reagents and exquisite selectivity. The utility of this reaction is demonstrated by non‐disruptive labeling of enzymes as well as bacteriophage to generate chemically modified phage libraries. Abstract We report a novel conjugation of N‐terminal cysteines (NCys) that proceeds with fast kinetics and exquisite selectivity, thereby enabling facile modification of NCys‐bearing proteins in complex biological milieu. This new NCys conjugation proceeds via a thiazolidine boronate (TzB) intermediate that results from fast (k2: ≈5000 m−1 s−1) and reversible conjugation of NCys with 2‐formylphenylboronic acid (FPBA). We designed a FPBA derivative that upon TzB formation elicits intramolecular acyl transfer to give N‐acyl thiazolidines. In contrast to the quick hydrolysis of TzB, the N‐acylated thiazolidines exhibit robust stability under physiologic conditions. The utility of the TzB‐mediated NCys conjugation is demonstrated by rapid and non‐disruptive labeling of two enzymes. Furthermore, applying this chemistry to bacteriophage allows facile chemical modification of phage libraries, which greatly expands the chemical space amenable to phage display.

Hydrogenase mimics in M12L24 nano‐spheres to control overpotential and activity in proton reduction catalysis

By Riccardo Zaffaroni, Nicole Orth, Ivana Ivanović-Burmazović, Joost Reek from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Hydrogenase enzymes are excellent proton reduction catalysts and therefore provide clear blueprints for the development of nature inspired synthetic analogs. Mimicking their catalytic center is straightforward but mimicking the protein matrix around the active site and all its functions remains challenging. Synthetic models lack this precisely controlled second coordination sphere that provides substrate preorganization and catalyst stability and, as a result, their performances are far from those of the natural enzyme. In this contribution we report a strategy to easily introduce a specific yet customizable second coordination sphere around synthetic hydrogenase models by encapsulation inside M 12 L 24 cages and at the same time create a proton‐rich nano‐environment by co‐encapsulation of ammonium salts, effectively providing substrate preorganization and intermediates stabilization. We show that catalyst encapsulation in these nano‐cages reduces the catalytic overpotential for proton reduction by 250 mV as compared to the uncaged catalyst while the proton‐rich nano‐environment created around the catalyst ensures that high catalytic rates are maintained.

A phosphanyl‐phosphagallene that functions as a frustrated Lewis pair

By Daniel W. N. Wison, Joey Feld, Jose Manuel Goicoechea from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Phosphagallenes ( 1a / 1b ) featuring a double bond between the phosphorus and gallium atoms have been synthesized for the first time by reaction of (phosphanyl)phosphaketenes with the gallium carbenoid (Nacnac)Ga (Nacnac = HC[C(Me)N(2,6‐ i ‐Pr 2 C 6 H 3 )] 2 ). The stability of these species was found to be dependent on the saturation of the phosphanyl moiety. 1a , which bares an unsaturated phosphanyl ring, rearranges in solution to yield a spirocyclic gallium compound 2 which contains a P–P double bond. The saturated variant 1b is stable even at elevated temperatures. 1b behaves as a masked frustrated Lewis pair capable of activation of hydrogen and forms a 1:1 adduct with CO 2 .

Temperature‐Dependent Tip‐Induced Motion of Ga Adatom on GaAs (110) Surface

By Shigeru Kaku, Junji Yoshino from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Temperature dependent adsorption sites and tip‐induced motions of Ga adatoms on a semiconductor GaAs (110) surface are explored in a real space image using scanning tunneling microscopy (STM). The surface adsorption potential profile of the Ga adatom on the GaAs (110) obtained by first‐principles calculations successfully demonstrates oberved temperature depending phenomena. Abstract The temperature‐dependent tip‐induced‐motion of a Ga adatom on a GaAs (110) surface is experimentally demonstrated using scanning tunneling microscopy (STM). The surface adsorption energy profile obtained by first‐principle electronic structure calculations reveals that the origin of the Ga motion observed at 78 K is attributable to the tip‐induced Ga adatom hopping between the most stable potential minima among the three local minima, whereas that observed at 4.2 K is attributable to the tip‐induced hopping and sliding motions through the next stable minima as well as the most stable minima. Furthermore, it is shown that a slight progressive modification of the adatom motion observed only at 4.2 K resulting from repeated STM line scans is consistent with the overall picture taking account of the heating of the adatom owing to the tip current.

Asymmetric transfer hydrogenation of gem‐difluoro‐cyclopropenyl esters. Access to enantio‐enriched gem‐difluorocyclopropanes

By Christophe Meyer, Khalil Yamani, Hugo Pierre, Alexis Archambeau, Janine Cossy from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

A catalytic enantioselective access to disubstituted functionalized gem ‐difluorocyclopropanes, which lie among emerging fluorinated motifs, was developed by asymmetric transfer hydrogenation of gem ‐difluorocyclopropenyl esters, catalyzed by Noyori‐Ikariya ( p ‐cymene)‐ruthenium(II) complex, with ( N ‐tosyl‐1,2‐diphenylethylenediamine) as chiral ligand and isopropanol as hydrogen donor. The resulting cis‐gem‐ difluorocyclopropyl esters were obtained with moderate to high enantiomeric purities (ee = 66‐99%) and post‐functionalization reactions enable access to valuable building blocks incorporating a cis ‐ or trans ‐ gem ‐difluorocyclopropyl motif.

Achieving Pure Green Electroluminescence with CIEy~0.69 and EQE~28.2% from a Novel Aza‐Fused Multi‐Resonance Emitter

By Yuewei Zhang, Dongdong Zhang, Jinbei Wei, Xiangchen Hong, Yang Lu, Deping Hu, Guomeng Li, Ziyang Liu, Yang Chen, Lian Duan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Pure green emitters are essential for realizing an ultrawide color gamut in next‐generation displays. Herein, by fusing the difficult‐to‐access aza‐aromatics onto B (boron)‐N (nitrogen) skeleton, a novel hybridized multi‐resonance and charge transfer (HMCT) molecule AZA‐BN was successfully synthesized through an effective one‐shot multiple cyclization method. AZA‐BN shows pure green fluorescence with photo‐luminance quantum yield of almost unity (99.7%). The corresponding green device exhibits a maximum external quantum efficiency and power efficiency of 28.2% and 121.7 lm W ‐1 , respectively, with a full width half maximum (FWHM) of merely 30 nm and Commission Internationale de l’Eclairage (CIE) coordinate y of 0.69: representing the purest green bottom‐emitting organic light‐emitting diode.

An Ultraviolet Thermally Activated Delayed Fluorescence OLED with Total External Quantum Efficiency over 9%

By Yanju Luo, Shuaibing Li, Yihuan Zhao, Chuan Li, Zhenguo Pang, Yan Huang, Minghui Yang, Liang Zhou, Xujun Zheng, Xuemei Pu, Zhiyun Lu from Wiley: Advanced Materials: Table of Contents. Published on Jul 02, 2020.

The first example of UV‐emissive thermally activated delayed fluorescence emitter, namely CZ‐MPS, is demonstrated successfully. An organic light‐emitting diode using CZ‐MPS as the guest material can emit efficient UV light with emission maximum (λEL) of 389 nm as well as a record‐breaking total external quantum efficiency (EQEmax) of 9.3%. Abstract Owing to the difficulty in acquiring compounds with combined high energy bandgaps and lower‐lying intramolecular charge‐transfer excited states, the development of ultraviolet (UV) thermally activated delayed fluorescence (TADF) materials is quite challenging. Herein, through interlocking of the diphenylsulfone (PS) acceptor unit of a reported deep‐blue TADF emitter (CZ‐PS) by a dimethylmethylene bridge, CZ‐MPS, a UV‐emissive TADF compound bearing a shallower LUMO energy level and a more rigid structure than those of CZ‐PS is achieved. This represents the first example of a UV‐emissive TADF compound. Organic light‐emitting diode (OLED) using CZ‐MPS as the guest material can emit efficient UV light with emission maximum of 389 nm and maximum total external quantum efficiency (EQEmax) of 9.3%. Note that this EQEmax value is twice as high as the current record EQEmax (4.6%) for UV‐OLEDs. This finding may shed light on the molecular design strategy for high‐performance UV‐OLED materials.

Outer Membrane Protease (OmpT)‐based E. coli Sensing with Anionic Polythiophene and Unlabeled Peptide Substrate

By Gaurav Sinsinbar, Sushanth Gudlur, Sarah E Wood, Gopal Ammanath, Hakan U Yildiz, Palaniappan Alagappan, Milan Mrksich, Bo Liedberg from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

E. coli and Salmonella are two of the most common bacterial pathogens involved in food and water borne related deaths. Hence, it is critical to develop rapid and sensitive detection strategies for near outbreak applications. We report a simple and specific assay to detect as low as 1 CFU/mL of E. coli in water within 6 hours by targeting the bacteria’s surface protease activity. The assay relies on polythiophene acetic acid (PTAA) as optical reporter and a short unlabeled peptide (LL37 FRRV ) previously optimized as substrate for OmpT, an outer membrane protease on E. coli . LL37 FRRV interacts with PTAA to enhance its fluorescence while also inducing the formation of a helical PTAA‐LL37 FRRV construct, as confirmed by Circular Dichroism. However, in the presence of E. coli , LL37 FRRV is cleaved and can no longer affect PTAA’s conformation and optical properties. This ability to distinguish between intact and cleaved peptide was investigated in detail using LL37 FRRV sequence variants.

Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry

By Shan He, Kaifeng Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Triplet energy transfer from inorganic nanocrystals to molecular acceptors has attracted strong attention as a promising approach to high‐efficiency photon upconversion that is important for energy‐related applications. Because energy transfer is a donor‐acceptor interfacial process, it is essential to simultaneously engineer the nanocrystal and molecular parameters in order to uncover unified physical principles that are transferable among different systems. Here we study this problem using CsPbBr 3 and CdSe nanocrystals as triplet donors and carboxylated anthracene isomers as acceptors. We find that the position of the carboxyl anchoring group on the molecule dictates the donor‐acceptor coupling to be either “through‐bond” or “through‐space”, while the relative strengths of the two coupling pathways is controlled by the “wavefunction‐leakage” of nanocrystals that can be quantitatively tuned by nanocrystal sizes or shell thicknesses. By simultaneously engineering molecular geometry and nanocrystal wavefunction, energy transfer and photon upconversion efficiencies of a nanocrystal/molecule system can be improved by orders of magnitude.

Coordination of Actinide Single Ions with Deformed Graphdiyne: Strategy on Essential Separation Processes in Nuclear Fuel Cycle

By Tianyu Yuan, Shijie Xiong, Xinghai Shen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

The coordination of actinides, lanthanides, as well as strontium and cesium with graphdiyne (GDY) was studied by experiments and theoretical calculations. On the basis of experimental results and/or theoretical calculations, it was suggested that Th 4+ , Pu 4+ , Am 3+ , Cm 3+ and Cs + exist in single ion states on the special triangle structure of GDY with various coordination patterns, in which GDY itself is deformed in different manners. Both experiments and theoretical calculations strongly support that UO 2 2+ , La 3+ , Eu 3+ , Tm 3+ and Sr 2+ are not adsorbed by GDY at all. The distinguished adsorption behaviors of GDY afford an important strategy for highly selective separation between actinides and lanthanides, Th 4+ and UO 2 2+ , Cs + and Sr 2+ in nuclear fuel cycle. Also, the present work sheds light on an approach to explore the unique functions and physicochemical properties of actinides in single ion states.

Intermolecular Dearomatization of Naphthalene Derivatives via a Photoredox‐Catalyzed 1,2‐Hydroalkylation

By Shuli You, Yuan-Zheng Cheng, Xu-Lun Huang, Wei-Hui Zhuang, Qing-Ru Zhao, Xiao Zhang, Tian-Sheng Mei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

An intermolecular hydroalkylative dearomatization of naphthalenes with commercially available α‐amino acids is achieved via visible‐light photoredox catalysis. With an organic photocatalyst, a series of multi‐substituted 1,2‐dihydronaphthalenes are obtained in good to excellent yields. Intriguingly, by tuning the substituents at the C2 position of naphthalenes, formal dearomative [3 + 2] cycloadditions occur exclusively via a hydroalkylative dearomatization‐cyclization sequence. This overall redox‐neutral method features mild reaction conditions, good tolerance of functionalities, and operational simplicity. Diverse downstream elaborations of the products are demonstrated. Preliminary mechanistic studies suggest the involvement of a radical‐radical coupling pathway.

Synthesis, Structures, and Properties of Highly Strained Cyclophenylene‐Ethynylenes with Axial and Helical Chirality

By Li-Hsiang Wang, Norihiko Hayase, Haruki Sugiyama, Juntaro Nogami, Hidehiro Uekusa, Ken Tanaka from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Single and double cyclophenylene‐ethynylenes (CPEs) with axial and helical chirality have been synthesized by the Sonogashira cross‐coupling of di‐ and tetra‐ethynyl biphenyls with a U‐shaped prearomatic diiodoparaphenylene followed by reductive aromatization. X‐ray crystallographic analyses and the DFT calculations revealed that these CPEs possess highly twisted bent structures. Bend angles on the edge of the paraphenylene units were close to the value of [5]cycloparaphenylene (CPP), the smallest CPP to date. Not only the double CPE but also the single CPE possessed stable chirality despite its flexible biphenyl structure due to the high strain in the diethynyl‐paraphenylene moiety. In both the single and double CPEs, orbital interactions along the biphenyl axis were observed by DFT calculations in LUMO and LUMO+2 of the single CPE and LUMO+1 of the double CPE, which were likely to cause the lowering of these orbital energies. Concerning chiroptical property, boosting of the g abs value was observed in the biphenyl‐based double CPE, as well as the binaphthyl‐based single CPE, compared to the biphenyl‐based single CPE.

Rational Control of Charge Transfer Excitons Toward High‐Contrast Reversible Mechanoresponsive Luminescent Switching: Magic of a Volatile Third Party in Donor‐Acceptor Assembly

By Qichun Zhang, Zongrui Wang, Fei Yu, Wangqiao Chen, Jianfeng Wang, Jinyu Liu, Changjiang yao, Jianfeng zhao, Huanli Dong Dong, Wenping Hu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Realizing mechanochromism in rigid molecular systems is very important and highly desirable to broaden their potential applications. Here, a novel and practicable strategy to rationally obtain the reversible mechanochromic luminescent (MCL) material with high‐contrast ratio (green versus red) has been established. Namely, by introducing a volatile third party (small‐sized solvent molecules) into the lattice of charge transfer (CT) cocrystal of mixed‐stacking 1:1 coronene (Cor.) and napthalenetetracarboxylic diimide (NDI), a noteworthy reconfigurable molecular assembly is ingeniously achieved due to the loosely packing arrangement as well as weakened intermolecular interactions. Accordingly, the CT excited state, strongly corresponding to the molecular stacking modes, can be intentionally tailored through external stimulus (i.e. heating, grinding, or solvent), accompanying with distinct changes in photophysical properties. Subsequently, a high‐contrast reversible MCL with highly sensitive and good reproducibility is realized and the underlying mechanism is thoroughly revealed.

Solar‐Assisted eBiorefinery: Photoelectrochemical Pairing of Oxyfunctionalization and Hydrogenation Reactions

By Da Som Choi, Jinhyun Kim, Frank Hollmann, Chan Beum Park from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

A biocatalytic photoelectrochemical platform for solar‐assisted dual biotransformations is constructed by wiring a Mo‐doped BiVO4 photocathode and a hierarchical porous ITO electrode. The deliberate integration of enzymatic redox processes into the photoelectrochemical cell simultaneously facilitates peroxygenase‐ and ene‐reductase‐mediated enantioselective synthesis of high‐value chemicals using solar‐powered electrons and water. Abstract Inspired by natural photosynthesis, biocatalytic photoelectrochemical (PEC) platforms are gaining prominence for the conversion of solar energy into useful chemicals by combining redox biocatalysis and photoelectrocatalysis. Herein, we report a dual biocatalytic PEC platform consisting of a molybdenum (Mo)‐doped BiVO4 (Mo:BiVO4) photoanode and an inverse opal ITO (IO‐ITO) cathode that gives rise to the coupling of peroxygenase and ene‐reductase‐mediated catalysis, respectively. In the PEC cell, the photoexcited electrons generated from the Mo:BiVO4 are transferred to the IO‐ITO and regenerate reduced flavin mononucleotides to drive ene‐reductase‐catalyzed trans‐hydrogenation of ketoisophrone to (R)‐levodione. Meanwhile, the photoactivated Mo:BiVO4 evolves H2O2 in situ via a two‐electron water‐oxidation process with the aid of an applied bias, which simultaneously supplies peroxygenases to drive selective hydroxylation of ethylbenzene into enantiopure (R)‐1‐phenyl‐1‐hydroxyethane. Thus, the deliberate integration of PEC systems with redox biocatalytic reactions can simultaneously produce valuable chemicals on both electrodes using solar‐powered electrons and water.

Tue 17 Nov 16:00: Neutrino Oscillation: The Long and the Short of It

From All Talks (aka the CURE list). Published on Jul 02, 2020.

Neutrino Oscillation: The Long and the Short of It

Abstract not available

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Immobilization of an Iridium Pincer Complex in a Microporous Polymer for Application in Room‐Temperature Gas Phase Catalysis

By Michaela König, Massimo Rigo, Nicolas Chaoui, Trung Tran Ngoc, Jan Dirk Epping, Johannes Schmidt, Pradip Pachfule, Meng-Yang Ye, Matthias Trunk, Johannes Teichert, Matthias Drieß, Arne Thomas from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

An iridium dihydride pincer complex [IrH 2 (POCOP)] is immobilized in a hydroxy‐functionalized microporous polymer network using the concepts of surface organometallic chemistry. The introduction of this novel, truly innocent support with remote OH‐groups enables the formation of isolated active metal sites embedded in a chemically robust and highly inert environment. The catalyst maintained high porosity and without prior activation exhibited efficacy in the gas phase hydrogenation of ethene and propene at room temperature and low pressure. The catalyst can be recycled for at least four times.

Covalent Assembly of MoS2 Nanosheets with SnS Nanodots as Linkages for Lithium/Sodium‐Ion Batteries

By Jiajia Ru, Ting He, Binjie Chen, Yutong Feng, Lianhai Zu, Zhijun Wang, Qiaobao Zhang, Tianzi Hao, Ruijin Meng, Renchao Che, Chi Zhang, Jinhu Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Nanosheets meet nanodots: A novel covalent assembly strategy is proposed for MoS2 nanosheets to realize unique MoS2/SnS hollow super‐assemblies by using SnS nanodots as covalent linkages. The strategy enables effective across‐interlayer electron transfer, facilitated ion diffusion kinetics, and high mechanical stability for high‐performance electrochemical lithium/sodium storage. Abstract Weak van der Waals interactions between interlayers of two‐dimensional layered materials result in disabled across‐interlayer electron transfer and poor layered structural stability, seriously deteriorating their performance in energy applications. Herein, we propose a novel covalent assembly strategy for MoS2 nanosheets to realize unique MoS2/SnS hollow superassemblies (HSs) by using SnS nanodots as covalent linkages. The covalent assembly based on all‐inorganic and carbon‐free concept enables effective across‐interlayer electron transfer, facilitated ion diffusion kinetics, and outstanding mechanical stability, which are evidenced by experimental characterization, DFT calculations, and mechanical simulations. Consequently, the MoS2/SnS HSs exhibit superb rate performance and long cycling stability in lithium‐ion batteries, representing the best comprehensive performance in carbon‐free MoS2‐based anodes to date. Moreover, the MoS2/SnS HSs also show excellent sodium storage performance in sodium‐ion batteries.

d–d Dative Bonding Between Iron and the Alkaline‐Earth Metals Calcium, Strontium, and Barium

By Philipp Stegner, Christian Färber, Jan Oetzel, Ulrich Siemeling, Michael Wiesinger, Jens Langer, Sudip Pan, Nicole Holzmann, Gernot Frenking, Uta Albold, Biprajit Sarkar, Sjoerd Harder from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

To d or not to d: Ferrocene complexes of Ca, Sr, and Ba show clear evidence for Fe⋅⋅⋅metal bonding while no such interaction is present in the Mg complex. Analysis with the QTAIM and EDA‐NOCV methods points to Fe→Ae bonds that involve vacant d‐orbitals of alkaline‐earth metals. Abstract Double deprotonation of the diamine 1,1′‐(tBuCH2NH)‐ferrocene (1‐H2) by alkaline‐earth (Ae) or EuII metal reagents gave the complexes 1‐Ae (Ae=Mg, Ca, Sr, Ba) and 1‐Eu. 1‐Mg crystallized as a monomer while the heavier complexes crystallized as dimers. The Fe⋅⋅⋅Mg distance in 1‐Mg is too long for a bonding interaction, but short Fe⋅⋅⋅Ae distances in 1‐Ca, 1‐Sr, and 1‐Ba clearly support intramolecular Fe⋅⋅⋅Ae bonding. Further evidence for interactions is provided by a tilting of the Cp rings and the related 1H NMR chemical‐shift difference between the Cp α and β protons. While electrochemical studies are complicated by complex decomposition, UV/Vis spectral features of the complexes support Fe→Ae dative bonding. A comprehensive bonding analysis of all 1‐Ae complexes shows that the heavier species 1‐Ca, 1‐Sr, and 1‐Ba possess genuine Fe→Ae bonds which involve vacant d‐orbitals of the alkaline‐earth atoms and partially filled d‐orbitals on Fe. In 1‐Mg, a weak Fe→Mg donation into vacant p‐orbitals of the Mg atom is observed.

Partially Pyrolyzed Binary Metal–Organic Framework Nanosheets for Efficient Electrochemical Hydrogen Peroxide Synthesis

By Mengjun Wang, Nan Zhang, Yonggang Feng, Zhiwei Hu, Qi Shao, Xiaoqing Huang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

A new class of partially pyrolyzed NiFe metal–organic framework nanosheets (MOF NSs) was created for the electrochemical synthesis of H2O2 by two‐electron oxygen reduction reaction (ORR) for the first time. The optimized MOF NSs‐300 exhibits the highest activity for ORR with near‐zero overpotential and excellent H2O2 selectivity (ca. 99 %) in 0.1 m KOH, outperforming most electrocatalysts reported to date. Abstract Herein, we developed a partially controlled pyrolysis strategy to create evenly distributed NiO nanoparticles within NiFe‐MOF nanosheets (MOF NSs) for electrochemical synthesis of H2O2 by a two‐electron oxygen reduction reaction (ORR). The elemental Ni can be partially transformed to NiO and uniformly distributed on the surface of the MOF NSs, which is crucial for the formation of the particular structure. The optimized MOF NSs‐300 exhibits the highest activity for ORR with near‐zero overpotential and excellent H2O2 selectivity (ca. 99 %) in 0.1 m KOH solution. A high‐yield H2O2 production rate of 6.5 mol gcat−1 h−1 has also been achieved by MOF NSs‐300 in 0.1 m KOH and at 0.6 V (vs. RHE). In contrast to completely pyrolyzed products, the enhanced catalytic activities of partially pyrolyzed MOF NSs‐300 originates mainly from the retained MOF structure and the newly generated NiO nanoparticles, forming the coordinatively unsaturated Ni atoms and tuning the performance towards electrochemical H2O2 synthesis.

Reversibly Switching the Charge State and Adsorption Location of A Single Potassium Atom on Ultrathin CuO Films

By Zhantao Peng, Bin Di, Wentao Li, Dan Liu, Xiaojie Wen, Hao Zhu, Huanjun Song, Yajie Zhang, Cen Yin, Xiong Zhou, Kai Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

The switch: Combined XPS, STM, and local work function measurements verify that the charge states and locations of potassium species on monolayered CuO films can be reversibly switched by polarity‐reversed STM bias voltage pulses. Abstract Potassium (K) cations are spontaneously formed upon thermal deposition of low‐coverage K onto an ultrathin CuO monolayer grown on Cu(110) and they were explored by low‐temperature scanning tunneling microscopy (STM) and X‐ray photoemission spectroscopy. The formed K cations are highly immobile and thermally stable. The local work function around an individual K cation decreases by 1.5±0.3 eV, and a charging zone underneath it is established within about 1.0 nm. The cationic and neutral states of the K atom are switchable upon application of an STM bias voltage pulse, which is simultaneously accompanied by an adsorption site relocation.

The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

By Bogdan M. Benin, Kyle M. McCall, Michael Wörle, Viktoriia Morad, Marcel Aebli, Sergii Yakunin, Yevhen Shynkarenko, Maksym V. Kovalenko from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

The Rb7Sb3Cl16 phase, comprised of isolated octahedra and edge‐shared dimers, demonstrates photoluminescence centered at 560 nm with a quantum yield of 3.8 % at 296 K (99.4 % at 77 K) and a specific temperature sensitivity above 0.06 K−1 at 300 K. Utilizing DFT and chemical substitution with Bi3+ in the Rb7Bi3−3xSb3xCl16 (x≤1) family, the [Sb2Cl10]4− dimer is presented as a design principle for Sb‐based luminescent materials. Abstract Low‐dimensional ns2‐metal halide compounds have received immense attention for applications in solid‐state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb2+ or unstable Sn2+, and a stable inorganic luminescent material has yet to be found. Here, the zero‐dimensional Rb7Sb3Cl16 phase, comprised of isolated [SbCl6]3− octahedra and edge‐sharing [Sb2Cl10]4− dimers, shows room‐temperature photoluminescence (RT PL) centered at 560 nm with a quantum yield of 3.8±0.2 % at 296 K (99.4 % at 77 K). The temperature‐dependent PL lifetime rivals that of previous low‐dimensional materials with a specific temperature sensitivity above 0.06 K−1 at RT, making it an excellent thermometric material. Utilizing both DFT and chemical substitution with Bi3+ in the Rb7Bi3−3xSb3xCl16 (x≤1) family, we present the edge‐shared [Sb2Cl10]4− dimer as a design principle for Sb‐based luminescent materials.

Phosphorus‐Doped Iron Nitride Nanoparticles Encapsulated by Nitrogen‐Doped Carbon Nanosheets on Iron Foam In Situ Derived from Saccharomycetes Cerevisiae for Electrocatalytic Overall Water Splitting

By Guixiang Li, Jiayuan Yu, Wanqiang Yu, Linjing Yang, Xiaoli Zhang, Xiaoyan Liu, Hong Liu, Weijia Zhou from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Saccharomycetes cerevisiae is used as a nitrogen source to safely produce metal nitride instead of the high‐cost and hazardous NH3. Elemental diffusion pattern and contact form for S. cerevisiae affect the composition and phase of products. The obtained P‐Fe3N@NC NSs/IF with Fe sites as the active center and P‐doping regulating H‐binding strength exhibits excellent electrocatalytic performance for overall water splitting. Abstract It is vitally essential to propose a novel, economical, and safe preparation method to design highly efficient electrocatalysts. Herein, phosphorus‐doped iron nitride nanoparticles encapsulated by nitrogen‐doped carbon nanosheets are grown directly on the iron foam substrate (P‐Fe3N@NC NSs/IF) by in situ deriving from Saccharomycetes cerevisiae (S. cerevisiae), where anion elements of C, N, and P all from S. cerevisiae replace the hazardous CH4, NH3, and H3P. The diffusion pattern of N, P in S. cerevisiae and contact form between metal and S. cerevisiae observably affect the composition and phase of the product during high‐temperature calcination. The obtained P‐Fe3N@NC NSs/IF demonstrates superior electrocatalytic performance for the hydrogen evolution reaction and oxygen evolution reaction, also satisfying durability. Theoretical calculation confirms that Fe sites of P‐Fe3N serve as the active center, and N sites and P doping regulate the hydrogen binding strength to enhance catalytic ability. Additionally, the two‐electrode electrolyzer assembled by P‐Fe3N@NC NSs/IF as both anode and cathode electrodes needs only 1.61 V to reach 10 mA cm−2 for overall water splitting with a superb stability. The S. cerevisiae‐based process presents a feasible approach for synthesis of nitrides, carbides, phosphides, and electrocatalytic applications.

Hierarchically Well‐Developed Porous Graphene Nanofibers Comprising N‐Doped Graphitic C‐Coated Cobalt Oxide Hollow Nanospheres As Anodes for High‐Rate Li‐Ion Batteries

By Jae Seob Lee, Min Su Jo, Rakesh Saroha, Dae Soo Jung, Young Hoe Seon, Jun Su Lee, Yun Chan Kang, Dong‐Won Kang, Jung Sang Cho from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Hierarchically well‐developed porous graphene nanofibers comprising N‐doped graphitic C‐coated cobalt oxide hollow nanospheres are introduced as anodes for high‐rate Li‐ion batteries. In view of the highly efficient Li+ ion/electron diffusion and high structural stability, the unique nanostructuring strategy has a huge potential in opening new frontiers for high‐rate and long‐lived stable energy storage systems. Abstract Hierarchically well‐developed porous graphene nanofibers comprising N‐doped graphitic C (NGC)‐coated cobalt oxide hollow nanospheres are introduced as anodes for high‐rate Li‐ion batteries. For this, three strategies, comprising the Kirkendall effect, metal–organic frameworks, and compositing with highly conductive C, are applied to the 1D architecture. In particular, NGC layers are coated on cobalt oxide hollow nanospheres as a primary transport path of electrons followed by graphene‐nanonetwork‐constituting nanofibers as a continuous and secondary electron transport path. Superior cycling performance is achieved, as the unique nanostructure delivers a discharge capacity of 823 mAh g−1 after 500 cycles at 3.0 A g−1 with a low decay rate of 0.092% per cycle. The rate capability is also noteworthy as the structure exhibits high discharge capacities of 1035, 929, 847, 787, 747, 703, 672, 650, 625, 610, 570, 537, 475, 422, 294, and 222 mAh g−1 at current densities of 0.5, 1.5, 3, 5, 7, 10, 12, 15, 18, 20, 25, 30, 40, 50, 80, and 100 A g−1, respectively. In view of the highly efficient Li+ ion/electron diffusion and high structural stability, the present nanostructuring strategy has a huge potential in opening new frontiers for high‐rate and long‐lived stable energy storage systems.

Graphitic Carbon Nitride Stabilizers Meet Microfluidics: From Stable Emulsions to Photoinduced Synthesis of Hollow Polymer Spheres

By Naresh Yandrapalli, Tom Robinson, Markus Antonietti, Baris Kumru from Wiley: Small: Table of Contents. Published on Jul 02, 2020.

Surface modified graphitic carbon nitrides are excellent candidates as Pickering stabilizers in microfluidics for oil‐in‐water and water‐in‐oil emulsions. Electrostatic stability of carbon nitride in the oil phase grants centered water‐oil‐water double emulsions. When the oil phase consists of monomer, carbon nitride can be utilized both as stabilizer and photoinitiator for synthesis of hollow polymer spheres in a facile fashion. Abstract Graphitic carbon nitride (g‐CN) has been utilized as a heterogeneous catalyst, but is usually not very well dispersible. The amphiphilic character of g‐CN can be altered by surface modifications of g‐CN nanopowders. Introducing hydrophilicity or hydrophobicity is a promising avenue for producing advanced emulsion systems. In this study, a special surface‐modified g‐CN is used to form stable Pickering emulsions. Using a PDMS‐based microfluidic device designed for stable production of both single and double emulsions, it is shown that surface‐modified g‐CNs allow the manufacture of unconventionally stable and precise Pickering emulsions. Shell thickness of the double emulsions is varied to emphasize the robustness of the device and also to demonstrate the extraordinary stabilization brought by the surface‐modified carbon nitride used in this study. Due to the electrostatic stabilization also in the oil phase, double emulsions are centered. Finally, when produced from polymerizable styrene, hollow polymer microparticles are formed with precise and tunable sizes, where g‐CN is utilized as the only stabilizer and photoinitiator.

Tue 03 Nov 16:00: Tetraquarks

From All Talks (aka the CURE list). Published on Jul 02, 2020.

Tetraquarks

Abstract not available

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Tue 06 Oct 16:00: RPV and long lived SUSY

From All Talks (aka the CURE list). Published on Jul 02, 2020.

RPV and long lived SUSY

Abstract not available

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A Divergent Enantioselective Total Synthesis of Post‐Iboga Indole Alkaloids

By Fu-She Han, Jie Zhou, Dong-Xing Tan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

Divergent enantioselective total syntheses of five naturally occurring post‐iboga indole alkaloids, dippinine B ( 3 ) and C ( 4 ), 10,11‐demethoxychippiine ( 8 ), 3‐ O ‐methyl‐10,11‐demethoxychippiine ( 9 ), and 3‐hydroxy‐3,4‐secocoronaridine ( 11 ), and two analogues 11‐demethoxydippinine A ( 2 ) and D ( 6 ), were presented for the first time. The enantioenriched aza[3.3.1]‐bridged cycle, common core intermediate to the target molecules, was constructed through an asymmetric phase‐transfer‐catalyzed Michael/aldol cascade reaction. The challenging azepane ring fused around the indole ring and the [3.3.1]‐bridged cycle was installed via an intromolecular S N 2’–type reaction. These cyclization strategies allowed for a rapid construction of the [6.5.6.6.7]‐pentacyclic core at an early stage. The late stage syntheses were highlighted by a Pd‐catalyzed Stille coupling and a catalyst‐controlled highly stereoselective hydrogenation to incorporate the side chain at C 20 with both R and S conformations in the natural products.

Periodically Ordered, Nuclease‐Resistant DNA Nanowires Decorated with Cell‐Specific Aptamers as Selective Theranostic Agents

By Chang Xue, Songbai Zhang, Xin Yu, Shuyao Hu, Yi Lu, Zai-Sheng Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 02, 2020.

DNA nanostructures have shown potentials in cancer therapy. However, current clinical practice is hampered by the difficulty to deliver them into cancer cells and susceptibility to nuclease degradation. To overcome these limitations, we report herein a periodically‐ordered nick‐hidden DNA nanowire (NW) with high serum stability and active targeting functionality. The inner core is made of multiple‐connected DNA double helices and the outer shell is composed of regularly‐arranged standing‐up hairpin aptamers. All terminals of the components are hidden from nuclease attacks while the target‐binding sites are exposed to allow delivery to the cancer target. The DNA NW remains intact over 24‐h incubation in serum solution. Animal imaging and cell apoptosis show that the anticancer drugs formulated NW displays long blood‐circulation time and high specificity in inducing cancer cell apoptosis. Treatment of tumor‐bearing mice validates in vivo therapeutic efficacy, demonstrating an ideal theranostic vehicle for targeted imaging and therapy of cancers.

[ASAP] Designing Polymeric Interphases for Stable Lithium Metal Deposition

By Sanjuna Stalin†?, Mukul Tikekar‡?, Prayag Biswal†, Gaojin Li†, Hillis E. N. Johnson§, Yue Deng?, Qing Zhao†, Duylinh Vu†, Geoffrey W. Coates§, and Lynden A. Archer*† from Nano Letters: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01501

[ASAP] Type-II Ising Superconductivity and Anomalous Metallic State in Macro-Size Ambient-Stable Ultrathin Crystalline Films

By Yi Liu†?, Yong Xu‡§?, Jian Sun†?, Chong Liu‡??, Yanzhao Liu†, Chong Wang‡?, Zetao Zhang‡, Kaiyuan Gu†, Yue Tang†, Cui Ding‡, Haiwen Liu?, Hong Yao‡?, Xi Lin*†#?, Lili Wang*‡, Qi-Kun Xue‡#, and Jian Wang*†‡#? from Nano Letters: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01356

[ASAP] Sharp Negative Differential Resistance from Vibrational Mode Softening in Molecular Junctions

By Junjie Liu† and Dvira Segal*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02230

[ASAP] Quantifying Carbon Edge Sites on Depressing Hydrogen Evolution Reaction Activity

By Go Bong Choi†, Seungki Hong†, Jae-Hyung Wee†, Doo-Won Kim‡, Tae Hoon Seo§, Keita Nomura?, Hirotomo Nishihara??, and Yoong Ahm Kim*† from Nano Letters: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01842

[ASAP] Control of Spin–Orbit Torques by Interface Engineering in Topological Insulator Heterostructures

By Fre´de´ric Bonell*†?, Minori Goto‡, Guillaume Sauthier†, Juan F. Sierra†, Adriana I. Figueroa†, Marius V. Costache†, Shinji Miwa‡, Yoshishige Suzuki‡, and Sergio O. Valenzuela*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01850

[ASAP] Remotely Triggered Liquefaction of Hydrogel Materials

By Søren L. Pedersen†, Tin H. Huynh†, Philipp Po¨schko†, Anne Sofie Fruergaard†, Morten T. Jarlstad Olesen†, Yaqing Chen†‡, Henrik Birkedal†‡, Guruprakash Subbiahdoss§, Erik Reimhult§, Jan Thøgersen†, and Alexander N. Zelikin*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04522

[ASAP] Wearable Triboelectric–Human–Machine Interface (THMI) Using Robust Nanophotonic Readout

By Bowei Dong†‡#, Yanqin Yang†‡#, Qiongfeng Shi†‡#, Siyu Xu†‡, Zhongda Sun†‡, Shiyang Zhu§, Zixuan Zhang†‡, Dim-Lee Kwong§, Guangya Zhou‡?, Kah-Wee Ang†‡, and Chengkuo Lee*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03728

[ASAP] Magneto-Optics of Excitons Interacting with Magnetic Ions in CdSe/CdMnS Colloidal Nanoplatelets

By Elena V. Shornikova*†, Dmitri R. Yakovlev*†‡, Danil O. Tolmachev†‡, Vitalii Yu. Ivanov?, Ina V. Kalitukha‡, Victor F. Sapega‡, Dennis Kudlacik†, Yuri G. Kusrayev‡, Aleksandr A. Golovatenko‡, Sushant Shendre§, Savas Delikanli§?, Hilmi Volkan Demir§?, and Manfred Bayer†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04048

[ASAP] Dynamic Evolution of Solid–Liquid Electrochemical Interfaces over Single-Atom Active Sites

By Hui Su†, Wanlin Zhou†, Hui Zhang†, Wu Zhou‡, Xu Zhao†, Yuanli Li†, Meihuan Liu†, Weiren Cheng*†, and Qinghua Liu*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04231

[ASAP] A Concise, Enantiospecific Total Synthesis of Chilocorine C Fueled by a Reductive Cyclization/Mannich Reaction Cascade

By Vladislav G. Lisnyak and Scott A. Snyder* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04914

[ASAP] Bottom-up Synthesis of Nitrogen-Doped Porous Graphene Nanoribbons

By Re´my Pawlak*†#, Xunshan Liu‡?#, Silviya Ninova‡, Philipp D’Astolfo†, Carl Drechsel†, Sara Sangtarash§, Robert Ha¨ner‡, Silvio Decurtins‡, Hatef Sadeghi§, Colin J. Lambert?, Ulrich Aschauer‡, Shi-Xia Liu*‡, and Ernst Meyer*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03946

[ASAP] Palladium-Catalyzed meta-C–H Allylation of Arenes: A Unique Combination of a Pyrimidine-Based Template and Hexafluoroisopropanol

By Sukdev Bag†, Surya K†, Arup Mondal†, Ramasamy Jayarajan†, Uttam Dutta†, Sandip Porey†, Raghavan B. Sunoj*†, and Debabrata Maiti*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05223

[ASAP] Multimodal Structure Solution with 19F NMR Crystallography of Spin Singlet Molybdenum Oxyfluorides

By Fenghua Ding†?, Kent J. Griffith†?, Can P. Koc¸er§, Richard J. Saballos‡, Yiran Wang†, Chi Zhang‡, Matthew L. Nisbet†, Andrew J. Morris*?, James M. Rondinelli*‡, and Kenneth R. Poeppelmeier*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04019

[ASAP] Transmembrane Epitope Delivery by Passive Protein Threading through the Pores of the OmpF Porin Trimer

By Sejeong Lee†, Nicholas G. Housden‡, Sandra A. Ionescu†, Matthew H. Zimmer†§, Renata Kaminska‡, Colin Kleanthous‡, and Hagan Bayley*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c02362

[ASAP] Photoresponsive Dithienylethene-Containing Tris(8-hydroxyquinolinato)aluminum(III) Complexes with Photocontrollable Electron-Transporting Properties for Solution-Processable Optical and Organic Resistive Memory Devices

By Cheok-Lam Wong, Maggie Ng, Eugene Yau-Hin Hong, Yi-Chun Wong, Mei-Yee Chan, and Vivian Wing-Wah Yam* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03057

[ASAP] Isothermal Titration Calorimetry to Explore the Parameter Space of Organophosphorus Agrochemical Adsorption in MOFs

By Riki J. Drout†, Satoshi Kato†, Haoyuan Chen‡, Florencia A. Son†, Ken-ichi Otake†$, Timur Islamoglu†, Randall Q. Snurr‡, and Omar K. Farha*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04668

[ASAP] Fast Proton Transfer and Hydrogen Evolution Reactivity Mediated by [Co13C2(CO)24]4–

By Cody R. Carr, Atefeh Taheri, and Louise A. Berben* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04034

[ASAP] Photochemical Phase Transitions Enable Coharvesting of Photon Energy and Ambient Heat for Energetic Molecular Solar Thermal Batteries That Upgrade Thermal Energy

By Zhao-Yang Zhang†, Yixin He†, Zhihang Wang‡, Jiale Xu§, Mingchen Xie†, Peng Tao§, Deyang Ji?, Kasper Moth-Poulsen*‡, and Tao Li*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03748

[ASAP] Arylphosphonate-Directed Ortho C–H Borylation: Rapid Entry into Highly-Substituted Phosphoarenes

By Feiyang Xu†‡, Olivia M. Duke†, Daniel Rojas†, Hanka M. Eichelberger†‡, Raphael S. Kim†, Timothy B. Clark*‡, and Donald A. Watson*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04159

[ASAP] Visible-Light-Enabled Ortho-Selective Aminopyridylation of Alkenes with N-Aminopyridinium Ylides

By Yonghoon Moon†‡, Wooseok Lee†‡, and Sungwoo Hong*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05025

[ASAP] Large-Cavity Coronoids with Different Inner and Outer Edge Structures

By Marco Di Giovannantonio*†?, Xuelin Yao‡?, Kristjan Eimre†?, Jose´ I. Urgel†, Pascal Ruffieux†, Carlo A. Pignedoli*†, Klaus Mu¨llen*‡§, Roman Fasel†?, and Akimitsu Narita*‡? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05268

[ASAP] Regioselective and Stereospecific Rhodium-Catalyzed Allylic Cyanomethylation with an Acetonitrile Equivalent: Construction of Acyclic ß-Quaternary Stereogenic Nitriles

By Mai-Jan Tom† and P. Andrew Evans*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c02316

[ASAP] Stereoretentive Ring-Opening Metathesis Polymerization to Access All-cis Poly(p-phenylenevinylene)s with Living Characteristics

By Ting-Wei Hsu†, Cheoljae Kim†‡, and Quentin Michaudel* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04068

[ASAP] Microporous Hydrogen-Bonded Organic Framework for Highly Efficient Turn-Up Fluorescent Sensing of Aniline

By Bin Wang†‡#, Ru He‡§#, Lin-Hua Xie?, Zu-Jin Lin‡, Xin Zhang‡, Jing Wang‡, Hongliang Huang?, Zhangjing Zhang*†, Kirk S. Schanze‡, Jian Zhang?, Shengchang Xiang†, and Banglin Chen*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 02, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05277

Publisher Correction: 2D phase transitions: Freezing and melting skyrmions in 2D

By Mathias Kläui from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jul 02, 2020.

Nature Nanotechnology, Published online: 02 July 2020; doi:10.1038/s41565-020-0745-y

Publisher Correction: 2D phase transitions: Freezing and melting skyrmions in 2D

Phase selective synthesis of nickel silicide nanocrystals in molten salts for electrocatalysis of the oxygen evolution reaction

By David Portehault from RSC - Nanoscale latest articles. Published on Jul 02, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR04284F, Paper
Ram Kumar, Mounib Bahri, Yang Song, francisco gonell, Cyril Thomas, Ovidiu Ersen, Clément Sanchez, Christel Laberty-Robert, David Portehault
We report phase selective synthesis of intermetallic nickel silicide nanocrystals in inorganic molten salts. NiSi and Ni2Si nanocrystals are obtained by reacting a nickel (II) salt and sodium silicide Na4Si4...
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Sub-5 nm Monolayer Germanium Selenide (GeSe) MOSFETs:towards High Performance and Stable Device

By Jing Lu from RSC - Nanoscale latest articles. Published on Jul 02, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR02170A, Paper
ying guo, Feng Pan, Gaoyang Zhao, Yajie Ren, Binbin Yao, Hong Li, Jing Lu
Two-dimensional (2D) black phosphorene (BP) field-effect transistors (FETs) have an excellent device performance but suffer from serious instability at ambient conditions. Isoelectronic 2D germanium selenide (GeSe) shares many similar properties...
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Elucidating the role of shape anisotropy in faceted magnetic nanoparticles using biogenic magnetosomes as a model

By Mª Luisa Fdez-Gubieda from RSC - Nanoscale latest articles. Published on Jul 02, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR02189J, Paper
Open Access Open Access
David Gandia, Lucía Gandarias, Lourdes Marcano, Iñaki Orue, David Gil-Cartón, Javier Alonso, Alfredo García-Arribas, Alicia Muela, Mª Luisa Fdez-Gubieda
A model based on finite element techniques has been developed to calculate the shape-anisotropy energy of magnetic nanoparticles.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Quantifying the level of nanoparticle uptake in mammalian cells using flow cytometry

By Ji Youn Lee from RSC - Nanoscale latest articles. Published on Jul 02, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR01627F, Paper
Open Access Open Access
HyeRim Shin, Minjeong Kwak, Tae Geol Lee, Ji Youn Lee
Reliable quantification of nanoparticle uptake in mammalian cells is essential to study the effects of nanoparticles in the fields of medicine and environmental science. Most conventional quantification methods, such as...
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Efficient full-color emitting carbon-dot-based composite phosphors by chemical dispersion

By Youjin Zheng from RSC - Nanoscale latest articles. Published on Jul 02, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR02021D, Paper
Mingye Sun, Yue Han, Xi Yuan, Pengtao Jing, Lei Zhang, Jialong Zhao, Youjin Zheng
Realizing full-color emission plays a key role in exploring the luminescence mechanisms and promoting the applications in light-emitting diodes (LEDs) for carbon dots (CDots). Herein, a synthesis strategy for full-color...
The content of this RSS Feed (c) The Royal Society of Chemistry

Strong influence of strain gradient on lithium diffusion: A theoretical study

By Daining Fang from RSC - Nanoscale latest articles. Published on Jul 02, 2020.

Nanoscale, 2020, Accepted Manuscript
DOI: 10.1039/D0NR03746J, Paper
Gao Xu, Feng Hao, Mouyi Weng, Jiawang Hong, Feng Pan, Daining Fang
Lithium ion batteries (LIBs) work under sophisticated external force field and its electrochemical properties could be modulated by strain. Owing to the electromechanical coupling, the change of micro-local-structures can greatly...
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Surface Ligand Management Aided by a Secondary Amine Enables Increased Synthesis Yield of CsPbI3 Perovskite Quantum Dots and High Photovoltaic Performance

By Yao Wang, Jianyu Yuan, Xuliang Zhang, Xufeng Ling, Bryon W. Larson, Qian Zhao, Yingguo Yang, Yao Shi, Joseph M. Luther, Wanli Ma from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Di‐n‐propylamine solution in methyl acetate as an efficient solid‐state treatment for CsPbI3 perovskite quantum dot (PQD) solar cells is successfully demonstrated, and a record power conversion efficiency of ≈15% and high reproducibility are achieved for CsPbI3 PQD solar cells. Abstract Lead‐halide perovskite quantum dots (PQDs) or more broadly, nanocrystals possess advantageous features for solution‐processed photovoltaic devices. The nanocrystal surface ligands play a crucial role in the transport of photogenerated carriers and ultimately affect the overall performance of PQD solar cells. Significantly improved CsPbI3 PQD synthetic yield and solar‐cell performance through surface ligand management are demonstrated. The treatment of a secondary amine, di‐n‐propylamine (DPA), provides a mild and efficient approach to control the surface ligand density of PQDs, which has an apparently different working mechanism compared to previously reported surface treatments. Using an optimal DPA concentration, the treatment can simultaneously remove both long‐chain insulating surface ligands of oleic acid and oleylamine, even for unpurified PQDs with high ligand density. As a result, the electrical coupling between PQDs is enhanced, leading to improved charge transport, reduced carrier recombination, and a high power conversion efficiency approaching 15% for CsPbI3‐PQD‐based solar cells. In addition, the production yield of CsPbI3 PQDs can be increased by a factor of 8. These results highlight the importance of developing new ligand‐management strategies, specifically for emerging PQDs to achieve scalable and high‐performance perovskite‐based optoelectronic devices.

An Iron‐Decorated Carbon Aerogel for Rechargeable Flow and Flexible Zn–Air Batteries

By Kunze Wu, Lei Zhang, Yifei Yuan, Linxin Zhong, Zhongxin Chen, Xiao Chi, Hao Lu, Zehong Chen, Ren Zou, Tingzhen Li, Chengyu Jiang, Yongkang Chen, Xinwen Peng, Jun Lu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

The designed strategy of a mechanically integrated air electrode, realized by directional freeze‐casting, generates a 3D honeycomb nanostructured Fe‐decorated carbon aerogel with satisfactory mechanical stability and gas/electrolyte diffusion channels. Such an integrated monolith with superb bifunctional electrocatalytic activity shows a remarkable performance as the free‐standing air cathode in a flow Zn–air battery (ZAB) and flexible solid‐state ZAB. Abstract Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal–air batteries. Herein, a directional freeze‐casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P‐doped carbon aerogel incorporating in situ grown FeP/Fe2O3 nanoparticles as the cathode in a flexible Zn–air battery (ZAB). The aqueous rechargeable Zn–air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g−1 at a current density of 20 mA cm−2 with a good long‐term durability, outperforming those assembled with commercial Pt/C+RuO2 catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid‐state Zn–air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g−1 and an energy density of 517 Wh kg−1 at 5 mA cm−2 together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.

Ineffective OH Pinning of the Flipping Dynamics of a Spherical Guest within a Tight‐Fitting Tube

By Taisuke Matsuno, Maki Someya, Sota Sato, Satoshi Maeda, Hiroyuki Isobe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Turn and flip: A C59N+ cation has been trapped by ethanol or water in a tubular host to fix an oxy substituent on the fullerene guest. The substituent was found to modulate the guest motion, with the up‐and‐down flipping motions of the guest facilitated by the OH group sliding along the inner wall of the host while staying attached through OH‐π hydrogen bonds, whereas an ethoxy substituent halted such motions. Abstract A supramolecular/synthetic method has been devised to affix a sterically hindered substituent onto a fullerene guest encapsulated in a tubular host. A two‐wheeled complex of (C59N)‐(C59N) with a tubular host was oxidatively bisected to afford a C59N+ cation captured in the tube. The C59N+ cation in the tube was then trapped by ethanol or water, which led to an oxy substituent pinned on the guest. The guest motions within the tube were modulated by the pinned substituent, and up‐and‐down flipping motions were halted by an ethoxy substituent. A hydroxy substituent, however, was ineffective in halting the flipping motions, despite the tight‐fitting relationship between the tubular host and the spherical guest. Theoretical calculations of the dynamics revealed that the flipping motions were assisted by OH‐π hydrogen bonds between the guest and the carbon‐rich wall and that sliding motions of the OH group were also facilitated by deformations of the tube.

Polymer Transformers: Interdigitating Reaction Networks of Fueled Monomer Species to Reconfigure Functional Polymer States

By Mo Sun, Jie Deng, Andreas Walther from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Adaptivity is an essential trait of life. Its mimicry using chemical systems remains a grand challenge. One type of adaptivity is the reconfiguration of functional system states by correlating sensory inputs. We report “polymer transformers” that can adaptively reconfigure their composition from a state of a mixed copolymer to being enriched in either monomer A or B. This is achieved by embedding and hierarchically interconnecting two chemically fueled activation/deactivation enzymatic reaction networks for both monomers via a joint activation pathway (network level) and an AB linker monomer reactive to both A and B (species level). We show that the ratio of enzymes governing the individual deactivation pathways, i.e. our external signals, control the enrichment behavior in the dynamic state. The method shows high programmability of the reconfigured state, rejuvenation of transformation cycles, and quick in situ adaptation. As proof‐of‐concept application, we showcase this dynamic reconfiguration for colloidal surface functionalities.

Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions

By Kamila B. Muchowska, Dominic J. Pascoe, Stefan Borsley, Ivan V. Smolyar, Ioulia K. Mati, Catherine Adam, Gary S. Nichol, Kenneth B. Ling, Scott L. Cockroft from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Carbonyls reconciled: Electrostatics and orbital interactions have both been implicated in governing carbonyl interactions. A combined experimental and computational approach reconciles these conflicting explanations of the physiochemical origin of the interaction, demonstrating that orbital delocalisation augments electrostatic control, but for very close carbonyl contacts. Abstract Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance‐dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short‐range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions.

Manganese‐Catalyzed anti‐Selective Asymmetric Hydrogenation of α‐Substituted β‐Ketoamides

By Linli Zhang, Zheng Wang, Zhaobin Han, Kuiling Ding from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A Mn‐catalyzed diastereo‐ and enantioselective asymmetric hydrogenation of α‐substituted β‐ketoamides was realized by using lutidine‐based chiral PNN ligands via a dynamic kinetic resolution to afford optically active anti‐α‐substituted β‐hydroxy amides in high yields with excellent stereoselectivity (up to >99 % dr and >99 % ee). The anti stereoselectivity is ascribed to an attractive π⋅⋅⋅π stacking between the substrate phenyl and ligand pyridyl rings. Abstract A Mn‐catalyzed diastereo‐ and enantioselective hydrogenation of α‐substituted β‐ketoamides has been realized for the first time under dynamic kinetic resolution conditions. anti‐α‐Substituted β‐hydroxy amides, which are useful building blocks for the synthesis of bioactive molecules and chiral drugs, were prepared in high yields with excellent selectivity (up to >99 % dr and >99 % ee) and unprecedentedly high activity (TON up to 10000). The origin of the excellent stereoselectivity was clarified by DFT calculations.

Transformations of Aryl Ketones via Ligand‐Promoted C−C Bond Activation

By Hanyuan Li, Biao Ma, Qi‐Sheng Liu, Mei‐Ling Wang, Zhen‐Yu Wang, Hui Xu, Ling‐Jun Li, Xing Wang, Hui‐Xiong Dai from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The unstrained carbon–carbon bond of an aryl ketone can be activated by a Pd‐catalyzed ligand‐promoted β‐carbon elimination reaction. In this way, aryl ketones can be transformed into useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The utility of this strategy was demonstrated by the late‐stage diversification of several drug molecules. Abstract The coupling of aromatic electrophiles (aryl halides, aryl ethers, aryl acids, aryl nitriles etc.) with nucleophiles is a core methodology for the synthesis of aryl compounds. Transformations of aryl ketones in an analogous manner via carbon–carbon bond activation could greatly expand the toolbox for the synthesis of aryl compounds due to the abundance of aryl ketones. An exploratory study of this approach is typically based on carbon–carbon cleavage triggered by ring‐strain release and chelation assistance, and the products are also limited to a specific structural motif. Here we report a ligand‐promoted β‐carbon elimination strategy to activate the carbon–carbon bonds, which results in a range of transformations of aryl ketones, leading to useful aryl borates, and also to biaryls, aryl nitriles, and aryl alkenes. The use of a pyridine‐oxazoline ligand is crucial for this catalytic transformation. A gram‐scale borylation reaction of an aryl ketone via a simple one‐pot operation is reported. The potential utility of this strategy is also demonstrated by the late‐stage diversification of drug molecules probenecid, adapalene, and desoxyestrone, the fragrance tonalid as well as the natural product apocynin.

Oxidation, Coordination, and Nickel‐Mediated Deconstruction of a Highly Electron‐Rich Diboron Analogue of 1,3,5‐Hexatriene

By Alexander Hermann, Felipe Fantuzzi, Merle Arrowsmith, Theresa Zorn, Ivo Krummenacher, Benedikt Ritschel, Krzysztof Radacki, Bernd Engels, Holger Braunschweig from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A complex twist: A highly electron‐rich N‐heterocyclic carbene stabilized 1,2‐divinyldiborene, which displays no delocalized π conjugation because of twisting of the C2B2C2 chain, coordinates to CuI and Pt0 in a η2‐B2 and η4‐C2B2 mode, respectively, while undergoing a complex rearrangement to a η4‐1,3‐diborete upon complexation with Ni0. Abstract The reductive coupling of an N‐heterocyclic carbene (NHC) stabilized (dibromo)vinylborane yields a 1,2‐divinyldiborene, which, although isoelectronic to a 1,3,5‐triene, displays no extended π conjugation because of twisting of the C2B2C2 chain. While this divinyldiborene coordinates to copper(I) and platinum(0) in an η2‐B2 and η4‐C2B2 fashion, respectively, it undergoes a complex rearrangement to an η4‐1,3‐diborete upon complexation with nickel(0).

Cooperative Ni/Cu‐Catalyzed Asymmetric Propargylic Alkylation of Aldimine Esters

By Lingzi Peng, Zhuozhuo He, Xianghong Xu, Chang Guo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

It takes two: A highly efficient propargylic alkylation reaction was developed that delivers high yields with excellent enantiomeric ratios through dual Ni/Cu catalysis (up to 99 % ee). This Ni/Cu bimetallic system provides a reliable and a versatile approach for the development of a wide range of useful stereocontrolled reactions. Abstract A novel Ni/Cu dual catalysis gives rise to fundamentally new cooperative reactivity and enables the regio‐ and enantioselective propargylic alkylation reaction. A diverse set of α‐quaternary propargylated amino ester derivatives were synthesized in good yields with excellent enantioselectivity (up to 99 % ee). This work highlights the power of cooperative catalysis, which can be expected to have broad implications in homogeneous catalysis beyond the highly valuable synthetic intermediates.

InP Quantum Dots: Synthesis and Lighting Applications

By Bing Chen, Dongyu Li, Feng Wang from Wiley: Small: Table of Contents. Published on Jul 01, 2020.

InP nanocrystals are promising alternatives to classic Cd/Pb‐based quantum dots (QDs) for applications in practical settings owing to the low toxicity and high emission efficiency. This work focuses on the recent advances in the synthesis and surface modification of InP QDs as well as their applications in light‐emitting diodes. Abstract InP quantum dots (QDs) are typical III–V group semiconductor nanocrystals that feature large excitonic Bohr radius and high carrier mobility. The merits of InP QDs include large absorption coefficient, broad color tunability, and low toxicity, which render them promising alternatives to classic Cd/Pb‐based QDs for applications in practical settings. Over the past two decades, the advances in wet‐chemistry methods have enabled the synthesis of small‐sized colloidal InP QDs with the assistance of organic ligands. By proper selection of synthetic protocols and precursor materials coupled with surface passivation, the QYs of InP QDs are pushed to near unity with modest color purity. The state‐of‐the‐art InP QDs with appealing optical and electronic properties have excelled in many applications with the potential for commercialization. This work focuses on the recent development of wet‐chemistry protocols and various precursor materials for the synthesis and surface modification of InP QDs. Current methods for constructing light‐emitting diodes using novel InP‐based QDs are also summarized.

A High‐Energy‐Density Hybrid Supercapacitor with P‐Ni(OH)2@Co(OH)2 Core–Shell Heterostructure and Fe2O3 Nanoneedle Arrays as Advanced Integrated Electrodes

By Kunzhen Li, Bangchuan Zhao, Jin Bai, Hongyang Ma, Zhitang Fang, Xuebin Zhu, Yuping Sun from Wiley: Small: Table of Contents. Published on Jul 01, 2020.

A P‐Ni(OH)2@Co(OH)2/NF integrated electrode is fabricated through a stepwise hydrothermal approach. Such an amazing hierarchical core–shell heterostructure can not only efficiently ensure the synergetic effect of the two component materials, but also promote the diffusion and migration of electrolyte ions during the rapid charge/discharge process. Moreover, a hybrid supercapacitor assembled by P‐Ni(OH)2@Co(OH)2/NF and Fe2O3/CC electrodes achieves high energy density. Abstract Transition metal hydro/oxides (TMH/Os) are treated as the most promising alternative supercapacitor electrodes thanks to their high theoretical capacitance due to the various oxidation states and abundant cheap resources of TMH/Os. However, the poor conductivity and logy reaction kinetics of TMH/Os severely restrict their practical application. Herein, hierarchical core–shell P‐Ni(OH)2@Co(OH)2 micro/nanostructures are in situ grown on conductive Ni foam (P‐Ni(OH)2@Co(OH)2/NF) through a facile stepwise hydrothermal process. The unique heterostructure composed of P‐Ni(OH)2 rods and Co(OH)2 nanoflakes boost the charge transportation and provide abundant active sites when used as the intergrated cathode for supercapacitors. It delivers an ultrahigh areal specific capacitance of 4.4 C cm−2 at 1 mA cm−2 and the capacitance can maintain 91% after 10 000 cycles, showing an ultralong cycle life. Additionally, a hybrid supercapacitor composed with P‐Ni(OH)2@Co(OH)2/NF cathode and Fe2O3/CC anode shows a wider voltage window of 1.6 V, a remarkable energy density of 0.21 mWh cm−2 at the power density of 0.8 mW cm−2, and outstanding cycling stability with about 81% capacitance retention after 5000 cycles. This innovative study not only supplies a newfashioned electronic apparatus with high‐energy density and cycling stability but offers a fresh reference and enlightenment for synthesizing advanced integrated electrodes for high‐performance hybrid supercapacitors.

A Unique Double‐Layered Carbon Nanobowl‐Confined Lithium Borohydride for Highly Reversible Hydrogen Storage

By Ruyan Wu, Xin Zhang, Yongfeng Liu, Lingchao Zhang, Jianjiang Hu, Mingxia Gao, Hongge Pan from Wiley: Small: Table of Contents. Published on Jul 01, 2020.

A double‐layered carbon nanobowl‐confined LiBH4 composite is prepared by a facile melt infiltration process. The composite readily desorbs and absorbs ≈8.5 wt% of H2 at 300 °C and 100 bar of hydrogen pressure. The practical volumetric energy density reaches as high as 82.4 g L−1 with considerable dehydriding kinetics after cold pressing to form a pellet. Abstract Poor reversibility and high desorption temperature restricts the practical use of lithium borohydride (LiBH4) as an advanced hydrogen store. Herein, a LiBH4 composite confined in unique double‐layered carbon nanobowls prepared by a facile melt infiltration process is demonstrated, thanks to powerful capillary effect under 100 bar of H2 pressure. The gradual formation of double‐layered carbon nanobowls is witnessed by transmission electron microscopy (TEM) observation. Benefiting from the nanoconfinement effect and catalytic function of carbon, this composite releases hydrogen from 225 °C and peaks at 353 °C, with a hydrogen release amount up to 10.9 wt%. The peak temperature of dehydriding is lowered by 112 °C compared with bulk LiBH4. More importantly, the composite readily desorbs and absorbs ≈8.5 wt% of H2 at 300 °C and 100 bar H2, showing a significant reversibility of hydrogen storage. Such a high reversible capacity has not ever been observed under the identical conditions. The usable volumetric energy density reaches as high as 82.4 g L−1 with considerable dehydriding kinetics. The findings provide insights in the design and development of nanosized complex hydrides for on‐board applications.

Efficient Bifunctional Catalytic Electrodes with Uniformly Distributed NiN2 Active Sites and Channels for Long‐Lasting Rechargeable Zinc–Air Batteries

By Zihe Cai, Shengxuan Lin, Jiajia Xiao, Tahir Muhmood, Yuhang Chen, Yifan Wang, Xiaobin Hu, Lirong Zheng from Wiley: Small: Table of Contents. Published on Jul 01, 2020.

A 3D hierarchical self‐supported air electrode composed of NiN2 active sites and Ni nanoparticles encapsulated in carbon nanotubes exhibits superior oxygen reduction and oxygen evolution catalytic activities. The rechargeable zinc–air batteries based on the as‐prepared air electrode show outstanding long term stability, high power density, and specific capacity. Abstract Freestanding bifunctional electrodes with outstanding oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) properties are of great significance for zinc–air batteries, attributed to the avoided use of organic binder and strong adhesion with substrates. Herein, a strategy is developed to fabricate freestanding bifunctional electrodes from the predeposited nickel nanoparticles (Ni‐NCNT) on carbon fiber paper. The steric effect of monodispersed SiO2 nanospheres limits the configuration of carbon atoms forming 3D interconnected nanotubes with uniformly distributed NiN2 active sites. The bifunctional electrodes (Ni‐NCNT) demonstrate ideal ORR and OER properties. The zinc–air batteries assembled with Ni‐NCNT directly exhibit extremely outstanding long term stability (2250 cycles with 10 mA cm−2 charge/discharge current density) along with high power density of 120 mV cm−2 and specific capacity of 834.1 mA h g−1. This work provides a new view to optimize the distribution of active sites and the electrode structure.

Device Postannealing Enabling over 12% Efficient Solution‐Processed Cu2ZnSnS4 Solar Cells with Cd2+ Substitution

By Zhenghua Su, Guangxing Liang, Ping Fan, Jingting Luo, Zhuanghao Zheng, Zhigao Xie, Wei Wang, Shuo Chen, Juguang Hu, Yadong Wei, Chang Yan, Jialiang Huang, Xiaojing Hao, Fangyang Liu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A method of device annealing including an indium tin oxide (ITO) layer is proposed, acheiving an efficiency of 12.6% for Cd‐alloyed Cu2ZnSnS4 thin‐film solar cells. The VOC is increased by the reduction of both interface traps and deep‐level defects, and fill factor enhancement is based on the favorable band alignment (conduction band offset) and ITO improvement after postannealing. Abstract Kesterite Cu2ZnSnS4 is a promising photovoltaic material containing low‐cost, earth‐abundant, and stable semiconductor elements. However, the highest power conversion efficiency of thin‐film solar cells based on Cu2ZnSnS4 is only about 11% due to low open‐circuit voltage and fill factor mainly caused by antisite defects and unfavorable heterojunction interface. In this work, a postannealing procedure is proposed to complete a Cd‐alloyed Cu2ZnSnS4 device. The postannealing to complete the device significantly enhances the performance of the indium tin oxide and promotes the moderate interdiffusion of elements between the layers in the device. As a result of the diffusion of Cu, Zn, In, and Sn, the interfacial electron and hole densities are improved, leading to the achievement of a suitable band alignment for carrier transport. The postannealing also reduces the interface traps and deep‐level defects, contributing to decreased nonradiative recombination. Therefore, the open‐circuit voltage and fill factor are both improved, and an efficiency over 12% for pure sulfide‐based kesterite thin‐film solar cells is obtained.

High‐Performance Semitransparent Organic Solar Cells with Excellent Infrared Reflection and See‐Through Functions

By Di Wang, Ran Qin, Guanqing Zhou, Xue Li, Ruoxi Xia, Yuhao Li, Lingling Zhan, Haiming Zhu, Xinhui Lu, Hin‐Lap Yip, Hongzheng Chen, Chang‐Zhi Li from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

High‐performance semitransparent organic solar cells are achieved through the combined design efforts on the formulation of near‐infrared ternary blends and optical control over photonic reflectors, which exhibit excellent features of power generation, they being see‐through, and infrared reflection. Abstract Clean energy production and saving play vital impacts on the sustainability of the global community. Herein, high‐performance semitransparent organic solar cells (ST‐OSCs) with excellent features of power generation, being see‐through, and infrared reflection of heat dissipation, with promising perspectives for building‐integrated photovoltaics (BIPVs) are reported. To simultaneously improve average visible transmittance (AVT) and power conversion efficiency (PCE), formally in a trade‐off relationship, of ST‐OSCs, new ternary blends with alloy‐like near‐infrared (NIR) acceptors are employed, which are effective to improve device efficiency while maintaining visible absorption unchanged, resulting in PCEs of 16.8% for opaque devices and 13.1% for semitransparent OSCs (AVT of 22.4% and infrared photon radiation rejection (IRR) of 77%). Further, multifunctional ST‐OSCs are realized via introducing simple, yet effective photonic reflectors, together with optical simulation, leading to not only perfect fitting of the visible transmittance peak (555 nm) to the photopic response of the human eye but also an excellent IRR of 90% (780–2500 nm), along with 23% AVT and over 12% PCE. This is thought to be the best‐performing multifunctional ST‐OSC with promising prospects as BIPVs in terms of power generation, heat dissipation, and being see‐through.

α‐CsPbI3 Bilayers via One‐Step Deposition for Efficient and Stable All‐Inorganic Perovskite Solar Cells

By Cheng Liu, Yi Yang, Olga A. Syzgantseva, Yong Ding, Maria A. Syzgantseva, Xianfu Zhang, Abdullah M. Asiri, Songyuan Dai, Mohammad Khaja Nazeeruddin from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A gradient grain‐sized (GGS) CsPbI3 bilayer is developed to stabilize the α phase via a single‐step film‐deposition process. The perovskite solar cell based on the GGS CsPbI3 bilayer shows an efficiency of 15.5% and operates stably for 1000 h under ambient conditions. Abstract The emerging inorganic CsPbI3 perovskites are promising wide‐bandgap materials for application in tandem solar cells, but they tend to transit from a black α phase to a yellow δ phase in ambient conditions. Herein, a gradient grain‐sized (GGS) CsPbI3 bilayer is developed to stabilize the α phase via a single‐step film deposition process. The spontaneously upward migration of (adamantan‐1‐yl)methanammonium (ADMA) based on the hot‐casting technique causes self‐assembly of the hierarchical morphology for the perovskite layers. Due to the strong steric effect of the surficial ADMA cation, a self‐assembly tiny grain‐sized CsPbI3 layer is in situ formed at the surface site, which exhibits notably enhanced phase stability by its high surface energy. Meanwhile, a large grain‐sized CsPbI3 layer is obtained at the bottom site with high charge mobility and low trap density of states, which benefits from the regulated growth rates by the interaction between ADMA and perovskites. The perovskite solar cell (PSC) based on the GGS CsPbI3 bilayer shows an efficiency of 15.5% and operates stably for 1000 h under ambient conditions. This work confirms that redistributing the surface energy of perovskite films is a facile strategy to stabilize metastable PSCs without the cost of efficiency loss.

Temperature‐Dependent Chemical and Physical Microstructure of Li Metal Anodes Revealed through Synchrotron‐Based Imaging Techniques

By Keegan R. Adair, Mohammad Norouzi Banis, Yang Zhao, Toby Bond, Ruying Li, Xueliang Sun from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

The influence of temperature on the electrochemical behavior of Li metal anodes in carbonate electrolyte is revealed through a series of synchrotron‐based imaging techniques. X‐ray computed tomography as well as energy‐dependent X‐ray fluorescence mappings coupled with micro‐X‐ray absorption near edge structure are used to study the physical and chemical evolution of the Li metal anode from the micro to macroscales. Abstract The Li metal anode has been long sought‐after for application in Li metal batteries due to its high specific capacity (3860 mAh g−1) and low electrochemical potential (−3.04 V vs the standard hydrogen electrode). Nevertheless, the behavior of Li metal in different environments has been scarcely reported. Herein, the temperature‐dependent behavior of Li metal anodes in carbonate electrolyte from the micro‐ to macroscales are explored with advanced synchrotron‐based characterization techniques such as X‐ray computed tomography and energy‐dependent X‐ray fluorescence mapping. The importance of testing methodology is exemplified, and the electrochemical behavior and failure modes of Li anodes cycled at different temperatures are discussed. Moreover, the origin of cycling performance at different temperatures is identified through analysis of Coulombic efficiencies, surface morphology, and the chemical composition of the solid electrolyte interphase in quasi‐3D space with energy‐dependent X‐ray fluorescence mappings coupled with micro‐X‐ray absorption near edge structure. This work provides new characterization methods for Li metal anodes and serves as an important basis toward the understanding of their electrochemical behavior in carbonate electrolytes at different temperatures.

A Highly Conductive Titanium Oxynitride Electron‐Selective Contact for Efficient Photovoltaic Devices

By Xinbo Yang, Yuanbao Lin, Jiang Liu, Wenzhu Liu, Qunyu Bi, Xin Song, Jingxuan Kang, Fuzong Xu, Lujia Xu, Mohamed N. Hedhili, Derya Baran, Xiaohong Zhang, Thomas D. Anthopoulos, Stefaan De Wolf from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

TiOxNy films are demonstrated to be an excellent electron‐selective contact for both crystalline silicon and organic solar cells. Remarkable efficiency of 22.3% and 17.02% is achieved for crystalline silicon and organic solar cells, respectively. Abstract High‐quality carrier‐selective contacts with suitable electronic properties are a prerequisite for photovoltaic devices with high power conversion efficiency (PCE). In this work, an efficient electron‐selective contact, titanium oxynitride (TiOxNy), is developed for crystalline silicon (c‐Si) and organic photovoltaic devices. Atomic‐layer‐deposited TiOxNy is demonstrated to be highly conductive with a proper work function (4.3 eV) and a wide bandgap (3.4 eV). Thin TiOxNy films simultaneously provide a moderate surface passivation and enable a low contact resistivity on c‐Si surfaces. By implementation of an optimal TiOxNy‐based contact, a state‐of‐the‐art PCE of 22.3% is achieved for a c‐Si solar cell featuring a full‐area dopant‐free electron‐selective contact. Simultaneously, conductive TiOxNy is proven to be an efficient electron‐transport layer for organic photovoltaic (OPV) devices. A remarkably high PCE of 17.02% is achieved for an OPV device with an electron‐transport TiOxNy layer, which is superior to conventional ZnO‐based devices with a PCE of 16.10%. Atomic‐layer‐deposited TiOxNy ETL on a large area with a high uniformity may help accelerate the commercialization of emerging solar technologies.

Exerting Spatial Control During Nanoparticle Occlusion within Calcite Crystals

By Yin Ning, Yide Han, Lijuan Han, Matthew J. Derry, Steven P. Armes from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

In principle, nanoparticle occlusion within crystals provides a straightforward and efficient route to make new nanocomposite materials. However, developing a deeper understanding of the design rules underpinning this strategy is highly desirable. In particular, controlling the spatial distribution of the guest nanoparticles within the host crystalline matrix remains a formidable challenge. Herein, we show that the surface chemistry of the guest nanoparticles and the [Ca 2+ ] concentration play critical roles in determining the precise spatial location of the nanoparticles within calcite crystals. Moreover, in situ studies provide important mechanistic insights regarding surface‐confined nanoparticle occlusion. Overall, this study not only provides useful guidelines for efficient nanoparticle occlusion, but also enables the rational design of patterned calcite crystals using model anionic block copolymer vesicles.

Functionalization of Zr‐based Metal‐Organic Layers with Tailored Pore‐Environments for Heterogeneous Catalysis

By Junsheng Qin, Guan-Yu Qiao, Shuai Yuan, Jiandong Pang, Heng Rao, Christina T. Lollar, Dongbin Dang, Hong-Cai Zhou, Jihong Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Intriguing properties and functions are expected to implant into metal‐organic layers (MOLs) to achieve tailored pore environments and multiple functionalities owing to the synergies among multiple components. Herein, we demonstrated a facile one‐pot synthetic strategy to incorporate multi‐functionalities into stable zirconium MOLs via secondary ligand pillaring. Through the combination of Zr 6 −BTB (BTB = benzene‐1,3,5‐tribenzoate) layers and diverse secondary ligands (including ditopic and tetratopic linkers), 31 MOFs with multi‐functionalities were systematically prepared. Notably, a metal‐phthalocyanine fragment was successfully incorporated into this Zr‐MOL system, giving rise to an ideal platform for the selective oxidation of anthracene. We demonstrate that the organic functionalization of two‐dimensional MOLs can generate tunable porous structures and environments, which may facilitate the excellent catalytic performance of as‐synthesized materials.

Making and breaking leupeptin protease inhibitors in pathogenic gammaproteobacteria

By Jhe-Hao Li, Joonseok Oh, Sabine Kienesberger, Nam Yoon Kim, David J. Clarke, Ellen L. Zechner, Jason Crawford from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Leupeptin is a bacterial small molecule that is used worldwide as a protease inhibitor. However, its biosynthesis and genetic distribution remain unknown. Here, we identified a family of leupeptins in gammaproteobacterial pathogens, including Photorhabdus, Xenorhabdus, and Klebsiella species, amongst others. Through genetic, metabolomic, and heterologous expression analyses, we established their construction from discretely expressed ligases and accessory enzymes. In Photorhabdus species, a hypothetical protein required for colonizing nematode hosts was established as a new class of proteases. This enzyme cleaved the tripeptide aldehyde protease inhibitors, leading to the formation of “pro‐pyrazinones” featuring a hetero‐tricyclic architecture. In Klebsiella oxytoca, the pathway was enriched in clinical isolates associated with respiratory tract infections. Thus, the bacterial production and proteolytic degradation of leupeptins can be associated with animal colonization phenotypes.

Excitonic aspect in polymeric photocatalysts

By Hui Wang, Sen Jin, Xiaodong Zhang, Yi Xie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Owing to the intrinsically low dielectric properties, robust Coulomb interactions between photoinduced electrons and holes lead to dramatically strong exciton effects in polymeric photocatalysts. Such effects endow polymeric matrixes with nontrivial photoexcitation processes that are closely associated with photocatalytic solar energy utilization. In this Minireview, we describe recent progress in the investigation of excitonic aspect in polymeric photocatalysts. On the basis of the understanding of excitonic effects in polymeric semiconductors, we outline the relationships between excitonic behaviors and photocatalytic behaviors. Advances in excitonic regulation for gaining high‐efficiency polymeric semiconductor‐based photocatalysis are summarized. We also discuss the challenges in the field of exciton‐involved photocatalysis and forecast the directions for future research.

Sulfone Group as a Versatile and Removable Directing Group for Asymmetric Transfer Hydrogenation of Ketones

By Vijyesh K. Vyas, Guy J. Clarkson, Martin Wills from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

En route: The sulfone group facilitates the formation of a range of reduction substrates through asymmetric transfer hydrogenation (ATH) of ketones, and its ready removal provides a route to challenging enantiomerically enriched alcohols. Abstract The sulfone functional group has a strong capacity to direct the asymmetric transfer hydrogenation (ATH) of ketones in the presence of [(arene)Ru(TsDPEN)H] complexes by adopting a position distal to the η6‐arene ring. This preference provides a means for the prediction of the sense of asymmetric reduction. The sulfone group also facilitates the formation of a range of reduction substrates, and its ready removal provides a route to enantiomerically enriched alcohols that would otherwise be extremely difficult to prepare by direct ATH of the corresponding ketones.

Identification of Histone‐deacetylase (HDAC)‐associated Proteins with DNA‐Programmed Affinity Labeling

By Jianfu Zhang, Jianzhao Peng, Yiran Huang, Ling Meng, Qingrong Li, Feng Xiong, Xiaoyu Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Histone deacetylase (HDAC) is a major class of deacetylation enzymes. Many HDACs exist in large protein complexes in cells and their functions strongly depend on the complex composition. The identification of HDAC‐associated proteins is highly important in understanding their molecular mechanisms. Although affinity probes have been developed to study HDACs, they were mostly targeting the direct binder HDAC, while other proteins in the complex remain under‐explored. We report a DNA‐based affinity labeling method capable of presenting different probe configurations without the need for preparing multiple probes. Using one binding probe, 9 probe configurations were created to profile HDAC complexes. Notably, this method identified indirect HDAC binders that may be inaccessible to traditional affinity probes, and it also revealed new biological implications for HDAC‐associated proteins. This study provided a simple and broadly applicable method for characterizing protein‐protein interactions.

Single‐molecule analysis determines isozymes of human alkaline phosphatase in serum

By Yu Jiang, Xiang Li, David Walt from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Alkaline phosphatase (ALP) is an important biomarker, as high levels of ALP in blood can indicate liver disease or bone disorders. However, current clinical blood tests only measure the total concentration of ALP but are unable to distinguish enzyme isotypes. Here, we demonstrate a novel and rapid approach to profile various ALP isozymes in blood via a single‐molecule‐analysis platform. The microarray platform provides enzyme kinetics of hundreds of individual molecules at high throughput. Using these single molecule kinetics, we characterize the different activity profiles of ALP isotypes. By analyzing both healthy and disease samples, we found the single molecule activity distribution of ALP in serum reflects the health status of patients. This result demonstrates the potential utility of the method for improving the conventional ALP test, as well as for analyzing other enzymatic biomarkers, including enzyme isotypes.

Organocatalytic trans Phosphinoboration of Internal Alkynes

By Russell G. Fritzemeier, Jan Nekvinda, Christopher M. Vogels, Carol Ann Rosenblum, Carla Slebodnick, Stephen A. Westcott, Webster L. Santos from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

PB&J? Phosphinoboration across a triple bond catalyzed by tributyl phosphine was achieved. The trans‐α‐phosphino‐β‐boryl acrylate products are obtained in moderate to good yield with high regio‐ and Z‐selectivity. This reaction operates under mild conditions and demonstrates good atom economy, requiring only a modest excess of the phosphinoboronate. Abstract We report the first trans phosphinoboration of internal alkynes. With an organophosphine catalyst, alkynoate esters and the phosphinoboronate Ph2P‐Bpin are efficiently converted into the corresponding trans‐α‐phosphino‐β‐boryl acrylate products in moderate to good yield with high regio‐ and Z‐selectivity. This reaction operates under mild conditions and demonstrates good atom economy, requiring only a modest excess of the phosphinoboronate. X‐ray crystallography experiments allowed structural assignment of the unprecedented and densely functionalized (Z)‐α‐phosphino‐β‐boryl acrylate products.

Synthesis and Characterization of the Highly Unstable Metalloid Cluster Ag64(PnBu3)16Cl6

By Maximilian Diecke, Claudio Schrenk, Andreas Schnepf from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Light up the dark! The reduction of (nBu3P)AgCl with LiBH(sBu)3 in toluene gives the highly unstable metalloid silver cluster Ag64(PnBu3)16Cl6 as dark red, temperature‐ and light‐sensitive single crystals in high yield. This is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only. Abstract The reduction of (nBu3P)AgCl with LiBH(sBu)3 in toluene gives the metalloid silver cluster Ag64(PnBu3)16Cl6 (1) as dark red, temperature‐ and light‐sensitive single crystals in high yield. 1 is the largest structurally characterized metalloid silver cluster exhibiting chlorine and phosphine substituents only. The silver atoms in 1 show an overall brick‐shape arrangement, where structural resemblance to the close‐packed fcc and hcp structures is realized. Within 1 a 58 electron closed shell system is present. The light sensitivity renders 1 as a model compound for the primary seeds of the photo process, whereby this sensitivity, together with the high‐yield synthesis show that 1 is a perfect starting compound for further investigations like silver‐plating processes.

Distinguishing Enantiomers by Tip‐Enhanced Raman Scattering: Chemically Modified Silver Tip with an Asymmetric Atomic Arrangement

By Thanyada Sukmanee, Kanet Wongravee, Yasutaka Kitahama, Sanong Ekgasit, Tamitake Itoh, Prompong Pienpinijtham, Yukihiro Ozaki from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Scatter about: An asymmetric electric field produced by an asymmetric arrangement of silver atoms in conjunction with charge‐transfer transitions enables the discrimination of enantiomeric compounds using tip‐enhanced Raman scattering (TERS) without chiral reagents. The unique TERS phenomenon, wherein the number of hydrogen bonds formed by functional groups on the analyte modulates the degree of discrimination, is a result of the near‐field effect of the asymmetric electric field. Abstract Discrimination between enantiomers is achieved by tip‐enhanced Raman scattering (TERS) using a silver tip that is chemically modified by an achiral para‐mercaptopyridine (pMPY) probe molecule. Differences in the relative intensities of the pMPY spectra were monitored for three pairs of enantiomers containing hydroxy (−OH) and/or amino (−NH2) groups. The N: or N+−H functionality of the pMPY‐modified tip participates in hydrogen‐bond interactions with a particular molecular orientation of each chiral isomer. The asymmetric arrangement of silver atoms at the apex of the tip induces an asymmetric electric field, which causes the tip to become a chiral center. Differences in the charge‐transfer (CT) states of the metal‐achiral probe system in conjunction with the asymmetric electric field produce different enhancements in the Raman signals of the two enantiomers. The near‐field effect of the asymmetric electric field, which depends on the number of analyte functional groups capable of hydrogen‐bond formation, improves the degree of discrimination.

Methanol Synthesis at a Wide Range of H2/CO2 Ratios over a Rh‐In Bimetallic Catalyst

By Molly Meng‐Jung Li, Hanbo Zou, Jianwei Zheng, Tai‐Sing Wu, Ting‐Shan Chan, Yun‐Liang Soo, Xin‐Ping Wu, Xue‐Qing Gong, Tianyi Chen, Kanak Roy, Georg Held, Shik Chi Edman Tsang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The bimetallic Rh‐In catalyst offers selective sites for capturing hydrogen and CO2 to approach methanol formation under H2‐deficient feedstock compositions with high methanol yield but minimizing the reverse water‐gas shift reaction. Using this catalyst, a convenient methanol synthesis based on renewable biomass‐derived feedstocks with lower energy costs can be established. Abstract There is increasing interest in capturing H2 generated from renewables with CO2 to produce methanol. However, renewable hydrogen production is expensive and in limited quantity compared to CO2. Excess CO2 and limited H2 in the feedstock gas is not favorable for CO2 hydrogenation to methanol, causing low activity and poor methanol selectivity. Now, a class of Rh‐In catalysts with optimal adsorption properties to the intermediates of methanol production is presented. The Rh‐In catalyst can effectively catalyze methanol synthesis but inhibit the reverse water‐gas shift reaction under H2‐deficient gas flow and shows the best competitive methanol productivity under industrially applicable conditions in comparison with reported values. This work demonstrates a strong potential of Rh‐In bimetallic composition, from which a convenient methanol synthesis based on flexible feedstock compositions (such as H2/CO2 from biomass derivatives) with lower energy cost can be established.

Interlocked DNA Nanojoints for Reversible Thermal Sensing

By Yinzhou Ma, Mathias Centola, Daniel Keppner, Michael Famulok from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A precise thermal sensing DNA nanojoint comprised of two interlocked DNA rings switches reversibly between a static and mobile state at different temperatures. The temperature response range is tuned by changing the length or sequence of the hybridizing region between two rings, which, unlike non‐interlocked systems, is independent from its concentration. Abstract The ability to precisely measure and monitor temperature at high resolution at the nanoscale is an important task for better understanding the thermodynamic properties of functional entities at the nanoscale in complex systems, or at the level of a single cell. However, the development of high‐resolution and robust thermal nanosensors is challenging. The design, assembly, and characterization of a group of thermal‐responsive deoxyribonucleic acid (DNA) joints, consisting of two interlocked double‐stranded DNA (dsDNA) rings, is described. The DNA nanojoints reversibly switch between the static and mobile state at different temperatures without a special annealing process. The temperature response range of the DNA nanojoint can be easily tuned by changing the length or the sequence of the hybridized region in its structure, and because of its interlocked structure the temperature response range of the DNA nanojoint is largely unaffected by its own concentration; this contrasts with systems that consist of separated components.

A Highly Selective and Sensitive Chemiluminescent Probe for Real‐Time Monitoring of Hydrogen Peroxide in Cells and Animals

By Sen Ye, Nir Hananya, Ori Green, Hansen Chen, Angela Qian Zhao, Jiangang Shen, Doron Shabat, Dan Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Peroxide triggered, peroxide excited: Real‐time monitoring of hydrogen peroxide (H2O2) in rat brains has been achieved by combining a unique H2O2 sensing strategy and a peroxide bond excited chemiluminescent scaffold. This direct activation of phenoxy‐dioxetane by a tandem Payne/Dakin reaction provides a highly selective, sensitive, and rapid detection of H2O2 in chemical systems, the cellular environment, and living animals. Abstract Selective and sensitive molecular probes for hydrogen peroxide (H2O2), which plays diverse roles in oxidative stress and redox signaling, are urgently needed to investigate the physiological and pathological effects of H2O2. A lack of reliable tools for in vivo imaging has hampered the development of H2O2 mediated therapeutics. By combining a specific tandem Payne/Dakin reaction with a chemiluminescent scaffold, H2O2‐CL‐510 was developed as a highly selective and sensitive probe for detection of H2O2 both in vitro and in vivo. A rapid 430‐fold enhancement of chemiluminescence was triggered directly by H2O2 without any laser excitation. Arsenic trioxide induced oxidative damage in leukemia was successfully detected. In particular, cerebral ischemia‐reperfusion injury‐induced H2O2 fluxes were visualized in rat brains using H2O2‐CL‐510, providing a new chemical tool for real‐time monitoring of H2O2 dynamics in living animals.

Cross‐Linked Polyphosphazene Hollow Nanosphere‐Derived N/P‐Doped Porous Carbon with Single Nonprecious Metal Atoms for the Oxygen Reduction Reaction

By Xuan Wei, Diao Zheng, Ming Zhao, Hongzhong Chen, Xun Fan, Bin Gao, Long Gu, Yi Guo, Jianbin Qin, Jing Wei, Yanli Zhao, Guangcheng Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A facile template‐free method is developed for the synthesis of functional cross‐linked polyphosphazene nanospheres with tunable hollow structures and properties. After coordinating with metal ions, these nanospheres are directly pyrolyzed to afford mesoporous hollow carbon nanospheres with single atom Co‐N2P2 sites for superior electrocatalysis. Abstract Heteroatom‐doped polymers or carbon nanospheres have attracted broad research interest. However, rational synthesis of these nanospheres with controllable properties is still a great challenge. Herein, we develop a template‐free approach to construct cross‐linked polyphosphazene nanospheres with tunable hollow structures. As comonomers, hexachlorocyclotriphosphazene provides N and P atoms, tannic acid can coordinate with metal ions, and the replaceable third comonomer can endow the materials with various properties. After carbonization, N/P‐doped mesoporous carbon nanospheres were obtained with small particle size (≈50 nm) and high surface area (411.60 m2 g−1). Structural characterization confirmed uniform dispersion of the single atom transition metal sites (i.e., Co‐N2P2) with N and P dual coordination. Electrochemical measurements and theoretical simulations revealed the oxygen reduction reaction performance. This work provides a solution for fabricating diverse heteroatom‐containing polymer nanospheres and their derived single metal atom doped carbon catalysts.

Nickel‐Catalyzed Allylmethylation of Alkynes with Allylic Alcohols and AlMe3: Facile Access to Skipped Dienes and Trienes

By Wanfang Li, Shun Yu, Jincan Li, Yu Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Just a hop and a skip away: A simple and mild dicarbofunctionalization of internal alkynes was developed by using Ni(COD)2/PPh3 as the catalyst and free allylic alcohols and AlMe3 as the inexpensive reagents (see scheme). Diversiform polyenes were prepared by this method with high stereoselectivity. Abstract We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD)2, triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all‐carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes.

Revisiting the Polymerization of Diphenylacetylenes with Tungsten(VI) Chloride and Tetraphenyltin: An Alternative Mechanism by a Metathesis Catalytic System

By Mami Miyairi, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A migratory insertion mechanism has been proposed for the polymerization of diphenylacetylenes by a classic metathesis catalytic system composed of tungsten(VI) chloride (WCl6 or WOCl4) and Ph4Sn. The polymerization is initiated by addition of a phenyl group coming from Ph4Sn to diphenylacetylene monomers and has two possible termination processes. Abstract An alternative reaction mechanism of the polymerization of diphenylacetylelnes using a catalytic system composed of tungsten(VI) chloride and tetraphenyltin has been proposed through the optimization of reaction conditions and investigation of the effect of the electronic nature of diphenylacetylene monomers on the polymerizability. The detailed structures of the polymers have been suggested by mass spectrometric analysis of the obtained polymers and oligomers, which suggested that a phenyl group of tetraphenyltin has been introduced to an initiating end of the polymer chain. Mass spectrometric analysis also provided information about the termination processes of the polymerization. The experimental results strongly suggested that the polymerization of diphenylacetylenes using tungsten(VI) chloride and tetraphenyltin proceeds through a migratory insertion mechanism rather than the long‐accepted metathesis mechanism.

On the Dynamic Interaction of n‐Butane with Imidazolium‐Based Ionic Liquids

By Radha G. Bhuin, Leonhard Winter, Matthias Lexow, Florian Maier, Hans‐Peter Steinrück from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The adsorption dynamics of n‐butane on a series of imidazolium‐based ionic liquids (ILs) is investigated. The adsorption energy increases with increasing length of the IL alkyl chain, whereas the ionic headgroups seem to interact only weakly with n‐butane. The absence of adsorption on the C1‐ and C2‐ILs is attributed to a too short residence time on the ionic liquid surface to form nuclei for condensation. Abstract The impact of a reactant from the gas phase on the surface of a liquid and its transfer through this gas/liquid interface are crucial for various concepts applying ionic liquids (ILs) in catalysis. We investigated the first step of the adsorption dynamics of n‐butane on a series of 1‐alkyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide ILs ([CnC1Im][Tf2N]; n=1, 2, 3, 8). Using a supersonic molecular beam in ultra‐high vacuum, the trapping of n‐butane on the frozen ILs was determined as a function of surface temperature, between 90 and 125 K. On the C8‐ and C3‐ILs, n‐butane adsorbs at 90 K with an initial trapping probability of ≈0.89. The adsorption energy increases with increasing length of the IL alkyl chain, whereas the ionic headgroups seem to interact only weakly with n‐butane. The absence of adsorption on the C1‐ and C2‐ILs is attributed to a too short residence time on the IL surface to form nuclei for condensation even at 90 K.

Metal‐Free Photocatalytic Hydrogenation Using Covalent Triazine Polymers

By Yongpan Hu, Wei Huang, Hongshuai Wang, Qing He, Yuan Zhou, Ping Yang, Youyong Li, Yanguang Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A covalent triazine polymeric photocatalyst with unique donor‐acceptor units was designed. It enabled the metal‐free photocatalytic hydrogenation of maleic acid to succinic acid, as well as furfural to furfuryl alcohol, with an incredible production rate, great stability, and recyclability. Abstract Photocatalytic hydrogenation of biomass‐derived organic molecules transforms solar energy into high‐energy‐density chemical bonds. Reported herein is the preparation of a thiophene‐containing covalent triazine polymer as a photocatalyst, with unique donor‐acceptor units, for the metal‐free photocatalytic hydrogenation of unsaturated organic molecules. Under visible‐light illumination, the polymeric photocatalyst enables the transformation of maleic acid into succinic acid with a production rate of about 2 mmol g−1 h−1, and furfural into furfuryl alcohol with a production rate of about 0.5 mmol g−1 h−1. Great catalyst stability and recyclability are also measured. Given the structural diversity of polymeric photocatalysts and their readily tunable optical and electronic properties, metal‐free photocatalytic hydrogenation represents a highly promising approach for solar energy conversion.

Rational Design of Cyclometalated Iridium(III) Complexes for Three‐Photon Phosphorescence Bioimaging

By Chengzhi Jin, Fengyin Liang, Jinquan Wang, Lili Wang, Jiangping Liu, Xinxing Liao, Thomas W. Rees, Bo Yuan, Hui Wang, Yong Shen, Zhong Pei, Liangnian Ji, Hui Chao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Cyclometalated iridium(III) complexes were developed as mitochondria‐targeted three‐photon phosphorescence agents for confocal imaging and phosphorescence lifetime imaging. The agents can be used from monolayer cells to the living body, with both large penetration depth and great resolution at excitation wavelength of 980 nm. Abstract Compared to 2PE (two‐photon excitation) microscopy, 3PE microscopy has superior spatial resolution, deeper tissue penetration, and less defocused interference. The design of suitable agents with a large Stokes shift, good three‐photon absorption (3PA), subcellular targeting, and fluorescence lifetime imaging (FLIM) properties, is challenging. Now, two IrIII complexes (3PAIr1 and 3PAIr2) were developed as efficient three‐photon phosphorescence (3PP) agents. Calculations reveal that the introduction of a new group to the molecular scaffold confers a quadruple promotion in three‐photon transition probability. Confocal and lifetime imaging of mitochondria using IrIII complexes as 3PP agents is shown. The complexes exhibit low working concentration (50 nm), fast uptake (5 min), and low threshold for three‐photon excitation power (0.5 mW at 980 nm). The impressive tissue penetration depth (ca. 450 μm) allowed the 3D imaging and reconstruction of brain vasculature from a living specimen.

Helical Toroids Self‐Assembled from a Binary System of Polypeptide Homopolymer and its Block Copolymer

By Pengfei Xu, Liang Gao, Chunhua Cai, Jiaping Lin, Liquan Wang, Xiaohui Tian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A binary system, containing polypeptide homopolymer and its block copolymer, hierarchically self‐assembles into helical nanotoroids in which the homopolymers aggregate into fibrils and then convolve into a toroidal template. The block copolymers form helical patterns on the toroids. Abstract Toroids and helices are fundamental geometrical structures in nature. Polymers can self‐assemble into various nanostructures, including both toroids and helices; however, nanostructures combining toroidal and helical morphologies (that is, helical toroids) are rarely observed. A binary system is reported containing polypeptide homopolymer and its block copolymer, which can hierarchically self‐assemble into uniform helical nanotoroids in solution. The formation of the helical toroids is a successive two‐step process. First, the homopolymers aggregate into fibrils and convolve into toroids, thereby resembling the toroidal condensation of deoxyribonucleic acid (DNA) chains. Second, the block copolymers self‐assemble on the homopolymer toroids and result in helical surface patterns. Additionally, the chirality of the surface helical patterns can be varied by the chirality of the polypeptide block copolymers.

Emission of Toxic HCN During NOx Removal by Ammonia SCR in the Exhaust of Lean‐Burn Natural Gas Engines

By Deniz Zengel, Pirmin Koch, Bentolhoda Torkashvand, Jan‐Dierk Grunwaldt, Maria Casapu, Olaf Deutschmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

HCN formation over common SCR catalysts: Natural gas engines emit less CO2 in comparison to common liquid fuel combustion engines and are therefore an attractive alternative. Nevertheless, they still require emission control devices for NOx removal. As HCHO is present in the exhaust, this study was focused on the interplay of HCHO and other compounds of an SCR gas mixture and revealed the formation of HCN over a broad variety of common NH3‐SCR catalysts. Abstract Reducing greenhouse gas and pollutant emissions is one of the most stringent priorities of our society to minimize their dramatic effects on health and environment. Natural gas (NG) engines, in particular at lean conditions, emit less CO2 in comparison to combustion engines operated with liquid fuels but NG engines still require emission control devices for NOx removal. Using state‐of‐the‐art technologies for selective catalytic reduction (SCR) of NOx with NH3, we evaluated the interplay of the reducing agent NH3 and formaldehyde, which is always present in the exhaust of NG engines. Our results show that a significant amount of highly toxic hydrogen cyanide (HCN) is formed. All catalysts tested partially convert formaldehyde to HCOOH and CO. Additionally, they form secondary emissions of HCN due to catalytic reactions of formaldehyde and its oxidation intermediates with NH3. With the present components of the exhaust gas aftertreatment system the HCN emissions are not efficiently converted to non‐polluting gases. The development of more advanced catalyst formulations with improved oxidation activity is mandatory to solve this novel critical issue.

PST‐24: A Zeolite with Varying Intracrystalline Channel Dimensionality

By Donghui Jo, Jingjing Zhao, Jung Cho, Jeong Hwan Lee, Yang Liu, Chang-jun Liu, Xiaodong Zou, Suk Bong Hong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Herein we report the synthesis, structure solution, and catalytic properties of PST‐24, a novel channel‐based medium‐pore zeolite. This zeolite was synthesized using pentamethylimidazolium ions as an organic structure‐directing agent via the excess fluoride approach. A combination of three‐dimensional (3D) electron diffraction and high‐resolution transmission electron microscopy shows that its structure is built by composite cas‐zigzag ( cas‐zz ) building chains, which are connected by double 5‐ring ( d5r ) columns. While the cas‐zz building chains are ordered in the PST‐24 framework, the d5r columns adopt one of two possible arrangements; the two adjacent d5r columns are either at the same height or at different heights, denoted arrangements S and D, which can be regarded as open and closed “valves” that connect the channels, respectively. A framework with arrangement D only has a 2D 10‐ring channel system, whereas that with arrangement S only contains 3D channels. In actual PST‐24 crystals, the open and closed valves are almost randomly dispersed to yield a zeolite framework where the channel dimensionality varies locally from 2D to 3D. Such a unique pore structure renders PST‐24 highly selective for 1,3‐butanediol dehydration.

Thu 17 Sep 15:00: Title to be confirmed ***Please note this seminar will take place online at 3pm***

From All Talks (aka the CURE list). Published on Jul 01, 2020.

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From All Talks (aka the CURE list). Published on Jul 01, 2020.

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Rabies Virus‐Inspired Metal‐Organic Frameworks for Targeted Imaging and Chemotherapy of Glioma

By Chaoqiang Qiao, Ruili Zhang, Yongdong Wang, Qian Jia, Xiaofei Wang, Zuo Yang, Tengfei Xue, Renchuan Ji, Xiufang Cui, Zhongliang Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The blood–brain barrier (BBB) restricts access to the brain of more than 98% of therapeutic agents and is largely responsible for treatment failure of glioblastoma multiforme (GBM). Therefore, it is of great importance to develop a safe and efficient strategy for more effective drug delivery across the BBB into the brain. Inspired by the extraordinary capability of rabies virus (RABV) to enter the central nervous system, we report the development and evaluation of the metal–organic framework‐based nanocarrier MILB@LR, which closely mimicked both the bullet‐shape structure and surface functions of natural RABV. MILB@LR benefited from a more comprehensive RABV‐mimic strategy than mimicking individual features of RABV and exhibited significantly enhanced BBB penetration and brain tumor targeting. MILB@LR also displayed superior inhibition of tumor growth when loaded with oxaliplatin. The results demonstrated that MILB@LR may be valuable for GBM targeting and treatment.

A Planar, Conjugated N4‐macrocyclic Cobalt Complex for Heterogeneous Electrocatalytic CO2 Reduction with High Activity

By Xin Wang, Libo Sun, Zhenfeng Huang, Vikas Reddu, Tan Su, Adrian C. Fisher from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Metal complexes have been widely investigated as promising electrocatalysts for CO 2 reduction. Most of the current research efforts mainly focus on ligands based on pyrrole subunits and the reported activities are still far from satisfactory. A novel planar and conjugated N4‐macrocyclic cobalt complex (Co(II)CPY) derived from phenanthroline subunits is prepared herein, which delivers high activity for heterogeneous CO 2 electrocatalysis to CO in an aqueous medium and outperforms most of the metal complexes reported so far. At a molar loading of 5.93×10 ‐8 mol cm ‐2 , it exhibits a Faradaic efficiency of 96% and a turnover frequency of 9.59 s ‐1 towards CO at ‐0.70 V vs . RHE. The unraveling of electronic structural features suggests a synergistic effect from ligand to cobalt in Co(II)CPY plays a critical role in boosting its activity. As a result, the free energy difference for the formation of *COOH is lower than that on cobalt porphyrin, leading to enhanced CO production.

Engineering Co2MnAlxSi1−x Heusler Compounds as a Model System to Correlate Spin Polarization, Intrinsic Gilbert Damping, and Ultrafast Demagnetization

By Charles Guillemard, Wei Zhang, Gregory Malinowski, Claudia de Melo, Jon Gorchon, Sebastien Petit‐Watelot, Jaafar Ghanbaja, Stéphane Mangin, Patrick Le Fèvre, Francois Bertran, Stéphane Andrieu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

High‐crystalline‐quality Heusler compounds, Co2MnAlxSi1–x, are grown. Correlation between the degree of spin polarization at the Fermi energy (ranging from 60% to 100%) and the Gilbert damping (ranging from 1.1 × 10−3 to 4 × 10−4) is obtained. An inverse relationship between demagnetization time and Gilbert damping is established. Abstract Engineering of magnetic materials for developing better spintronic applications relies on the control of two key parameters: the spin polarization and the Gilbert damping, responsible for the spin angular momentum dissipation. Both of them are expected to affect the ultrafast magnetization dynamics occurring on the femtosecond timescale. Here, engineered Co2MnAlxSi1‐x Heusler compounds are used to adjust the degree of spin polarization at the Fermi energy, P, from 60% to 100% and to investigate how they correlate with the damping. It is experimentally demonstrated that the damping decreases when increasing the spin polarization from 1.1 × 10−3 for Co2MnAl with 63% spin polarization to an ultralow value of 4.6 × 10−4 for the half‐metallic ferromagnet Co2MnSi. This allows the investigation of the relation between these two parameters and the ultrafast demagnetization time characterizing the loss of magnetization occurring after femtosecond laser pulse excitation. The demagnetization time is observed to be inversely proportional to 1 – P and, as a consequence, to the magnetic damping, which can be attributed to the similarity of the spin angular momentum dissipation processes responsible for these two effects. Altogether, the high‐quality Heusler compounds allow control over the band structure and therefore the channel for spin angular momentum dissipation.

Giant Piezospintronic Effect in a Noncollinear Antiferromagnetic Metal

By Huixin Guo, Zexin Feng, Han Yan, Jiuzhao Liu, Jia Zhang, Xiaorong Zhou, Peixin Qin, Jialin Cai, Zhongming Zeng, Xin Zhang, Xiaoning Wang, Hongyu Chen, Haojiang Wu, Chengbao Jiang, Zhiqi Liu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A giant piezospintronic effect is discovered in a hexagonal noncollinear antiferromagnet, Mn3Ga. Furthermore, it is found that its Fermi surface and density of states are very sensitive to the spin structure perturbation. Consequently, a nanoscale antiferromagnetic tunnel junction built on Mn3Ga and operated by piezoelectric strain exhibits a more than 10% tunneling resistance modulation at room temperature. Abstract One of the main bottleneck issues for room‐temperature antiferromagnetic spintronic devices is the small signal read‐out owing to the limited anisotropic magnetoresistance in antiferromagnets. However, this could be overcome by either utilizing the Berry‐curvature‐induced anomalous Hall resistance in noncollinear antiferromagnets or establishing tunnel‐junction devices based on effective manipulation of antiferromagnetic spins. In this work, the giant piezoelectric strain modulation of the spin structure and the anomalous Hall resistance in a noncollinear antiferromagnetic metal—D019 hexagonal Mn3Ga—is demonstrated. Furthermore, tunnel‐junction devices are built with a diameter of 200 nm to amplify the maximum tunneling resistance ratio to more than 10% at room‐temperature, which thus implies significant potential of noncollinear antiferromagnets for large signal‐output and high‐density antiferromagnetic spintronic device applications.

Engineered PD‐L1‐Expressing Platelets Reverse New‐Onset Type 1 Diabetes

By Xudong Zhang, Yang Kang, Jinqiang Wang, Junjie Yan, Qian Chen, Hao Cheng, Peng Huang, Zhen Gu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Platelets are genetically engineered to overexpress programmed death‐ligand 1 (PD‐L1) to maintain immune tolerance in the pancreas and reverse new‐onset Type 1 diabetes in non‐obese diabetic (NOD) mice. The PD‐L1‐expressing platelets may suppress the activity of pancreas autoreactive T cells and increase the percentage of the regulatory T cells in newly hyperglycemic NOD mice, protecting the insulin‐producing β‐cells from destruction. Abstract The pathogenesis of Type 1 diabetes (T1D) arises from the destruction of insulin‐producing β‐cells by islet‐specific autoreactive T cells. Inhibition of islet‐specific autoreactive T cells to rescue β‐cells is a promising approach to treat new‐onset T1D. The immune checkpoint signal axis programmed death‐1/programmed death‐ligand 1 (PD‐1/PD‐L1) can effectively regulate the activity of T cells and prevent autoimmune attack. Here, megakaryocyte progenitor cells are genetically engineered to overexpress PD‐L1 to produce immunosuppressive platelets. The PD‐L1‐overexpressing platelets (designated PD‐L1 platelets) accumulate in the inflamed pancreas and may suppress the activity of pancreas autoreactive T cells in newly hyperglycemic non‐obese diabetic (NOD) mice, protecting the insulin‐producing β‐cells from destruction. Moreover, PD‐L1 platelet treatment also increases the percentage of the regulatory T cells (Tregs) and maintains immune tolerance in the pancreas. It is demonstrated that the rescue of β‐cells by PD‐L1 platelets can effectively maintain normoglycemia and reverse diabetes in newly hyperglycemic NOD mice.

Plasmonic Janus Microspheres Created from Pickering Emulsion Drops

By Jong Bin Kim, Su Yeon Lee, Nam Gi Min, Seung Yeol Lee, Shin‐Hyun Kim from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Plasmonic Janus microspheres are designed from Pickering emulsions. A regular array of dimples is prepared on the surface of the microspheres using an array of particles at the emulsion interface as templates, on which plasmonic nanostructures are created by directional deposition of metal. This class of plasmonic microgranules with a controlled plasmonic property will provide new opportunities for various optical applications. Abstract Metal nanostructures have been created in a film format to develop unique plasmonic properties. Here, well‐defined metal nanostructures are designed on the surface of microspheres to provide plasmonic microgranules. As conventional techniques are inadequate for nanofabrication on spherical surfaces, photocurable emulsion drops with a regular array of silica particles are employed at the interface to create periodic nanostructures. The silica particles, originating from the dispersed phase, fully cover the interface by forming a non‐close‐packed hexagonal array after drop generation, and slowly protrude to the continuous phase during aging while their interparticle separation decreases. Therefore, hexagonal arrays of spherical dimples with controlled geometry and separation are created on the surface of microspheres by photocuring the drops and removing the particles. Directional deposition of either aluminum or gold results in a continuous film with a hexagonal array of holes on the outermost surface and isolated curved disks in dimples, which renders the hemisphere of microspheres plasmonically colored. The resonant wavelength is controlled by adjusting the aging time, metal thickness, and size of silica particles, providing various plasmonic colors. This granular format of the plasmonic Janus microspheres will open a new avenue of optical applications including active color pixels, optical barcodes, and microsensors.

In Situ Formation of Oxygen Vacancies Achieving Near‐Complete Charge Separation in Planar BiVO4 Photoanodes

By Songcan Wang, Tianwei He, Peng Chen, Aijun Du, Kostya (Ken) Ostrikov, Wei Huang, Lianzhou Wang from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A new sulfur oxidation process is developed to synthesize planar BiVO4 thin films with in‐situ‐formed oxygen vacancies in the whole film, achieving a record charge‐separation efficiency of 98.2%. By depositing an efficient NiFeOx oxygen evolution cocatalyst, a high and stable photocurrent density of 5.54 mA cm−2 for photoelectrochemical water splitting is achieved. Abstract Despite a suitable bandgap of bismuth vanadate (BiVO4) for visible light absorption, most of the photogenerated holes in BiVO4 photoanodes are vanished before reaching the surfaces for oxygen evolution reaction due to the poor charge separation efficiency in the bulk. Herein, a new sulfur oxidation strategy is developed to prepare planar BiVO4 photoanodes with in situ formed oxygen vacancies, which increases the majority charge carrier density and photovoltage, leading to a record charge separation efficiency of 98.2% among the reported BiVO4 photoanodes. Upon loading NiFeOx as an oxygen evolution cocatalyst, a stable photocurrent density of 5.54 mA cm−2 is achieved at 1.23 V versus the reversible hydrogen electrode (RHE) under AM 1.5 G illumination. Remarkably, a dual‐photoanode configuration further enhances the photocurrent density up to 6.24 mA cm−2, achieving an excellent applied bias photon‐to‐current efficiency of 2.76%. This work demonstrates a simple thermal treatment approach to generate oxygen vacancies for the design of efficient planar photoanodes for solar hydrogen production.

Photomodulation of Charge Transport in All‐Semiconducting 2D–1D van der Waals Heterostructures with Suppressed Persistent Photoconductivity Effect

By Zhaoyang Liu, Haixin Qiu, Can Wang, Zongping Chen, Björn Zyska, Akimitsu Narita, Artur Ciesielski, Stefan Hecht, Lifeng Chi, Klaus Müllen, Paolo Samorì from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Mixed‐dimensional van der Waals heterostructures (VDWHs) are fabricated based on 1D graphene nanoribbons onto 2D MoS2, showing a significantly suppressed persistent photoconductivity effect of MoS2. Photomodulation of the charge transport of the obtained VDWHs field‐effect transistor is realized by interfacing with photochromic molecules, demonstrating its great potential for multilevel memories, which are promising for future development of ultrathin multifunctional optoelectronics. Abstract Van der Waals heterostructures (VDWHs), obtained via the controlled assembly of 2D atomically thin crystals, exhibit unique physicochemical properties, rendering them prototypical building blocks to explore new physics and for applications in optoelectronics. As the emerging alternatives to graphene, monolayer transition metal dichalcogenides and bottom‐up synthesized graphene nanoribbons (GNRs) are promising candidates for overcoming the shortcomings of graphene, such as the absence of a bandgap in its electronic structure, which is essential in optoelectronics. Herein, VDWHs comprising GNRs onto monolayer MoS2 are fabricated. Field‐effect transistors (FETs) based on such VDWHs show an efficient suppression of the persistent photoconductivity typical of MoS2, resulting from the interfacial charge transfer process. The MoS2‐GNR FETs exhibit drastically reduced hysteresis and more stable behavior in the transfer characteristics, which is a prerequisite for the further photomodulation of charge transport behavior within the MoS2‐GNR VDWHs. The physisorption of photochromic molecules onto the MoS2‐GNR VDWHs enables reversible light‐driven control over charge transport. In particular, the drain current of the MoS2‐GNR FET can be photomodulated by 52%, without displaying significant fatigue over at least 10 cycles. Moreover, four distinguishable output current levels can be achieved, demonstrating the great potential of MoS2‐GNR VDWHs for multilevel memory devices.

Regulating the Interfacial Electronic Coupling of Fe2N via Orbital Steering for Hydrogen Evolution Catalysis

By Yishang Wu, Jinyan Cai, Yufang Xie, Shuwen Niu, Yipeng Zang, Shaoyang Wu, Yun Liu, Zheng Lu, Yanyan Fang, Yong Guan, Xusheng Zheng, Junfa Zhu, Xiaojing Liu, Gongming Wang, Yitai Qian from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

The interfacial electronic coupling between Fe2N and H* can be effectively tuned by nitrogen‐vacancy‐induced orbital steering. Moreover, real‐time X‐ray absorption fine structure studies indicate that the OH cleavage that originates from the ionic hydration effect can also affect the acidic hydrogen evolution kinetics. The capability of manipulating the interfacial electronic coupling provides new opportunities to achieve on‐demand functionalities of catalysts. Abstract The capability of manipulating the interfacial electronic coupling is the key to achieving on‐demand functionalities of catalysts. Herein, it is demonstrated that the electronic coupling of Fe2N can be effectively regulated for hydrogen evolution reaction (HER) catalysis by vacancy‐mediated orbital steering. Ex situ refined structural analysis reveals that the electronic and coordination states of Fe2N can be well manipulated by nitrogen vacancies, which impressively exhibit strong correlation with the catalytic activities. Theoretical studies further indicate that the nitrogen vacancy can uniquely steer the orbital orientation of the active sites to tailor the electronic coupling and thus benefit the surface adsorption capability. This work sheds light on the understanding of the catalytic mechanism in real systems and could contribute to revolutionizing the current catalyst design for HER and beyond.

Guanidinium‐Assisted Surface Matrix Engineering for Highly Efficient Perovskite Quantum Dot Photovoltaics

By Xufeng Ling, Jianyu Yuan, Xuliang Zhang, Yuli Qian, Shaik M. Zakeeruddin, Bryon W. Larson, Qian Zhao, Junwei Shi, Jiacheng Yang, Kang Ji, Yannan Zhang, Yongjie Wang, Chunyang Zhang, Steffen Duhm, Joseph M. Luther, Michael Grätzel, Wanli Ma from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A ligand‐assisted matrix to regulate surface and packing states of perovskite quantum dots (QDs) is demonstrated, which involves a ligand exchange and a mild thermal annealing process that are triggered by guanidinium thiocyanate. Consequently, the CsPbI3 QD solar cells (QDSCs) deliver a champion power conversion efficiency of 15.21%, which is the highest report among all CsPbI3 QDSCs. Abstract Metal halide perovskite quantum dots (Pe‐QDs) are of great interest in new‐generation photovoltaics (PVs). However, it remains challenging in the construction of conductive and intact Pe‐QD films to maximize their functionality. Herein, a ligand‐assisted surface matrix strategy to engineer the surface and packing states of Pe‐QD solids is demonstrated by a mild thermal annealing treatment after ligand exchange processing (referred to as “LE‐TA”) triggered by guanidinium thiocyanate. The “LE‐TA” method induces the formation of surface matrix on CsPbI3 QDs, which is dominated by the cationic guanidinium (GA+) rather than the SCN−, maintaining the intact cubic structure and facilitating interparticle electrical interaction of QD solids. Consequently, the GA‐matrix‐confined CsPbI3 QDs exhibit remarkably enhanced charge mobility and carrier diffusion length compared to control ones, leading to a champion power conversion efficiency of 15.21% when assembled in PVs, which is one of the highest among all Pe‐QD solar cells. Additionally, the “LE‐TA” method shows similar effects when applied to other Pe‐QD PV systems like CsPbBr3 and FAPbI3 (FA = formamidinium), indicating its versatility in regulating the surfaces of various Pe‐QDs. This work may afford new guidelines to construct electrically conductive and structurally intact Pe‐QD solids for efficient optoelectronic devices.

A Bottom‐Up Strategy for the Synthesis of Highly Siliceous Faujasite‐Type Zeolite

By Dali Zhu, Linying Wang, Dong Fan, Nana Yan, Shengjun Huang, Shutao Xu, Peng Guo, Miao Yang, Jianming Zhang, Peng Tian, Zhongmin Liu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

High‐silica zeolite Y with tunable SiO2/Al2O3 ratio up to 15.6 is synthesized through a cooperative strategy that involves the use of FAU nuclei, a bulky organic structure‐directing agent (OSDA), and a gel system with low alkalinity. The obtained materials show greatly improved (hydro)thermal stability, high concentration of strong acid sites, and superior catalytic cracking performance. Abstract High‐silica zeolite Y is a desired catalytic material for oil refining and the petrochemical industry. However, its direct synthesis remains a symbolic challenge in the field of zeolite synthesis, with a limited improvement of the framework SiO2/Al2O3 ratio (SAR) from ≈5 to 9 over the past 60 years. Here, the synthesis of highly siliceous zeolite Y with tunable SAR up to 15.6 through a cooperative strategy is reported, which involves the use of FAU nuclei, a bulky organic structure‐directing agent (OSDA), and a gel system with low alkalinity (named NOA‐co strategy). A series of quaternary alkylammonium ions is discovered as effective OSDAs based on the NOA‐co strategy, and the relevant crystallization mechanism is elucidated. Moreover, the high‐silica products are demonstrated to have greatly improved (hydro)thermal stability, high concentration of strong acid sites, and uniform acid distribution, which lead to superior catalytic performance in the cracking of bulky hydrocarbons. It is anticipated that this synthetic strategy will benefit the synthesis and development of zeolitic catalysts in a wide range of reaction processes.

Identifying Dense NiSe2/CoSe2 Heterointerfaces Coupled with Surface High‐Valence Bimetallic Sites for Synergistically Enhanced Oxygen Electrocatalysis

By Xuerong Zheng, Xiaopeng Han, Yanhui Cao, Yan Zhang, Dennis Nordlund, Jihui Wang, Shulei Chou, Hui Liu, Lanlan Li, Cheng Zhong, Yida Deng, Wenbin Hu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Heterostructured NiSe2/CoSe2 nanohybrids with different interfacial densities are synthesized via an innovative strategy of successive ion injection. Advanced synchrotron techniques and theoretical calculations demonstrate that the dense nanointerface structure can enhance the performance for oxygen electrocatalysis via increasing the intrinsic reactivity of metallic atoms and introducing a synergistic effect with surface electrochemically in‐situ‐formed oxides/hydroxides. Abstract Constructing heterostructures with abundant interfaces is essential for integrating the multiple functionalities in single entities. Herein, the synthesis of NiSe2/CoSe2 heterostructures with different interfacial densities via an innovative strategy of successive ion injection is reported. The resulting hybrid electrocatalyst with dense heterointerfaces exhibits superior electrocatalytic properties in an alkaline electrolyte, superior to other benchmarks and precious metal catalysts. Advanced synchrotron techniques, post structural characterizations, and density functional theory (DFT) simulations reveal that the introduction of atomic‐level interfaces can lower the oxidation overpotential of bimetallic Ni and Co active sites (whereas Ni2+ can be more easily activated than Co2+) and induce the electronic interaction between the core selenides and surface in situ generated oxides/hydroxides, which play a critical role in synergistically reducing energetic barriers and accelerating reaction kinetics for catalyzing the oxygen evolution. Hence, the heterointerface structure facilitates the catalytic performance enhancement via increasing the intrinsic reactivity of metallic atoms and enhancing the synergistic effect between the inner selenides and surface oxidation species. This work not only complements the understanding on the origins of the activity of electrocatalysts based on metal selenides, but also sheds light on further surface and interfacial engineering of advanced hybrid materials.

Quasi‐Binary Transition Metal Dichalcogenide Alloys: Thermodynamic Stability Prediction, Scalable Synthesis, and Application

By Zahra Hemmat, John Cavin, Alireza Ahmadiparidari, Alexander Ruckel, Sina Rastegar, Saurabh N. Misal, Leily Majidi, Khagesh Kumar, Shuxi Wang, Jinglong Guo, Radwa Dawood, Francisco Lagunas, Prakash Parajuli, Anh Tuan Ngo, Larry A. Curtiss, Sung Beom Cho, Jordi Cabana, Robert F. Klie, Rohan Mishra, Amin Salehi‐Khojin from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A theory‐guided synthesis approach is employed to achieve unexplored quasi‐binary TMDC alloys through computationally predicted stability maps. The synthesized alloys can be exfoliated into 2D‐structures, and some of them exhibit: i) outstanding thermal stability tested up to 1230 K, ii) exceptionally high electrochemical activity for CO2 reduction reaction, iii) excellent energy efficiency in a high‐rate Li–air battery, and iv) high break‐down current‐density. Abstract Transition metal dichalcogenide (TMDCs) alloys could have a wide range of physical and chemical properties, ranging from charge density waves to superconductivity and electrochemical activities. While many exciting behaviors of unary TMDCs have been demonstrated, the vast compositional space of TMDC alloys has remained largely unexplored due to the lack of understanding regarding their stability when accommodating different cations or chalcogens in a single‐phase. Here, a theory‐guided synthesis approach is reported to achieve unexplored quasi‐binary TMDC alloys through computationally predicted stability maps. Equilibrium temperature–composition phase diagrams using first‐principles calculations are generated to identify the stability of 25 quasi‐binary TMDC alloys, including some involving non‐isovalent cations and are verified experimentally through the synthesis of a subset of 12 predicted alloys using a scalable chemical vapor transport method. It is demonstrated that the synthesized alloys can be exfoliated into 2D structures, and some of them exhibit: i) outstanding thermal stability tested up to 1230 K, ii) exceptionally high electrochemical activity for the CO2 reduction reaction in a kinetically limited regime with near zero overpotential for CO formation, iii) excellent energy efficiency in a high rate Li–air battery, and iv) high break‐down current density for interconnect applications. This framework can be extended to accelerate the discovery of other TMDC alloys for various applications.

Tuning the Kinetics of Zinc‐Ion Insertion/Extraction in V2O5 by In Situ Polyaniline Intercalation Enables Improved Aqueous Zinc‐Ion Storage Performance

By Sucheng Liu, He Zhu, Binghao Zhang, Gen Li, Hekang Zhu, Yang Ren, Hongbo Geng, Yang Yang, Qi Liu, Cheng Chao Li from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

An in situ polyaniline (PANI) intercalation strategy is developed to facilitate the Zn2+ (de)intercalation kinetics in V2O5. PANI not only expands the diffusion channels for facilitating Zn2+ diffusion, but also maintains the structural stability as interlayer pillars. Especially, its unique π‐conjugated structure, serving as electron‐reservoir, simultaneously shields the electrostatic interactions between Zn2+ and V2O5 host. Abstract Rechargeable zinc‐ion batteries (ZIBs) are emerging as a promising alternative for Li‐ion batteries. However, the developed cathodes suffer from sluggish Zn2+ diffusion kinetics, leading to poor rate capability and inadequate cycle life. Herein, an in situ polyaniline (PANI) intercalation strategy is developed to facilitate the Zn2+ (de)intercalation kinetics in V2O5. In this way, a remarkably enlarged interlayer distance (13.90 Å) can be constructed alternatively between the VO layers, offering expediting channels for facile Zn2+ diffusion. Importantly, the electrostatic interactions between the Zn2+ and the host O2−, which is another key factor in hindering the Zn2+ diffusion kinetics, can be effectively blocked by the unique π‐conjugated structure of PANI. As a result, the PANI‐intercalated V2O5 exhibits a stable and highly reversible electrochemical reaction during repetitive Zn2+ insertion and extraction, as demonstrated by in situ synchrotron X‐ray diffraction and Raman studies. Further first‐principles calculations clearly reveal a remarkably lowered binding energy between Zn2+ and host O2−, which explains the favorable kinetics in PANI‐intercalated V2O5. Benefitting from the above, the overall electrochemical performance of PANI‐intercalated V2O5 electrode is remarkable improved, exhibiting excellent high rate capability of 197.1 mAh g−1 at current density of 20 A g−1 with capacity retention of 97.6% over 2000 cycles.

Bioinspired Soft Microrobots with Precise Magneto‐Collective Control for Microvascular Thrombolysis

By Meihua Xie, Wei Zhang, Chengying Fan, Chu Wu, Qishuai Feng, Jiaojiao Wu, Yingze Li, Rui Gao, Zhenguang Li, Qigang Wang, Yu Cheng, Bin He from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A biomimetic magnetic microrobot inspired by the highly organized magnetosomes in magnetotactic bacteria shows speedy motion capacity and accurate positioning in a low‐Reynolds‐number biofluid. The microrobot enables delivery and release of drug molecules via a magneto‐collective manner for microvascular thrombolysis, making ultra‐minimal invasive surgery and drug delivery promising. Abstract New‐era soft microrobots for biomedical applications need to mimic the essential structures and collective functions of creatures from nature. Biocompatible interfaces, intelligent functionalities, and precise locomotion control in a collective manner are the key parameters to design soft microrobots for the complex bio‐environment. In this work, a biomimetic magnetic microrobot (BMM) inspired by magnetotactic bacteria (MTB) with speedy motion response and accurate positioning is developed for targeted thrombolysis. Similar to the magnetosome structure in MTB, the BMM is composed of aligned iron oxide nanoparticle (MNP) chains embedded in a non‐swelling microgel shell. Linear chains in BMMs are achieved due to the interparticle dipolar interactions of MNPs under a static magnetic field. Simulation results show that, the degree and speed of assembly is proportional to the field strength. The BMM achieves the maximum speed of 161.7 µm s−1 and accurate positioning control under a rotating magnetic field with less than 4% deviation. Importantly, the locomotion analyses of BMMs demonstrate the frequency‐dependent synchronization under 8 Hz and asynchronization at higher frequencies due to the increased drag torque. The BMMs can deliver and release thrombolytic drugs via magneto‐collective control, which is promising for ultra‐minimal invasive thrombolysis.

Multifunctional Bio‐Nanocomposite Coatings for Perishable Fruits

By Seohui Jung, Yufei Cui, Morgan Barnes, Chinmay Satam, Shenxiang Zhang, Reaz A. Chowdhury, Aparna Adumbumkulath, Onur Sahin, Corwin Miller, Seyed M. Sajadi, Lucas M. Sassi, Yue Ji, Matthew R. Bennett, Miao Yu, Jefferson Friguglietti, Fatima A. Merchant, Rafael Verduzco, Soumyabrata Roy, Robert Vajtai, J. Carson Meredith, Jeffrey P. Youngblood, Nikhil Koratkar, Muhammad M. Rahman, Pulickel M. Ajayan from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A conformal bio‐nanocomposite coating based on cellulose nanocrystals and poly(albumen) is developed that increases the shelf‐life of fresh produce by retarding ripening, dehydration, and microbial attack. The coating is edible, easily washable, and made from readily available inexpensive materials, which makes it a promising solution to combat food wastage. Abstract Hunger and chronic undernourishment impact over 800 million people, which translates to ≈10.7% of the world's population. While countries are increasingly making efforts to reduce poverty and hunger by pursuing sustainable energy and agricultural practices, a third of the food produced around the globe still is wasted and never consumed. Reducing food shortages is vital in this effort and is often addressed by the development of genetically modified produce or chemical additives and inedible coatings, which create additional health and environmental concerns. Herein, a multifunctional bio‐nanocomposite comprised largely of egg‐derived polymers and cellulose nanomaterials as a conformal coating onto fresh produce that slows down food decay by retarding ripening, dehydration, and microbial invasion is reported. The coating is edible, washable, and made from readily available inexpensive or waste materials, which makes it a promising economic alternative to commercially available fruit coatings and a solution to combat food wastage that is rampant in the world.

Strategies for High‐Performance Solid‐State Triplet–Triplet‐Annihilation‐Based Photon Upconversion

By Ting‐An Lin, Collin F. Perkinson, Marc A. Baldo from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Solid‐state triplet–triplet‐annihilation‐based photon‐upconversion systems are subject to losses from back transfer, molecular aggregation, and triplet–charge annihilation. Following strategies provided to mitigate these losses, a dry‐processed solid‐state device having comparable upconversion efficiency and threshold intensity to solution‐processed solid‐state systems is developed, offering a route for high‐performance upconversion devices compatible with applications sensitive to solvent damage. Abstract Photon upconversion via triplet–triplet annihilation (TTA) has achieved high efficiencies in solution and within polymer matrices that support molecular migration systems. It has diverse potential applications including bioimaging, optical sensors, and photovoltaics. To date, however, the reported performance of TTA in rigid solid‐state systems is substantially inferior, which may complicate the integration of TTA in other solid‐state devices. Here, solid‐state loss mechanisms in a green‐to‐blue upconversion system are investigated, and three specific losses are identified: energy back transfer, sensitizer aggregation, and triplet–charge annihilation. Strategies are demonstrated to mitigate energy back transfer and sensitizer aggregation, and a completely dry‐processed solid‐state TTA upconversion system having an upconversion efficiency of ≈2.5% (by the convention of maximum efficiency being 100%) at a relatively low excitation intensity of 238 mW cm−2 is reported. This device is the first demonstration of dry‐processed solid‐state TTA comparable to solution‐processed solid‐state systems. The strategies reported here can be generalized to other upconversion systems and offer a route to achieving higher‐performance solid‐state TTA upconversion devices that are compatible with applications sensitive to solvent damage.

Water‐Resistant Conformal Hybrid Electrodes for Aquatic Endurable Electrocardiographic Monitoring

By Shaobo Ji, Changjin Wan, Ting Wang, Qingsong Li, Geng Chen, Jianwu Wang, Zhiyuan Liu, Hui Yang, Xijian Liu, Xiaodong Chen from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Water‐resistant stretchable electrodes are fabricated with a specially designed polymer. The polymer is adhesive underwater to bridge the electrode and skin, and ionic‐conductive to transmit electrophysiological signals. The conformal electrodes realize reliable electrocardiography (ECG) detection when moving the body or being impacted with water flow, which enables stable wireless real‐time ECG collection during swimming with a wearable device. Abstract Underwater vital signs monitoring of respiratory rate, blood pressure, and the heart's status is essential for healthcare and sports management. Real‐time electrocardiography (ECG) monitoring underwater can be one solution for this. However, the current electrodes used for ECGs are not suitable for aquatic applications since they may lose their adhesiveness to skin, stable conductivity, or/and structural stability when immersed into water. Here, the design and fabrication of water‐resistant electrodes to repurpose stretchable electrodes for applications in an aquatic environment are reported. The electrodes are composed of stretchable metal–polymer composite film as the substrate and dopamine‐containing polymer as a coating. The polymer is designed to possess underwater adhesiveness from the dopamine motif, water stability from the main scaffold, and ionic conductivity from the carboxyl groups for signal transmission. Stable underwater conductivity and firm adhesion to skin allow the electrodes to collect reliable ECG signals under various conditions in water. It is shown that wearable devices incorporated with the water‐resistant electrodes can acquire real‐time ECG signals during swimming, which can be used for revealing the heart condition. These water‐resistant electrodes realize underwater detection of ECG signals and can be used for health monitoring and sports management during aquatic activities.

Graded 2D/3D Perovskite Heterostructure for Efficient and Operationally Stable MA‐Free Perovskite Solar Cells

By Qin Yao, Qifan Xue, Zhenchao Li, Kaicheng Zhang, Teng Zhang, Ning Li, Shihe Yang, Christoph J. Brabec, Hin‐Lap Yip, Yong Cao from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

The efficiency and operational stability of MA‐free FA0.95Cs0.05PbI3 perovskite solar cells can be simultaneously enhanced by the incorporation of the β‐guanidinopropionic acid (β‐GUA) molecule. The introduction of β‐GUA forms a 2D/3D hybrid perovskite phase, which effectively passivates the surface defects, resulting in an impressive power conversion efficiency of 22.2% with a substantial increase in Voc (from 1.01 to 1.14 V). Abstract Almost all highly efficient perovskite solar cells (PVSCs) with power conversion efficiencies (PCEs) of greater than 22% currently contain the thermally unstable methylammonium (MA) molecule. MA‐free perovskites are an intrinsically more stable optoelectronic material for use in solar cells but compromise the performance of PVSCs with relatively large energy loss. Here, the open‐circuit voltage (Voc) deficit is circumvented by the incorporation of β‐guanidinopropionic acid (β‐GUA) molecules into an MA‐free bulk perovskite, which facilitates the formation of quasi‐2D structure with face‐on orientation. The 2D/3D hybrid perovskites embed at the grain boundaries of the 3D bulk perovskites and are distributed through half the thickness of the film, which effectively passivates defects and minimizes energy loss of the PVSCs through reduced charge recombination rates and enhanced charge extraction efficiencies. A PCE of 22.2% (certified efficiency of 21.5%) is achieved and the operational stability of the MA‐free PVSCs is improved.

A High‐Performance Carbonate‐Free Lithium|Garnet Interface Enabled by a Trace Amount of Sodium

By Xingjie Fu, Tiantian Wang, Wenzhong Shen, Miaoli Jiang, Youwei Wang, Qiushi Dai, Da Wang, Zhenping Qiu, Yelong Zhang, Kuirong Deng, Qingguang Zeng, Ning Zhao, Xiangxin Guo, Zheng Liu, Jianjun Liu, Zhangquan Peng from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

The lithium|garnet interface challenge is addressed by melt‐casting 0.5 wt% sodium‐doped lithium onto a garnet electrolyte surface. The doped lithium melt phase‐transfers the Li2CO3 from the grain boundaries of the garnet electrolyte pellet surface to the top of the doped lithium melt and therefore facilitates the wetting process. Abstract Garnet‐type solid‐state electrolytes (SSEs) are promising for the realization of next‐generation high‐energy‐density Li metal batteries. However, a critical issue associated with the garnet electrolytes is the poor physical contact between the Li anode and the garnet SSE and the resultant high interfacial resistance. Here, it is reported that the Li|garnet interface challenge can be addressed by using Li metal doped with 0.5 wt% Na (denoted as Li*) and melt‐casting the Li* onto the garnet SSE surface. A mechanistic study, using Li6.4La3Zr1.4Ta0.6O12 (LLZTO) as a model SSE, reveals that Li2CO3 resides within the grain boundaries of newly polished LLZTO pellet, which is difficult to remove and hinders the wetting process. The Li* melt can phase‐transfer the Li2CO3 from the LLZTO grain boundary to the Li*’s top surface, and therefore facilitates the wetting process. The obtained Li*|LLZTO demonstrates a low interfacial resistance, high rate capability, and long cycle life, and can find applications in future all‐solid‐state batteries (e.g., Li*|LLZTO|LiFePO4).

Continuous “Snowing” Thermotherapeutic Graphene

By Yangyong Sun, Zengzhen Chen, Huiping Gong, Xueqiao Li, Zhenfei Gao, Shichen Xu, Xiaodong Han, Bing Han, Xianwei Meng, Jin Zhang from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A continuous and scalable “snowing” process for preparation of graphene with high quality and high purity is demonstrated. Based on the intrinsic characteristics of this graphene, in particular the low‐frequency microwave absorption property and good thermal transformation ability, a graphene‐based combination therapeutic system for microwave thermal therapy is achieved. Abstract Finding the best applications of graphene, and the continuous and scalable preparation of graphene with high quality and high purity, are still two major challenges. Herein, a “pulse‐etched” microwave‐induced “snowing” (PEMIS) process is developed for continuous and scalable preparation of high‐quality and high‐purity graphene directly in the gas phase, which is found to have excellent thermotherapeutic effects. The obtained graphene exhibits small size (≈180 nm), high quality, low oxygen content, and high purity, together with a high gas–solid conversion efficiency of ≈10.46%. Considering the intrinsic characteristics of this high‐purity and small‐sized biocompatible graphene, in particular the low‐frequency microwave absorption property as well as the good thermal transformation ability, a graphene‐based combination therapeutic system is demonstrated for microwave thermal therapy (MTT) for the first time, exhibiting a high tumor ablation rate of ≈86.7%. This is different from the principle of ions vibrating in a confined space used by current MTT sensitization materials. Not limited to this application, it is foreseen that this PEMIS‐based high‐quality graphene will allow the search for further suitable applications of graphene.

Controlling Crystal Growth via an Autonomously Longitudinal Scaffold for Planar Perovskite Solar Cells

By Xiaopeng Duan, Xiang Li, Licheng Tan, Zengqi Huang, Jia Yang, Gengling Liu, Zhuojia Lin, Yiwang Chen from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

An autonomously longitudinal scaffold constructed by the interspersion of in situ polymerized methyl methacrylate in PbI2 is introduced to effectively eliminate the dependence of sequential deposition on mesoporous TiO2, and is applied in planar perovskite solar cells, with excellent performance. Moreover, this scaffold's cross‐linking grains are capable of releasing mechanical stress, impeding ion migration, and water/oxygen permeation. Abstract Sequential deposition is certified as an effective technology to obtain high‐performance perovskite solar cells (PVSCs), which can be derivatized into large‐scale industrial production. However, dense lead iodide (PbI2) causes incomplete reaction and unsatisfactory solution utilization of perovskite in planar PVSCs without mesoporous titanium dioxide as a support. Here, a novel autonomously longitudinal scaffold constructed by the interspersion of in situ self‐polymerized methyl methacrylate (sMMA) in PbI2 is introduced to fabricate efficient PVSCs with excellent flexural endurance and environmental adaptability. By this strategy perovskite solution can be confined within an organic scaffold with vertical crystal growth promoted, effectively inhibiting exciton accumulation and recombination at grain boundaries. Additionally, sMMA cross‐linked perovskite network can release mechanical stress and occupy the main channels for ion migration and water/oxygen permeation to significantly improve operational stability, which opens up a new strategy for the commercial development of large‐area PVSCs in flexible electronics.

Localized Surface Plasmon Resonance Enhanced Light Absorption in AuCu/CsPbCl3 Core/Shell Nanocrystals

By Maogang Gong, Mohammed Alamri, Dan Ewing, Seyed M. Sadeghi, Judy Z. Wu from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A colloidal process is developed for synthesis of monodispersed AuCu/CsPbCl3 core/shell perovskite nanocrystals in which an all‐inorganic perovskite CsPbCl3 crystalline shell forms through heteroepitaxy on a AuCu crystalline core that exhibits strong localized surface plasmonic response. This core/shell structure enables a highly efficient plasmon–exciton coupling, resulting in enhancement of 5–7 times in photoluminescence and 33 times in photoresponse. Abstract Localized surface plasmon resonance (LSPR) is shown to be effective in trapping light for enhanced light absorption and hence performance in photonic and optoelectronic devices. Implementation of LSPR in all‐inorganic perovskite nanocrystals (PNCs) is particularly important considering their unique advantages in optoelectronics. Motivated by this, the first success in colloidal synthesis of AuCu/CsPbCl3 core/shell PNCs and observation of enhanced light absorption by the perovskite CsPbCl3 shell of thickness in the range of 2–4 nm, enabled by the LSPR AuCu core of an average diameter of 7.1 nm, is reported. This enhanced light absorption leads to a remarkably enhanced photoresponse in PNCs/graphene nanohybrid photodetectors using the AuCu/CsPbCl3 core/shell PNCs, by more than 30 times as compared to the counterparts with CsPbCl3 PNCs only (8–12 nm in dimension). This result illustrates the feasibility in implementation of LSPR light trapping directly in core/shell PNCs for high‐performance optoelectronics.

Spin‐Selective Full‐Dimensional Manipulation of Optical Waves with Chiral Mirror

By Zhancheng Li, Wenwei Liu, Hua Cheng, Duk‐Yong Choi, Shuqi Chen, Jianguo Tian from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A new design principle of chiral mirrors is proposed to realize full‐dimensional independent manipulation of circular‐polarized waves. By simply changing three structural variables of the chiral mirrors, the proposed design principle can arbitrarily and independently empower the spin‐selective manipulation of amplitude, phase, and operation wavelength of circular‐polarized waves with a large modulation depth. Abstract Realizing arbitrary manipulation of optical waves, which still remains a challenge, plays a key role in the implementation of optical devices with on‐demand functionalities. However, it is hard to independently manipulate multiple dimensions of optical waves because the optical dimensions are basically associated with each other when adjusting the optical response of the devices. Here, the concise design principle of a chiral mirror is utilized to realize the full‐dimensional independent manipulation of circular‐polarized waves. By simply changing three structural variables of the chiral mirror, the proposed design principle can arbitrarily and independently empower the spin‐selective manipulation of amplitude, phase, and operation wavelength of circular‐polarized waves with a large modulation depth. This approach provides a simple solution for the realization of spin‐selective full‐dimensional manipulation of optical waves and shows ample application possibilities in the areas of optical encryption, imaging, and detection.

A Lipid‐Nanopillar‐Array‐Based Immunosorbent Assay

By Jieun Kim, Sungi Kim, Junhyoung Ahn, JaeJong Lee, Jwa‐Min Nam from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A lipid‐nanopillar‐array‐based immunosorbent assay (LNAIA) is developed for rapid, sensitive, and quantitative detection of viruses. 3D nanopillar array structures and fluid antibodies with fluorophores on the LNAIA platform facilitate efficient, fast target binding and fluorophore localization for detecting as low as 150 viruses with five‐order dynamic range on a conventional fluorescence microscopy setup. Abstract Since infectious diseases, particularly viral infections, have threatened human health and caused huge economical losses globally, a rapid, sensitive, and selective virus detection platform is highly demanded. Enzyme‐linked immunosorbent assay (ELISA) with flat solid substrates has been dominantly used in detecting whole viruses for its straightforwardness and simplicity in assay protocols, but it often suffers from limited sensitivity, poor quantification range, and a time‐consuming assay procedure. Here, a lipid‐nanopillar‐array‐based immunosorbent assay (LNAIA) is developed with a nanopillar‐supported lipid bilayer substrate with fluorophore‐modified antibodies for rapid, sensitive, and quantitative detection of viruses. 3D nanopillar array structures and fluid antibodies with fluorophores facilitate faster and efficient target binding and rapid fluorophore localization for quick, reliable analysis on binding events with a conventional fluorescence microscopy setup. LNAIA enables quantification of H1N1 virus that targets down to 150 virus particles with 5‐orders‐of‐magnitude dynamic range within 25 min, which cannot be achieved with conventional ELISA platforms.

High‐Safety and High‐Energy‐Density Lithium Metal Batteries in a Novel Ionic‐Liquid Electrolyte

By Hao Sun, Guanzhou Zhu, Yuanmin Zhu, Meng‐Chang Lin, Hui Chen, Yuan‐Yao Li, Wei Hsuan Hung, Bo Zhou, Xi Wang, Yunxiang Bai, Meng Gu, Cheng‐Liang Huang, Hung‐Chun Tai, Xintong Xu, Michael Angell, Jing‐Jong Shyue, Hongjie Dai from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A nonflammable ionic‐liquid electrolyte is developed for high‐safety and high‐energy‐density Li metal batteries, allowing practically useful cathode mass loading up to 16 mg cm−2, realizing high specific capacity and energy density (199 mAh g−1 and 765 Wh kg−1) with impressive cycling performances. The robust passivation interphases formed on both electrodes are key to realizing impressive battery performances. Abstract Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic‐liquid (IL) electrolyte composed of 1‐ethyl‐3‐methylimidazolium (EMIm) cations and high‐concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite‐free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm−2. Li anodes paired with lithium cobalt oxide (LiCoO2) and lithium nickel cobalt manganese oxide (LiNi0.8Co0.1Mn0.1O2, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g−1 and ≈765 Wh kg−1 respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.

Efficient Nitrate Synthesis via Ambient Nitrogen Oxidation with Ru‐Doped TiO2/RuO2 Electrocatalysts

By Min Kuang, Yu Wang, Wei Fang, Huiteng Tan, Mengxin Chen, Jiandong Yao, Chuntai Liu, Jianwei Xu, Kun Zhou, Qingyu Yan from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

A novel Ru‐doped TiO2/RuO2 composite catalyst is designed and applied to the electrochemical nitrogen oxidation reaction, which enables the efficient conversion of nitrogen gas to aqueous nitrate under ambient conditions. The optimized Ru‐doped TiO2/RuO2 catalyst shows a considerable nitrate yield rate of 161.9 µmol h−1 gcat−1 and a highest nitrate Faradaic efficiency of 26.1%. Abstract A facile pathway of the electrocatalytic nitrogen oxidation reaction (NOR) to nitrate is proposed, and Ru‐doped TiO2/RuO2 (abbreviated as Ru/TiO2) as a proof‐of‐concept catalyst is employed accordingly. Density functional theory (DFT) calculations suggest that Ruδ+ can function as the main active center for the NOR process. Remarkably doping Ru into the TiO2 lattice can induce an upshift of the d‐band center of the Ru site, resulting in enhanced activity for accelerating electrochemical conversion of inert N2 to active NO*. Overdoping of Ru ions will lead to the formation of additional RuO2 on the TiO2 surface, which provides oxygen evolution reaction (OER) active sites for promoting the redox transformation of the NO* intermediate to nitrate. However, too much RuO2 in the catalyst is detrimental to both the selectivity of the NOR and the Faradaic efficiency due to the dominant OER process. Experimentally, a considerable nitrate yield rate of 161.9 µmol h−1 gcat−1 (besides, a total nitrate yield of 47.9 µg during 50 h) and a highest nitrate Faradaic efficiency of 26.1% are achieved by the Ru/TiO2 catalyst (with the hybrid composition of RuxTiyO2 and extra RuO2 by 2.79 wt% Ru addition amount) in 0.1 m Na2SO4 electrolyte.

Masthead: (Adv. Mater. 26/2020)

By from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Contents: (Adv. Mater. 26/2020)

By from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Plasmonic Microspheres: Plasmonic Janus Microspheres Created from Pickering Emulsion Drops (Adv. Mater. 26/2020)

By Jong Bin Kim, Su Yeon Lee, Nam Gi Min, Seung Yeol Lee, Shin‐Hyun Kim from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

In article 2001384, Shin‐Hyun Kim and co‐workers design plasmonic Janus microspheres using emulsion drops whose interface is decorated by particles. The emulsion drops made of acrylate resin are photopolymerized and the particles are removed. The directional deposition of the metal renders the top hemispheres as plasmonically colored and the position of the particles at the interface is precisely controlled by aging, which enables the tuning of the plasmonic property. The plasmonic colors can be switched on and off by controlling the orientation of the Janus microspheres with an external electric field.

Detection of Viruses: A Lipid‐Nanopillar‐Array‐Based Immunosorbent Assay (Adv. Mater. 26/2020)

By Jieun Kim, Sungi Kim, Junhyoung Ahn, JaeJong Lee, Jwa‐Min Nam from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

In article number 2001360, Jwa‐Min Nam and co‐workers report a lipid‐nanopillar‐array‐based immunosorbent assay (LNAIA) for rapid, sensitive, and quantitative detection of viruses. LNAIA is based on fluid fluorophore‐labeled antibodies on lipid‐modified nanopillar array structures, and it enables reliable quantification of H1N1 virus targets down to 150 viruses within 25 min on a conventional fluorescence microscopy setup.

Water Splitting: In Situ Formation of Oxygen Vacancies Achieving Near‐Complete Charge Separation in Planar BiVO4 Photoanodes (Adv. Mater. 26/2020)

By Songcan Wang, Tianwei He, Peng Chen, Aijun Du, Kostya (Ken) Ostrikov, Wei Huang, Lianzhou Wang from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

In article number 2001385, Lianzhou Wang and co‐workers develop a planar BiVO4 photoanode with in‐situ‐formed oxygen vacancies in the whole film for efficient photoelectrochemical water splitting. They reveal that, under AM 1.5 G illumination, oxygen vacancies increase the majority charge carrier density and photovoltage, leading to an excellent applied bias photon‐to‐current efficiency of 2.76%.

Bio‐Nanocomposite Coatings: Multifunctional Bio‐Nanocomposite Coatings for Perishable Fruits (Adv. Mater. 26/2020)

By Seohui Jung, Yufei Cui, Morgan Barnes, Chinmay Satam, Shenxiang Zhang, Reaz A. Chowdhury, Aparna Adumbumkulath, Onur Sahin, Corwin Miller, Seyed M. Sajadi, Lucas M. Sassi, Yue Ji, Matthew R. Bennett, Miao Yu, Jefferson Friguglietti, Fatima A. Merchant, Rafael Verduzco, Soumyabrata Roy, Robert Vajtai, J. Carson Meredith, Jeffrey P. Youngblood, Nikhil Koratkar, Muhammad M. Rahman, Pulickel M. Ajayan from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

In article 1908291, Muhammad M. Rahman, Pulickel M. Ajayan, and co‐workers present a conformal bio‐nanocomposite coating based on cellulose nanocrystals and poly(albumen) that increases the shelf‐life of fresh produce by retarding ripening, dehydration, and microbial attack. The coating is edible, easily washable, and made from readily available inexpensive materials, which makes it a promising solution to combat food wastage.

Charge Transport: Photomodulation of Charge Transport in All‐Semiconducting 2D–1D van der Waals Heterostructures with Suppressed Persistent Photoconductivity Effect (Adv. Mater. 26/2020)

By Zhaoyang Liu, Haixin Qiu, Can Wang, Zongping Chen, Björn Zyska, Akimitsu Narita, Artur Ciesielski, Stefan Hecht, Lifeng Chi, Klaus Müllen, Paolo Samorì from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

In article number 2001268, Paolo Samorì and co‐workers report the fabrication of all‐semiconducting mixed‐dimensional van der Waals heterostructures based on monolayer 2D MoS2 and bottom‐up synthesized 1D graphene nanoribbons, which efficiently suppress the typical persistent photoconductivity effect of MoS2. Upon interfacing with physisorbed photochromic molecules, the charge transport of MoS2–graphene nanoribbons in field‐effect transistors can be significantly photomodulated, which corresponds to multilevel output currents for high‐performance optoelectronics.

Recent Advances on High‐Entropy Alloys for 3D Printing

By Changjun Han, Qihong Fang, Yusheng Shi, Shu Beng Tor, Chee Kai Chua, Kun Zhou from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

3D printing of high‐entropy alloys (HEAs) has great potential for manufacturing geometrically complex and/or customized HEA products with desirable performances, inspiring their increased appearance in industrial applications. A comprehensive review of the recent advances on the 3D printing of HEAs is provided, with regard to the aspects of their powder development, printing processes, microstructures, mechanical properties, functionalities, and potential applications. Abstract Boosted by the success of high‐entropy alloys (HEAs) manufactured by conventional processes in various applications, the development of HEAs for 3D printing has been advancing rapidly in recent years. 3D printing of HEAs gives rise to a great potential for manufacturing geometrically complex HEA products with desirable performances, thereby inspiring their increased appearance in industrial applications. Herein, a comprehensive review of the recent achievements of 3D printing of HEAs is provided, in the aspects of their powder development, printing processes, microstructures, properties, and potential applications. It begins with the introduction of the fundamentals of 3D printing and HEAs, as well as the unique properties of 3D‐printed HEA products. The processes for the development of HEA powders, including atomization and mechanical alloying, and the powder properties, are then presented. Thereafter, typical processes for printing HEA products from powders, namely, directed energy deposition, selective laser melting, and electron beam melting, are discussed with regard to the phases, crystal features, mechanical properties, functionalities, and potential applications of these products (particularly in the aerospace, energy, molding, and tooling industries). Finally, perspectives are outlined to provide guidance for future research.

On the Mechanistic Understanding of Photovoltage Loss in Iron Pyrite Solar Cells

By Mohammad Rahman, Gerrit Boschloo, Anders Hagfeldt, Tomas Edvinsson from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Iron pyrite (FeS2) is predicted to be the lowest‐cost material for solar electricity production. However, its solar energy conversion efficiency is below 3% because of low photovoltage (

Structured Perovskite Light Absorbers for Efficient and Stable Photovoltaics

By Tingwei He, Yuanzhi Jiang, Xiangyu Xing, Mingjian Yuan from Wiley: Advanced Materials: Table of Contents. Published on Jul 01, 2020.

Perovskites with different dimensional structures attract wide attention in the field of photovoltaics. There are three main perovskite structures that can be obtained by tuning the A‐site cations, i.e., 3D perovskite, reduced‐dimensional perovskite, and 2D/3D hybrid perovskite, which exhibit different properties, characters, and intrinsic weaknesses. With the use of efficient and targeted tactics, such materials show great potential for perovskite solar cells. Abstract Organic–inorganic hybrid lead‐halide perovskite materials (ABX3) have attracted widespread attention in the field of photovoltaics owing to their impressive optical and electrical properties. However, obstacles still exist in the commercialization of perovskite photovoltaics, such as poor stability, hysteresis, and human toxicity. A‐site cation engineering is considered to be a powerful tool to tune perovskite structures and the resulting optoelectronic properties. Based on the selection and combination of A‐site cations, three types of perovskite structures, i.e., 3D perovskite, reduced‐dimensional (2D/quasi‐2D) perovskite, and 2D/3D hybrid perovskite can be formed. Herein, the remarkable breakthroughs resulting from these three perovskite structures are summarized, and their corresponding properties and characteristics, as well as their intrinsic disadvantages, are highlighted. By summarizing recent research progress, a new viewpoint for improving the performance and stability of perovskite photovoltaics is provided.

Air‐Stable Oxyallyl Patterns and a Switchable N‐Heterocyclic Carbene

By Eder Tomás‐Mendivil, Marc Devillard, Vianney Regnier, Jacques Pecaut, David Martin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Hand in hand: The 1,3‐diaminooxyallyl pattern, usually short‐lived at room temperature, becomes air‐ and moisture‐stable when associated with amidinium derivatives. It can even co‐exist with an N‐heterocyclic carbene moiety. In turn, the electronic properties of the carbene ligand can be switched by protonation/deprotonation at the oxygen atom of the oxyallyl moiety. Abstract Oxyallyl derivatives are typically elusive compounds. Even recently reported “stabilized” 1,3‐diaminooxyallyl species are still highly reactive and have short lifetimes at room temperature. Herein, we report the synthesis and preliminary study of mesoionic pyrimidine derivatives that feature 1,3‐bis(dimethylamino)oxyallyl patterns with an unprecedented level of stabilization. The latter are not only insensitive towards air and moisture, but they are also compatible with the formation of an ancillary stable N‐heterocyclic carbene moiety. As the oxyallyl pattern is proton‐responsive, it allows the reversible switching of the electronic properties of the carbene, as a ligand.

Nanoformulated Single‐Stranded RNA‐Based Adjuvant with a Coordinative Amphiphile as an Effective Stabilizer: Inducing Humoral Immune Response by Activation of Antigen‐Presenting Cells

By Hyo‐Jung Park, Eun‐Kyoung Bang, Jung Joo Hong, Sang‐Myeong Lee, Hae Li Ko, Hye Won Kwak, Hyelim Park, Kyung Won Kang, Rhoon‐Ho Kim, Seung Rok Ryu, Green Kim, Hanseul Oh, Hye‐Jung Kim, Kyuri Lee, Minjeong Kim, Soo Young Kim, Jae‐Ouk Kim, Karim El‐Baz, Hyukjin Lee, Manki Song, Dae Gwin Jeong, Gyochang Keum, Jae‐Hwan Nam from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

An ssRNA adjuvant formulated with coordinative amphiphiles, bearing a zinc/dipicolylamine complex moiety (Zn/DPA) as a coordinative phosphate binder, promoted effective recognition and antigen‐presenting cell (APC) activation. NP=nanoparticle. Abstract As agonists of TLR7/8, single‐stranded RNAs (ssRNAs) are safe and promising adjuvants that do not cause off‐target effects or innate immune overactivation. However, low stability prevents them from mounting sufficient immune responses. This study evaluates the adjuvant effects of ssRNA derived from the cricket paralysis virus intergenic region internal ribosome entry site, formulated as nanoparticles with a coordinative amphiphile, containing a zinc/dipicolylamine complex moiety as a coordinative phosphate binder, as a stabilizer for RNA‐based adjuvants. The nanoformulated ssRNA adjuvant was resistant to enzymatic degradation in vitro and in vivo, and that with a coordinative amphiphile bearing an oleyl group (CA‐O) was approximately 100 nm, promoted effective recognition, and improved activation of antigen‐presenting cells, leading to better induction of neutralizing antibodies following single immunization. Hence, CA‐O may increase the efficacy of ssRNA‐based adjuvants, proving useful to meet the urgent need for vaccines during pathogen outbreaks.

Graphdiyne: Bridging SnO2 and Perovskite in Planar Solar Cells

By Suicai Zhang, Haonan Si, Wenqiang Fan, Mingyue Shi, Minghua Li, Chenzhe Xu, Zheng Zhang, Qingliang Liao, Abdul Sattar, Zhuo Kang, Yue Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

SnO2 and perovskite have been bridged with multifunctional graphdiyne. Such delicate interface modification boosted the performance of solar cells in energy band alignment, electron mobility improvement, controllable perovskite growth inducement, and interface defect passivation. Abstract The matching of charge transport layer and photoactive layer is critical in solar energy conversion devices, especially for planar perovskite solar cells based on the SnO2 electron‐transfer layer (ETL) owing to its unmatched photogenerated electron and hole extraction rates. Graphdiyne (GDY) with multi‐roles has been incorporated to maximize the matching between SnO2 and perovskite regarding electron extraction rate optimization and interface engineering towards both perovskite crystallization process and subsequent photovoltaic service duration. The GDY doped SnO2 layer has fourfold improved electron mobility due to freshly formed C−O σ bond and more facilitated band alignment. The enhanced hydrophobicity inhibits heterogeneous perovskite nucleation, contributing to a high‐quality film with diminished grain boundaries and lower defect density. Also, the interfacial passivation of Pb−I anti‐site defects has been demonstrated via GDY introduction.

Molecular Intercalation and Electronic Two Dimensionality in Layered Hybrid Perovskites

By Tariq Sheikh, Vaibhav Nawale, Nithin Pathoor, Chinmay Phadnis, Arindam Chowdhury, Angshuman Nag from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Trial separation: 2D layered Pb‐ and Sn‐halide perovskites show surprising optical properties, such as dual excitonic emissions. Such unusual properties are shown to arise through to the interaction between the 2D inorganic layers. Separating the inorganic layers either by molecular intercalation or by increasing the length organic spacer ion reversibly switches the optical properties. Abstract In layered hybrid perovskites, such as (BA)2PbI4 (BA=C4H9NH3), electrons and holes are considered to be confined in atomically thin two dimensional (2D) Pb–I inorganic layers. These inorganic layers are electronically isolated from each other in the third dimension by the insulating organic layers. Herein we report our experimental findings that suggest the presence of electronic interaction between the inorganic layers in some parts of the single crystals. The extent of this interaction is reversibly tuned by intercalation of organic and inorganic molecules in the layered perovskite single crystals. Consequently, optical absorption and emission properties switch reversibly with intercalation. Furthermore, increasing the distance between inorganic layers by increasing the length of the organic spacer cations systematically decreases these electronic interactions. This finding that the parts of the layered hybrid perovskites are not strictly electronically 2D is critical for understanding the electronic, optical, and optoelectronic properties of these technologically important materials.

Squaramides and Ureas: A Flexible Approach to Polymerase‐Compatible Nucleic Acid Assembly

By Arun Shivalingam, Lapatrada Taemaitree, Afaf H. El‐Sagheer, Tom Brown from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

3′‐ and 5′‐amino oligonucleotides are chemically ligated through the formation of urea and squaramide artificial backbones. The squaramide linkage can be formed in mild reagent‐free buffered conditions, read‐through accurately by specific polymerases, and even cleaved and reformed on demand. To demonstrate its utility, the RNA‐to‐DNA reverse transcription step of RT‐qPCR is replaced with squaramide chemical ligation for direct RNA detection. Abstract Joining oligonucleotides together (ligation) is a powerful means of retrieving information from the nanoscale. To recover this information, the linkages created must be compatible with polymerases. However, enzymatic ligation is restrictive and current chemical ligation methods lack flexibility. Herein, a versatile ligation platform based on the formation of urea and squaramide artificial backbones from minimally modified 3′‐ and 5′‐amino oligonucleotides is described. One‐pot ligation gives a urea linkage with excellent read‐through speed, or a squaramide linkage that is read‐through under selective conditions. The squaramide linkage can be broken and reformed on demand, while stable pre‐activated precursor oligonucleotides expand the scope of the ligation reaction to reagent‐free, mild conditions. The utility of our system is demonstrated by replacing the enzymatically biased RNA‐to‐DNA reverse transcription step of RT‐qPCR with a rapid nucleic‐acid‐template‐dependent DNA chemical ligation system, that allows direct RNA detection.

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

By Zhenyou Li, Bhaghavathi P. Vinayan, Piotr Jankowski, Christian Njel, Ananyo Roy, Tejs Vegge, Julia Maibach, Juan Maria García Lastra, Maximilian Fichtner, Zhirong Zhao‐Karger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Put into storage: Cathodes allowing fast cation mobility are demonstrated in a VS4 structure for high‐energy, multivalent (Mg and Ca) batteries. The flexible VS4 electronic structure enables cationic and anionic redox processes with multi‐electron transfer. Abstract The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi‐electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single‐electron transfer, which are not ideal for multivalent‐ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope‐like voltage profiles with insertion/extraction redox of less than one electron. Taking VS4 as a model material, reversible two‐electron redox with cationic–anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g−1 at a current density of 100 mA g−1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg−1 for RMBs and >500 Wh kg−1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg2+ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS4.

Incorporating Rare‐Earth Terbium(III) Ions into Cs2AgInCl6:Bi Nanocrystals toward Tunable Photoluminescence

By Ying Liu, Ximing Rong, Mingze Li, Maxim S. Molokeev, Jing Zhao, Zhiguo Xia from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Tb luminescent in halide perovskite: Combined crystallographic and theoretical evidence demonstrate the incorporation of Tb3+ ions into Cs2AgInCl6 nanocrystals (NCs). By controlling the concentration of Tb3+ ions, the emission colors of Bi‐doped Cs2Ag(In1−xTbx)Cl6 NCs could be tuned from green to orange, through the efficient energy transfer channel from self‐trapped excitons to Tb3+ ions. Abstract The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs2AgInCl6 NCs to impart and tune the optical performances in the visible light region. Tb3+ ions were incorporated into Cs2AgInCl6 NCs and occupied In3+ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (5D4→7F6‐3) of Tb3+ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb3+. By controlling Tb3+ ions concentration, the emission colors of Bi‐doped Cs2Ag(In1−xTbx)Cl6 NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb3+ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.

2‐Aminobenzenethiol‐Functionalized Silver‐Decorated Nanoporous Silicon Photoelectrodes for Selective CO2 Reduction

By Miao Kan, Zhifei Wang Yan, Xingtao Wang, Jeremy L. Hitt, Langqiu Xiao, Jeffrey M. McNeill, Yong Wang, Yixin Zhao, Thomas E. Mallouk from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Silver lining: The adsorption of 2‐aminobenzenethiol (2‐ABT) onto nanoporousp‐type black silicon (b‐Si) photocathodes decorated with Ag nanoparticle catalysts lowers the overpotential and improves the selectivity of CO2 reduction to CO. Abstract A molecularly thin layer of 2‐aminobenzenethiol (2‐ABT) was adsorbed onto nanoporous p‐type silicon (b‐Si) photocathodes decorated with Ag nanoparticles (Ag NPs). The addition of 2‐ABT alters the balance of the CO2 reduction and hydrogen evolution reactions, resulting in more selective and efficient reduction of CO2 to CO. The 2‐ABT adsorbate layer was characterized by Fourier transform infrared (FTIR) spectroscopy and modeled by density functional theory calculations. Ex situ X‐ray photoelectron spectroscopy (XPS) of the 2‐ABT modified electrodes suggests that surface Ag atoms are in the +1 oxidation state and coordinated to 2‐ABT via Ag−S bonds. Under visible light illumination, the onset potential for CO2 reduction was −50 mV vs. RHE, an anodic shift of about 150 mV relative to a sample without 2‐ABT. The adsorption of 2‐ABT lowers the overpotentials for both CO2 reduction and hydrogen evolution. A comparison of electrodes functionalized with different aromatic thiols and amines suggests that the primary role of the thiol group in 2‐ABT is to anchor the NH2 group near the Ag surface, where it serves to bind CO2 and also to assist in proton transfer.

Stereoselective [4+2]‐Cycloaddition with Chiral Alkenylboranes

By Dongshun Ni, Brittany P. Witherspoon, Hong Zhang, Chen Zhou, K. N. Houk, M. Kevin Brown from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Stereoselective [4+2]‐cycloaddition of alkenylboranes and dienes was accomplished through the introduction of chiral N‐protonated alkenyl oxazaborolidines as dieneophiles. The reaction gives products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C−B bond such as oxidation and homologation. DFT calculations uncovered a surprising effect of the counterion on stereoselectivity. Abstract A method for the stereoselective [4+2]‐cycloaddition of alkenylboranes and dienes is presented. This transformation was accomplished through the introduction of a new strategy that involves the use of chiral N‐protonated alkenyl oxazaborolidines as dieneophiles. The reaction leads to the formation of products that can be readily derivatized to more complex structural motifs through stereospecific transformations of the C−B bond such as oxidation and homologation. Detailed computation evaluation of the reaction has uncovered a surprising role of the counterion on stereoselectivity.

Charge Storage Mechanism and Structural Evolution of Viologen Crystals as the Cathode of Lithium Batteries

By Ting Ma, Luojia Liu, Jiaqi Wang, Yong Lu, Jun Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Performance enhancers: Ionic crystals of ethyl viologen iodide (EVI2) and ethyl viologen diperchlorate (EV(ClO4)2) have shown excellent electrochemical performance, such as high rate performance and excellent cycling stability, as cathode materials of lithium batteries. The good electron conduction of ClO4− layers results in EV(ClO4)2 having a theoretical capacity of 78 % even at 5 C. Abstract Although organic ionic crystals represent an attractive class of active materials for rechargeable batteries owing to their high capacity and low solubility in electrolytes, they generally suffer from limited electronic conductivity and moderate voltage. Furthermore, the charge storage mechanism and structural evolution during the redox processes are still not clearly understood. Here we describe ethyl viologen iodide (EVI2) and ethyl viologen diperchlorate (EV(ClO4)2) as cathode materials of lithium batteries which crystallize in a monoclinic system with alternating organic EV2+ layers and inorganic I−/ClO4− layers. The EVI2 electrode exhibits a high initial discharge plateau of 3.7 V (vs. Li+/Li) because of its anion storage ability. When I− is replaced by ClO4−, the obtained EV(ClO4)2 electrode displays excellent rate performance with a theoretical capacity of 78 % even at 5 C owing to the good electron conductivity of ClO4− layers. EVI2 and EV(ClO4)2 also show excellent cycling stability (capacity retention >96 % after 200 cycles).

A Hydrogen‐Deficient Nickel–Cobalt Double Hydroxide for Photocatalytic Overall Water Splitting

By Min Wang, Jia‐Qi Wang, Cong Xi, Chuan‐Qi Cheng, Cheng‐Qin Zou, Rui Zhang, Ya‐Meng Xie, Zhong‐Lu Guo, Cheng‐Chun Tang, Cun‐Ku Dong, Yong‐Jun Chen, Xi‐Wen Du from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A single‐phase photocatalyst, a hydrogen‐deficient nickel–cobalt double hydroxide, was generated by laser ablation. This photocatalyst can drive overall water splitting under solar light irradiation in the absence of sacrificial agents and noble metal co‐catalysts because of its unique composition and structure, with partially removed hydrogen atoms as well as O2− and Co3+ ions exposed on the surface. Abstract Developing highly efficient and low‐cost photocatalysts for overall water splitting has long been a pursuit for converting solar power into clean hydrogen energy. Herein, we demonstrate that a nonstoichiometric nickel–cobalt double hydroxide can achieve overall water splitting by itself upon solar light irradiation, avoiding the consumption of noble‐metal co‐catalysts. We employed an intensive laser to ablate a NiCo alloy target immersed in alkaline solution, and produced so‐called L‐NiCo nanosheets with a nonstoichiometric composition and O2−/Co3+ ions exposed on the surface. The nonstoichiometric composition broadens the band gap, while O2− and Co3+ ions boost hydrogen and oxygen evolution, respectively. As such, the photocatalyst achieves a H2 evolution rate of 1.7 μmol h−1 under AM 1.5G sunlight irradiation and an apparent quantum yield (AQE) of 1.38 % at 380 nm.

Divergent Chemistry Paths for 3D and 1D Metallo‐Covalent Organic Frameworks (COFs)

By Hai‐Sen Xu, Yi Luo, Pei Zhen See, Xing Li, Zhongxin Chen, Yi Zhou, Xiaoxu Zhao, Kai Leng, In‐Hyeok Park, Runlai Li, Cuibo Liu, Fangzheng Chen, Shibo Xi, Junliang Sun, Kian Ping Loh from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

What far from tangled webs we weave: By combining dynamic covalent chemistry (DCC) and coordination chemistry, divergent paths for the construction of three‐dimensional (3D) woven covalent organic frameworks (COFs) or one‐dimensional (1D) metallo‐COFs (mCOFs) are identified. The paths are distinguished by the absence or presence of ligand exchange. Abstract The marriage of dynamic covalent chemistry (DCC) and coordination chemistry is a powerful tool for assembling complex architectures from simple building units. Recently, the synthesis of woven covalent organic frameworks (COFs) with topologically fascinating structures has been achieved using this approach. However, the scope is highly limited and there is a need to discover new pathways that can assemble covalently linked organic threads into crystalline frameworks. Herein, we have identified branching pathways leading to the assembly of three‐dimensional (3D) woven COFs or one‐dimensional (1D) metallo‐COFs (mCOFs), where the mechanism is underpinned by the absence or presence of ligand exchange.

Polymer Lamellae as Reaction Intermediates in the Formation of Copper Nanospheres as Evidenced by In Situ X‐ray Studies

By Valeria Mantella, Michal Strach, Kilian Frank, James R. Pankhurst, Dragos Stoian, Chethana Gadiyar, Bert Nickel, Raffaella Buonsanti from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Sphere we go: The synthesis of monodisperse Cu nanosphere (NSs) is monitored using in situ X‐ray techniques. The formation follows a nonclassical nucleation pathway in which a coordination polymer, arranged into lamellae, occupies a local energy minimum as a pre‐nucleation intermediate and converts into the final Cu NSs upon a reduction reaction allowing a burst of nucleation that leads to monodisperse NSs. Abstract The classical nucleation theory (CNT) is the most common theoretical framework used to explain particle formation. However, nucleation is a complex process with reaction pathways which are often not covered by the CNT. Herein, we study the formation mechanism of copper nanospheres using in situ X‐ray absorption and scattering measurements. We reveal that their nucleation involves coordination polymer lamellae as pre‐nucleation structures occupying a local minimum in the reaction energy landscape. Having learned this, we achieved a superior monodispersity for Cu nanospheres of different sizes. This report exemplifies the importance of developing a more realistic picture of the mechanism involved in the formation of inorganic nanoparticles to develop a rational approach to their synthesis.

Adsorption Site Regulation to Guide Atomic Design of Ni–Ga Catalysts for Acetylene Semi‐Hydrogenation

By Yueqiang Cao, Hao Zhang, Shufang Ji, Zhijun Sui, Zheng Jiang, Dingsheng Wang, Francisco Zaera, Xinggui Zhou, Xuezhi Duan, Yadong Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Atomically regulating the Ni sites towards complete isolation by introducing Ga is theoretically predicted to lead to both preferential acetylene π‐adsorption and enhanced ethylene desorption. This concept is validated by experimental observations of the well‐designed NiGa intermetallic catalyst with completely isolated Ni sites for superior acetylene semi‐hydrogenation. Abstract Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory‐guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi‐hydrogenation processes. Such Ni sites show not only preferential acetylene π‐adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration‐corrected high‐resolution scanning transmission electron microscopy and X‐ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni5Ga3 intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi‐atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation.

NIR‐Sensitized Activated Photoreaction between Cyanines and Oxime Esters: Free‐Radical Photopolymerization

By Yulian Pang, Shuheng Fan, Qunying Wang, Dennis Oprych, Alfred Feilen, Knut Reiner, Dietmar Keil, Yuriy L. Slominsky, Sergey Popov, Yingquan Zou, Bernd Strehmel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Tackling the impossible: Photoinduced electron transfer between an NIR sensitizer and oxime esters results in unexpected initiation of radical photopolymerization using cyanines as sensitizers. This strategy facilitates unexpected chemistry with environmentally friendly devices. Abstract Cyanines comprising either a benzo[e]‐ or benzo[c,d]indolium core facilitate initiation of radical photopolymerization combined with high power NIR‐LED prototypes emitting at 805 nm, 860 nm, or 870 nm, while different oxime esters function as radical coinitiators. Radical photopolymerization followed an initiation mechanism based on the participation of excited states, requiring additional thermal energy to overcome an existing intrinsic activation barrier. Heat released by nonradiative deactivation of the sensitizer favored the system, even under conditions where a thermally activated photoinduced electron transfer controls the reaction protocol. The heat generated internally by the NIR sensitizer promotes generation of the initiating reactive radicals. Sensitizers with a barbiturate group at the meso‐position preferred to bleach directly, while sensitizers carrying a cyclopentene moiety unexpectedly initiated the photosensitized mechanism.

Secondary Amino Alcohols: Traceless Cleavable Linkers for Use in Affinity Capture and Release

By Sebastian Pomplun, Christopher R. Shugrue, Adeline M. Schmitt, Carly K. Schissel, Charlotte E. Farquhar, Bradley L. Pentelute from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Catch and release: A new cleavable linker based on secondary amino alcohols is reported for application in peptide discovery. The linker is easily incorporated into peptides during on‐resin synthesis and is shown to be rapidly cleaved in the presence of NaIO4. Peptide‐library and cell‐based experiments demonstrate that this linker enables the recovery of hit sequences after affinity capture. Abstract Capture and release of peptides is often a critical operation in the pathway to discovering materials with novel functions. However, the best methods for efficient capture impede facile release. To overcome this challenge, we report linkers based on secondary amino alcohols for the release of peptides after capture. These amino alcohols are based on serine (seramox) or isoserine (isoseramox) and can be incorporated into peptides during solid‐phase peptide synthesis through reductive amination. Both linkers are quantitatively cleaved within minutes under NaIO4 treatment. Cleavage of isoseramox produced a native peptide N‐terminus. This linker also showed broad substrate compatibility; incorporation into a synthetic peptide library resulted in the identification of all sequences by nanoLC‐MS/MS. The linkers are cell compatible; a cell‐penetrating peptide that contained this linker was efficiently captured and identified after uptake into cells. These findings suggest that such secondary amino alcohol based linkers might be suitable tools for peptide‐discovery platforms.

Chiroptical Helices of N‐Terminal Aryl Amino Acids through Orthogonal Noncovalent Interactions

By Zhuoer Wang, Aiyou Hao, Pengyao Xing from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Orthogonal noncovalent interactions allow the fabrication of hierarchical helical coassemblies exhibiting diversified chiroptical properties. Alanine and phenylglycine, with appended pyrene segments, self‐assembled into α‐helix‐like structures with induced supramolecular tilted chirality of the achiral pyrenes. These structures bind melamine and electron‐deficient units through H‐bond and charge‐transfer interactions, respectively, forming ternary coassemblies having giant tubular structures. Abstract In the solid state, amino acids (alanine and phenylglycine) with appended pyrene segments self‐assembled into α‐helix‐like structures by asymmetrical H‐bonds between carboxylic acid and amide segments, further inducing supramolecular tilted chirality of the achiral pyrenes. These structures bind melamine and electron‐deficient units through H‐bond and charge‐transfer interactions, respectively. Charge‐transfer interactions enhance the dissymmetry g‐factor of absorption (gabs; up to 1.4×10−2) with an extended Cotton effect active region (from 250 to 600 nm). Incorporating melamine inverts the handedness of circularly polarized luminescence and boosts the dissymmetry g‐factor (glum). Melamine also induces macroscopic chirality at the nanoscale, whereby the 2D lamellar structures are transformed into 1D helices at the nanoscale, leading to giant tubular structures at the microscale.

Observation of the Low‐Frequency Spectrum of the Water Trimer as a Sensitive Test of the Water‐Trimer Potential and the Dipole‐Moment Surface

By Raffael Schwan, Chen Qu, Devendra Mani, Nitish Pal, Gerhard Schwaab, Joel M. Bowman, Gregory S. Tschumper, Martina Havenith from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

On the count of three: The first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 is reported. The assignments provide a benchmark for state‐of‐the‐art water potentials and dipole‐moment surfaces, especially with respect to three‐body interactions. Abstract Intermolecular interactions in bulk water are dominated by pairwise and non‐pairwise cooperative interactions. While accurate descriptions of the pairwise interactions are available and can be tested by precise low‐frequency spectra of the water dimer up to 550 cm−1, the same does not hold for the three‐body interactions. Here, we report the first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 using helium‐nanodroplet isolation and free‐electron lasers. By comparison to accompanying high‐level quantum calculations, the experimentally observed intermolecular bands can be assigned. The transition frequencies of the degenerate translation, the degenerate in‐plane and the non‐degenerate out‐of‐plane libration, as well as additional bands of the out‐of‐plane librational mode are reported for the first time. These provide a benchmark for state‐of‐the‐art water potentials and dipole‐moment surfaces, especially with respect to three‐body interactions.

Multiplexed Discrimination of Single Amino Acid Residues in Polypeptides in a Single SERS Hot Spot

By Jian‐An Huang, Mansoureh Z. Mousavi, Giorgia Giovannini, Yingqi Zhao, Aliaksandr Hubarevich, Miguel A. Soler, Walter Rocchia, Denis Garoli, Francesco De Angelis from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Sequencing in a hot spot: Sequencing of single proteins by surface‐enhanced Raman spectroscopy (SERS) suffers from the signal dominance of aromatic amino acid residues and backbones, which hampers the ability to detect nonaromatic amino acid residues. A single, localized SERS hot spot in an electroplasmonic trap that allows the discrimination of aromatic and nonaromatic residues in single polypeptides is presented. Abstract The SERS‐based detection of protein sequences with single‐residue sensitivity suffers from signal dominance of aromatic amino acid residues and backbones, impeding detection of non‐aromatic amino acid residues. Herein, we trap a gold nanoparticle in a plasmonic nanohole to generate a single SERS hot spot for single‐molecule detection of 2 similar polypeptides (vasopressin and oxytocin) and 10 distinct amino acids that constitute the 2 polypeptides. Significantly, both aromatic and non‐aromatic amino acids are detected and discriminated at the single‐molecule level either at individual amino acid molecules or within the polypeptide chains. Correlated with molecular dynamics simulations, our results suggest that the signal dominance due to large spatial occupancy of aromatic rings of the polypeptide sidechains on gold surfaces can be overcome by the high localization of the single hot spot. The superior spectral and spatial discriminative power of our approach can be applied to single‐protein analysis, fingerprinting, and sequencing.

Photoredox‐Catalyzed Isomerization of Highly Substituted Allylic Alcohols by C−H Bond Activation

By Kai Guo, Zhongchao Zhang, Anding Li, Yuanhe Li, Jun Huang, Zhen Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Photoredox‐catalyzed isomerization of highly substituted allylic alcohols to the corresponding carbonyl compounds was achieved for the first time by C−H bond activation. DFT calculations show that the carbonyl group at the γ‐position of allylic alcohols contributes to the completion of the photoredox catalytic cycle. PRC=photoredox catalyst; HAT=hydrogen‐atom transfer; HBA=hydrogen‐bond acceptor. Abstract Photoredox‐catalyzed isomerization of γ‐carbonyl‐substituted allylic alcohols to their corresponding carbonyl compounds was achieved for the first time by C−H bond activation. This catalytic redox‐neutral process resulted in the synthesis of 1,4‐dicarbonyl compounds. Notably, allylic alcohols bearing tetrasubstituted olefins can also be transformed into their corresponding carbonyl compounds. Density functional theory calculations show that the carbonyl group at the γ‐position of allylic alcohols are beneficial to the formation of their corresponding allylic alcohol radicals with high vertical electron affinity, which contributes to the completion of the photoredox catalytic cycle.

Highly Reversible Cuprous Mediated Cathode Chemistry for Magnesium Batteries

By Xiangyang Cheng, Zhonghua Zhang, Qingyu Kong, Qinghua Zhang, Tao Wang, Shanmu Dong, Lin Gu, Xiao Wang, Jun Ma, Pengxian Han, Hong‐ji Lin, Chien‐Te Chen, Guanglei Cui from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The right chemistry: A chemical, rather than electrochemical, magnesiation/de‐magnesiation process with the assistance of the Cu+ equilibrium is revealed. It guarantees fast charging/discharging processes and long‐term durability of rechargeable Mg batteries under practically high mass‐loading conditions. Abstract Sluggish kinetics and poor reversibility of cathode chemistry is the major challenge for magnesium batteries to achieve high volumetric capacity. Introduction of the cuprous ion (Cu+) as a charge carrier can decouple the magnesiation related energy storage from the cathode electrochemistry. Cu+ is generated from a fast equilibrium between copper selenide electrode and Mg electrolyte during standing time, rather than in the electrochemical process. A reversible chemical magnesiation/de‐magnesiation can be driven by this solid/liquid equilibrium. During a typical discharge process, Cu+ is reduced to Cu and drives the equilibrium to promote the magnesiation process. The reversible Cu to Cu+ redox promotes the recharge process. This novel Cu+ mediated cathode chemistry of Mg battery leads to a high reversible areal capacity of 12.5 mAh cm−2 with high mass loading (49.1 mg cm−2) of the electrode. 80 % capacity retention can be achieved for 200 cycles after a conditioning process.

The 9‐Borataphenanthrene Anion

By Tyler A. Bartholome, Aishvaryadeep Kaur, David J. D. Wilson, Jason L. Dutton, Caleb D. Martin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The 9‐borataphenanthrene anion is prepared which exhibits surprisingly diverse reactivity. Reactions with metal precursors revealed η2 or η6 coordination modes of the anion to the metal while the B=C carbon is alkylated upon reaction with methyl iodide. Pinacolborane adds theH−B unit across the B=C bond to generate a unique hydroboration products. Abstract The 9‐borataphenanthrene anion is easily accessed by deprotonation of a 9,10‐dihydro‐9‐boraphenanthrene and its diverse reactivity is investigated. Alkylation occurs at the carbon atom adjacent to boron, and room temperature hydroboration occurs across the B=C bond. The π‐manifold of the central BC5 ring coordinates to chromium in an η6 fashion while only the B=C unit binds η2 to gold, indicating versatility of the 9‐borataphenanthrene anion as a ligand. Supporting calculations rationalize the reactivity and aromaticity is corroborated by nucleus‐independent chemical shift (NICS) indices.

Regio‐ and Enantioselective Synthesis of Trifluoromethyl‐Substituted Homoallylic α‐Tertiary NH2‐Amines by Reactions Facilitated by a Threonine‐Based Boron‐Containing Catalyst

By Diana C. Fager, Ryan J. Morrison, Amir H. Hoveyda from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A method for catalytic regio‐ and enantioselective synthesis of trifluoromethyl‐substituted and aryl‐, heteroaryl‐, alkenyl‐, and alkynyl‐substituted homoallylic α‐tertiary NH2‐amines is introduced. Various chemo‐, regio‐, and diastereoselective transformations of the α‐tertiary homoallylic NH2‐amine products highlight the utility of the approach. Abstract A method for catalytic regio‐ and enantioselective synthesis of trifluoromethyl‐substituted and aryl‐, heteroaryl‐, alkenyl‐, and alkynyl‐substituted homoallylic α‐tertiary NH2‐amines is introduced. Easy‐to‐synthesize and robust N‐silyl ketimines are converted to NH‐ketimines in situ, which then react with a Z‐allyl boronate. Transformations are promoted by a readily accessible l‐threonine‐derived aminophenol‐based boryl catalyst, affording the desired products in up to 91 % yield, >98:2 α:γ selectivity, >98:2 Z:E selectivity, and >99:1 enantiomeric ratio. A commercially available aminophenol may be used, and allyl boronates, which may contain an alkyl‐, a chloro‐, or a bromo‐substituted Z‐alkene, can either be purchased or prepared by catalytic stereoretentive cross‐metathesis. What is more, Z‐trisubstituted allyl boronates may be used. Various chemo‐, regio‐, and diastereoselective transformations of the α‐tertiary homoallylic NH2‐amine products highlight the utility of the approach; this includes diastereo‐ and regioselective epoxide formation/trichloroacetic acid cleavage to generate differentiated diol derivatives.

A Structurally Robust Chiral Borate Ion: Molecular Design, Synthesis, and Asymmetric Catalysis

By Daisuke Uraguchi, Fumito Ueoka, Naoya Tanaka, Tomohito Kizu, Wakana Takahashi, Takashi Ooi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A chiral borate ion comprising an O,N,N,O‐tetradentate backbone was developed. The corresponding hydrogen borate acted as a catalyst for the asymmetric protonative Prins‐type cyclization through precise control of the prochiral oxonium ion intermediate and the final deprotonation pathway. Abstract Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.

Tunable Electrochemical C−N versus N−N Bond Formation of Nitrogen‐Centered Radicals Enabled by Dehydrogenative Dearomatization: Biological Applications

By Shide Lv, Xiaoxin Han, Jian‐Yong Wang, Mingyang Zhou, Yanwei Wu, Li Ma, Liwei Niu, Wei Gao, Jianhua Zhou, Wei Hu, Yuezhi Cui, Jianbin Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Tunable C−N versus N−N bond formation of nitrogen‐centered radicals was achieved by an electrochemical dehydrogenative dearomatization strategy. Control experiments, DFT calculations, and investigations of the electrode material elucidated the origin of the chemoselectivity. Bioactivity assays demonstrated that pyrido[1,2‐a]benzimidazoles displayed antimicrobial activity and cytotoxicity against human cancer cells. Abstract Herein, an environmentally friendly electrochemical approach is reported that takes advantage of the captodative effect and delocalization effect to generate nitrogen‐centered radicals (NCRs). By changing the reaction parameters of the electrode material and feedstock solubility, dearomatization enabled a selective dehydrogenative C−N versus N−N bond formation reaction. Hence, pyrido[1,2‐a]benzimidazole and tetraarylhydrazine frameworks were prepared through a sustainable transition‐metal‐ and exogenous oxidant‐free strategy with broad generality. Bioactivity assays demonstrated that pyrido[1,2‐a]benzimidazoles displayed antimicrobial activity and cytotoxicity against human cancer cells. Compound 21 exhibited good photochemical properties with a large Stokes shift (approximately 130 nm) and was successfully applied to subcellular imaging. A preliminary mechanism investigation and density functional theory (DFT) calculations revealed the possible reaction pathway.

Long‐Lived Charge‐Transfer State Induced by Spin‐Orbit Charge Transfer Intersystem Crossing (SOCT‐ISC) in a Compact Spiro Electron Donor/Acceptor Dyad

By Dongyi Liu, Ahmed M. El‐Zohry, Maria Taddei, Clemens Matt, Laura Bussotti, Zhijia Wang, Jianzhang Zhao, Omar F. Mohammed, Mariangela Di Donato, Stefan Weber from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A rigid, simple, spiro compact electron donor/acceptor (D/A) dyad shows a long‐lived triplet charge transfer (3CT) state (0.94 μs) with a high energy level (ca. 2.12 eV), based on a new electron spin‐control method using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC) (1NI*→1CT→3NI*→3CT; NI=naphthalimide), without heavy atoms or chromophores with intrinsic intersystem crossing (ISC) ability. Abstract We prepared conceptually novel, fully rigid, spiro compact electron donor (Rhodamine B, lactam form, RB)/acceptor (naphthalimide; NI) orthogonal dyad to attain the long‐lived triplet charge‐transfer (3CT) state, based on the electron spin control using spin‐orbit charge transfer intersystem crossing (SOCT‐ISC). Transient absorption (TA) spectra indicate the first charge separation (CS) takes place within 2.5 ps, subsequent SOCT‐ISC takes 8 ns to produce the 3NI* state. Then the slow secondary CS (125 ns) gives the long‐lived 3CT state (0.94 μs in deaerated n‐hexane) with high energy level (ca. 2.12 eV). The cascade photophysical processes of the dyad upon photoexcitation are summarized as 1NI*→1CT→3NI*→3CT. With time‐resolved electron paramagnetic resonance (TREPR) spectra, an EEEAAA electron‐spin polarization pattern was observed for the naphthalimide‐localized triplet state. Our spiro compact dyad structure and the electron spin‐control approach is different to previous methods for which invoking transition‐metal coordination or chromophores with intrinsic ISC ability is mandatory.

Photocatalytic Difunctionalization of Vinyl Ureas by Radical Addition Polar Truce–Smiles Rearrangement Cascades

By Roman Abrams, Jonathan Clayden from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Cascade formation of two C−C bonds at an electron‐rich alkene is made possible by sequential capture of a radical (by intermolecular addition) and an anion (by intramolecular aromatic substitution), each formed in the photoredox cycle from the same organic photocatalyst. Abstract We report tandem alkyl‐arylations and phosphonyl‐arylations of vinyl ureas by way of a photocatalytic radical‐polar crossover mechanism. Addition of photoredox‐generated radicals to the alkene forms a new C−C or C−P bond and generates a product radical adjacent to the urea function. Reductive termination of the photocatalytic cycle generates an anion that undergoes a polar Truce–Smiles rearrangement, forming a C−C bond. The reaction is successful with a range of α‐fluorinated alkyl sodium sulfinate salts and diarylphosphine oxides as radical precursors, and the conformationally accelerated Truce–Smiles rearrangement is not restricted by the electronic nature of the migrating aromatic ring. Formally the reaction constitutes an α,β‐difuctionalisation of a carbon–carbon double bond, and proceeds under mild conditions with visible light and a readily available organic photocatalyst. The products are α,α‐diaryl alkylureas typically functionalized with F or P substituents that may be readily converted into α,α‐diaryl alkylamines.

Quantitative Prediction of Aggregation‐Induced Emission: A Full Quantum Mechanical Approach to the Optical Spectra

By Wei Zhang, Jinfeng Liu, Xinsheng Jin, Xinggui Gu, Xiao Cheng Zeng, Xiao He, Hui Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Reproducing to better understand: The calculational method electrostatically embedded generalized molecular fractionation is a full quantum mechanical (FQM) approach that can nearly reproduce the experimental optical absorption and emission spectra of the prototype fluorophore di(p‐methoxylphenyl)dibenzofulvene, which displays aggregation‐induced emission, in both condensed phases. Abstract Full quantum mechanical (FQM) calculation of the excited state of aggregation‐induced‐emission (AIE) materials is highly sought but still a challenging task. Herein, we employed the recently developed electrostatically embedded generalized molecular fractionation (EE‐GMF) method, a method based on the systematic fragmentation approach, to predict, for the first time, the spectra of a prototype AIE fluorophore: di(p‐methoxylphenyl)dibenzofulvene (FTPE). Compared to the single molecular or QM/MM calculations, the EE‐GMF method shows significantly improved accuracy, nearly reproducing the experimental optical spectra of FTPE in both condensed phases. Importantly, we show that the conventional restriction of the intramolecular rotation mechanism cannot fully account for AIE, whereas the two‐body intermolecular quantum mechanical interaction plays a crucial role in AIE.

Sequence‐Based Prediction of Promiscuous Acyltransferase Activity in Hydrolases

By Henrik Müller, Ann‐Kristin Becker, Gottfried J. Palm, Leona Berndt, Christoffel P. S. Badenhorst, Simon P. Godehard, Lukas Reisky, Michael Lammers, Uwe T. Bornscheuer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

What's the score? Promiscuous acyltransferase activity of esterases strongly correlates with active‐site hydrophobicity. A hydrophobicity scoring concept was developed that enables the accurate prediction of promiscuous acyltransferase activity simply from the amino acid sequence of the enzyme cap domain. Abstract Certain hydrolases preferentially catalyze acyl transfer over hydrolysis in an aqueous environment. However, the molecular and structural reasons for this phenomenon are still unclear. Herein, we provide evidence that acyltransferase activity in esterases highly correlates with the hydrophobicity of the substrate‐binding pocket. A hydrophobicity scoring system developed in this work allows accurate prediction of promiscuous acyltransferase activity solely from the amino acid sequence of the cap domain. This concept was experimentally verified by systematic investigation of several homologous esterases, leading to the discovery of five novel promiscuous acyltransferases. We also developed a simple yet versatile colorimetric assay for rapid characterization of novel acyltransferases. This study demonstrates that promiscuous acyltransferase activity is not as rare as previously thought and provides access to a vast number of novel acyltransferases with diverse substrate specificity and potential applications.

Discovery of Chemicals to Either Clear or Indicate Amyloid Aggregates by Targeting Memory‐Impairing Anti‐Parallel Aβ Dimers

By Jinny Claire Lee, Hye Yun Kim, Sejin Lee, Jisu Shin, Hyunjin Vincent Kim, Kyeonghwan Kim, Seungyeop Baek, Donghee Lee, Hanna Jeon, DaWon Kim, Seung‐Hoon Yang, Gyoonhee Han, Keunwan Park, Jaeho Choi, Jinwoo Park, Jason A. Moss, Kim D. Janda, YoungSoo Kim from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

On target: Parallel and anti‐parallel amyloid‐β (Aβ) homodimers were fabricated and screened, and the anti‐parallel dimers induced cognitive impairment with increased amyloidogenesis and cytotoxicity. In vitro/vivo assessments of the drugs Oxytetracycline and Sunitinib show that they target Aβ dimers and larger aggregates, thus identifying therapeutic and diagnostic agents for Alzheimer disease. Abstract Amyloid‐β (Aβ) oligomers are implicated in Alzheimer disease (AD). However, their unstable nature and heterogeneous state disrupts elucidation of their explicit role in AD progression, impeding the development of tools targeting soluble Aβ oligomers. Herein parallel and anti‐parallel variants of Aβ(1–40) dimers were designed and synthesized, and their pathogenic properties in AD models characterized. Anti‐parallel dimers induced cognitive impairments with increased amyloidogenesis and cytotoxicity, and this dimer was then used in a screening platform. Through screening, two FDA‐approved drugs, Oxytetracycline and Sunitinib, were identified to dissociate Aβ oligomers and plaques to monomers in 5XFAD transgenic mice. In addition, fluorescent Astrophloxine was shown to detect aggregated Aβ in brain tissue and cerebrospinal fluid samples of AD mice. This screening platform provides a stable and homogeneous environment for observing Aβ interactions with dimer‐specific molecules.

Revealing the Role of Tin(IV) Halides in the Anisotropic Growth of CsPbX3 Perovskite Nanoplates

By Luiz G. Bonato, Raphael F. Moral, Gabriel Nagamine, Arthur Alo, José C. Germino, Douglas S. Silva, Diogo B. Almeida, Luiz F. Zagonel, Fernando Galembeck, Lázaro A. Padilha, Ana Flávia Nogueira from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

CsPbX3 perovskite nanoplate (PNPL) synthesis was driven by SnX4 (X=Cl, Br, I) salts. The role played by these hard Lewis acids in directing the formation of PNPLs is addressed. Sn4+ disturbs the acid–base equilibrium of the system, increasing the protonation rate of oleylamine and inducing an anisotropic growth of the nanocrystals. Abstract CsPbX3 perovskite nanoplates (PNPLs) were formed in a synthesis driven by SnX4 (X=Cl, Br, I) salts. The role played by these hard Lewis acids in directing PNPL formation is addressed. Sn4+ disturbs the acid–base equilibrium of the system, increasing the protonation rate of oleylamine and inducing anisotropic growth of nanocrystals. Sn4+ cations influence the reaction dynamics owing to complexation with oleylamine molecules. By monitoring the photoluminescence excitation and photoluminescence (PL) spectra of the PNPLs grown at different temperatures, the influence of the thickness on their optical properties is mapped. Time‐resolved and spectrally resolved PL for colloidal dispersions with different optical densities reveals that the dependence of the overall PL lifetime on the emission wavelength do not originate from energy transfer between PNPLs but from the contribution of PNPLs with distinct thickness, indicating that thicker PNPLs exhibit longer PL lifetimes.

Hydrosulfonylation of Alkenes with Sulfonyl Chlorides under Visible Light Activation

By Sandrine M. Hell, Claudio F. Meyer, Antonio Misale, Jeroen B. I. Sap, Kirsten E. Christensen, Michael C. Willis, Andrés A. Trabanco, Véronique Gouverneur from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Radical new approach: Sulfonyl chlorides have been applied in the radical hydrosulfonylation of alkenes. Tris(trimethylsilyl)silane is an ideal hydrogen atom donor enabling highly effective photoredox‐catalyzed hydrosulfonylation of electron‐deficient alkenes with sulfonyl chlorides. To increase the generality of this transformation, polarity‐reversal catalysis was successfully implemented for alkenes bearing alkyl substituents. Abstract Sulfonyl chlorides are inexpensive reactants extensively explored for functionalization, but never considered for radical hydrosulfonylation of alkenes. Herein, we report that tris(trimethylsilyl)silane is an ideal hydrogen atom donor enabling highly effective photoredox‐catalyzed hydrosulfonylation of electron‐deficient alkenes with sulfonyl chlorides. To increase the generality of this transformation, polarity‐reversal catalysis (PRC) was successfully implemented for alkenes bearing alkyl substituents. This late‐stage functionalization method tolerates a remarkably wide range of functional groups, is operationally simple, scalable, and allows access to building blocks which are important for medicinal chemistry and drug discovery.

Asymmetric Guerbet Reaction to Access Chiral Alcohols

By Kun Wang, Lin Zhang, Weijun Tang, Huaming Sun, Dong Xue, Ming Lei, Jianliang Xiao, Chao Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Commercially available, classic Noyori RuII‐diamine‐diphosphine catalysts catalyze the cross coupling of racemic secondary alcohols with primary alcohols in the presence of a base, affording new chiral alcohols with enantiomeric ratios of up to 99:1. Abstract The first example of an asymmetric Guerbet reaction has been developed. Using commercially available, classic Noyori RuII‐diamine‐diphosphine catalysts, well‐known in asymmetric hydrogenation, racemic secondary alcohols are shown to couple with primary alcohols in the presence of a base, affording new chiral alcohols with enantiomeric ratios of up to 99:1. Requiring no reducing agents, the protocol provides an easy, alternative route for the synthesis of chiral alcohols. Mechanistic studies reveal that the reaction proceeds via a Ru‐catalyzed asymmetric hydrogen autotransfer process in concert with a base‐promoted allylic alcohol isomerization.

A Memristive Element Based on an Electrically Controlled Single‐Molecule Reaction

By Haipeng B. Li, Behabitu E. Tebikachew, Cedrik Wiberg, Kasper Moth‐Poulsen, Joshua Hihath from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

At the flick of a switch: An electrically controllable reaction at the single‐molecule level is demonstrated. The reversible reaction can be electrically controlled to perform switching and memory functions, where the conductance values of two molecular isomers are encoded as 0 and 1. Multiple switching cycles are observed when a voltage signal is applied, and the absence of stochastic switching suggests application as a memory device. Abstract The exponential proliferation of data during the information age has required the continuous exploration of novel storage paradigms, materials, and devices with increasing data density. As a step toward the ultimate limits in data density, the development of an electrically controllable single‐molecule memristive element is reported. In this device, digital information is encoded through switching between two isomer states by applying a voltage signal to the molecular junction, and the information is read out by monitoring the electrical conductance of each isomer. The two states are cycled using an electrically controllable local‐heating mechanism for the forward reaction and catalyzed by a single charge‐transfer process for the reverse switching. This single‐molecule device can be modulated in situ, is fully reversible, and does not display stochastic switching. The I–V curves of this single‐molecule system also exhibit memristive character. These features suggest a new approach for the development of molecular switching systems and storage‐class memories.

Nanoimprint Lithography‐Directed Self‐Assembly of Bimetallic Iron–M (M=Palladium, Platinum) Complexes for Magnetic Patterning

By Zhengong Meng, Guijun Li, Sze‐Chun Yiu, Nianyong Zhu, Zhen‐Qiang Yu, Chi‐Wah Leung, Ian Manners, Wai‐Yeung Wong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Back in print: Top‐down lithography is coupled with bottom‐up self‐assembly. The molecular self‐assembly of bimetallic complexes to give nanoparticles is precisely controlled to prepare ordered patterns of nanoparticle assemblies with a high throughput. Abstract Self‐assembly of d8 metal polypyridine systems is a well‐established approach for the creation of 1D organometallic assemblies but there are still challenges for the large‐scale construction of nanostructured patterns from these building blocks. We describe herein the use of high‐throughput nanoimprint lithography (NIL) to direct the self‐assembly of the bimetallic complexes [4′‐ferrocenyl‐(2,2′:6′,2′′‐terpyridine)M(OAc)]+(OAc)− (M=Pd or Pt; OAc=acetate). Uniform nanorods are fabricated from the molecular self‐organization and evidenced by morphological characterization. More importantly, when top‐down NIL is coupled with the bottom‐up self‐assembly of the organometallic building blocks, regular arrays of nanorods can be accessed and the patterns can be controlled by changing the lithographic stamp, where the mold imposes a confinement effect on the nanorod growth. In addition, patterns consisting of the products formed after pyrolysis are studied. The resulting arrays of ferromagnetic FeM alloy nanorods suggest promising potential for the scalable production of ordered magnetic arrays and fabrication of magnetic bit‐patterned media.

Rapid and Scalable Access to Sequence‐Controlled DHDM Multiblock Copolymers by FLP Polymerization

By Yun Bai, Huaiyu Wang, Jianghua He, Yuetao Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Non‐touching superbase: An organophosphorus superbase‐containing frustrated Lewis pair was employed to achieve sequence‐controlled tripentacontablock copolymer (n=53, k=4, dpn=50) with the highest reported block number (n=53) and molecular weight (Mn=310 kg mol−1) within 30 min. Abstract An immortal N‐(diphenylphosphanyl)‐1,3‐diisopropyl‐4,5‐dimethyl‐1,3‐dihydro‐2H‐imidazol‐2‐imine/diisobutyl (2,6‐di‐tert‐butyl‐4‐methylphenoxy) aluminum (P(NIiPr)Ph2/(BHT)AliBu2)‐based frustrated Lewis pair (FLP) polymerization strategy is presented for rapid and scalable synthesis of the sequence‐controlled multiblock copolymers at room temperature. Without addition of extra initiator or catalyst and complex synthetic procedure, this method enabled a tripentacontablock copolymer (n=53, k=4, dpn=50) to be achieved with the highest reported block number (n=53) and molecular weight (Mn=310 kg mol−1) within 30 min. More importantly, this FLP polymerization strategy provided access to the multiblock copolymers with tailored properties by precisely adjusting the monomer sequence and block numbers.

Lithium Bonds in Lithium Batteries

By Xiang Chen, Yun‐Ke Bai, Chen‐Zi Zhao, Xin Shen, Qiang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Lithium bonds that are present in lithium batteries are discussed in this Viewpoint, including historical developments, comparisons with hydrogen bonds, and their potential applications. Discourse on the chemistry of the Li bond can provide fruitful insight into the fundamental interactions within Li batteries and thus deliver a deeper understanding of their working mechanism. Abstract Lithium bonds are analogous to hydrogen bonds and are therefore expected to exhibit similar characteristics and functions. Additionally, the metallic nature and large atomic radius of Li bestow the Li bond with special features. As one of the most important applications of the element, Li batteries afford emerging opportunities for the exploration of Li bond chemistry. Herein, the historical development and concept of the Li bond are reviewed, in addition to the application of Li bonds in Li batteries. In this way, a comprehensive understanding of the Li bond in Li batteries and an outlook on its future developments is presented.

GDCh and DBG Awards 2020

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Graphical Abstract: Angew. Chem. Int. Ed. 28/2020

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Cover Picture: Tunable Electrochemical C−N versus N−N Bond Formation of Nitrogen‐Centered Radicals Enabled by Dehydrogenative Dearomatization: Biological Applications (Angew. Chem. Int. Ed. 28/2020)

By Shide Lv, Xiaoxin Han, Jian‐Yong Wang, Mingyang Zhou, Yanwei Wu, Li Ma, Liwei Niu, Wei Gao, Jianhua Zhou, Wei Hu, Yuezhi Cui, Jianbin Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The electrode potential is generally utilized for tuning the chemoselectivity in organic electrosynthesis. In contrast to this concept, J. Chen et al. employ in their Research Article on page 11583 a novel reaction parameter, current density, to enable versatile C−N bond‐forming reactions. Pyrido[1,2‐a]benzimidazole and tetraarylhydrazine frameworks were generated in a sustainable manner with broad substrate scope.

Inside Back Cover: A Memristive Element Based on an Electrically Controlled Single‐Molecule Reaction (Angew. Chem. Int. Ed. 28/2020)

By Haipeng B. Li, Behabitu E. Tebikachew, Cedrik Wiberg, Kasper Moth‐Poulsen, Joshua Hihath from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A single‐molecule memory element can be electrically controlled by using two distinct reaction mechanisms as reported by K. Moth‐Poulsen, J. Hihath, and co‐workers in their Research Article on page 11641. By using separate electrically controllable reactions for the forward and reverse reactions, the bistable norbornadiene–quadricyclane system can be set in either state. The device can be switched through multiple cycles when a square‐wave voltage signal is applied to the molecule. Each state has a unique conductance value allowing the system to act as a switch or memory device.

Frontispiece: Key Intermediate Species Reveal the Copper(II)‐Exchange Pathway in Biorelevant ATCUN/NTS Complexes

By Radosław Kotuniak, Marc J. F. Strampraad, Karolina Bossak‐Ahmad, Urszula E. Wawrzyniak, Iwona Ufnalska, Peter‐Leon Hagedoorn, Wojciech Bal from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Bioinorganic Chemistry W. Bal et al. demonstrate in their Communication on page 11234 that CuII binding to GGH peptide proceeds via partially coordinated species. A 2N‐coordinated species with CuII/CuI redox activity is the long‐sought reactive intermediate for extracellular copper delivery.

Frontispiece: Observation of the Low‐Frequency Spectrum of the Water Trimer as a Sensitive Test of the Water‐Trimer Potential and the Dipole‐Moment Surface

By Raffael Schwan, Chen Qu, Devendra Mani, Nitish Pal, Gerhard Schwaab, Joel M. Bowman, Gregory S. Tschumper, Martina Havenith from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Water Clusters In their Research Article on page 11399, M. Havenith et al. report the first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1. Quantum calculations allowed assigning the experimentally observed bands.

Back Cover: Asymmetric Guerbet Reaction to Access Chiral Alcohols (Angew. Chem. Int. Ed. 28/2020)

By Kun Wang, Lin Zhang, Weijun Tang, Huaming Sun, Dong Xue, Ming Lei, Jianliang Xiao, Chao Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

The Guerbet reaction was discovered more than 100 years ago. The use of Noyori's catalyst has now enabled the development of the first asymmetric version of this reaction, and thus the highly enantioselective synthesis of chiral alcohols, as described by C. Wang and co‐workers in their Research Article on page 11408.

Inside Cover: Application and Structural Analysis of Triazole‐Bridged Disulfide Mimetics in Cyclic Peptides (Angew. Chem. Int. Ed. 28/2020)

By Andrew M. White, Simon J. Veer, Guojie Wu, Peta J. Harvey, Kuok Yap, Gordon J. King, Joakim E. Swedberg, Conan K. Wang, Ruby H. P. Law, Thomas Durek, David J. Craik from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

1,5‐Disubstituted 1,2,3‐triazoles can be used to mimic disulfide bonds and overcome their redox instability. As T. Durek, D. J. Craik, and co‐workers show in their Communication on page 11273, the triazole motif can be incorporated into backbone cyclic peptides based on the sunflower trypsin inhibitor‐1 scaffold. NMR and X‐ray structural analyses show that the triazole linkage has exceptional mimicry, whilst maintaining activity and improving metabolic stability compared to its disulfide counterpart.

Molecular Engineering for Metal‐Free Amorphous Materials with Room‐Temperature Phosphorescence

By Ting Zhang, Xiang Ma, Hongwei Wu, Liangliang Zhu, Yanli Zhao, He Tian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

All aglow: Amorphous metal‐free materials with room‐temperature phosphorescence display unique photophysical properties and present promising applications. This Minireview summarizes recent progress and gives insightful perspectives in this rapidly developing field, which will be beneficial to the future development of luminescent materials. Abstract Materials displaying room‐temperature phosphorescence (RTP) have been attracting wide attention in recent years due to their distinctive characteristics including long emissive lifetime and large Stokes shift, and their various applications. Most synthesized RTP materials are metal complexes that display enhanced intersystem crossing and crystallization is a common way to restrict nonradiative transition. Amorphous metal‐free RTP materials, which do not rely on expensive and toxic metals and can be prepared in a straightforward fashion, have become an important branch of the field. This Minireview summarizes recent progress in amorphous RTP materials according to the approaches used to immobilize phosphors: host–guest interactions, molecule doping, copolymers, and small‐molecule self‐assembly. Some existing challenges and insightful perspectives are given at the end of the Minireview, which should benefit the future design and development of amorphous metal‐free RTP materials.

EGF‐like and Other Disulfide‐rich Microdomains as Therapeutic Scaffolds

By Benjamin J. Tombling, Conan K. Wang, David J. Craik from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Disulfide‐rich microdomains are underexplored scaffolds for therapeutic drug design. In this Review, the most abundant domains present in the animal and plant kingdoms are highlighted, and their structures and functional activities are analysed to provide an insight into their use in design of next‐generation peptide therapeutics. Abstract Disulfide bonds typically introduce conformational constraints into peptides and proteins, conferring improved biopharmaceutical properties and greater therapeutic potential. In our opinion, disulfide‐rich microdomains from proteins are potentially a rich and under‐explored source of drug leads. A survey of the UniProt protein database shows that these domains are widely distributed throughout the plant and animal kingdoms, with the EGF‐like domain being the most abundant of these domains. EGF‐like domains exhibit large diversity in their disulfide bond topologies and calcium binding modes, which we classify in detail here. We found that many EGF‐like domains are associated with disease phenotypes, and the interactions they mediate are potential therapeutic targets. Indeed, EGF‐based therapeutic leads have been identified, and we further propose that these domains can be optimized to expand their therapeutic potential using chemical design strategies. This Review highlights the potential of disulfide‐rich microdomains as future peptide therapeutics.

Melanin Biopolymers: Tailoring Chemical Complexity for Materials Design

By Marco d'Ischia, Alessandra Napolitano, Alessandro Pezzella, Paul Meredith, Markus Buehler from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Chemical complexity, emerging from structural disorder, redox behavior, and self‐assembly, is nature's strategy to achieve multipurpose, adaptive, and tunable functionality in melanin biopolymers, which can be disentangled, modelled and rationally tailored to an expanding range of applications in materials science. Abstract Melanins, a group of dark insoluble pigments found widespread in nature, have become the focus of growing interest in materials science for various biomedical and technological applications, including opto‐bioelectronics, nanomedicine and mussel‐inspired surface coating. Recent progress in the understanding of melanin optical, paramagnetic redox, and conductivity properties, including photoconductivity, would point to a revision of the traditional concept of structural disorder in terms of more sophisticated and interrelated levels of chemical complexity which however have never been defined and codified. Herein, we bring to focus the various levels of structural disorder that emerged from spectral and chemical signatures over the past decade. A revised approach to structure–property relationships in terms of intermolecular interactions is also provided that may pave the way towards the rational design of next‐generation melanin‐based functional materials.

IDM‐1: A Zeolite with Intersecting Medium and Extra‐Large Pores Built as an Expansion of Zeolite MFI

By Luis A. Villaescusa, Jian Li, Zihao Gao, Junliang Sun, Miguel A. Camblor from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

IDM‐1, a highly stable silica zeolite, was constructed as a structural expansion of zeolite ZSM‐5 by alternating pentasil layers and interrupted layers, thus giving rise to an intersecting system of straight medium pores and undulating extra‐large lobed pores. The synthesis is directed by a diquat resembling two rigidly joined tetrapropylammonium cations. Abstract IDM‐1 is a new silica zeolite with an ordered and well‐defined framework constructed by alternating pentasil layers and interrupted layers, giving rise to an intersecting system of straight medium pores and undulating extra‐large lobed pores. This unique structure was solved by rotation electron diffraction and refined against synchrotron powder X‐ray diffraction data. Despite the presence of both Si(OSi)3(OH) and Si(OSi)2(OH)2 sites, this new zeolite presents high thermal stability, withstanding calcination even to 1000 °C. The location of defects at specific sites of the structure results in alternating hydrophobic SiO2 and hydrophilic SiO(2−x)(OH)2x intracrystalline regions. This peculiar combination of intersecting medium and extra‐large pores and alternating regions of different chemical character may provide this zeolite with unique catalytic properties.

Application and Structural Analysis of Triazole‐Bridged Disulfide Mimetics in Cyclic Peptides

By Andrew M. White, Simon J. Veer, Guojie Wu, Peta J. Harvey, Kuok Yap, Gordon J. King, Joakim E. Swedberg, Conan K. Wang, Ruby H. P. Law, Thomas Durek, David J. Craik from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Made to measure: Disulfide mimetics are an important tool to overcome the redox instability of disulfide‐rich peptides for therapeutic application. The installation and structural characterisation of a triazole motif (blue) is reported that provides exceptional mimicry of disulfide linkages (yellow). This approach was demonstrated for a series of backbone‐cyclic serine protease inhibitors. Abstract Ruthenium‐catalysed azide–alkyne cycloaddition (RuAAC) provides access to 1,5‐disubstituted 1,2,3‐triazole motifs in peptide engineering applications. However, investigation of this motif as a disulfide mimetic in cyclic peptides has been limited, and the structural consequences remain to be studied. We report synthetic strategies to install various triazole linkages into cyclic peptides through backbone cyclisation and RuAAC cross‐linking reactions. These linkages were evaluated in four serine protease inhibitors based on sunflower trypsin inhibitor‐1. NMR and X‐ray crystallography revealed exceptional consensus of bridging distance and backbone conformations (RMSD

Transition Metal Nitrides as Promising Catalyst Supports for Tuning CO/H2 Syngas Production from Electrochemical CO2 Reduction

By Yumeng Liu, Dong Tian, Akash N. Biswas, Zhenhua Xie, Sooyeon Hwang, Ji Hoon Lee, Hong Meng, Jingguang G. Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Palladium‐modified transition metal nitrides are investigated as electrochemical CO2 reduction reaction (CO2RR) catalysts. Combined in‐situ X‐ray characterization and DFT results demonstrate niobium nitride as an effective support material to enhance CO2RR activity. Abstract The electrochemical carbon dioxide reduction reaction (CO2RR) to produce synthesis gas (syngas) with tunable CO/H2 ratios has been studied by supporting Pd catalysts on transition metal nitride (TMN) substrates. Combining experimental measurements and density functional theory (DFT) calculations, Pd‐modified niobium nitride (Pd/NbN) is found to generate much higher CO and H2 partial current densities and greater CO Faradaic efficiency than Pd‐modified vanadium nitride (Pd/VN) and commercial Pd/C catalysts. In‐situ X‐ray diffraction identifies the formation of PdH in Pd/NbN and Pd/C under CO2RR conditions, whereas the Pd in Pd/VN is not fully transformed into the active PdH phase. DFT calculations show that the stabilized *HOCO and weakened *CO intermediates on PdH/NbN are critical to achieving higher CO2RR activity. This work suggests that NbN is a promising substrate to modify Pd, resulting in an enhanced electrochemical conversion of CO2 to syngas with a potential reduction in precious metal loading.

Extending the Sensitivity of CEST NMR Spectroscopy to Micro‐to‐Millisecond Dynamics in Nucleic Acids Using High‐Power Radio‐Frequency Fields

By Atul Rangadurai, Honglue Shi, Hashim M. Al‐Hashimi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

I′ve got the power: High‐power radio‐frequency fields extend the sensitivity of chemical exchange saturation transfer (CEST) NMR spectroscopy to enable the detection of conformational exchange on the micro‐to‐millisecond timescale. This is applied to the detection of nucleic‐acid dynamics. Abstract Biomolecules undergo motions on the micro‐to‐millisecond timescale to adopt low‐populated transient states that play important roles in folding, recognition, and catalysis. NMR techniques, such as Carr–Purcell–Meiboom–Gill (CPMG), chemical exchange saturation transfer (CEST), and R1ρ are the most commonly used methods for characterizing such transitions at atomic resolution under solution conditions. CPMG and CEST are most effective at characterizing motions on the millisecond timescale. While some implementations of the R1ρ experiment are more broadly sensitive to motions on the micro‐to‐millisecond timescale, they entail the use of selective irradiation schemes and inefficient 1D data acquisition methods. Herein, we show that high‐power radio‐frequency fields can be used in CEST experiments to extend the sensitivity to faster motions on the micro‐to‐millisecond timescale. Given the ease of implementing high‐power fields in CEST, this should make it easier to characterize micro‐to‐millisecond dynamics in biomolecules.

An Autonomous Chemical Robot Discovers the Rules of Inorganic Coordination Chemistry without Prior Knowledge

By Luzian Porwol, Daniel J. Kowalski, Alon Henson, De‐Liang Long, Nicola L. Bell, Leroy Cronin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A chemical robot was designed, assembled and utilised for the discovery of supramolecular architectures through the exploration of a chemical space exceeding 109 possible reactions. By searching for reactivity differences, a range of new 1‐benzyl‐(1,2,3‐triazol‐4‐yl)‐N‐alkyl‐(2‐pyridinemethanimine) ligands were found and four new complexes of Fe and Co were discovered, autonomously discovering the rules of self‐assembly for these systems. Abstract We present a chemical discovery robot for the efficient and reliable discovery of supramolecular architectures through the exploration of a huge reaction space exceeding ten billion combinations. The system was designed to search for areas of reactivity found through autonomous selection of the reagent types, amounts, and reaction conditions aiming for combinations that are reactive. The process consists of two parts where reagents are mixed together, choosing from one type of aldehyde, one amine and one azide (from a possible family of two amines, two aldehydes and four azides) with different volumes, ratios, reaction times, and temperatures, whereby the reagents are passed through a copper coil reactor. Next, either cobalt or iron is added, again from a large number of possible quantities. The reactivity was determined by evaluating differences in pH, UV‐Vis, and mass spectra before and after the search was started. The algorithm was focused on the exploration of interesting regions, as defined by the outputs from the sensors, and this led to the discovery of a range of 1‐benzyl‐(1,2,3‐triazol‐4‐yl)‐N‐alkyl‐(2‐pyridinemethanimine) ligands and new complexes: [Fe(L1)2](ClO4)2 (1); [Fe(L2)2](ClO4)2 (2); [Co2(L3)2](ClO4)4 (3); [Fe2(L3)2](ClO4)4 (4), which were crystallised and their structure confirmed by single‐crystal X‐ray diffraction determination, as well as a range of new supramolecular clusters discovered in solution using high‐resolution mass spectrometry.

Ultrathin ZnIn2S4 Nanosheets Anchored on Ti3C2TX MXene for Photocatalytic H2 Evolution

By Gancheng Zuo, Yuting Wang, Wei Liang Teo, Aming Xie, Yang Guo, Yuxuan Dai, Weiqiang Zhou, Deblin Jana, Qiming Xian, Wei Dong, Yanli Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

MXene nanosheets are used to support the in situ growth of ultrathin ZnIn2S4. The obtained sandwich‐like hierarchical heterostructure could effectively suppress photoexcited electron–hole recombination and boost photoexcited charge transfer and separation, exhibiting efficient photocatalytic H2 evolution performance and excellent stability. Abstract Photocatalysts derived from semiconductor heterojunctions that harvest solar energy and catalyze reactions still suffer from low solar‐to‐hydrogen conversion efficiency. Now, MXene (Ti3C2TX) nanosheets (MNs) are used to support the in situ growth of ultrathin ZnIn2S4 nanosheets (UZNs), producing sandwich‐like hierarchical heterostructures (UZNs‐MNs‐UZNs) for efficient photocatalytic H2 evolution. Opportune lateral epitaxy of UZNs on the surface of MNs improves specific surface area, pore diameter, and hydrophilicity of the resulting materials, all of which could be beneficial to the photocatalytic activity. Owing to the Schottky junction and ultrathin 2D structures of UZNs and MNs, the heterostructures could effectively suppress photoexcited electron–hole recombination and boost photoexcited charge transfer and separation. The heterostructure photocatalyst exhibits improved photocatalytic H2 evolution performance (6.6 times higher than pristine ZnIn2S4) and excellent stability.

Nucleobase Modifiers Identify TET Enzymes as Bifunctional DNA Dioxygenases Capable of Direct N‐Demethylation

By Uday Ghanty, Tong Wang, Rahul M. Kohli from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

TET family enzymes are robust and direct N‐demethylases, and this activity is comparable to its normal activity in the oxidation of 5‐methylcytosine, as determined using a nucleobase‐modification strategy. This remarkable N‐demethylase activity highlights the plasticity of the TET active site and suggests broader biological roles for TET enzymes beyond impacting DNA‐methylation dynamics. Abstract TET family enzymes are known for oxidation of the 5‐methyl substituent on 5‐methylcytosine (5mC) in DNA. 5mC oxidation generates the stable base 5‐hydroxymethylcytosine (5hmC), starting an indirect, multi‐step process that ends with reversion of 5mC to unmodified cytosine. While probing the nucleobase determinants of 5mC recognition, we discovered that TET enzymes are also proficient as direct N‐demethylases of cytosine bases. We find that N‐demethylase activity can be readily observed on substrates lacking a 5‐methyl group and, remarkably, TET enzymes can be similarly proficient in either oxidation of 5mC or demethylation of N4‐methyl substituents. Our results indicate that TET enzymes can act as both direct and indirect demethylases, highlight the active‐site plasticity of these FeII/α‐ketoglutarate‐dependent dioxygenases, and suggest activity on unexplored substrates that could reveal new TET biology.

Room‐Temperature Guerbet Reaction with Unprecedented Catalytic Efficiency and Enantioselectivity

By Teng Wei Ng, Gang Liao, Kai Kiat Lau, Hui‐Jie Pan, Yu Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A highly efficient Guerbet‐type reaction at room temperature (catalytic TON up to >6000) is reported. This β‐alkylation of secondary methyl carbinols with primary alcohols delivers higher‐order secondary alcohols in an economical, redox‐neutral fashion. This first enantioselective Guerbet reaction has also been achieved using a commercially available chiral ruthenium complex to deliver secondary alcohols with moderate yield and up to 92 % ee. Abstract We report herein an unprecedented highly efficient Guerbet‐type reaction at room temperature (catalytic TON up to >6000). This β‐alkylation of secondary methyl carbinols with primary alcohols has significant advantage of delivering higher‐order secondary alcohols in an economical, redox‐neutral fashion. In addition, the first enantioselective Guerbet reaction has also been achieved using a commercially available chiral ruthenium complex to deliver secondary alcohols with moderate yield and up to 92 % ee. In both reactions, the use of a traceless ketone promoter proved to be beneficial for the catalytic efficiency.

Planar Chiral Organoboranes with Thermoresponsive Emission and Circularly Polarized Luminescence: Integration of Pillar[5]arenes with Boron Chemistry

By Jin‐Fa Chen, Xiaodong Yin, Bowen Wang, Kai Zhang, Guoyun Meng, Songhe Zhang, Yafei Shi, Nan Wang, Suning Wang, Pangkuan Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Two examples of planar chiral systems were achieved by axial functionalization of a pillar[5]arene with sufficiently bulky, rigid, π‐conjugated and highly luminescent triarylborane and triarylamine moieties, leading to enantiomeric resolution and circularly polarized luminescence (CPL). They represent the first chiral luminescent systems based on planar chiral pillar[5]arenes. Abstract Enantiopure molecules based on macrocyclic architecture are unique for applications in enantioselective host‐guest recognition, chiral sensing and asymmetric catalysis. Taking advantage of the chiral transfer from the intrinsically planar chirality of pillar[5]arenes, we herein present an efficient and straightforward approach to achieve early examples of highly luminescent chiral systems (P5NN and P5BN). The optical resolution of their enantiomers has been carried out via preparative chiral HPLC, which was ascribed to the molecular functionalization of pillar[5]arenes with π‐conjugated, sterically bulky triarylamine (Ar3N) as an electron donor and triarylborane (Ar3B) as an acceptor. This crucial design enabled investigations of the chiroptical properties, including circular dichroism (CD) and circularly polarized luminescence (CPL) in the solid state. The intramolecular charge transfer (ICT) nature in P5BN afforded an interesting thermochromic shift of the emission over a wide temperature range.

A Free‐Radical Prompted Barrierless Gas‐Phase Synthesis of Pentacene

By Long Zhao, Ralf I. Kaiser, Wenchao Lu, Musahid Ahmed, Mikhail M. Evseev, Eugene K. Bashkirov, Valeriy N. Azyazov, Christina Tönshoff, Florian Reicherter, Holger F. Bettinger, Alexander M. Mebel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

PAH for the course: Pentacene, a polycyclic aromatic hydrocarbon (PAH), can be formed through molecular mass growth processes via ring annulation at low temperatures via the reaction of 2‐tetracenyl radicals with vinylacetylene. It thus disputes the conventional hypotheses that synthesis of PAHs solely proceeds at elevated temperatures. Abstract A representative, low‐temperature gas‐phase reaction mechanism synthesizing polyacenes via ring annulation exemplified by the formation of pentacene (C22H14) along with its benzo[a]tetracene isomer (C22H14) is unraveled by probing the elementary reaction of the 2‐tetracenyl radical (C18H11.) with vinylacetylene (C4H4). The pathway to pentacene—a prototype polyacene and a fundamental molecular building block in graphenes, fullerenes, and carbon nanotubes—is facilitated by a barrierless, vinylacetylene mediated gas‐phase process thus disputing conventional hypotheses that synthesis of polycyclic aromatic hydrocarbons (PAHs) solely proceeds at elevated temperatures. This low‐temperature pathway can launch isomer‐selective routes to aromatic structures through submerged reaction barriers, resonantly stabilized free‐radical intermediates, and methodical ring annulation in deep space eventually changing our perception about the chemistry of carbon in our universe.

Cell Engineering with Functional Poly(oxanorbornene) Block Copolymers

By Derek C. Church, Jonathan K. Pokorski from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Polymer–cell conjugates: By incorporating a short polymer block (2–5 repeat units) containing long hydrophobic chains, block copolymers can be synthesized that quickly label cell surfaces and can incorporate advanced functionalities. Abstract Cell‐based therapies are gaining prominence in treating a wide variety of diseases and using synthetic polymers to manipulate these cells provides an opportunity to impart function that could not be achieved using solely genetic means. Herein, we describe the utility of functional block copolymers synthesized by ring‐opening metathesis polymerization (ROMP) that can insert directly into the cell membrane via the incorporation of long alkyl chains into a short polymer block leading to non‐covalent, hydrophobic interactions with the lipid bilayer. Furthermore, we demonstrate that these polymers can be imbued with advanced functionalities. A photosensitizer was incorporated into these polymers to enable spatially controlled cell death by the localized generation of 1O2 at the cell surface in response to red‐light irradiation. In a broader context, we believe our polymer insertion strategy could be used as a general methodology to impart functionality onto cell‐surfaces.

Cocrystallization‐Induced Spontaneous Deracemization: A General Thermodynamic Approach to Deracemization

By Michael Guillot, Joséphine Meester, Sarah Huynen, Laurent Collard, Koen Robeyns, Olivier Riant, Tom Leyssens from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

One model to fit all: As a general approach to deracemization, cocrystallization‐induced spontaneous deracemization takes advantage of the universal dimension of cocrystallization to create a pair of diastereomers and combines it with a racemization reaction in solution (see picture). This model was successfully applied to a fungicide, the deracemization of which was not possible by established methods. Abstract Processes leading to enantiomerically pure compounds are of utmost importance, in particular for the pharmaceutical industry. Starting from a racemic mixture, crystallization‐induced diastereomeric transformation allows in theory for 100 % transformation of the desired enantiomer. However, this method has the inherent limiting requirement for the organic compound to form a salt. Herein, this limitation is lifted by introducing cocrystallization in the context of thermodynamic deracemization, with the process applied to a model chiral fungicide. We report a new general single thermodynamic deracemization process based on cocrystallization for the deracemization of (R,S)‐4,4‐dimethyl‐1‐(4‐fluorophenyl)‐2‐(1H‐1,2,4‐triazol‐1‐yl)pentan‐3‐one. This study demonstrates the feasibility of this novel approach and paves the way to further development of such processes.

A General Regioselective Synthesis of Alcohols by Cobalt‐Catalyzed Hydrogenation of Epoxides

By Weiping Liu, Thomas Leischner, Wu Li, Kathrin Junge, Matthias Beller from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Non‐noble‐metal catalysis: The cobalt‐catalyzed hydrogenation of epoxides for the synthesis of anti‐Markovnikov alcohols is reported. This method is suitable for internal, as well as terminal, epoxides and works smoothly even with multi‐substituted derivatives under mild conditions. Abstract A straightforward methodology for the synthesis of anti‐Markovnikov‐type alcohols is presented. By using a specific cobalt triphos complex in the presence of Zn(OTf)2 as an additive, the hydrogenation of epoxides proceeds with high yields and selectivities. The described protocol shows a broad substrate scope, including multi‐substituted internal and terminal epoxides, as well as a good functional‐group tolerance. Various natural‐product derivatives, including steroids, terpenoids, and sesquiterpenoids, gave access to the corresponding alcohols in moderate‐to‐excellent yields.

Spectrally Combined Encoding for Profiling Heterogeneous Circulating Tumor Cells Using a Multifunctional Nanosphere‐Mediated Microfluidic Platform

By Ling‐Ling Wu, Zhi‐Ling Zhang, Man Tang, Dong‐Liang Zhu, Xiao‐Juan Dong, Jiao Hu, Chu‐Bo Qi, Hong‐Wu Tang, Dai‐Wen Pang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A spectrally combined encoding strategy was proposed for multiplex biomarker profiling of heterogeneous circulating tumor cells (CTCs) using a multifunctional nanosphere‐mediated microfluidic platform. Different cellular biomarkers simultaneously encoded with both magnetic tags and distinct optical signatures, enabled efficient isolation and in situ on‐chip spectrally combined encoding of heterogeneous CTCs at single‐cell resolution. Abstract Comprehensive phenotypic profiling of heterogeneous circulating tumor cells (CTCs) at single‐cell resolution has great importance for cancer management. Herein, a novel spectrally combined encoding (SCE) strategy was proposed for multiplex biomarker profiling of single CTCs using a multifunctional nanosphere‐mediated microfluidic platform. Different cellular biomarkers uniquely labeled by multifunctional nanosphere barcodes, possessing identical magnetic tags and distinct optical signatures, enabled isolation of heterogeneous CTCs with over 91.6 % efficiency and in situ SCE of phenotypes. By further trapping individual CTCs in ordered microstructures on chip, composite single‐cell spectral signatures were conveniently and efficiently obtained, allowing reliable spectral‐readout for multiplex biomarker profiling. This SCE strategy exhibited great potential in multiplex profiling of heterogeneous CTC phenotypes, offering new avenues for cancer study and precise medicine.

Concise Synthesis of (+)‐[13C4]‐Anatoxin‐a by Dynamic Kinetic Resolution of a Cyclic Iminium Ion

By Jacob J. Lacharity, Artur K. Mailyan, Karen Y. Chen, Armen Zakarian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Label it! Reported here is an asymmetric total synthesis of the isotopically labelled cyanotoxin [13C4]‐anatoxin‐a. A critical feature of the synthesis is the unique enantioselective Morita–Baylis–Hillman cyclization that leverages a cyclic iminium ion racemization to achieve dynamic kinetic resolution. The substantial quantities of this internal standard with 99.1 % isotope incorporation will enable the development of an analytical method for the precise quantification of anatoxin‐a in freshwater. Abstract An asymmetric total synthesis of [13C4]‐anatoxin‐a ([13C4]‐1) has been developed from commercially available ethyl [13C4]‐acetoacetate ([13C4]‐15). The unique requirements associated with isotope incorporation inspired a new, robust, and highly scalable route, providing access to 0.110 g of this internal standard for use in the detection and precise quantification of anatoxin‐a in freshwater. A highlight of the synthesis is a method that leverages a cyclic iminium ion racemization to achieve dynamic kinetic resolution in an enantioselective Morita–Baylis–Hillman (MBH) cyclization.

Reductive Deamination with Hydrosilanes Catalyzed by B(C6F5)3

By Huaquan Fang, Martin Oestreich from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

I mean defunct. Combinations of the boron Lewis acid B(C6F5)3 and hydrosilanes enable the reductive cleavage ofC−N bonds in various, mainly benzylic amines and heterocumulenes. By this, these functionalized substrates can be converted into the corresponding hydrocarbons in moderate to good yields. Abstract The strong boron Lewis acid tris(pentafluorophenyl)borane B(C6F5)3 is known to catalyze the dehydrogenative coupling of certain amines and hydrosilanes at elevated temperatures. At higher temperature, the dehydrogenation pathway competes with cleavage of the C−N bond and defunctionalization is obtained. This can be turned into a useful methodology for the transition‐metal‐free reductive deamination of a broad range of amines as well as heterocumulenes such as an isocyanate and an isothiocyanate.

Efficient Light‐Harvesting Antennae Resulting from the Dense Organization of Dyes into DNA Junctions through d‐Threoninol

By Hiromu Kashida, Hidenori Azuma, Ryoko Maruyama, Yasuyuki Araki, Takehiko Wada, Hiroyuki Asanuma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Sensitive antennae: Light‐harvesting antennae were prepared by organizing fluorophores into DNA junctions. By using d‐threoninol as a linker, donors could be accommodated in each arm at very high density. An acceptor was located at the center of each junction to evaluate antenna effects (see picture). Six‐ and eight‐way junctions showed the highest antenna effects. Distinct odd–even effects were also observed in yields of DNA junctions. Abstract Herein we report the construction of efficient light‐harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d‐threoninol. Six pyrene donors could be incorporated into each arm without self‐quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three‐ to eight‐way junctions were systematically compared. Six‐ and eight‐way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even‐numbered junctions had higher efficiencies than odd‐numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd–even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems.

Unusual Skeletal Reorganization of Oxetanes for the Synthesis of 1,2‐Dihydroquinolines

By Guannan Wang, Hai Huang, Wengang Guo, Chenxiao Qian, Jianwei Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

An unusual skeletal reorganization of oxetanes is described, in which oxetane‐tethered anilines reacted unexpectedly to form 1,2‐dihydroquinolines in the presence of In(OTf)3 as catalyst. This process proceeds through an intriguing mechanism involving a series of bond cleavage and formation steps. Abstract Skeletal reorganization is a type of fascinating transformations owing to their intriguing mechanisms and utility in complex molecule synthesis. However, only a limited amount of examples are known for most functional groups. Herein, we describe such an unusual process of oxetanes. In the presence of In(OTf)3 as catalyst, oxetane‐tethered anilines reacted unexpectedly to form 1,2‐dihydroquinolines. This process not only provides expedient access to dihydroquinolines, but also represents a new reaction of oxetane. Mechanistically, it is believed that the reaction proceeds through initial nitrogen attack rather than arene attack followed by a series of bond cleavage and formation events. Control experiments provided important insights into the mechanism.

Unifying the Aminohexopyranose‐ and Peptidyl‐Nucleoside Antibiotics: Implications for Antibiotic Design

By Catherine M. Serrano, Hariprasada Reddy Kanna Reddy, Daniel Eiler, Michael Koch, Ben I. C. Tresco, Louis R. Barrows, Ryan T. VanderLinden, Charles A. Testa, Paul R. Sebahar, Ryan E. Looper from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Oldies but goodies: Amicetin, first isolated in the 1950s is demonstrated to be the first prokaryotic‐selective inhibitor of the ribosomal P‐site. Simplification of amicetin's structure provides compounds with comparable biochemical and whole‐cell activity against Mycobacterium tuberculosis. Given this selectivity, lack of cytotoxicity and dramatic structural changes that can be tolerated, amicetin holds promise as an anti‐tubercular lead. Abstract In search of new anti‐tuberculars compatible with anti‐retroviral therapy we re‐identified amicetin as a lead compound. Amicetin's binding to the 70S ribosomal subunit of Thermus thermophilus (Tth) has been unambiguously determined by crystallography and reveals it to occupy the peptidyl transferase center P‐site of the ribosome. The amicetin binding site overlaps significantly with that of the well‐known protein synthesis inhibitor balsticidin S. Amicetin, however, is the first compound structurally characterized to bind to the P‐site with demonstrated selectivity for the inhibition of prokaryotic translation. The natural product‐ribosome structure enabled the synthesis of simplified analogues that retained both potency and selectivity for the inhibition of prokaryotic translation.

A Vinyl Cyclopropane Ring Expansion and Iridium‐Catalyzed Hydrogen Borrowing Cascade

By Simon Wübbolt, Choon Boon Cheong, James R. Frost, Kirsten E. Christensen, Timothy J. Donohoe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A vinyl cyclopropane/cyclopentene rearrangement process has been embedded in an iridium‐catalyzed hydrogen borrowing reaction, enabling the formation of substituted, stereo‐defined cyclopentanes containing up to four contiguous stereogenic centres—all from reaction of pentamethylphenyl (Ph*) methylketone and a variety of cyclopropyl alcohols. Abstract A vinyl cyclopropane rearrangement embedded in an iridium‐catalyzed hydrogen borrowing reaction enabled the formation of substituted stereo‐defined cyclopentanes from Ph* methyl ketone and cyclopropyl alcohols. Mechanistic studies provide evidence for the ring‐expansion reaction being the result of a cascade based on oxidation of the cyclopropyl alcohols, followed by aldol condensation with the pentamethyl phenyl‐substituted ketone to form an enone containing the vinyl cyclopropane. Subsequent single electron transfer (SET) to this system initiates a rearrangement, and the catalytic cycle is completed by reduction of the new enone. This process allows for the efficient formation of diversely substituted cyclopentanes as well as the construction of complex bicyclic carbon skeletons containing up to four contiguous stereocentres, all with high diastereoselectivity.

Single‐Layered Chiral Nanosheets with Dual Chiral Void Spaces for Highly Efficient Enantiomer Absorption

By Xiaopeng Feng, Bowen Shen, Bo Sun, Jehan Kim, Xin Liu, Myongsoo Lee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Being picky: Single‐layered chiral 2D sheet structures with dual chiral void spaces are formed in aqueous methanol solution from discrete clusters of planar aromatic segments with in‐plane up and down AB packing. The slipped cofacial stacks of aromatic segments induce the chirality of the sheet. The nanosheets absorb rapidly one enantiomer from a solution of the racemic mixture with greater than 99 % ee. Abstract Although considerable effort in recent years has been devoted to the development of two‐dimensional nanostructures, single‐layered chiral sheet structures with a lateral assembly of discrete clusters remain elusive. Here, we report single‐layered chiral 2D sheet structures with dual chiral void spaces in which discrete clusters of planar aromatic segments are arranged with in‐plane AB order in aqueous methanol solution. The chirality of the sheet is induced by the slipped‐cofacial stacks of rectangular plate‐like aromatic segments in the discrete clusters which are arranged laterally with up and down packing, resulting in dual chiral void spaces. The chiral nanosheets function as superfast enantiomer separation nanomaterials, which rapidly absorb a single enantiomer from a racemic mixture with greater than 99 % ee.

Total Synthesis of α‐ and β‐Amanitin

By Christian Lutz, Werner Simon, Susanne Werner‐Simon, Andreas Pahl, Christoph Müller from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A scalable route to α‐ and β‐amanitin: The bicyclic octapeptide is built up by solid‐phase assembly of a linear octamer followed by two consecutive cyclization steps in solution. The key non‐proteinogenic amino acids, 6‐hydroxytryptophan and (3R,4R)‐dihydroxyisoleucine, are accessible via multistep synthesis on a multigram scale. Amatoxins are important for the development of new payload linkers for antibody–drug conjugates. Abstract α‐Amanitin and related amatoxins have been studied for more than six decades mostly by isolation from death cap mushrooms. The total synthesis, however, remained challenging due to unique structural features. α‐Amanitin is a potent inhibitor of RNA polymerase II. Interrupting the basic transcription processes of eukaryotes leads to apoptosis of the cell. This unique mechanism makes the toxin an ideal payload for antibody–drug conjugates (ADCs). Only microgram quantities of toxins, when delivered selectively to tumor sites through conjugation to antibodies, are sufficient to eliminate malignant tumor cells of almost every origin. By solving the stereoselective access to dihydroxyisoleucine, a photochemical synthesis of the tryptathion precursor, solid‐phase peptide synthesis, and macrolactamization we obtained a scalable synthetic route towards synthetic α‐amanitin. This makes α‐amanitin and derivatives now accessible for the development of new ADCs.

Guest Binding Drives Host Redistribution in Libraries of CoII4L4 Cages

By Marion Kieffer, Rana A. Bilbeisi, John D. Thoburn, Jack K. Clegg, Jonathan R. Nitschke from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A statistical library of dynamic tetrahedral cages was formed by self‐assembly of building blocks of similar sizes. ESI‐MS was used to probe the subtle effects of anion binding on the dynamic library formed. Upon the addition of anions able to bind within the library members, an increase or decrease of the proportion of each congener of the library was observed, allowing for information on relative binding affinities to be gained via MS. Abstract Two CoII4L4 tetrahedral cages prepared from similar building blocks showed contrasting host–guest properties. One cage did not bind guests, whereas the second encapsulated a series of anions, due to electronic and geometric effects. When the building blocks of both cages were present during self‐assembly, a library of five CoIILAxLB4−x cages was formed in a statistical ratio in the absence of guests. Upon incorporation of anions able to interact preferentially with some library members, the products obtained were redistributed in favor of the best anion binders. To quantify the magnitudes of these templation effects, ESI‐MS was used to gauge the effect of each template upon library redistribution.

Gamma‐Ray Irradiation to Accelerate Crystallization of Mesoporous Zeolites

By Xinqing Chen, Minghuang Qiu, Shenggang Li, Chengguang Yang, Lei Shi, Shiju Zhou, Gan Yu, Lixia Ge, Xing Yu, Ziyu Liu, Nannan Sun, Kun Zhang, Hui Wang, Mouhua Wang, Liangshu Zhong, Yuhan Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Gamma‐ray irradiation was introduced for zeolite synthesis. The crystallization processes of zeolite NaA, NaY, Silicalite‐1, and ZSM‐5 were accelerated. More mesopores were created during the process; the adsorption capacity of CO2 in NaA thus increased 6‐fold relative to withoutγ‐ray irradiation. Hydroxyl free radicals generated by γ‐rays accelerated the crystallization of zeolite NaA. Abstract Gamma‐ray (γ‐ray) irradiation was introduced into zeolite synthesis. The crystallization process of zeolite NaA, NaY, Silicalite‐1, and ZSM‐5 were greatly accelerated. The crystallization time of NaA zeolite was significantly decreased to 18 h under γ‐ray irradiation at 20 °C, while more than 102 h was needed for the conventional process. Unexpectedly, more mesopores were created during this process, and thus the adsorption capacity of CO2 increased by 6‐fold compared to the NaA prepared without γ‐ray irradiation. Solid experimental evidence and density function theory (DFT) calculations demonstrated that hydroxyl free radicals (OH*) generated by γ‐rays accelerated the crystallization of zeolite NaA. Besides NaA, mesoporous ZSM‐5 with MFI topology was also successfully synthesized under γ‐ray irradiation, which possessed excellent catalytic performance for methanol conversion, suggesting the universality of this new synthetic strategy for various zeolites.

Palladium‐Catalyzed Asymmetric [4+2] Cycloaddition of 2‐Methylidenetrimethylene Carbonate with Alkenes: Access to Chiral Tetrahydropyran‐Fused Spirocyclic Scaffolds

By Biming Mao, Honglei Liu, Zhengyang Yan, Yi Xu, Jiaqing Xu, Wei Wang, Yongjun Wu, Hongchao Guo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A palladium‐catalyzed asymmetric [4+2] cycloaddition of 2‐methylidenetrimethylene carbonate was successfully developed, affording chiral pharmacologically interesting tetrahydropyran‐fused spirocyclic scaffolds. The target compounds were generated in good to excellent yields and with high enantioselectivity (up to 99 % ee). Further transformations of the products provided other useful chiral spiropyrazolone and spiroindandione derivatives. Abstract A palladium‐catalyzed asymmetric [4+2] cycloaddition of 2‐methylidenetrimethylene carbonate with alkenes derived from pyrazolones, indandione, or barbiturate has been successfully developed, affording pharmacologically interesting chiral tetrahydropyran‐fused spirocyclic scaffolds. The target compounds were generated in good to excellent yields and with high enantioselectivity (up to 99 % ee). Furthermore, this cycloaddition reaction could be efficiently scaled up, and several synthetic transformations were accomplished for the construction of other useful chiral spiropyrazolone and spiroindandione derivatives.

Key Intermediate Species Reveal the Copper(II)‐Exchange Pathway in Biorelevant ATCUN/NTS Complexes

By Radosław Kotuniak, Marc J. F. Strampraad, Karolina Bossak‐Ahmad, Urszula E. Wawrzyniak, Iwona Ufnalska, Peter‐Leon Hagedoorn, Wojciech Bal from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

ATCUN/NTS motifs participate in physiological CuII exchange. Using kinetic methods, spectroscopy, and electrochemistry, it was demonstrated that CuII binding to GGH, an ATCUN/NTS representative, proceeds via partially coordinated species. The 2N‐coordinated complex with t1/2≈100 ms (pH 6.0) and CuII/CuI redox activity is the long‐sought reactive intermediate for extracellular copper delivery. Abstract The amino‐terminal copper and nickel/N‐terminal site (ATCUN/NTS) present in proteins and bioactive peptides exhibits high affinity towards CuII ions and have been implicated in human copper physiology. Little is known, however, about the rate and exact mechanism of formation of such complexes. We used the stopped‐flow and microsecond freeze‐hyperquenching (MHQ) techniques supported by steady‐state spectroscopic and electrochemical data to demonstrate the formation of partially coordinated intermediate CuII complexes formed by glycyl–glycyl–histidine (GGH) peptide, the simplest ATCUN/NTS model. One of these novel intermediates, characterized by two‐nitrogen coordination, t1/2≈100 ms at pH 6.0 and the ability to maintain the CuII/CuI redox pair is the best candidate for the long‐sought reactive species in extracellular copper transport.

N‐Heterocyclic Carbene Copper(I) Rotaxanes Mediate Sequential Click Ligations with All Reagents Premixed

By Fang‐Che Hsueh, Chi‐You Tsai, Chien‐Chen Lai, Yi‐Hung Liu, Shie‐Ming Peng, Sheng‐Hsien Chiu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Sequential click ligations occur efficiently in a sealed flask containing all coupling partners (azides, alkynes) in their unprotected forms and a photolabile interlocked N‐heterocyclic carbene‐CuI catalyst. Abstract We have prepared NHC‐CuI complexes with a rotaxane structure and used them as sterically sensitive catalysts for one‐pot sequential copper‐catalyzed azide/alkyne cycloadditions in solutions containing all of the coupling partners premixed in unprotected form. Most notably, a photolabile and sterically encumbered complex first catalyzed the coupling of a less bulky azide/alkyne pair; after removing the protective macrocyclic component from the rotaxane structure, through irradiation with light, the exposed dumbbell‐shaped NHC‐CuI complex catalyzed the second click reaction of a bulkier azide/alkyne pair. Using this approach, we obtained predominantly, from a single sealed pot, a bis‐triazole product (84 %) from a mixture of two sterically distinct azides and a diyne.

Molecular Thorium Trihydrido Clusters Stabilized by Cyclopentadienyl Ligands

By Runhai Chen, Guorui Qin, Shihui Li, Alison J. Edwards, Ross O. Piltz, Iker Del Rosal, Laurent Maron, Dongmei Cui, Jianhua Cheng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Molecular actinide trihydrido complexes, [(CpR)Th(μ‐H)3]n (n=5, 6, 7, 8) were isolated and structurally characterized. The nuclearity of each metal cluster increases with the decreasing steric demand of the alkyl‐substituted cyclopentadienyl ligand (CpR). Hydride positions in complex [(CpMe4)ThH3]8 were verified by single‐crystal neutron diffraction (Th green, H red, CpMe4 gray). Abstract Hydrogenolysis of alkyl‐substituted cyclopentadienyl (CpR) ligated thorium tribenzyl complexes [(CpR)Th(p‐CH2‐C6H4‐Me)3] (1–6) afforded the first examples of molecular thorium trihydrido complexes [(CpR)Th(μ‐H)3]n (CpR=C5H2(tBu)3 or C5H2(SiMe3)3, n=5; C5Me4SiMe3, n=6; C5Me5, n=7; C5Me4H, n=8; 7–10 and 12) and [(Cp#)12Th13H40] (Cp#=C5H4SiMe3; 13). The nuclearity of the metal hydride clusters depends on the steric profile of the cyclopentadienyl ligands. The hydrogenolysis intermediate, tetra‐nuclear octahydrido thorium dibenzylidene complex [(Cpttt)Th(μ‐H)2]4(μ‐p‐CH‐C6H4‐Me)2 (Cpttt=C5H2(tBu)3) (11) was also isolated. All of the complexes were characterized by NMR spectroscopy and single‐crystal X‐ray analysis. Hydride positions in [(CpMe4)Th(μ‐H)3]8 (CpMe4=C5Me4H) were further precisely confirmed by single‐crystal neutron diffraction. DFT calculations strengthen the experimental assignment of the hydride positions in the complexes 7 to 12.

A Photoinduced Nonadiabatic Decay‐Guided Molecular Motor Triggers Effective Photothermal Conversion for Cancer Therapy

By Jen‐Shyang Ni, Xun Zhang, Guang Yang, Tianyi Kang, Xiangwei Lin, Menglei Zha, Yaxi Li, Lidai Wang, Kai Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Like a heat wave: Molecular motor‐like agents with excellent photothermal conversion performance, attributed to highly efficient deactivation through a nonradiative conical intersection (CI) pathway, were combined with a heat shock protein 70 inhibitor for low‐temperature photothermal therapy. Abstract It remains highly challenging to identify small molecule‐based photothermal agents with a high photothermal conversion efficiency (PTCE). Herein, we adopt a double bond‐based molecular motor concept to develop a new class of small photothermal agents to break the current design bottleneck. As the double‐bond is twisted by strong twisted intramolecular charge transfer (TICT) upon irradiation, the excited agents can deactivate non‐radiatively through the conical intersection (CI) of internal conversion, which is called photoinduced nonadiabatic decay. Such agents possess a high PTCE of 90.0 %, facilitating low‐temperature photothermal therapy in the presence of a heat shock protein 70 inhibitor. In addition, the behavior and mechanism of NIR laser‐triggered molecular motions for generating heat through the CI pathway have been further understood through theoretical and experimental evidence, providing a design principle for highly efficient photothermal and photoacoustic agents.

Bi3+‐Er3+ and Bi3+‐Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near‐Infrared Emitters

By Habibul Arfin, Jagjit Kaur, Tariq Sheikh, Sudip Chakraborty, Angshuman Nag from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Bi3+‐Ln3+ (Ln=Er, Yb) codoping imparts optical functionality to Cs2AgInCl6 double perovskite. Bi3+ tailors optical absorption, thereafter non‐radiatively exciting Er3+ or Yb3+ f‐electrons, which then de‐excite by emitting 1540 and 994 nm near‐infrared (NIR) light, respectively. Abstract Bi3+ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi3+ and lanthanide ions. Codoping of Bi3+ and Ln3+ (Ln=Er and Yb) in Cs2AgInCl6 double perovskite is presented. Bi3+‐Er3+ codoped Cs2AgInCl6 shows Er3+ f‐electron emission at 1540 nm (suitable for low‐loss optical communication). Bi3+ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi3+‐Er3+ codoped Cs2AgInCl6 shows ca. 45 times higher emission intensity compared to the Er3+ doped Cs2AgInCl6. Similar results are also observed in Bi3+‐Yb3+ codoped sample emitting at 994 nm. A combination of temperature‐dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.

Organocatalytic Enantioselective Synthesis of Atropisomeric Aryl‐p‐Quinones: Platform Molecules for Diversity‐Oriented Synthesis of Biaryldiols

By Ye‐Hui Chen, Heng‐Hui Li, Xiao Zhang, Shao‐Hua Xiang, Shaoyu Li, Bin Tan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A class of atropisomeric aryl‐p‐quinones were efficiently assembled by means of chiral phosphoric acid catalyzed enantioselective arylation of p‐quinones through a central‐to‐axial chirality transfer process. This novel axially chiral framework served as a platform for diversity‐oriented synthesis of a wide range of highly functionalized non‐C2 symmetric biaryldiols with preservation of the chirality. Abstract Presented here is a class of novel axially chiral aryl‐p‐quinones as platform molecules for the preparation of non‐C2 symmetric biaryldiols. Two sets of aryl‐p‐quinone frameworks were synthesized with remarkable enantiocontrol by means of chiral phosphoric acid catalyzed enantioselective arylation of p‐quinones by central‐to‐axial chirality conversion. These aryl‐p‐quinones were then used to access a wide spectrum of highly functionalized non‐C2 symmetric biaryldiols with excellent retention of the enantiopurity.

Rapid Generation of Hierarchically Porous Metal–Organic Frameworks through Laser Photolysis

By Kun‐Yu Wang, Liang Feng, Tian‐Hao Yan, Shengxiang Wu, Elizabeth A. Joseph, Hong‐Cai Zhou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

Mesopores within microporous MOFs were generated in milliseconds by controlled photolytic removal of linkers. The photolabile linkers are eliminated by irradiation with a UV laser without affecting the overall crystallinity and integrity of the original framework. Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP‐MOFs with remarkable application potential in multiple fields. Recently, new methods such as linker labilization for the construction of HP‐MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate “photolabile” linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing‐cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP‐MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis.

Stereoselective Palladium‐Catalyzed C−F Bond Alkynylation of Tetrasubstituted gem‐Difluoroalkenes

By Qiao Ma, Yanhui Wang, Gavin Chit Tsui from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

A stereoselective Pd(PPh3)4‐catalyzed C−F bond alkynylation of tetrasubstituted gem‐difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety of conjugated monofluoroenynes bearing a tetrasubstituted alkene moiety with well‐defined stereochemistry (E/Z>99:1). Chelation‐assisted oxidative addition of Pd to theC−F bond is proposed to account for the high level of stereocontrol. Abstract A stereoselective Pd(PPh3)4‐catalyzed C−F bond alkynylation of tetrasubstituted gem‐difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety of conjugated monofluoroenynes bearing a tetrasubstituted alkene moiety with well‐defined stereochemistry. Chelation‐assisted oxidative addition of Pd to the C−F bond is proposed to account for the high level of stereocontrol. An X‐ray crystal structure of a key monofluorovinyl PdII intermediate has been obtained for the first time as evidence for the proposed mechanism.

Hiroshi Kitagawa

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jul 01, 2020.

“The secrets of being a successful scientist are dreams, imagination, and lots of effort. The biggest challenge facing scientists is the room‐temperature superconductor …” Find out more about Hiroshi Kitagawa in his Author Profile.

[ASAP] Hydrophilic Mechano-Bactericidal Nanopillars Require External Forces to Rapidly Kill Bacteria

By Amin Valiei†?, Nicholas Lin†?, Jean-Francois Bryche‡§, Geoffrey McKay?, Michael Canva‡§, Paul G. Charette‡§, Dao Nguyen??#, Christopher Moraes*†??, and Nathalie Tufenkji*† from Nano Letters: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01343

[ASAP] Ultrasensitive Phototransistor Based on WSe2–MoS2 van der Waals Heterojunction

By Gwang Hyuk Shin†, Cheolmin Park†, Khang June Lee, Hyeok Jun Jin, and Sung-Yool Choi* from Nano Letters: Latest Articles (ACS Publications). Published on Jul 01, 2020.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.0c01460

[ASAP] Synthesis of Atomically Thin Hexagonal Diamond with Compression

By Feng Ke*†‡§, Lingkong Zhang†, Yabin Chen??, Ketao Yin#, Chenxu Wang‡, Yan-Kai Tzeng?, Yu Lin§, Hongliang Dong†, Zhenxian Liu?, John S. Tse#, Wendy L. Mao‡§, Junqiao Wu?, and Bin Chen*† from Nano Letters: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01872

[ASAP] A Unidirectional Surface-Anchored N-Heterocyclic Carbene Rotor

By Jindong Ren†‡?, Matthias Freitag§?, Christian Schwermann??, Anne Bakker†‡, Saeed Amirjalayer†‡?, Andreas Ru¨hling§, Hong-Ying Gao†‡?, Nikos L. Doltsinis*?, Frank Glorius*§, and Harald Fuchs*†‡# from Nano Letters: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01884

[ASAP] Stimulated Raman Scattering from Mie-Resonant Subwavelength Nanoparticles

By George P. Zograf†, Daniil Ryabov†, Viktoria Rutckaia‡, Pavel Voroshilov†, Pavel Tonkaev†, Dmitry V. Permyakov†, Yuri Kivshar*†§, and Sergey V. Makarov*† from Nano Letters: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01646

[ASAP] A Superconducting Praseodymium Nickelate with Infinite Layer Structure

By Motoki Osada*†‡, Bai Yang Wang‡§?, Berit H. Goodge??, Kyuho Lee‡§, Hyeok Yoon‡?, Keita Sakuma#, Danfeng Li‡?, Masashi Miura?#, Lena F. Kourkoutis??, and Harold Y. Hwang*‡? from Nano Letters: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01392

[ASAP] Near-Infrared Light Triggered Phototherapy and Immunotherapy for Elimination of Methicillin-Resistant Staphylococcus aureus Biofilm Infection on Bone Implant

By Yuan Li†, Xiangmei Liu*‡, Bo Li?, Yufeng Zheng§, Yong Han?, Da-fu Chen#, Kelvin Wai Kwok Yeung¶, Zhenduo Cui†, Yanqin Liang†, Zhaoyang Li†, Shengli Zhu†, Xianbao Wang‡, and Shuilin Wu*† from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01486

[ASAP] Direct Z-Scheme Heterojunction of Semicoherent FAPbBr3/Bi2WO6 Interface for Photoredox Reaction with Large Driving Force

By Haowei Huang†, Jiwu Zhao‡, Yijie Du§, Chen Zhou?, Menglong Zhang?, Zhuan Wang§, Yuxiang Weng§, Jinlin Long*‡, Johan Hofkens¶#, Julian A. Steele*†, and Maarten B. J. Roeffaers*† from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03146

[ASAP] Durian-Inspired Design of Bismuth–Antimony Alloy Arrays for Robust Sodium Storage

By Jiangfeng Ni†, Xinyan Li†, Menglei Sun†, Yifei Yuan‡, Tongchao Liu‡, Liang Li*†, and Jun Lu*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04366

[ASAP] Direct Laser Writing of Four-Dimensional Structural Color Microactuators Using a Photonic Photoresist

By Marc del Pozo†, Colm Delaney‡, Cees W. M. Bastiaansen†§, Dermot Diamond?, Albert P. H. J. Schenning*†, and Larisa Florea*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02481

[ASAP] Dielectric Confinement and Excitonic Effects in Two-Dimensional Nanoplatelets

By Botao Ji†‡, Eran Rabani§??, Alexander L. Efros#, Roman Vaxenburg?, Or Ashkenazi?, Doron Azulay??, Uri Banin†, and Oded Millo*? from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01950

[ASAP] Nanopore and Nanoparticle Formation with Lipids Undergoing Polymorphic Phase Transitions

By Diana Cholakova, Desislava Glushkova, Slavka Tcholakova, and Nikolai Denkov* from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02946

[ASAP] Supramolecular Self-Assembly of Perylene Bisimide-Based Rigid Giant Tetrahedra

By Jiahao Huang†‡#, He Ren‡§#, Rongchun Zhang†, Lidong Wu?, Yuanming Zhai?, Qingyi Meng?, Jing Wang†, Zebin Su‡, Ruimeng Zhang‡, Shuqi Dai†, Stephen Z. D. Cheng*†‡, and Mingjun Huang*† from ACS Nano: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01971

[ASAP] o-Carborane-Based and Atomically Precise Metal Clusters as Hypergolic Materials

By Qian-You Wang†#, Jie Wang†#, Shan Wang†, Zhao-Yang Wang†, Man Cao†, Chun-Lin He§, Jun-Qing Yang‡, Shuang-Quan Zang*†, and Thomas C. W. Mak†? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04638

[ASAP] Discovery of a Potent and Selective Covalent Inhibitor and Activity-Based Probe for the Deubiquitylating Enzyme UCHL1, with Antifibrotic Activity

By Nattawadee Panyain†, Aure´lien Godinat†, Thomas Lanyon-Hogg†, Sofi´a Lachiondo-Ortega†?, Edward J. Will†, Christelle Soudy‡, Milon Mondal†, Katie Mason§, Sarah Elkhalifa§, Lisa M. Smith§, Jeanine A. Harrigan§, and Edward W. Tate*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04527

[ASAP] Optically Active Flavaglines-Inspired Molecules by a Palladium-Catalyzed Decarboxylative Dearomative Asymmetric Allylic Alkylation

By Meng-Yue Cao†?§, Bin-Jie Ma†?, Zhi-Qi Lao†?, Hongliang Wang§, Jing Wang†?, Juan Liu‡, Kuan Xing†?, Yu-Hao Huang†?, Kang-Ji Gan†?§, Wei Gao‡, Huaimin Wang†?, Xin Hong§, and Hai-Hua Lu*†?‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05113

[ASAP] A Stable Ferryl Porphyrin at the Active Site of Y463M BthA

By Kimberly Rizzolo†#, Andrew C. Weitz†‡#, Steven E. Cohen§, Catherine L. Drennan§??, Michael P. Hendrich‡, and Sean J. Elliott*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04023

[ASAP] Fluorescent Membrane Tension Probes for Super-Resolution Microscopy: Combining Mechanosensitive Cascade Switching with Dynamic-Covalent Ketone Chemistry

By Jose´ Garci´a-Calvo, Jimmy Maillard, Ina Fureraj, Karolina Strakova, Adai Colom, Vincent Mercier, Aurelien Roux, Eric Vauthey, Naomi Sakai, Alexandre Fu¨rstenberg*, and Stefan Matile* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04942

[ASAP] Structure, Spectroscopy, and Reactivity of a Mononuclear Copper Hydroxide Complex in Three Molecular Oxidation States

By Tong Wu†, Samantha N. MacMillan§, Khashayar Rajabimoghadam†, Maxime A. Siegler#, Kyle M. Lancaster*§, and Isaac Garcia-Bosch*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03867

[ASAP] Enantioselective Diarylcarbene Insertion into Si–H Bonds Induced by Electronic Properties of the Carbenes

By Liang-Liang Yang†, Declan Evans‡, Bin Xu†, Wen-Tao Li†, Mao-Lin Li†, Shou-Fei Zhu*†, K. N. Houk*‡, and Qi-Lin Zhou*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04725

[ASAP] Versatile Cp*Co(III)(LX) Catalyst System for Selective Intramolecular C–H Amidation Reactions

By Jia Lee†‡§, Jeonghyo Lee†‡§, Hoimin Jung†‡, Dongwook Kim‡†, Juhyeon Park†‡, and Sukbok Chang*‡† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04448

[ASAP] Catalytic Allylation of Aldehydes Using Unactivated Alkenes

By Shun Tanabe, Harunobu Mitsunuma*, and Motomu Kanai* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jul 01, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04735

A Cationic Oligomer as an Organic Template for Direct Synthesis of Aluminosilicate ITH Zeolite

By Chi Lei, Zhuoya Dong, Cristina Martínez, Joaquín Martínez‐Triguero, Wei Chen, Qinming Wu, Xiangju Meng, Andrei‐Nicolae Parvulescu, Trees De Baerdemaeker, Ulrich Müller, Anmin Zheng, Yanhang Ma, Weiping Zhang, Toshiyuki Yokoi, Bernd Marler, Dirk E. De Vos, Ute Kolb, Avelino Corma, Feng‐Shou Xiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Oligomers to the aid of ITH: A way to directly synthesize aluminosilicate ITH (Al‐ITH) zeolite using a cationic oligomer as an organic template is presented: The strong complexation ability with aluminum species is a key factor for the successful preparation. Abstract There are a large number of zeolites, such as ITH, that cannot be prepared in the aluminosilicate form. Now, the successful synthesis of aluminosilicate ITH zeolite using a simple cationic oligomer as an organic template is presented. Key to the success is that the cationic oligomer has a strong complexation ability with aluminum species combined with a structural directing ability for the ITH structure similar to that of the conventional organic template. The aluminosilicate ITH zeolite has very high crystallinity, nanosheet‐like crystal morphology, large surface area, fully four‐coordinated Al species, and abundant acidic sites. Methanol‐to‐propylene (MTP) tests reveal that the Al‐ITH zeolite shows much higher selectivity for propylene and longer lifetime than commercial ZSM‐5. FCC tests show that Al‐ITH zeolite is a good candidate as a shape‐selective FCC additive for enhancing propylene and butylene selectivity.

Enantioselective Intramolecular Allylic Substitution via Synergistic Palladium/Chiral Phosphoric Acid Catalysis: Insight into Stereoinduction through Statistical Modeling

By Cheng‐Che Tsai, Christopher Sandford, Tao Wu, Buyun Chen, Matthew S. Sigman, F. Dean Toste from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

A palladium catalyst and a chiral phosphoric acid act synergistically to induce enantiocontrol in intramolecular allylic substitution reactions, and statistical modeling has identified multiple noncovalent interactions. These mechanistic studies led to an expansion of synthetic scope to the formation of challenging tertiary ether stereocenters. Abstract The mode of asymmetric induction in an enantioselective intramolecular allylic substitution reaction catalyzed by a combination of palladium and a chiral phosphoric acid was investigated by a combined experimental and statistical modeling approach. Experiments to probe nonlinear effects, the reactivity of deuterium‐labeled substrates, and control experiments revealed that nucleophilic attack to the π‐allylpalladium intermediate is the enantio‐determining step, in which the chiral phosphate anion is involved in stereoinduction. Using multivariable linear regression analysis, we determined that multiple noncovalent interactions with the chiral environment of the phosphate anion are integral to enantiocontrol in the transition state. The synthetic protocol to form chiral pyrrolidines was further applied to the asymmetric construction of C−O bonds at fully substituted carbon centers in the synthesis of chiral 2,2‐disubstituted benzomorpholines.

Adaptive Flexible Sialylated Nanogels as Highly Potent Influenza A Virus Inhibitors

By Sumati Bhatia, Malte Hilsch, Jose Luis Cuellar‐Camacho, Kai Ludwig, Chuanxiong Nie, Badri Parshad, Matthias Wallert, Stephan Block, Daniel Lauster, Christoph Böttcher, Andreas Herrmann, Rainer Haag from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Fighting influenza: Through the combination of flexibility and multivalent binding, a sialylated nanogel is able to bind and adapt onto the influenza A virus surface. The resulting flexible nanogel efficiently blocks the virus binding onto the cell and inhibits infection at low pM concentrations. Abstract Flexible multivalent 3D nanosystems that can deform and adapt onto the virus surface via specific ligand–receptor multivalent interactions can efficiently block virus adhesion onto the cell. We here report on the synthesis of a 250 nm sized flexible sialylated nanogel that adapts onto the influenza A virus (IAV) surface via multivalent binding of its sialic acid (SA) residues with hemagglutinin spike proteins on the virus surface. We could demonstrate that the high flexibility of sialylated nanogel improves IAV inhibition by 400 times as compared to a rigid sialylated nanogel in the hemagglutination inhibition assay. The flexible sialylated nanogel efficiently inhibits the influenza A/X31 (H3N2) infection with IC50 values in low picomolar concentrations and also blocks the virus entry into MDCK‐II cells.

A 2‐Tyr‐1‐carboxylate Mononuclear Iron Center Forms the Active Site of a Paracoccus Dimethylformamidase

By Chetan Kumar Arya, Swati Yadav, Jonathan Fine, Ana Casanal, Gaurav Chopra, Gurunath Ramanathan, Kutti R. Vinothkumar, Ramaswamy Subramanian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Break it down again: Certain bacteria can break down N,N‐dimethyl formamide (DMF) through the action of a dimethylformamidase (DMFase). The structure and mechanism of a DMFase from a bacterium of the genus Paracoccus are presented. The enzyme comprises a multimeric α2β2 or (α2β2)2 complex, and the active site consists of FeIII coordinated by two Tyr side‐chain phenolates and one carboxylate from Glu in an unusual square pyramidal geometry. Abstract N,N‐dimethyl formamide (DMF) is an extensively used organic solvent but is also a potent pollutant. Certain bacterial species from genera such as Paracoccus, Pseudomonas, and Alcaligenes have evolved to use DMF as a sole carbon and nitrogen source for growth via degradation by a dimethylformamidase (DMFase). We show that DMFase from Paracoccus sp. strain DMF is a halophilic and thermostable enzyme comprising a multimeric complex of the α2β2 or (α2β2)2 type. One of the three domains of the large subunit and the small subunit are hitherto undescribed protein folds of unknown evolutionary origin. The active site consists of a mononuclear iron coordinated by two Tyr side‐chain phenolates and one carboxylate from Glu. The Fe3+ ion in the active site catalyzes the hydrolytic cleavage of the amide bond in DMF. Kinetic characterization reveals that the enzyme shows cooperativity between subunits, and mutagenesis and structural data provide clues to the catalytic mechanism.

Conformational Design Principles in Total Synthesis

By Renzhi Chen, Yang Shen, Sihan Yang, Yandong Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Conformational design through purposeful control of the conformation population of molecules significantly facilitates the construction of both stereochemistry and rings in the total synthesis of complex natural products. This Minireview summarizes the progress of this field in the last two decades and especially emphasizes the critical role of implementing a C−H functionalization strategy in natural‐product synthesis. Abstract Conformation is one of the most fundamental concepts in organic chemistry for chemists to visualize a molecule as a three‐dimensional object in addition to its constitution and configuration. Conformational factors significantly affect the physical properties, chemical reactivities, and biological activities of a molecule. The significance of conformational design has been generally recognized since its successful application in the total synthesis of complex natural products, such as vitamin B12 and erythronolide. Conformational analysis, especially intentional control of conformational preferences by conformational design, could play a critical role in the synthesis of complex organic molecules by guiding the formation of bonds, stereocenters, or rings. This Minireview highlights selected examples of conformational design in natural‐product synthesis, with particular emphasis on the applications and new insights advanced in the last 20 years. The examples discussed herein are divided into three categories by structural features of the substrates: open‐chain type, cyclohexane type, and medium‐ and large‐ring type.

Enantioselective Preparation of Arenes with β‐Stereogenic Centers: Confronting the 1,1‐Disubstituted Olefin Problem Using CuH/Pd Cooperative Catalysis

By Zhaohong Lu, Stephen L. Buchwald from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

It takes two: CuH/Pd‐catalyzed enantioselective hydroarylation of 1,1‐disubstituted alkenes proceeds with anti‐Markovnikov regioselectivity under mild conditions to access β‐stereogenic arenes. A wide range of aryl bromides, including several heterocycle‐containing substrates, can be used with good efficiency and enantioselectivity. Various 1,1‐disubstituted alkenes were also examined. Abstract Arenes with β‐stereogenic centers are important substructures in pharmaceuticals and natural products. We have developed an asymmetric anti‐Markovnikov hydroarylation of 1,1‐disubstituted olefins by dual palladium and copper hydride catalysis as a convenient and general approach to access these substructures. This efficient one‐step process addresses several limitations of the traditional stepwise approaches. The use of cesium benzoate as a base and a common phosphine ligand for both the Cu‐ and Pd‐catalyzed processes were important discoveries that allow these challenging olefin substrates to be efficiently transformed. A variety of aryl bromide coupling partners, including numerous heterocycles, were coupled with 1,1‐disubstituted alkenes to generate arenes with β‐stereogenic centers.

Elucidation of the Intersystem Crossing Mechanism in a Helical BODIPY for Low‐Dose Photodynamic Therapy

By Zhijia Wang, Ling Huang, Yuxin Yan, Ahmed M. El‐Zohry, Antonio Toffoletti, Jianzhang Zhao, Antonio Barbon, Bernhard Dick, Omar F. Mohammed, Gang Han from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

PDT with a twist: The intersystem crossing (ISC) mechanism of a heavy atom‐free helical bodipy derivative was elucidated. Due to the intense absorption at long wavelengths (ϵ=1.76×105 m−1 cm−1 at 630 nm), satisfactory triplet quantum yield (ΦT=52 %), and long‐lived triplet state (τT=492 μs), a record low‐dose photodynamic therapy (PDT)‐augmented immunotherapy was achieved. Abstract Intersystem crossing (ISC) of triplet photosensitizers is a vital process for fundamental photochemistry and photodynamic therapy (PDT). Herein, we report the co‐existence of efficient ISC and long triplet excited lifetime in a heavy atom‐free bodipy helicene molecule. Via theoretical computation and time‐resolved EPR spectroscopy, we confirmed that the ISC of the bodipy results from its twisted molecular structure and reduced symmetry. The twisted bodipy shows intense long wavelength absorption (ϵ=1.76×105 m−1 cm−1 at 630 nm), satisfactory triplet quantum yield (ΦT=52 %), and long‐lived triplet state (τT=492 μs), leading to unprecedented performance as a triplet photosensitizer for PDT. Moreover, nanoparticles constructed with such helical bodipy show efficient PDT‐mediated antitumor immunity amplification with an ultra‐low dose (0.25 μg kg−1), which is several hundred times lower than that of the existing PDT reagents.

Nature of the Arsonium‐Ylide Ph3As=CH2 and a Uranium(IV) Arsonium–Carbene Complex

By John A. Seed, Helen R. Sharpe, Harry J. Futcher, Ashley J. Wooles, Stephen T. Liddle from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

A new route to the classical ylide Ph3As=CH2 resolves previous difficulties in its synthesis and isolation. Its structural authentication, 45 years after it was first made, confirms that the ylide is pyramidal not planar, and it enables the synthesis of a uranium–arsonium–carbene, the first structurally characterised example of an arsonium–carbene complex of any metal. Abstract Treatment of [Ph3EMe][I] with [Na{N(SiMe3)2}] affords the ylides [Ph3E=CH2] (E=As, 1As; P, 1P). For 1As this overcomes prior difficulties in the synthesis of this classical arsonium‐ylide that have historically impeded its wider study. The structure of 1As has now been determined, 45 years after it was first convincingly isolated, and compared to 1P, confirming the long‐proposed hypothesis of increasing pyramidalisation of the ylide‐carbon, highlighting the increasing dominance of E+−C− dipolar resonance form (sp3‐C) over the E=C ene π‐bonded form (sp2‐C), as group 15 is descended. The uranium(IV)–cyclometallate complex [U{N(CH2CH2NSiPri3)2(CH2CH2SiPri2CH(Me)CH2)}] reacts with 1As and 1P by α‐proton abstraction to give [U(TrenTIPS)(CHEPh3)] (TrenTIPS=N(CH2CH2NSiPri3)3; E=As, 2As; P, 2P), where 2As is an unprecedented structurally characterised arsonium‐carbene complex. The short U−C distances and obtuse U‐C‐E angles suggest significant U=C double bond character. A shorter U−C distance is found for 2As than 2P, consistent with increased uranium‐ and reduced pnictonium‐stabilisation of the carbene as group 15 is descended, which is supported by quantum chemical calculations.

Holey Lamellar High‐Entropy Oxide as an Ultra‐High‐Activity Heterogeneous Catalyst for Solvent‐free Aerobic Oxidation of Benzyl Alcohol

By Danyang Feng, Yangbo Dong, Liangliang Zhang, Xin Ge, Wei Zhang, Sheng Dai, Zhen‐An Qiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

A high‐entropy oxide material with mesoporous structure is prepared by an anchoring and merging process. It exhibits ultra‐high catalytic activity for the oxidation of benzyl alcohol. Benzoic acid or benzaldehyde can be selectively optimized as the main product by rational regulating the catalysis parameters. Abstract The development of noble‐metal‐free heterogeneous catalysts is promising for selective oxidation of aromatic alcohols; however, the relatively low conversion of non‐noble metal catalysts under solvent‐free atmospheric conditions hinders their industrial application. Now, a holey lamellar high entropy oxide (HEO) Co0.2Ni0.2Cu0.2Mg0.2Zn0.2O material with mesoporous structure is prepared by an anchoring and merging process. The HEO has ultra‐high catalytic activity for the solvent‐free aerobic oxidation of benzyl alcohol. Up to 98 % conversion can be achieved in only 2 h, to our knowledge, the highest conversion of benzyl alcohol by oxidation to date. By regulating the catalytic reaction parameters, benzoic acid or benzaldehyde can be selectively optimized as the main product. Analytical characterizations and calculations provide a deeper insight into the catalysis mechanism, revealing abundant oxygen vacancies and holey lamellar framework contribute to the ultra‐high catalytic activity.

Size‐Mediated Recurring Spinel Sub‐nanodomains in Li‐ and Mn‐Rich Layered Cathode Materials

By Biwei Xiao, Hanshuo Liu, Ning Chen, Mohammad Norouzi Banis, Haijun Yu, Jianwen Liang, Qian Sun, Tsun‐Kong Sham, Ruying Li, Mei Cai, Gianluigi A. Botton, Xueliang Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

The evolution of transition metals was studied in Li‐ and Mn‐rich layered cathode materials during long‐term cycling. The results reveal that the conversion of layer to spinel phase shows partial reversibility in each cycle on a sub‐nanometer scale depending on the particle size. Abstract Li‐ and Mn‐rich layered oxides are among the most promising cathode materials for Li‐ion batteries with high theoretical energy density. Its practical application is, however, hampered by the capacity and voltage fade after long cycling. Herein, a finite difference method for near‐edge structure (FDMNES) code was combined with in situ X‐ray absorption spectroscopy (XAS) and transmission electron microscopy/electron energy loss spectroscopy (TEM/EELS) to investigate the evolution of transition metals (TMs) in fresh and heavily cycled electrodes. Theoretical modeling reveals a recurring partially reversible LiMn2O4‐like sub‐nanodomain formation/dissolution process during each charge/discharge, which accumulates gradually and accounts for the Mn phase transition. From the modeling of spectra and maps of the valence state over large regions of the cathodes, it was found that the phase change is size‐dependent. After prolonged cycling, the TMs displayed different levels of inactivity.

Synthesis of Honeycomb‐Structured Beryllium Oxide via Graphene Liquid Cells

By Lifen Wang, Lei Liu, Ji Chen, Ali Mohsin, Jung Hwan Yum, Todd W. Hudnall, Christopher W. Bielawski, Tijana Rajh, Xuedong Bai, Shang‐Peng Gao, Gong Gu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Hexagonal, exceptional: In a graphene liquid cell, beryllium oxide can crystallize in a rare sp2‐coordinated, hexagonal BeO polymorph. The thickness of the crystals produced this way is beyond the thermodynamic ultra‐thin limit above which the wurtzite phase is energetically more favorable. Calculations show that the energy barrier of the phase transition is responsible for the observed occurrence of hexagonal layers. Abstract Using high‐resolution transmission electron microscopy and electron energy‐loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet‐chemistry approach. These liquid cells can feature van‐der‐Waals pressures up to 1 GPa, producing a miniaturized high‐pressure container for the crystallization in solution. The thickness of as‐received crystals is beyond the thermodynamic ultra‐thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near‐free‐standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous‐solution approaches of more metal‐oxide semiconductors with exotic phase structures and properties in graphene‐encapsulated confined cells.

Electrocatalysis as the nexus for sustainable renewable energy. The Gordian knot of activity, stability, and selectivity

By Justus Masa, Corina Andronescu, Wolfgang Schuhmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Coupling harnessing of renewable energies with electro­chemical technologies that convert the omnipresent molecules H 2 O, CO 2 and N 2 into chemical energy carriers and chemical feedstocks is at the frontier towards securing a sustainable green energy future. In this minireview, some weaknesses and incoherencies in the current predominant practices of determining electrocatalytic performance that have not only protracted progress towards realizing functional systems but also obstructed atomic and molecular scale insight into important fundamental properties and phenomena to inform rational bottom‐up catalyst design are discussed. We highlight examples of stark discrepancies in material properties and electrocatalytic activity and stability that manifest when materials are tested at conditions of their envisaged deployment as opposed to common laboratory condi­tions and thereby advocate for unified activity‐stability correlations at application relevant conditions and disambiguation of reporting elec­trocatalytic performance by contextualization with respect to funda­mental inquisition or progress towards application.

Light dynamics of retinal disease‐relevant G90D bovine rhodopsin mutant

By Nina Kubatova, Jiafei Mao, Carl Elias Eckert, Krishna Saxena, Santosh L. Gande, Josef Wachtveitl, Clemens Glaubitz, Harald Schwalbe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

The RHO gene encodes the GPCR rhodopsin. Numerous mutations associated with impaired visual cycle have been reported; the G90D mutation leads to a constitutively active mutant form of rhodopsin that causes CSNB disease. We report here on the structure investigation of the retinal configuration and conformation in the binding pocket in the dark and light‐activated state by solution and MAS‐NMR spectroscopy. We find two long‐lived dark states for the G90D mutant with the 11‐cis retinal bound as Schiff base in both populations. Thesecond minor population in the dark state is attributed to a slight shift in conformation of the covalently bound 11‐cis retinal caused by the mutation‐induced distortion on the salt bridge formation in the binding pocket. Time‐resolved UV/VIS spectroscopy monitors the functional dynamics of the G90D mutant rhodopsin for all relevant time scales of the photocycle. The G90D mutant retains its conformational heterogeneity during the photocycle.

Cryogenic OrbiSIMS Localizes Semi‐Volatile Molecules in Biological Tissues

By Clare Newell, Jean-Luc Vorng, James MacRae, Ian Gilmore, Alex Gould from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

OrbiSIMS is a recently developed instrument for label‐free imaging of chemicals with micron spatial resolution and high mass resolution. We report a cryogenic workflow for OrbiSIMS (Cryo‐OrbiSIMS) that improves chemical detection of lipids and other biomolecules in tissues. Cryo‐OrbiSIMS boosts ionization yield and decreases ion‐beam induced fragmentation, greatly improving the detection of biomolecules such as triacylglycerides. It also increases chemical coverage to include molecules with intermediate or high vapor pressures, such as free fatty acids and semi‐volatile organic compounds (SVOCs). We find that Cryo‐OrbiSIMS reveals the hitherto unknown localization patterns of SVOCs with high spatial and chemical resolution in diverse plant, animal and human tissues. We also show that Cryo‐OrbiSIMS can be combined with genetic analysis to identify enzymes regulating SVOC metabolism. Cryo‐OrbiSIMS is applicable to high resolution imaging of a wide variety of non‐volatile and semi‐volatile molecules across many areas of biomedicine.

Grubbs Metathesis Empowered by a Light‐Driven gem‐Hydrogenation of Internal Alkynes

By Alois Fürstner, Tobias Biberger, Raphael J. Zachmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

[(NHC)(cymene)RuCl 2 ] (NHC = N‐heterocyclic carbene) complexes instigate a light‐driven gem ‐hydrogenation of internal alkynes with concomitant formation of discrete Grubbs‐type ruthenium carbene species. This unorthodox reactivity mode is harnessed in form of a “hydrogenative metathesis” reaction, which converts an enyne substrate into a cyclic alkene. The intervention of ruthenium carbenes formed in the actual gem ‐hydrogenation step was proven by the isolation and crystallographic characterization of a rather unusual representative of this series carrying an unconfined alkyl group on a disubstituted carbene center.

Cs[Cl3F10]: A Propeller‐Shaped [Cl3F10]− Anion in a Peculiar A[5]B[5] Structure Type

By Benjamin Scheibe, Antti J. Karttunen, Ulrich Müller, Florian Kraus from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Reaction of CsF with ClF3 leads to Cs[Cl3F10]. It contains a molecular, propeller‐shaped [Cl3F10]− anion with a central µ3‐F atom and three T‐shaped ClF3 molecules coordinated to it. This anion represents the first example of a heteropolyhalide anion of higher ClF3 content than [ClF4]− and is the first Cl‐containing interhalogen species with a µ‐bridging F atom. The chemical bonds to the central µ3‐F atom are highly ionic and quite weak as the bond lengths within the coordinating XF3 units are almost unchanged in comparison to free XF3 molecules. Cs[Cl3F10] crystallizes in a very rarely observed A[5]B[5] structure type, where cations and anions are each pseudohexagonally close packed, and reside, each with coordination number five, in the trigonal bipyramidal voids of the other.

Templated‐assembly of CsPbBr3 perovskite nanocrystals into 2D photonic supercrystals with amplified spontaneous emission

By Lakshminarayana Polavarapu, David Vila-Liarte, Maximilian W. Feil, Aurora Manzi, Juan Luis Garcia-Pomar, He Huang, Markus Döblinger, Luis M Liz-Marzán, Jochen Feldmann, Agustín Mihi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Perovskite nanocrystals (NCs) have revolutionized optoelectronic devices because of their versatile optical properties. However, controlling and extending these functionalities often requires a light management strategy involving additional processing steps. Here, we introduce a simple approach to shape perovskite nanocrystals (NC) into photonic architectures that provide light management by directly shaping the active material. Pre‐patterned polydimethylsiloxane (PDMS) templates are used for the template‐induced self‐assembly of 10 nm CsPbBr 3 perovskite NC colloids into large area (1 cm 2 ) 2D photonic crystals with tunable lattice spacing, ranging from 400 nm up to several microns. The photonic crystal arrangement facilitates efficient light coupling to the nanocrystal layer, thereby increasing the electric field intensity within the perovskite film. As a result, CsPbBr 3 2D photonic crystals show amplified spontaneous emission (ASE) under lower optical excitation fluences in the near‐IR, in contrast to equivalent flat NC films prepared using the same colloidal ink. This is attributed to the enhanced multi‐photon absorption caused by light trapping in the photonic crystal.

Charge Reversion Simultaneously Enhances Tumor Accumulation and Cell Uptake of Layered Double Hydroxide Nanohybrids for Effective Imaging and Therapy

By Jianping Liu, Yilun Wu, Changkui Fu, Bei Li, Li Li, Run Zhang, Tiefeng Xu, Zhi Ping Xu from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

A charge‐reversible polymer‐modified layered double hydroxide (LDH) nanohybrid is devised to significantly enhance tumor accumulation and increase cancer cell uptake in precision nanomedicine. The LDH nanohybrids accumulated at the tumor site induce a strong synergistic effect on melanoma growth for combined RNAi and photothermal therapies. Abstract Nanotheranostics have been actively sought in precision nanomedicine in recent years. However, insufficient tumor accumulation and limited cell uptake often impede the nanotheranostic efficacy. Herein, pH‐sensitive charge‐reversible polymer‐coated layered double hydroxide (LDH) nanohybrids are devised to possess long circulation in blood but reserve surface charges in the weakly acidic tumor tissue to re‐expose therapeutic LDH nanoparticles for enhanced tumor accumulation and cell uptake. In vitro experimental data demonstrate that charge‐reversible nanohybrids mitigate the cell uptake in physiological conditions (pH 7.4), but remarkably facilitate internalization by tumor cells after charge reversion in the weakly acidic environment (pH 6.8). More significantly, about 6.0% of injected charge‐reversible nanohybrids accumulate in the tumor tissue at 24 h post injection, far higher than the average accumulation (0.7%) reported elsewhere for nanoparticles. This high tumor accumulation clearly shows the tumor tissues in T1‐weighted magnetic resonance imaging. As a consequence, >95% inhibition of tumor growth in the B16F0‐bearing mouse model is achieved via only one treatment combining RNAi and photothermal therapy under very mild irradiation (808 nm laser, 0.3 W cm−2 for 180 s). The current research thus demonstrates a new strategy to functionalize nanoparticles and simultaneously enhance their tumor accumulation and cell internalization for effective cancer theranostics.

How local structural modulations in zeolite crystals have been studied by Electron Microscopy

By Qing Zhang, Alvaro Mayoral, Junyan Li, Juanfang Ruan, Viveka Alfredsson, Yanhang Ma, Jihong Yu, Osamu Terasaki from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Zeolites are widely used in catalysis, gas separation, ion exchange, etc. due to their superior physicochemical properties, which are closely related to specific features of their framework structures. Although more than two hundred different framework types have been recognized through the years, it is of great interest to explore from a crystallographic perspective, the atomic positions, surface terminations, pore connectivity and structural defects that deviate from the ideal framework structures, namely local structural modulation. In this article, we review different types of local modulations in zeolite frameworks using various techniques, especially electron microscopy (EM). The most recent advances in resolving structural information at the atomic level with aberration corrected EM are also presented, commencing a new era to gain atomic structural information, not only for all tetrahedral atoms including point vacancies in framework but also for extra‐framework cations and surface terminations.

Nanospace‐Confinement Synthesis: Designing High‐Energy Anode Materials toward Ultrastable Lithium‐Ion Batteries

By Hao Jiang, Haoxuan Zhang, Ling Chen, Yanjie Hu, Chunzhong Li from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

Nanospace‐confined synthesis provides a proactive strategy to build novel multiscaled nanomaterials as high‐energy anode materials for lithium ion batteries with controllable internal void space for circumventing the intrinsic volume effects caused by the conversion and alloying mechanism during the charge/discharge process, which can guide the synthesis of customizable electrode materials in the applications of electrochemical energy storage. Abstract Exploiting high‐capacity and durable electrode materials is pivotal to developing lithium‐ion batteries (LIBs) and their applications. Multiscaled nanomaterials have been demonstrated to efficiently couple the advantages of each component on different scales in energy storage fields. However, the precise control of the microstructure remains a great challenge for maximizing their contributions. Nanospace‐confined synthesis provides a proactive strategy to build novel multiscaled nanomaterials with controllable internal void space for circumventing the intrinsic volume effects in the charge/discharge process. Herein, the rational design and synthesis of multiscaled high‐capacity anode materials are mainly summarized according to their electrochemical mechanisms by choosing 1D channel, 2D interlayer, and 3D space as representative confinement reaction environments. The structure–performance relationships are clarified with the assistance of quantitative calculations, molecular simulations, and so forth. Finally, future potentials and challenges of such a synthesis tactic in designing high‐performance electrode materials for next‐generation secondary batteries are outlooked.

Synthetic CXCR4 Antagonistic Peptide Assembling with Nanoscaled Micelles Combat Acute Myeloid Leukemia

By Jie Meng, Yangyang Ge, Haiyan Xing, Hui Wei, Shilin Xu, Jian Liu, Doudou Yan, Tao Wen, Min Wang, Xiaocui Fang, Lilusi Ma, Yanlian Yang, Chen Wang, Jianxiang Wang, Haiyan Xu from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

The CXCR4/CXCL12 axis is highly associated with drug resistance and relapse of acute myeloid leukemia. Synthetic CXCR4 antagonistic peptide assembling with nanomicelles effectively inhibits CXCL12‐mediated leukemic cells homing and engraftment as well as induces apoptosis and differentiation in the refractory acute myeloid leukemia (AML) mice model, prolongs the AML mice survival with safety, and long half‐life in blood. Abstract Acute myeloid leukemia (AML) is the most common adult acute leukemia with very low survival rate due to drug resistance and high relapse rate. The C‐X‐C chemokine receptor 4 (CXCR4) is highly expressed by AML cells, actively mediating chemoresistance and reoccurrence. Herein, a chemically synthesized CXCR4 antagonistic peptide E5 is fabricated to micelle formulation (M‐E5) and applied to refractory AML mice, and its therapeutic effects and pharmacokinetics are investigated. Results show that M‐E5 can effectively block the surface CXCR4 in leukemic cells separated from bone marrow (BM) and spleen, and inhibit the C‐X‐C chemokine ligand 12‐mediated migration. Subcutaneous administration of M‐E5 significantly inhibits the engraftment of leukemic cells in spleen and BM, and mobilizes residue leukemic cells into peripheral blood, reducing organs’ burden and significantly prolonging the survival of AML mice. M‐E5 can also increase the efficacy of combining regime of homoharringtonine and doxorubicin. Ribonucleic acid sequencing demonstrates that the therapeutic effect is contributed by inhibiting proliferation and enhancing apoptosis and differentiation, all related to the CXCR4 signaling blockade. M‐E5 reaches the concentration peak at 2 h after administration with a half‐life of 14.5 h in blood. In conclusion, M‐E5 is a novel promising therapeutic candidate for refractory AML treatment.

3D Two‐Photon Microprinting of Nanoporous Architectures

By Frederik Mayer, Daniel Ryklin, Irene Wacker, Ronald Curticean, Martin Čalkovský, Andreas Niemeyer, Zheqin Dong, Pavel A. Levkin, Dagmar Gerthsen, Rasmus R. Schröder, Martin Wegener from Wiley: Advanced Materials: Table of Contents. Published on Jun 30, 2020.

Combining self‐assembly on the nanoscale and two‐photon 3D laser printing on the micrometer scale, complex nanoporous 3D architectures are achieved. The underlying photoresist relies on polymerization‐induced phase separation between a polymer and a nonpolymerizable phase. Control of the porosity by the printing parameters is demonstrated by sample characterization based on ultramicrotomy, scanning electron microscopy, and optical transmission. Abstract A photoresist system for 3D two‐photon microprinting is presented, which enables the printing of inherently nanoporous structures with mean pore sizes around 50 nm by means of self‐organization on the nanoscale. A phase separation between polymerizable and chemically inert photoresist components leads to the formation of 3D co‐continuous structures. Subsequent washing‐out of the unpolymerized phase reveals the porous polymer structures. To characterize the volume properties of the printed structures, scanning electron microscopy images are recorded from ultramicrotome sections. In addition, the light‐scattering properties of the 3D‐printed material are analyzed. By adjusting the printing parameters, the porosity can be controlled during 3D printing. As an application example, a functioning miniaturized Ulbricht light‐collection sphere is 3D printed and tested.

Tunable Dual‐Emission in Monodispersed Sb3+/Mn2+ Codoped Cs2NaInCl6 Perovskite Nanocrystals through an Energy Transfer Process

By Xingyi Liu, Xi Xu, Ben Li, Lanlan Yang, Qi Li, Hong Jiang, Dongsheng Xu from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

By antimony doping, strong blue‐emission of Cs2NaInCl6 is obtained with a high photoluminescence quantum efficiency of 84%. Further, the Sb/Mn codoped Cs2NaInCl6 nanocrystals are synthesized by the hot‐injection method, showing a tunable dual‐emission. The studies of optical properties and dynamics reveal that an energy transfer process can occur between the self‐trapped excitons and Mn2+‐dopants. Abstract Double halide perovskites are a class of promising semiconductors applied in photocatalysis, photovoltaic devices, and emitters to replace lead halide perovskites, owing to their nontoxicity and chemical stability. However, most double perovskites always exhibit low photoluminescence quantum efficiency (PLQE) due to the indirect bandgap structure or parity‐forbidden transition problem, limiting their further applications. Herein, the self‐trapped excitons emission of Cs2NaInCl6 by Sb‐doping, showing a blue emission with high PLQE of 84%, is improved. Further, Sb/Mn codoped Cs2NaInCl6 nanocrystals are successfully synthesized by the hot‐injection method, showing a tunable dual‐emission covering the white‐light spectrum. The studies of PL properties and dynamics reveal that an energy transfer process can occur between the self‐trapped excitons and dopants (Mn2+). The work provides a new perspective to design novel lead‐free double perovskites for realizing a unique white‐light emission.

Polarized Light‐Emitting Diodes Based on Anisotropic Excitons in Few‐Layer ReS2

By Junyong Wang, Yong Justin Zhou, Du Xiang, Shiuan Jun Ng, Kenji Watanabe, Takashi Taniguchi, Goki Eda from Wiley: Advanced Materials: Table of Contents. Published on Jun 30, 2020.

Linearly polarized light‐emitting diodes are demonstrated using few‐layer ReS2, a 2D semiconductor with reduced in‐plane symmetry. Two excitonic electroluminescence peaks exhibiting high degrees of linear polarization of ≈80% are observed in near‐infrared frequencies. Hot hole injection through a hBN tunneling layer is shown to be key to the activation of hot exciton emission. Abstract An on‐chip polarized light source is desirable in signal processing, optical communication, and display applications. Layered semiconductors with reduced in‐plane symmetry have inherent anisotropic excitons that are attractive candidates as polarized dipole emitters. Herein, the demonstration of polarized light‐emitting diode based on anisotropic excitons in few‐layer ReS2, a 2D semiconductor with excitonic transition energy of 1.5–1.6 eV, is reported. The light‐emitting device is based on minority carrier (hole) injection into n‐type ReS2 through a hexagonal boron nitride (hBN) tunnel barrier in a metal–insulator–semiconductor (MIS) van der Waals heterostack. Two distinct emission peaks from excitons are observed at near‐infrared wavelength regime from few‐layer ReS2. The emissions exhibit a degree of polarization of 80% reflecting the nearly 1D nature of excitons in ReS2.

A Self‐Powered Angle Sensor at Nanoradian‐Resolution for Robotic Arms and Personalized Medicare

By Ziming Wang, Jie An, Jinhui Nie, Jianjun Luo, Jiajia Shao, Tao Jiang, Baodong Chen, Wei Tang, Zhong Lin Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 30, 2020.

Sensing angular information via the most energy‐efficient method is vitally important. After systematic optimization, a triboelectric self‐powered angle sensor provides high‐quality sensing signals while itself needing neither electric power supply nor a signal‐amplification module. In addition, its feasibility is proved by practical application in a robotic arm, precisely duplicating traditional Chinese calligraphy as well as medical brace monitoring joint motions. Abstract As the dominant component for precise motion measurement, angle sensors play a vital role in robotics, machine control, and personalized rehabilitation. Various forms of angle sensors have been developed and optimized over the past decades, but none of them would function without an electric power. Here, a highly sensitive triboelectric self‐powered angle sensor (SPAS) exhibiting the highest resolution (2.03 nano‐radian) after a comprehensive optimization is reported. In addition, the SPAS holds merits of light weight and thin thickness, which enables its extensive integrated applications with minimized energy consumption: a palletizing robotic arm equipped with the SPAS can precisely reproduce traditional Chinese calligraphy via angular data it collects. In addition, the SPAS can be assembled in a medicare brace to record the flexion/extension of joints, which may benefit personalized orthopedic recuperation. The SPAS paves a new approach for applications in the emerging fields of robotics, sensing, personalized medicare, and artificial intelligence.

Fast and long‐lasting Fe(Ⅲ) reduction by boron toward green and accelerated Fenton chemistry

By Peng Zhou, Wei Ren, Gang Nie, Xiaojie Li, Xiaoguang Duan, Yongli Zhang, Shaobin Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Generation of hydroxyl radicals in the Fenton system (Fe(II)/H 2 O 2 ) is seriously limited by the sluggish kinetics of Fe(III) reduction and fast Fe(III) precipitation. For the first time, we discover that boron crystals (C‐Boron) remarkably accelerate the Fe(III)/Fe(II) circulation in Fenton‐like systems (C‐Boron/Fe(III)/H 2 O 2 ) to produce a myriad of hydroxyl radicals with excellent efficiencies in oxidative degradation of various pollutants. The surface B‐B bonds and interfacial suboxide boron in the surface B 12 icosahedra are the active sites to donate electrons to promote fast Fe(III) reduction to Fe(II) and further enhance hydroxyl radical production via the Fenton chemistry. The C‐Boron/Fe(III)/H 2 O 2 system outperforms the benchmark Fenton (Fe(II)/H 2 O 2 ) and Fe(III)‐based sulfate radical systems. The reactivity and stability of crystalline boron is much higher than the popular molecular reducing agents, nanocarbons, and other metal/metal‐free nanomaterials. Therefore, the discovery opens up a new avenue to leveraging metal‐free boron for green oxidation and fast environmental decontamination.

Cell Behavior within Nanogrooved Sandwich Culture Systems

By Isabel M. Bjørge, Manuel Salmeron‐Sanchez, Clara R. Correia, João F. Mano from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

Nanogrooved sandwich‐culture systems with relative orientation to assess cell response while stimulating cell dorsal and ventral receptors, featuring single and double‐seeded substrates. Cells acquire the orientation of the substrate on which they are initially seeded, independently of the orientation or existence of preseeded cells on opposing substrates, whereas cell elongation is effectively conditioned within sandwich‐culture. Abstract Grooved topography and inherent cell contact guidance has shown promising results regarding cell proliferation, morphology, and lineage‐specific differentiation. Yet these approaches are limited to 2D applications. Sandwich‐culture conditions are developed to bridge the gap between 2D and 3D culture, enabling both ventral and dorsal cell surface stimulation. The effect of grooved surface topography is accessed on cell orientation and elongation in a highly controlled manner, with simultaneous and independent stimuli on two cell sides. Nanogrooved and non‐nanogrooved substrates are assembled into quasi‐3D systems with variable relative orientations. A plethora of sandwich‐culture conditions are created by seeding cells on lower, upper, or both substrates. Software image analysis demonstrates that F‐actin of cells acquires the orientation of the substrate on which cells are initially seeded, independently from the orientation of the second top substrate. Contrasting cell morphologies are observed, with a higher elongation for nanogrooved 2D substrates than nanogrooved sandwich‐culture conditions. Correlated with an increased pFAK activity and vinculin staining for sandwich‐culture conditions, these results point to an enhanced cell surface stimulation versus control conditions. The pivotal role of initial cell‐biomaterial contact on cellular alignment is highlighted, providing important insights for tissue engineering strategies aiming to guide cellular response through mechanotransduction approaches.

Lancing Drug Reservoirs into Subcutaneous Fat to Combat Obesity and Associated Metabolic Diseases

By Aung Than, Phan Khanh Duong, Ping Zan, Junjie Liu, Melvin Khee‐Shing Leow, Peng Chen from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

A self‐administrable and minimally invasive transdermal drug delivery strategy is developed using ultrathin, core‐shelled, polymeric micro‐lances (MLs). The therapeutic MLs can be readily fabricated by a thermal pressing molding method and totally implanted into subcutaneous fat by lancing through the skin. The potential of such an ML approach for long‐term home‐based treatment of obesity and associated metabolic diseases is demonstrated. Abstract Obesity is a serious epidemic health problem that can cause many other diseases including type 2 diabetes and cardiovascular diseases. Current approaches to combat obesity suffer from low effectiveness and adverse side effects. Here, a new self‐administrable and minimally invasive transdermal drug delivery strategy for home‐based long‐term treatment of obesity and other diseases is developed. Specifically, ultrathin, core‐shelled, and lance‐shaped polymeric drug reservoirs (micro‐lances [MLs]) are readily fabricated by a thermal pressing molding method and totally implanted into subcutaneous fat by lancing through the skin. Using a diet‐induced obese mouse model, it is shown that the development of obesity and associated metabolic disorders is effectively inhibited by applying therapeutic core‐shelled MLs once every 2 weeks. The outstanding therapeutic effects are attributable to highly localized and biphasic drug release, as well as combination therapy based on browning transformation of white fat and enhanced insulin sensitivity.

Boosting the Cycling Stability of Aqueous Flexible Zn Batteries via F Doping in Nickel–Cobalt Carbonate Hydroxide Cathode

By Xuejin Li, Yongchao Tang, Jiaxiong Zhu, Haiming Lv, Lianming Zhao, Wenlong Wang, Chunyi Zhi, Hongfei Li from Wiley: Small: Table of Contents. Published on Jun 30, 2020.

A F‐doping strategy is proposed to enhance the long‐term cycling stability of nickel–cobalt carbonate hydroxide (NiCo–CH) cathode for Zn batteries. Benefiting from the extremely high electronegativity, the phase and morphology stabilities as well as the electrical conductivity of NiCo–CH are remarkably enhanced by F incorporation. As a result, the capacity of the as‐assembled battery decays less than 10% even after 10 000 cycles. Abstract Cathodes of rechargeable Zn batteries typically face the issues of irreversible phase transformation, structure collapse, and volume expansion during repeated charge/discharge cycles, which result in an increased transfer resistance and poor long‐term cycling stability. Herein, a facile F doping strategy is developed to boost the cycling stability of nickel cobalt carbonate hydroxide (NiCo–CH) cathode. Benefiting from the extremely high electronegativity, the phase and morphology stabilities as well as the electrical conductivity of NiCo–CH are remarkably enhanced by F incorporation (NiCo–CH–F). Phase interface and amorphous microdomains are also introduced, which are favorable for the electrochemical performance of cathode. Benefiting from these features, NiCo–CH–F delivers a high capacity (245 mA h g−1), excellent rate capability (64% retention at 8 A g−1), and outstanding cycling stability (maintains 90% after 10 000 cycles). Moreover, the quasi‐solid‐state battery also manifests superior cycling stability (maintains 90% after 7200 cycles) and desirable flexibility. This work offers a general strategy to boost the cycling stability of cathode materials for aqueous Zn batteries.

Stereoselective On‐Surface Cyclodehydrofluorization of a Tetraphenylporphyrin and Homochiral Self‐Assembly

By Karl-Heinz Ernst, Hui Chen, Lei Tao, Dongfei Wang, Zhuo-Yan Wu, Jun-Long Zhang, Song Gao, Wende Xiao, Shixuan Du, Hong-Jun Gao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

The thermally induced cyclodehydrofluorization of irontetrakis(pentafluorophenyl)porphyrin proceeds highly stereo‐selectively into a prochiral product on a gold surface in ultrahigh vacuum, whereas dehydrocyclization of the respective irontetrakisphenylporphyrin does not show such selectivity. Stereoselectivity is predominantly observed for closely packed layers, which is an indication of intermolecular cooperativity and steric constrain induced by adjacent species. Density functional theory identifies intermolecular packing constrain as origin of such selectivity during reaction. Scanning tunneling microscopy reveals enantiopure two‐dimensional self‐assembly of the reaction product into a conglomerate of mirror domains. On‐surface two‐dimensional topochemistry, as reported here, may open new routes to stereoselective syntheses.

A Self‐Consistent Model for Sorption and Transport in Polyimide‐Derived Carbon Molecular Sieve Gas Separation Membranes

By Oishi Sanyal, Samuel S. Hays, Nicholas E. León, Yoseph A. Guta, Arun K. Itta, Ryan P. Lively, William J. Koros from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Demand for energy‐efficient gas separations exists across many industrial processes, and membranes can aid in meeting this demand. Carbon molecular sieve (CMS) membranes show exceptional separation performance and scalable processing attributes attractive for important, similar‐sized gas pairs. Herein, we outline a mathematical and physical framework to understand these attributes. This framework shares features with dual‐mode transport theory for glassy polymers; however, physical connections to CMS model parameters differ from glassy polymer cases. We present evidence in CMS membranes for a large volume fraction of microporous domains characterized by Langmuir sorption in local equilibrium with a minority continuous phase described by Henry’s law sorption. Using this framework, expressions are provided to relate measurable parameters for sorption and transport in CMS materials. We also outline a mechanism for formation of these environments and suggest future model refinements.

Surface oxide‐rich activation layer (SOAL) on Ni2Mo3N for rapid and durable oxygen evolution reaction

By Yao Yuan, Samira Adimi, Xuyun Guo, Tiju Thomas, Ye Zhu, Haichuan Guo, G. Sudha Priyanga, Pilsun Yoo, Jiacheng Wang, Jian Chen, Peilin Liao, J Paul Attfield, Minghui Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

The oxygen evolution reaction (OER) is key to renewable energy technologies such as water electrolysis and metal‐air batteries. However, the multiple steps associated with proton‐coupled electron transfer result in sluggish OER kinetics and catalysts are required. Here we demonstrate that a novel nitride, Ni2Mo3N, is a highly active OER catalyst that outperforms the benchmark material RuO2 . Ni2Mo3N exhibits a current density of 10 mA cm‐2 at a nominal overpotential of 270 mV in 0.1 M KOH with outstanding catalytic cyclability and durability. Structural characterization and computational studies reveal that the excellent activity stems from formation of a surface oxide‐rich activation layer (SOAL). Secondary Mo atoms on the surface act as electron pumps that stabilize oxygen‐containing species and facilitate continuity of the reactions. This discovery will stimulate further development of ternary nitrides with oxide surface layers as efficient OER catalysts for electrochemical energy devices.

Can an elusive Pt(III) oxidation state be exposed in an isolated complex?

By Simonetta Fornarini, Davide Corinti, Gilles Frison, Barbara Chiavarino, Elisabetta Gabano, Domenico Osella, Maria Elisa Crestoni from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Platinum(IV) complexes are extensively studied for their activity against cancer cells as potential substitutes for the widely used platinum(II) drugs. Pt(IV) complexes are kinetically inert and need to be reduced to Pt(II) species to play their pharmacological action, thus acting as prodrugs. The mechanism of the reduction step inside the cell is however still largely unknown. Gas‐phase activation of deprotonated platinum(IV) prodrugs was found to generate products in which platinum has a formal +3 oxidation state. IR multiple photon dissociation spectroscopy is thus used to obtain structural information helping to define the nature of both the platinum atom and the ligands. In particular, comparison of calculations at DFT, MP2 and CCSD levels with experimental results demonstrates that the localization of the radical is about equally shared between the d xz orbital of platinum and the p z  of nitrogen on the amino group, the latter acting as a non‐innocent ligand.

σ‐Aromaticity‐Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4– and [Cd6Ge16]4–

By Hong-Lei Xu, Ivan Popov, Nikolay Tkachenko, Zi-Chuan Wang, Alvaro Muñoz-Castro, Alexander I. Boldyrev, Zhong-Ming Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

In this work, the largest heterometallic supertetrahedral clusters, [Zn6Ge16]4– and [Cd6Ge16]4–, were directly self‐assembled through highly‐charged [Ge4]4– units and transition metal cations, in which 3‐center‐2‐electron σ bonding in Ge2Zn or Ge2Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time‐dependent HRESI‐MS spectra show that the larger clusters grow from smaller components with a single [Ge4]4– and ZnMes2 units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M6Ge16]4– (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.

Pseudo‐membrane jackets: Two‐dimensional coordination polymers achieving visible phase separation in cell membrane

By Ryo Ohtani, Kenichi Kawano, Masanao Kinoshita, Saeko Yanaka, Hikaru Watanabe, Kenji Hirai, Shiroh Futaki, Nobuaki Matsumori, Hiroshi Uji-i, Masaaki Ohba, Koichi Kato, Shinya Hayami from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Cell membranes contain lateral systems that consist of various lipid compositions and actin cytoskeleton, providing two‐dimensional (2D) platforms for chemical reactions. However, such complex 2D environments have not yet been used as a synthetic platform for artificial 2D nanomaterials. Herein, we demonstrate the direct synthesis of 2D coordination polymers (CPs) at the liquid−cell interface of the plasma membrane of living cells. The coordination‐driven self‐assembly of networking metal complex lipids produces cyanide‐bridged CP layers with metal ions, enabling ‘pseudo‐membrane jackets’ that produce long‐lived micro‐domains with a size of 1–5 μm. The resultant artificial and visible phase separation systems remain stable even in the absence of actin skeletons in cells. Moreover, the jackets achieved the enhancement of cellular calcium response to ATP. This confirms that the artificial nanomaterials formed via moderate coordinative intermolecular interactions create a 2D scaffold on complex cell membrane environments, thereby providing a unique tool for the chemical control of cell functions.

Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting

By Ralf B. Wehrspohn, Haojie Zhang, Dirk J. Hagen, Xiaopeng Li, Andreas Graff, Frank Heyroth, Bodo Fuhrmann, Ilya Kostanovskiy, Stefan L. Schweizer, Francesco Caddeo, A. Wouter Maijenburg, Stuart Parkin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Transition‐metal phosphides (TMP) prepared by atomic layer deposition (ALD) is reported for the first time. Ultrathin Co‐P films were deposited by using PH 3 plasma as the phosphorus source and H 2 plasma as an extra etching step to remove excess P in the growing films. The optimized ALD process followed the self‐limited layer‐by‐layer growth behavior, and the deposited Co‐P films were highly pure, smooth, and well‐crystallized. The Co‐P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction activities than similar Co‐P films prepared by the traditional post‐phosphorization method. Moreover, the deposition of ultrathin Co‐P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three‐dimensional (3D) architectures.

Tighter Confinement Increases Selectivity of D‐Glucose Isomerization Toward L‐Sorbose in Titanium Zeolites

By Michael J. Cordon, Juan Carlos Vega-Vila, Alyssa Casper, Zige Huang, Rajamani Gounder from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Aqueous‐phase isomerization of D‐glucose to D‐fructose and L‐sorbose are catalyzed in parallel by Lewis acidic Ti sites in siliceous frameworks. Glucose isomerization rates (per Ti, 373 K) are undetectable when Ti sites are confined within mesoporous voids (Ti‐MCM‐41, TiO2 ‐SiO2) and increase to detectable values when Ti sites are confined within the smaller twelve‐membered ring (12‐MR) micropores of Ti‐Beta. Isomerization rates decrease to lower values (by ~20×) with further decreases in micropore size as Ti sites are confined within 10‐MR pores (Ti‐MFI, Ti‐CON), likely because of intrapore reactant diffusion restrictions, and reach undetectable values within the 8‐MR pores of Ti‐CHA as size exclusion prevents glucose from accessing active sites. Remarkably, the selectivity toward L‐sorbose over D‐fructose increases systematically as spatial constraints around Ti sites become tighter, and is >10 on Ti‐MFI. These findings demonstrate the marked influence of confinement around Ti active sites on the selectivity between parallel stereoselective sugar isomerization pathways.

Revealing Interfacial Evolution of Lithium Dendrite and Its Solid Electrolyte Interphase Shell in Quasi‐Solid‐State Lithium Batteries

By Yang Shi, Jing Wan, Gui-Xian Liu, Tong-Tong Zuo, Yue-Xian Song, Bing Liu, Yu-Guo Guo, Rui Wen, Li-Jun Wan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Unstable electrode/solid‐state electrolyte interface and internal Li dendrite penetration hamper the widespread application of the solid‐state Li metal batteries (SSLMBs), which requires operando techniques to accurately disclose the underlying mechanisms. Herein, in situ optical microscopy insights into the Li plating/stripping processes in a gel polymer electrolyte reveal the corresponding dynamic evolution. Uniform Li deposits evolve into moss‐like and branch‐shaped Li dendrites with the increasing current density. Remarkably, the on‐site‐formed solid electrolyte interphase (SEI) shell on the Li dendrite is distinctly captured after Li stripping. Quantitative analyses additionally explore the elevated physical and chemical properties, and the favourable local ionic conductivity of SEI shell. Inducing on‐site‐formed SEI shell with enhanced modulus to wrap the Li precipitation densely and uniformly, can effectually regulate the dendrite‐free behaviors. An in‐depth comprehension of the Li dendrite evolution and its functional SEI shell will further yield more significant information for fundamental studies and prospective optimization of SSLMBs.

Lasso Proteins: Modular Design, Cellular Synthesis and Topological Transformation

By Yajie Liu, Wen-Hao Wu, Sumin Hong, Jing Fang, Fan Zhang, Geng-Xin Liu, Jongcheol Seo, Wenbin Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Entangled proteins have attracted significant research interest. Herein, we report the first rationally designed lasso proteins, or protein [1]rotaxanes, by using p53dim entwined dimer for intramolecular entanglement and SpyTag‐SpyCatcher reaction for side‐chain ring closure. The lasso structures were proven by evidence from proteolytic digestion, mutation, NMR spectrometry and controlled ligation. Their dynamic properties were probed by experiments such as end‐capping, proteolytic digestion, and heating/cooling. As a versatile topological intermediate, lasso proteins could be converted to rotaxanes, heterocatenanes, and “slide‐ring” networks. Being entirely genetically encoded, this robust and modular lasso protein motif is a valuable addition to the topological protein repertoire and promising candidate for protein‐based biomaterials.

Photo‐excited oxygen reduction and oxygen evolution reactions enabling a high‐performance Zn‐air battery

By Dongfeng Du, Shuo Zhao, Zhuo Zhu, Fujun Li, Jun Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Harvesting solar energy in battery systems is pivotal for a sustainable society and faced with challenges. Herein, a photo‐involved Zn‐air battery is constructed with two cathodes of poly(1,4‐di(2‐thienyl))benzene (PDTB) and TiO 2  grown on carbon papers to sandwich a Zn anode. The PDTB cathode is illuminated in a discharging process, where photoelectrons are excited into the conduction band of PDTB to promote oxygen reduction reaction (ORR) and raise the output voltage. In a reverse process, holes in the valence band of the illuminated TiO 2 cathode are driven for oxygen evolution reaction (OER) by an applied voltage. A record‐high discharge voltage of 1.90 V and an unprecedented low charge voltage of 0.59 V are achieved in the photo‐involved Zn‐air battery, regardless of the equilibrium voltage. This work offers an innovative pathway for photo‐energy utilization in rechargeable batteries.

Light/Electricity Energy Conversion and Storage for a Hierarchical Porous In2S3@CNT/SS Cathode towards a Flexible Li‐CO2 Battery

By De‐Hui Guan, Xiao‐Xue Wang, Ma‐Lin Li, Fei Li, Li‐Jun Zheng, Xiao‐Lei Huang, Ji‐Jing Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Battery life on Mars: A photoinduced flexible Li‐CO2 battery with hierarchical, porous, and free‐standing In2S3@CNT/SS as a bifunctional photoelectrode to accelerate both CO2 reduction and evolution is presented. The Li‐CO2 battery achieved a record‐high discharge voltage of 3.14 V (thermodynamic limit: 2.80 V), and an ultra‐low charge voltage of 3.20 V, and a roundtrip efficiency of 98.1 %. Abstract A photoinduced flexible Li‐CO2 battery with well‐designed, hierarchical porous, and free‐standing In2S3@CNT/SS (ICS) as a bifunctional photoelectrode to accelerate both the CO2 reduction and evolution reactions (CDRR and CDER) is presented. The photoinduced Li‐CO2 battery achieved a record‐high discharge voltage of 3.14 V, surpassing the thermodynamic limit of 2.80 V, and an ultra‐low charge voltage of 3.20 V, achieving a round trip efficiency of 98.1 %, which is the highest value ever reported (

Synthesis of Au‐Metal Oxide Core‐Satellite Nanostructure for In Situ SERS Study of CuO‐Catalyzed Photooxidation

By Kaifu Zhang, Ling Yang, Yanfang Hu, Chenghao Fan, Yaran Zhao, Lu Bai, Yonglong Li, Faxing Shi, Jun Liu, Wei Xie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

This work reports on an assembling‐calcining method for preparing Au‐metal oxide core‐satellite nanostructure, which enable surface‐enhanced Raman spectroscopic detection of chemical reactions on metal oxide nanoparticles. By using the nanostructure, we study the photooxidation of Si‐H catalyzed by CuO nanoparticles. As evidenced by the in situ spectroscopic results, oxygen vacancies of CuO are found to be very active sites for oxygen activation, and hydroxide radicals (*OH) adsorbed at the catalytic sites are likely to be the reactive intermediates that trigger the conversion from silanes to the corresponding silanols. According to our finding, oxygen vacancy‐rich CuO catalysts are confirmed to be of both high activity and selectivity in photooxidation of various silanes.

Spatial and Kinetic Regulation of Sulfur Electrochemistry on Semi‐Immobilized Redox Mediators in Working Batteries

By Jin Xie, Hong-Jie Peng, Yun-Wei Song, Bo-Quan Li, Ye Xiao, Meng Zhao, Hong Yuan, Jia-Qi Huang, Qiang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

The adoption of redox mediators (RMs) is regarded as an effective strategy to enhance reaction kinetics of multi‐electron sulfur electrochemistry. However, the soluble small‐molecule RMs usually aggravate the internal shuttle and thus further reduce the battery efficiency and cyclability. In this contribution, a semi‐immobilization strategy is proposed for RM design to effectively regulate the sulfur electrochemistry while circumvent the inherent shuttle issue in a working battery. Small imide molecules as the model RMs were co‐polymerized with moderate‐chained polyether, rendering a semi‐immobilized RM (PIPE) that is spatially restrained yet kinetically active. A small amount of PIPE (5% in cathode) extended the cyclability of sulfur cathode from 37 to 190 cycles with 80% capacity retention at 0.5 C. The semi‐immobilization strategy not only fills up the understanding of RM‐assisted sulfur electrochemistry in alkali metal batteries, but also enlightens the chemical design of active additives for advanced electrochemical energy storage devices.

Photocatalytic Vicinal Aminopyridylation of Methyl Ketones by a Double Umpolung Strategy

By Honggu Im, Wonjun Choi, Sungwoo Hong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

A photocatalytic double umpolung strategy for the vicinal aminopyridylation of ketones was developed using pyridinium N–N ylides. The inversion of the polarity of the pyridinium N–N ylides by single‐electron oxidation successfully enables radical‐mediated 1,3‐dipolar cycloadditions with enolsilanes formed in situ from ketones, followed by homolytic cleavage of the N–N bond. Intriguingly, the nucleophilic amino and electrophilic pyridyl groups in the ylides can be installed at the nucleophilic α‐position and electrophilic carbonyl carbon, respectively, which are typically inaccessible by their innate polarity‐driven reactivity. This method accommodates a broad scope, and the utility was further demonstrated by the late‐stage functionalization of complex biorelevant molecules. Moreover, the strategy can be successfully applied to enamides.

Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation

By Jie Zhu, Ryota Osuga, Ryo Ishikawa, Naoya Shibata, Yuichi Ikuhara, Junko N. Kondo, Masaru Ogura, Jihong Yu, Toru Wakihara, Zhendong Liu, Tatsuya Okubo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Encapsulating metal nanoclusters into zeolites enables a synergistic effect that combines superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy toward overcoming the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize with the rapid formation of nanoclusters. Such concept was proven by confining Pt and Sn nanoclusters into a ZSM‐5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn‐ZSM‐5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene, which further verified the successful encapsulation of metal clusters in zeolite. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.

A Yolk−Shell Structured FePO4 Cathode for High‐Rate and Long‐Cycling Sodium‐Ion Batteries

By Xiaosi Zhou, Zhuangzhuang Zhang, Yichen Du, Qin-Chao Wang, Jingyi Xu, Yong-Ning Zhou, Jianchun Bao, Jian Shen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 30, 2020.

Amorphous iron phosphate (FePO 4 ) has attracted enormous attention as a promising cathode material for sodium‐ion batteries (SIBs) because of its high theoretical specific capacity and superior electrochemical reversibility. Nevertheless, the low rate performance and rapid capacity decline seriously hamper its implementation in SIBs. Herein, we demonstrate a sagacious multi‐step templating approach to skillfully craft amorphous FePO 4 yolk−shell nanospheres with mesoporous nanoyolks supported inside the robust porous outer nanoshells. Their unique architecture and large surface area enable these amorphous FePO 4 yolk−shell nanospheres to manifest remarkable sodium storage properties with high reversible capacity, outstanding rate performance, and ultralong cycle life.

[ASAP] Unique Behavior of Poly(propylene glycols) Confined within Alumina Templates Having a Nanostructured Interface

By Magdalena Tarnacka*†‡, Marcin Wojtyniak†‡, Agnieszka Brzo´zka§, Agnieszka Talik†‡, Barbara Hachula?, Ewa Kamin´ska?, Grzegorz D. Sulka§, Kamil Kaminski*†‡, and Marian Paluch†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01116

[ASAP] Chiral Protein Supraparticles for Tumor Suppression and Synergistic Immunotherapy: An Enabling Strategy for Bioactive Supramolecular Chirality Construction

By Jin Yan*†, Yu Yao‡, Siqi Yan§, Ruqing Gao?, Wuyuan Lu*?, and Wangxiao He*#? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01757

[ASAP] Electrically Driven Hot-Carrier Generation and Above-Threshold Light Emission in Plasmonic Tunnel Junctions

By Longji Cui†‡§, Yunxuan Zhu†, Mahdiyeh Abbasi?, Arash Ahmadivand?, Burak Gerislioglu†, Peter Nordlander†??, and Douglas Natelson*†?? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02121

[ASAP] Correction to Considering the Effects of Microbiome and Diet on SARS-CoV-2 Infection: Nanotechnology Roles

By Kourosh Kalantar-Zadeh*, Stephanie A. Ward, Kamyar Kalantar-Zadeh, and Emad M. El-Omar from ACS Nano: Latest Articles (ACS Publications). Published on Jun 30, 2020.

ACS Nano
DOI: 10.1021/acsnano.0c04407

[ASAP] Direct Observation of One-Dimensional Peierls-type Charge Density Wave in Twin Boundaries of Monolayer MoTe2

By Li Wang†?, Ying Wu†?, Yayun Yu‡?, Aixi Chen†, Huifang Li†, Wei Ren†?, Shuai Lu†, Sunan Ding*†?, Hui Yang†, Qi-Kun Xue§, Fang-Sen Li*†?, and Guang Wang*‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02072

[ASAP] Citrate Coordination and Bridging of Gold Nanoparticles: The Role of Gold Adatoms in AuNP Aging

By David-Benjamin Grys†, Bart de Nijs†, Andrew R. Salmon†, Junyang Huang†, Wenting Wang†, Wei-Hsin Chen†, Oren A. Scherman‡, and Jeremy J. Baumberg*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03050

[ASAP] Estimation of Magnetic Anisotropy of Individual Magnetite Nanoparticles for Magnetic Hyperthermia

By Hiroaki Mamiya‡, Hiroya Fukumoto†, Jhon L. Cuya Huaman†, Kazumasa Suzuki†, Hiroshi Miyamura†, and Jeyadevan Balachandran*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02521

[ASAP] Epitaxial Aluminum Surface-Enhanced Raman Spectroscopy Substrates for Large-Scale 2D Material Characterization

By Soniya S. Raja†, Chang-Wei Cheng‡, Yungang Sang‡§, Chun-An Chen#, Xin-Quan Zhang#, Abhishek Dubey#, Ta-Jen Yen#, Yu-Ming Chang&, Yi-Hsien Lee#, and Shangjr Gwo*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03462

[ASAP] Chemical Funneling of Colloidal Gold Nanoparticles on Printed Arrays of End-Grafted Polymers for Plasmonic Applications

By Sami Pekdemir†‡, Ilker Torun†‡, Menekse Sakir†‡, Mahmut Ruzi‡, John A. Rogers*??, and M. Serdar Onses*†‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01987

[ASAP] Potent and Prolonged Innate Immune Activation by Enzyme-Responsive Imidazoquinoline TLR7/8 Agonist Prodrug Vesicles

By Bi Wang†, Simon Van Herck‡, Yong Chen‡, Xiangyang Bai†, Zifu Zhong§, Kim Deswarte?, Bart N. Lambrecht??, Niek N. Sanders§, Stefan Lienenklaus@, Hans W. Scheeren†, Sunil A. David#, Fabian Kiessling†, Twan Lammers*†??, Bruno G. De Geest*‡, and Yang Shi*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c01928

[ASAP] Interfacial Vibrational Dynamics of Ice Ih and Liquid Water

By Prerna Sudera†, Jene´e D. Cyran†§, Malte Deiseroth†, Ellen H. G. Backus*†‡, and Mischa Bonn*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04526

[ASAP] Correction to “Protein–Protein Cross-Coupling via Palladium–Protein Oxidative Addition Complexes from Cysteine Residues”

By Heemal H. Dhanjee, Azin Saebi, Ivan Buslov, Alexander R. Loftis, Stephen L. Buchwald*, and Bradley L. Pentelute* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06703

[ASAP] Correction to “Electrochemically Determined O–H Bond Dissociation Free Energies of NiO Electrodes Predict Proton-Coupled Electron Transfer Reactivity”

By Catherine F. Wise and James M. Mayer* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06397

[ASAP] Structural Oscillation Revealed in Gold Nanoparticles

By Nan Xia†‡?, Jinyun Yuan§?, Lingwen Liao†‡, Wenhao Zhang†‡, Jin Li?, Haiteng Deng?, Jinlong Yang*§, and Zhikun Wu*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c02117

[ASAP] Silver Double Nanorings with Circular Hot Zone

By Sungjae Yoo†, Junghwa Lee†, Jeongwon Kim†, Jae-Myoung Kim‡, MohammadNavid Haddadnezhad†, Sungwoo Lee†, Sungwoo Choi§, Doojae Park§, Jwa-Min Nam‡, and Sungho Park*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04419

[ASAP] Ferroelectric Instability Induced Ultralow Thermal Conductivity and High Thermoelectric Performance in Rhombohedral p-Type GeSe Crystal

By Debattam Sarkar†, Tanmoy Ghosh†, Subhajit Roychowdhury†, Raagya Arora‡, Sandra Sajan?, Goutam Sheet?, Umesh V. Waghmare‡§?, and Kanishka Biswas*†§? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03696

[ASAP] Correction to “A Heterotrimeric Dehydrogenase Complex Functions with 2 Distinct YcaO Proteins to Install 5 Azole Heterocycles in 35-Membered Sulfomycin Thiopeptides”

By Yanan Du, Yanping Qiu, Xiang Meng, Junyin Feng, Jiang Tao, and Wen Liu* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06689

[ASAP] Shape Matching in Superatom Chemistry and Assembly

By Jingjing Yang†, Feifan Wang†, Jake C. Russell†, Taylor J. Hochuli†, Xavier Roy†, Michael L. Steigerwald†, Xiaoyang Zhu†, Daniel W. Paley*‡, and Colin Nuckolls*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04321

[ASAP] Enantioselective Copper-Catalyzed Alkynylation of Benzylic C–H Bonds via Radical Relay

By Liang Fu†?, Zhihan Zhang‡?, Pinhong Chen†, Zhenyang Lin*‡, and Guosheng Liu*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05373

[ASAP] The Soft Molecular Polycrystalline Ferroelectric Realized by the Fluorination Effect

By Yongfa Xie†, Yong Ai†, Yu-Ling Zeng†, Wen-Hui He†, Xue-Qin Huang†, Da-Wei Fu*‡, Ji-Xing Gao‡, Xiao-Gang Chen‡, and Yuan-Yuan Tang*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05372

[ASAP] Regioselective, Photocatalytic a-Functionalization of Amines

By Lingying Leng†, Yue Fu‡, Peng Liu*‡, and Joseph M. Ready*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03758

[ASAP] How Water in Aliphatic Solvents Directs the Interference of Chemical Reactivity in a Supramolecular System

By Mathijs F. J. Mabesoone, Gijs M. ter Huurne, Anja R. A. Palmans, and E. W. Meijer* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04962

[ASAP] Dynamic Reoxidation/Reduction-Driven Atomic Interdiffusion for Highly Selective CO2 Reduction toward Methane

By Chia-Jui Chang§†, Sheng-Chih Lin§†, Hsiao-Chien Chen†, Jiali Wang†, Kai Jen Zheng†, Yanping Zhu†, and Hao Ming Chen*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c01859

[ASAP] Stereoselective Synthesis of Cis- and Trans-Tetrasubstituted Vinyl Silanes Using a Silyl-Heck Strategy and Hiyama Conditions for Their Cross-Coupling

By Michael F. Wisthoff‡, Sarah B. Pawley‡, Andrew P. Cinderella, and Donald A. Watson* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c05382

[ASAP] Ultrasensitive Detection of Attomolar Protein Concentrations by Dropcast Single Molecule Assays

By Connie Wu†‡, Padric M. Garden†‡, and David R. Walt*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04331

[ASAP] Continuous Electrical Conductivity Variation in M3(Hexaiminotriphenylene)2 (M = Co, Ni, Cu) MOF Alloys

By Tianyang Chen†, Jin-Hu Dou†, Luming Yang†, Chenyue Sun†, Nicole J. Libretto‡, Grigorii Skorupskii†, Jeffrey T. Miller‡, and Mircea Dinca?*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04458

[ASAP] Scalable Bifunctional Organoboron Catalysts for Copolymerization of CO2 and Epoxides with Unprecedented Efficiency

By Guan-Wen Yang, Yao-Yao Zhang, Rui Xie, and Guang-Peng Wu* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c03651

[ASAP] Sense-and-Release Logic-Gated Molecular Network Responding to Dimeric Cell Surface Proteins

By Simona Angerani and Nicolas Winssinger* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 30, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c04469

Author Correction: Scalable synthesis of hierarchically structured carbon nanotube–graphene fibres for capacitive energy storage

By Yuan Chen from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 30, 2020.

Nature Nanotechnology, Published online: 30 June 2020; doi:10.1038/s41565-020-0718-1

Author Correction: Scalable synthesis of hierarchically structured carbon nanotube–graphene fibres for capacitive energy storage

Electron inelastic mean free path in water

By Kristian Mølhave from RSC - Nanoscale latest articles. Published on Jun 30, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR04352D, Paper
Murat Nulati Yesibolati, Simone Laganá, Shima Kadkhodazadeh, Esben Kirk Mikkelsen, Hongyu Sun, Takeshi Kasama, Ole Hansen, Nestor J. Zaluzec, Kristian Mølhave
A nanochannel liquid cell was used to quantify the electron inelastic mean free path (λIMFP) in water. The experimental values show large offsets from the generally accepted models, and can be used to determine the liquid thickness in a liquid cell.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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Programming Diffusion and Localization of DNA Signals in 3D‐Printed DNA‐Functionalized Hydrogels

By Julia Müller, Anna Christina Jäkel, Dominic Schwarz, Lukas Aufinger, Friedrich C. Simmel from Wiley: Small: Table of Contents. Published on Jun 29, 2020.

DNA nanotechnology enables sequence‐programmable assembly and operation of nanoscale structures, devices, and systems. In order to harness DNA’s molecular programming power also at larger length scales, however, novel strategies are required. Here, a bioprinting approach is developed for DNA‐functionalized bioinks that facilitate sequence‐programmable assembly and diffusion processes in millimeter‐scaled 3D‐printed gel structures. Abstract Additive manufacturing enables the generation of 3D structures with predefined shapes from a wide range of printable materials. However, most of the materials employed so far are static and do not provide any intrinsic programmability or pattern‐forming capability. Here, a low‐cost 3D bioprinting approach is developed, which is based on a commercially available extrusion printer that utilizes a DNA‐functionalized bioink, which allows to combine concepts developed in dynamic DNA nanotechnology with additive patterning techniques. Hybridization between diffusing DNA signal strands and immobilized anchor strands can be used to tune diffusion properties of the signals, or to localize DNA strands within the gel in a sequence‐programmable manner. Furthermore, strand displacement mechanisms can be used to direct simple pattern formation processes and to control the availability of DNA sequences at specific locations. To support printing of DNA‐functionalized gel voxels at arbitrary positions, an open source python script that generates machine‐readable code (GCODE) from simple vector graphics input is developed.

Ferrocene‐Incorporated Cobalt Sulfide Nanoarchitecture for Superior Oxygen Evolution Reaction

By Pitchai Thangasamy, Saewoong Oh, Sanghee Nam, Hyacinthe Randriamahazaka, Il‐Kwon Oh from Wiley: Small: Table of Contents. Published on Jun 29, 2020.

A facile and one‐step solvothermal approach is demonstrated to reform the local electronic structure of cobalt sulfide nanostructures by the incorporation of Fe‐based compounds derived from ferrocene, and nitrogen‐doped carbon nanostructures for robust oxygen evolution reaction. Abstract Here, ferrocene(Fc)‐incorporated cobalt sulfide (CoxSy) nanostructures directly grown on carbon nanotube (CNT) or carbon fiber (CF) networks for electrochemical oxygen evolution reaction (OER) using a facile one‐step solvothermal method are reported. The strong synergistic interaction between Fc‐CoxSy nanostructures and electrically conductive CNTs results in the superior electrocatalytic activity with a very small overpotential of ≈304 mV at 10 mA cm−2 and a low Tafel slope of 54.2 mV dec−1 in 1 m KOH electrolyte. Furthermore, the Fc‐incorporated CoxSy (FCoS) nanostructures are directly grown on the acid pretreated carbon fiber (ACF), and the resulting fabricated electrode delivers excellent OER performance with a low overpotential of ≈315 mV at 10 mA cm−2. Such superior OER catalytic activity can be attributed to 3D Fc‐CoxSy nanoarchitectures that consist of a high concentration of vertical nanosheets with uniform distribution of nanoparticles that afford a large number of active surface areas and edge sites. Besides, the tight contact interface between ACF substrate and Fc‐CoxSy nanostructures could effectively facilitate the electron transfer rate in the OER. This study provides valuable insights for the rational design of energy storage and conversion materials by the incorporation of other transition metal into metal sulfide/oxide nanostructures utilizing metallocene.

Single Iron Site Nanozyme for Ultrasensitive Glucose Detection

By Min Chen, Huang Zhou, Xiaokang Liu, Tongwei Yuan, Wenyu Wang, Chao Zhao, Yafei Zhao, Fangyao Zhou, Xin Wang, Zhenggang Xue, Tao Yao, Can Xiong, Yuen Wu from Wiley: Small: Table of Contents. Published on Jun 29, 2020.

A porous netlike N‐doped graphene with uniform single Fe sites (Fe SSN) is designed and prepared by a support‐sacrificed strategy. The Fe SSN preforms prominent peroxidase‐mimicking activity, displaying high‐efficiency catalytic activity to glucose via a low‐cost integrated agarose‐based hydrogel colorimetric biosensor. This work expands a new application of single site catalysts in the fields of nanozymes and personal point‐of‐care technologies. Abstract Nanomaterials with enzyme‐mimicking characteristics have engaged great awareness in various fields owing to their comparative low cost, high stability, and large‐scale preparation. However, the wide application of nanozymes is seriously restricted by the relatively low catalytic activity and poor specificity, primarily because of the inhomogeneous catalytic sites and unclear catalytic mechanisms. Herein, a support‐sacrificed strategy is demonstrated to prepare a single iron site nanozyme (Fe SSN) dispersed on the porous N‐doped carbon. With well‐defined coordination structure and high density of active sites, the Fe SSN performs prominent peroxidase‐like activity by efficiently activating H2O2 into hydroxyl radical (•OH) species. Furthermore, the Fe SSN is applied in colorimetric detection of glucose through a multienzyme biocatalytic cascade platform. Moreover, a low‐cost integrated agarose‐based hydrogel colorimetric biosensor is designed and successfully achieves the visualization evaluation and quantitative detection of glucose. This work expands the application of single‐site catalysts in the fields of nanozyme‐based biosensors and personal biomedical diagnosis.

Photo‐Stimulated Polychromatic Room Temperature Phosphorescence of Carbon Dots

By Kai Jiang, Sizhe Hu, Yuci Wang, Zhongjun Li, Hengwei Lin from Wiley: Small: Table of Contents. Published on Jun 29, 2020.

A facile method for the preparation of photo‐stimulated multicolor room temperature phosphorescence (RTP) carbon dots (CDs) is proposed. The as‐obtained CDs not only exhibit fluorescence colors change (from blue to green) under diverse wavelengths of irradiation in the solid state, but also show remarkable RTP colors alteration (from cyan to yellow) with the irradiations just being switched off. Abstract Single‐component multicolor luminescence, particularly phosphorescence materials are highly attractive both in numerous applications and in‐depth understanding the light‐emission processes, but formidable challenges still exist for preparing such materials. Herein, a very facile approach is reported to synthesize carbon dots (CDs) (named MP‐CDs) that exhibit multicolor fluorescence (FL), and more remarkably, multicolor long‐lived room temperature phosphorescence (RTP) under ambient conditions. The FL and RTP colors of the CDs powder are observed to change from blue to green and cyan to yellow, respectively, with the excitation wavelength shifting from 254 to 420 nm. Further studies demonstrate that the multicolor emissions can be attributed to the existence of multiple emitting centers in the CDs and the relatively higher reaction temperature plays a critical role for achieving RTP. Given the unique optical properties, a preliminary application of MP‐CDs in advanced anti‐counterfeiting is presented. This study not only proposes a strategy to prepare photo‐stimulated multicolor RTP materials, but also reveals great potentials of CDs in exploiting novel optical materials with unique properties.

DNA‐Based Plasmonic Heterogeneous Nanostructures: Building, Optical Responses, and Bioapplications

By Yuan Zhao, Chuanlai Xu from Wiley: Advanced Materials: Table of Contents. Published on Jun 29, 2020.

DNA‐based plasmonic heterogeneous nanostructures are widely fabricated and allow the precise manipulation of light for coherent electron oscillations. The effects of structural parameters on the regulation of optical responses are analyzed. The potential applications and challenges of plasmonic heterogeneous nanostructures are discussed in the fields of biosensors and bioanalysis, in vivo monitoring, and phototheranostics. Abstract The integration of multiple functional nanoparticles into a specific architecture allows the precise manipulation of light for coherent electron oscillations. Plasmonic metals‐based heterogeneous nanostructures are fabricated by using DNA as templates. This comprehensive review provides an overview of the controllable synthesis and self‐assembly of heterogeneous nanostructures, and analyzes the effects of structural parameters on the regulation of optical responses. The potential applications and challenges of heterogeneous nanostructures in the fields of biosensors and bioanalysis, in vivo monitoring, and phototheranostics are discussed.

Ion Exchange Gels Allow Organic Electrochemical Transistor Operation with Hydrophobic Polymers in Aqueous Solution

By Connor G. Bischak, Lucas Q. Flagg, David S. Ginger from Wiley: Advanced Materials: Table of Contents. Published on Jun 29, 2020.

Inserting an ion exchange gel between the hydrophobic polymer active layer of an organic transistor and the aqueous electrolyte enables volumetric doping of the active layer and operation as an organic electrochemical transistor, rather than as an electrolyte‐gated organic field‐effect. With the ion gel, the transconductance increases by ≈10 000×, enabling the recording of biological action potentials. Abstract Conjugated‐polymer‐based organic electrochemical transistors (OECTs) are being studied for applications ranging from biochemical sensing to neural interfaces. While new polymers that interface digital electronics with the aqueous chemistry of life are being developed, the majority of high‐performance organic transistor materials are poor at transporting biologically relevant ions. Here, the operating mode of an organic transistor is changed from that of an electrolyte‐gated organic field‐effect transistor (EGOFET) to that of an OECT by incorporating an ion exchange gel between the active layer and the aqueous electrolyte. This device works by taking up biologically relevant ions from solution and injecting more hydrophobic ions into the active layer. Using poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl) thieno[3,2‐b]thiophene] as the active layer and a blend of an ionic liquid, 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, and poly(vinylidene fluoride‐co‐hexafluoropropylene) as the ion exchange gel, four orders of magnitude improvement in device transconductance and a 100‐fold increase in kinetics are demonstrated. The ability of the ion‐exchange‐gel OECT to record biological signals by measuring the action potentials of a Venus flytrap is demonstrated. These results show the possibility of using interface engineering to open up a wider palette of organic semiconductors as OECTs that can be gated by aqueous solutions.

Supramolecular Porous Organic Nanocomposites for Heterogeneous Photocatalysis of a Sulfur Mustard Simulant

By Yassine Beldjoudi, Ahmet Atilgan, Jacob A. Weber, Indranil Roy, Ryan M. Young, Jierui Yu, Pravas Deria, Alan E. Enciso, Michael R. Wasielewski, Joseph T. Hupp, J. Fraser Stoddart from Wiley: Advanced Materials: Table of Contents. Published on Jun 29, 2020.

A supramolecular photosensitizer with efficient intersystem crossing is achieved by combining the spin‐orbit coupling associated with heavy atoms and the photoinduced electron transfer in a donor–acceptor host–guest dyad. Incorporation of these supramolecular cationic photosensitizers with anionic polymer matrices generates porous nanocomposites with remarkable photocatalytic performances against sulfur mustard simulant. Abstract Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well‐defined spin structures. Confinement of the tetracationic cyclophane (ExBox4+) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g−1 in ExBox•PSS. Efficient intersystem crossing is achieved by combining the spin‐orbit coupling associated to Br heavy atoms in 1,3,5,8‐tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP⊂ExBox4+ supramolecular dyad. The TBP⊂ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed‐electronic states. The lowest triplet state (T1, 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP⊂ExBox4+, for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4, confirming the importance of the newly formed excited‐state manifold in TBP⊂ExBox4+ for the population of the low‐lying T1 state. The high stability, facile preparation, and high performance of the TBP⊂ExBox•PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host–guest chemistry.

Withdrawal: ‘Organic synthesis – Where now?’ is thirty years old. A reflection on the current state of affair

By T. Hudlicky from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Enantioselective Fluorescent Recognition of Free Amino Acids:  Challenges and Opportunities

By Lin Pu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Fluorescent probes that can discriminate enantiomers of amino acids in either organic media or aqueous solution are discussed.  This article focuses on the recent progresses in the study of three classes of probes including those made of cyclodextrins, 1,1’‐binaphthyls and nanomaterials and attempts to use these studies to illustrate the design strategies, applications and limitations in this area.  These probes are potentially useful for rapid analysis of the reactions for asymmetric amino acid synthesis as well as the real time imaging of amino acids in biological systems.  The challenges for these applications are analyzed.  Working in this field of enantioselective fluorescent recognition of amino acids is presented with great opportunities to make new scientific discoveries and to develop important practical applications.

Conformation‐Tuning Effect of Asymmetric Small Molecule Acceptors on Molecular Packing, Interaction, and Photovoltaic Performance

By Zhenghui Luo, Ruijie Ma, Yiqun Xiao, Tao Liu, Huiliang Sun, Mengyao Su, Qing Guo, Guanghao Li, Wei Gao, Yuzhong Chen, Yang Zou, Xugang Guo, Maojie Zhang, Xinhui Lu, He Yan, Chuluo Yang from Wiley: Small: Table of Contents. Published on Jun 29, 2020.

In this work, two novel A‐DA1D‐A‐type asymmetric SMAs are developed, namely C‐shaped BDTP‐4F and S‐shaped BTDTP‐4F. As a result, C‐shape BDTP‐4F‐based device yields a higher PCE (15.24%) than that of S‐shape BTDTP‐4F‐based device (13.12%), while for traditional A‐D‐A type SMAs, IDTP‐4F with S‐shape conformation is better than that of C‐shape IDTTP‐4F. Abstract Understanding the conformation effect on molecular packing, miscibility, and photovoltaic performance is important to open a new avenue for small‐molecule acceptor (SMA) design. Herein, two novel acceptor–(donor‐acceptor1‐donor)–acceptor (A‐DA1D‐A)‐type asymmetric SMAs are developed, namely C‐shaped BDTP‐4F and S‐shaped BTDTP‐4F. The BDTP‐4F‐based polymer solar cells (PSCs) with PM6 as donor, yields a power conversion efficiency (PCE) of 15.24%, significantly higher than that of the BTDTP‐4F‐based device (13.12%). The better PCE for BDTP‐4F‐based device is mainly attributed to more balanced charge transport, weaker bimolecular recombination, and more favorable morphology. Additionally, two traditional A‐D‐A‐type SMAs (IDTP‐4F and IDTTP‐4F) are also synthesized to investigate the conformation effect on morphology and device performance. Different from the device result above, here, IDTP‐4F with S‐shape conformation outperforms than IDTTP‐4F with C‐shape conformation. Importantly, it is found that for these two different types of SMA, the better performing binary blend has similar morphological characteristics. Specifically, both PM6:BDTP‐4F and PM6:IDTP‐4F blend exhibit perfect nanofibril network structure with proper domain size, obvious face‐on orientation and enhance donor‐acceptor interactions, thereby better device performance. This work indicates tuning molecular conformation plays pivotal role in morphology and device effciciency, shining a light on the molecular design of the SMAs.

A Self‐Assembled Hetero‐Structured Inverse‐Spinel and Anti‐Perovskite Nanocomposite for Ultrafast Water Oxidation

By Nana Ma, Gao Chen, Yanping Zhu, Hainan Sun, Jie Dai, Hang Chu, Ran Ran, Wei Zhou, Rui Cai, Zongping Shao from Wiley: Small: Table of Contents. Published on Jun 29, 2020.

A highly conductive inverse spinel (Fe3O4) and anti‐perovskite (Ni3FeN) hetero‐structured nanocomposite is facilely synthesized as a superior oxygen evolution electrocatalyst. Both high surface reactivity and bulk electronic transport ability can be realized during the partial reconstruction process. The anti‐structured Fe3O4/Ni3FeN grown on the carbon fiber paper demonstrates a world‐record oxygen evolution reaction performance. Abstract Spinel and perovskite with distinctive crystal structures are two of the most popular material families in electrocatalysis, which, however, usually show poor conductivity, causing a negative effect on the charge transfer process during electrochemical reactions. Herein, a highly conductive inverse spinel (Fe3O4) and anti‐perovskite (Ni3FeN) hetero‐structured nanocomposite is reported as a superior oxygen evolution electrocatalyst, which can be facilely prepared based on a one‐pot synthesis strategy. Thanks to the strong hybridization between Ni/Fe 3d and N 2p orbitals, the Ni3FeN is easily transformed into NiFe (oxy)hydroxide as the real active species during the oxygen evolution reaction (OER) process, while the Fe3O4 component with low O‐p band center relative to Fermi level is structurally stable. As a result, both high surface reactivity and bulk electronic transport ability are reached. By directly growing Fe3O4/Ni3FeN heterostructure on freestanding carbon fiber paper and testing based on the three‐electrode configuration, it requires only 160 mV overpotential to deliver a current density of 30 mA cm−2 for OER. Also, negligible performance decay is observed within a prolonged test period of 100 h. This work sheds light on the rational design of novel heterostructure materials for electrocatalysis.

Advances in Antimicrobial Microneedle Patches for Combating Infections

By Rezvan Jamaledin, Cynthia K.Y. Yiu, Ehsan N. Zare, Li‐Na Niu, Raffaele Vecchione, Guojun Chen, Zhen Gu, Franklin R. Tay, Pooyan Makvandi from Wiley: Advanced Materials: Table of Contents. Published on Jun 29, 2020.

Antimicrobial microneedle (MN) patches are portable medical devices for combating skin infections. Contrary to conventional topical administration, MNs enhance the bioavailability of antibacterial, antifungal and antiviral therapeutics to skin and eye. These promising armaments release their cargo in controlled release. They can respond to biosignals such as changes in pH and microbial enzyme load at the infection site. Abstract Skin infections caused by bacteria, viruses and fungi are difficult to treat by conventional topical administration because of poor drug penetration across the stratum corneum. This results in low bioavailability of drugs to the infection site, as well as the lack of prolonged release. Emerging antimicrobial transdermal and ocular microneedle patches have become promising medical devices for the delivery of various antibacterial, antifungal, and antiviral therapeutics. In the present review, skin anatomy and its barriers along with skin infection are discussed. Potential strategies for designing antimicrobial microneedles and their targeted therapy are outlined. Finally, biosensing microneedle patches associated with personalized drug therapy and selective toxicity toward specific microbial species are discussed.

Enantioselective Synthesis of β‐Amino Acid Derivatives Enabled by Ligand‐Controlled Reversal of Hydrocupration Regiochemistry

By Sheng Guo, Jiaqi Zhu, Stephen L. Buchwald from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

A Cu‐catalyzed enantioselective hydroamination of α,β‐unsaturated carbonyl compounds for the synthesis of  β ‐amino acid derivatives was achieved through ligand‐controlled reversal of the hydrocupration regioselectivity. While the hydrocupration of α,β‐unsaturated carbonyl compounds to form α‐cuprated species has been extensively investigated, we report  herein  that, in the presence of an appropriate ancillary chiral ligand, the alternative regiochemistry can be observed for cinnamic acid derivatives, leading to delivery of the copper to the  β‐position. This copper can react with an electrophilic aminating reagent, 1,2‐benzisoxazole, to provide enantioenriched β‐amino acid derivatives, which are important building blocks for the synthesis of natural products and bioactive small molecules.

Micro‐Lensed Fiber Laser Desorption Mass Spectrometry Imaging Reveals Subcellular Distribution of Drugs within Single Cells

By Wei Hang, Yifan Meng, Xiaoling Cheng, Tongtong Wang, Xiaoping Li, Wan Nie, Rong Liu, Zheng Lin, Le Hang, Zhibin Yin, Baolin Zhang, Xiaomei Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

The visualization of temporal and spatial changes in the intracellular environment has great significance for chemistry and bioscience research. Mass spectrometry imaging (MSI) is playing an increasingly important role in this field because of its unique advantages, such as being label‐free and high throughput, yet it remains a great challenge for laser‐based techniques due to limited lateral resolution. Here, we develop a simple, reliable and economic nanoscale MSI approach by introducing desorption laser with a micro‐lensed fiber. Using this integrated platform, we achieved 300 nm resolution MSI and successfully visualized the distribution of various small‐molecule drugs in subcellular locations. Moreover, exhaustive dynamic processes of anticancer drugs, including releasing from nanoparticle carriers entering nucleus of cells, can be readily acquired on an organelle scale. Considering the simplicity and universality of this nanoscale desorption device, it could be easily adapted to most of laser‐based mass spectrometry applications.

Synthesis and Structure of Functionalized Zigzag Hydrocarbon Belts

By Mei-Xiang Wang, Yang Zhang, Shuo Tong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Described in this paper are the synthesis and structure of novel and edge‐functionalized zigzag hydrocarbon belts. A stepwise fjord‐stitching strategy featuring repetitive intramolecular acylation reactions of a resorcin[4]arene derivative as the key steps afforded a biscarbonyl‐functionalized octahydrobelt[8]arene product. Facile ketone reduction with NaBH4 and nucleophilic addition reaction with n‐butyllithium produced secondary and tertiary alcohol‐containing molecular belts, respectively. Selective oxidation reactions of biscarbonyl‐bearing octahydrobelt[8]arene with m‐CPBA and (PhSeO)2O furnished the corresponding lactone‐ and 1,4‐quinone‐embedded molecular belts. Depending on the functional groups on the edges, the acquired belt molecules adopt different shapes such as square prism, truncated cone and elliptical cylinder.

Water‐Soluble Polymers with Appending Porphyrins as Bioinspired Catalysts for the Hydrogen Evolution Reaction

By Lisi Xie, Jia Tian, Yingjie Ouyang, Xinai Guo, Weian Zhang, Ulf‐Peter Apfel, Wei Zhang, Rui Cao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Water‐soluble polymers for HER: As inspired by enzymes, three water‐soluble polymers with appending Co porphyrins and different side‐chain groups are designed. These catalysts show high activity and stability for electro‐ and photocatalytic HER in neutral aqueous solutions. With the same Co porphyrin, the activity can be fine‐tuned by using different side‐chain groups. Abstract Molecular design to improve catalyst performance is significant but challenging. In enzymes, residue groups that are close to reaction centers play critical roles in regulating activities. Using this bioinspired strategy, three water‐soluble polymers were designed with appending Co porphyrins and different side‐chain groups to mimic enzyme reaction centers and activity‐controlling residue groups, respectively. With these polymers, high hydrogen evolution efficiency was achieved in neutral aqueous media for electro‐ (turnover frequency >2.3×104 s−1) and photocatalysis (turnover number >2.7×104). Porphyrin units are surrounded and protected by polymer chains, and more importantly, the activity can be tuned with different side‐chain groups. Therefore, instead of revising molecular structures that is difficult from both design and synthesis points of view, polymers can be used to improve molecular solubility and stability and simultaneously regulate activity by using side‐chain groups.

Hierarchically Structured Allotropes of Phosphorus from Data‐Driven Exploration

By Volker L. Deringer, Chris J. Pickard, Davide M. Proserpio from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Double helices and other hierarchical structures of elemental phosphorus can be built from the simple P8 cage. Machine‐learning‐driven and fragment‐based searches enable a rapid exploration of structural space, and dispersion‐corrected DFT computations reveal the resulting structures to be more stable than white phosphorus. Abstract The discovery of materials is increasingly guided by quantum‐mechanical crystal‐structure prediction, but the structural complexity in bulk and nanoscale materials remains a bottleneck. Here we demonstrate how data‐driven approaches can vastly accelerate the search for complex structures, combining a machine‐learning (ML) model for the potential‐energy surface with efficient, fragment‐based searching. We use the characteristic building units observed in Hittorf's and fibrous phosphorus to seed stochastic (“random”) structure searches over hundreds of thousands of runs. Our study identifies a family of hierarchically structured allotropes based on a P8 cage as principal building unit, including one‐dimensional (1D) single and double helix structures, nanowires, and two‐dimensional (2D) phosphorene allotropes with square‐lattice and kagome topologies. These findings yield new insight into the intriguingly diverse structural chemistry of phosphorus, and they provide an example for how ML methods may, in the long run, be expected to accelerate the discovery of hierarchical nanostructures.

Redox‐Active Hybrid Polyoxometalate‐Stabilised Gold Nanoparticles

By Carmen Martin, Katharina Kastner, Jamie M. Cameron, Elizabeth Hampson, Jesum Alves Fernandes, Emma K. Gibson, Darren A. Walsh, Victor Sans, Graham N. Newton from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Handy hybrids: A material based on gold nanoparticles stabilized by organic–inorganic hybrid polyoxometalates is described (see picture). The new nanomaterial exhibits unprecedented stability and photoactivity under visible light and can be reversibly reduced and oxidized at electrode surfaces, making it very promising for future photonic and electrochemical systems. Abstract We report the design and preparation of multifunctional hybrid nanomaterials through the stabilization of gold nanoparticles with thiol‐functionalised hybrid organic–inorganic polyoxometalates (POMs). The covalent attachment of the hybrid POM forms new nanocomposites that are stable at temperatures and pH values which destroy analogous electrostatically functionalised nanocomposites. Photoelectrochemical analysis revealed the unique photochemical and redox properties of these systems.

Absolute Configuration of Small Molecules by Co‐Crystallization

By Felix Krupp, Wolfgang Frey, Clemens Richert from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

The absolute configuration of difficult‐to‐crystallize small molecules can be obtained by rapid thermal co‐crystallization with TEO, a tetraaryladamantane octaether, and X‐ray crystallography. As little as 3–5 mg of analyte can produce both NMR and diffraction data within 48 hours. Abstract The most reliable method to determine the absolute configuration of chiral molecules is X‐ray crystallography, but small molecules can be difficult to crystallize. We report rapid co‐crystallization of tetraaryladamantanes with small molecules as different as n‐decane to nicotine to produce crystals for X‐ray analysis and the assignment of absolute configuration when the molecules are chiral. A screen of 52 diverse compounds gave inclusion in co‐crystals for 88 % of all cases and a high‐resolution structure in 77 % of cases. Furthermore, starting from three milligrams of analyte, a combination of NMR spectroscopy and X‐ray crystallography produced a full structure in less than three days using an adamantane crystallization chaperone that encapsulates the analyte at room temperature.

Optimization of Active Sites via Crystal Phase, Composition, and Morphology for Efficient Low‐Iridium Oxygen Evolution Catalysts

By Hui Chen, Lei Shi, Xiao Liang, Lina Wang, Tewodros Asefa, Xiaoxin Zou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

On top of the volcano: The importance of the anatase crystal phase in TiO2‐IrO2 solid solutions in forming highly active Ir sites for the oxygen evolution reaction (OER), around the top of the volcano plot, is shown through theoretical and experimental studies. Such highly active Ir sites are indirectly obtained by creating Sr‐deficient surfaces on SrTiO3‐SrIrO3 solid solutions in situ. Abstract Reducing the amount of iridium in oxygen evolution electrocatalysts without compromising their catalytic performances is one of the major requirements in proton‐exchange‐membrane water electrolyzers. Herein, with the help of theoretical studies, we show that anatase‐type TiO2‐IrO2 solid solutions possess more active iridium catalytic sites for the oxygen evolution reaction (OER) than IrO2, the benchmark OER catalyst. Note that the same is not observed for their rutile‐type counterparts. However, owing to their thermodynamic metastability, anatase‐type TiO2‐IrO2 solid solutions are generally hard to synthesize. Our theoretical studies demonstrate that such catalytically active anatase‐type solid‐solution phases can be created in situ on the surfaces of readily available SrTiO3‐SrIrO3 solid solutions during electrocatalysis in acidic solution as the solution can etch away Sr atoms. We experimentally show this with porous SrTiO3‐SrIrO3 solid‐solution nanotubes synthesized by a facile synthetic route that contain 56 % less iridium than IrO2 yet show an order of magnitude higher apparent catalytic activity for OER in acidic solution.

Double‐Shelled C@MoS2 Structures Preloaded with Sulfur: An Additive Reservoir for Stable Lithium Metal Anodes

By Huadong Yuan, Jianwei Nai, Yongjin Fang, Gongxun Lu, Xinyong Tao, Xiong Wen (David) Lou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Functional microcapsules for stable lithium metal anodes (LMAs) have been designed based on double‐shelled C@MoS2 nanostructures preloaded with sulfur. The as‐prepared C@MoS2/S structures can provide a long‐term supply of polysulfides, which serve as an effective additive for improving the stability of the solid electrolyte interphase on the LMA, thus prolonging the cycle life. Abstract The growth of Li dendrites hinders the practical application of lithium metal anodes (LMAs). In this work, a hollow nanostructure, based on hierarchical MoS2 coated hollow carbon particles preloaded with sulfur (C@MoS2/S), was designed to modify the LMA. The C@MoS2 hollow nanostructures serve as a good scaffold for repeated Li plating/stripping. More importantly, the encapsulated sulfur could gradually release lithium polysulfides during the Li plating/stripping, acting as an effective additive to promote the formation of a mosaic solid electrolyte interphase layer embedded with crystalline hybrid lithium‐based components. These two factors together effectively suppress the growth of Li dendrites. The as‐modified LMA shows a high Coulombic efficiency of 98 % over 500 cycles at the current density of 1 mA cm−2. When matched with a LiFePO4 cathode, the assembled full cell displays a highly improved cycle life of 300 cycles, implying the feasibility of the proposed LMA.

Profiling and Identification of Biocatalyzed Transformation of Sulfoxaflor In Vivo

By Liwei Xu, Lingling Guo, Zhongxing Wang, Xinxin Xu, Shuang Zhang, Xiaoling Wu, Hua Kuang, Chuanlai Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

The biotransformation of the neonicotinoid pesticide sulfoxaflor and the metabolic responses in Sprague‐Dawley rats was investigated. Sulfoxaflor transformation was catalyzed by cytochrome P450 while five phase I and four phase II metabolites were identified in vivo. Exposure to sulfoxaflor caused dysregulation of bile acid synthesis and reabsorption by the expression of farnesoid X receptor (FXR). Abstract In the present study, we investigated the biotransformation of the neonicotinoid pesticide sulfoxaflor and the metabolic responses in Sprague‐Dawley rats. Sulfoxaflor transformation was catalyzed by cytochrome P450 while five phase I and four phase II metabolites were identified for the first time in vivo. The experimental results demonstrated that sulfoxaflor brought about the metabolic profiling disturbances in liver and bile. Exposure to sulfoxaflor caused dysregulation of bile acid synthesis and reabsorption by the expression of farnesoid X receptor (FXR). Our data provided insights into biotransformation of chemicals while enabling the implementation of a new toolbox for the design of sulfoximine compounds.

Corrigendum: Vancomycin Resistance Is Overcome by Conjugation of Polycationic Peptides

By Florian Umstätter, Cornelius Domhan, Tobias Hertlein, Knut Ohlsen, Eric Mühlberg, Christian Kleist, Stefan Zimmermann, Barbro Beijer, Karel D. Klika, Uwe Haberkorn, Walter Mier, Philipp Uhl from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Cobalt Single‐Atom Catalysts with High Stability for Selective Dehydrogenation of Formic Acid

By Xiang Li, Annette‐Enrica Surkus, Jabor Rabeah, Muhammad Anwar, Sarim Dastigir, Henrik Junge, Angelika Brückner, Matthias Beller from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

The small print: Co‐N‐C single‐atom catalysts were derived from metal– organic frameworks and compared with related nanoparticles in the selective dehydrogenation of formic acid. The highly dispersed single CoIINx sites demonstrated improved reactivity and resistance to acid, constituting the current state‐of‐the‐art in low‐cost earth‐abundant catalyst for this transformation. Abstract Metal–organic framework (MOF)‐derived Co‐N‐C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co‐N‐C catalyst achieves superior activity, better acid resistance, and improved long‐term stability compared with nanoparticles synthesized by a similar route. High‐angle annular dark‐field–scanning transmission electron microscopy, X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and X‐ray absorption fine structure characterizations reveal the formation of CoIINx centers as active sites. The optimal low‐cost catalyst is a promising candidate for liquid H2 generation.

Building up Strain in One Step: Synthesis of an Edge‐Fused Double Silacyclobutene from an Extensively Trichlorosilylated Butadiene Dianion

By Isabelle Georg, Markus Bursch, Julius B. Stückrath, Edith Alig, Michael Bolte, Hans‐Wolfram Lerner, Stefan Grimme, Matthias Wagner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Upcycling: A sixfold trichlorosilylated butadiene dianion is accessible in one step from hexachlorobutadiene and the Si2Cl6/Cl− system. Cl− abstraction with AlCl3 causes a double cyclization reaction and quantitatively forms a six‐membered double silacyclobutene. Abstract The exhaustive trichlorosilylation of hexachloro‐1,3‐butadiene was achieved in one step by using a mixture of Si2Cl6 and [nBu4N]Cl (7:2 equiv) as the silylation reagent. The corresponding butadiene dianion salt [nBu4N]2[1] was isolated in 36 % yield after recrystallization. The negative charges of [1]2− are mainly delocalized across its two carbanionic (Cl3Si)2C termini (α‐effect of silicon) such that the central bond possesses largely C=C double‐bond character. Upon treatment with 4 equiv of HCl, [1]2− is converted into neutral 1,2,3,4‐tetrakis(trichlorosilyl)but‐2‐ene, 3. The Cl− acceptor AlCl3, induces a twofold ring‐closure reaction of [1]2− to form a six‐membered bicycle 4 in which two silacyclobutene rings are fused along a shared C=C double bond (84 %). Compound 4, which was structurally characterized by X‐ray crystallography, undergoes partial ring opening to a monocyclic silacyclobutene 2 in the presence of HCl, but is thermally stable up to at least 180 °C.

Cs2PtI6 Halide Perovskite is Stable to Air, Moisture, and Extreme pH: Application to Photoelectrochemical Solar Water Oxidation

By Muhammed Hamdan, Aravind Kumar Chandiran from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Stability: Despite the excellent optoelectronic properties of halide perovskites, their stability under ambient conditions and, more importantly, in aqueous medium are poor, thus limiting their application in solar photoelectrochemical (PEC) devices. Reported here is an extremely stable vacancy ordered halide perovskite, Cs2PtI6, which is stable for at least one year under ambient conditions and for 24 hours in extreme pH conditions. It also demonstrated 12 hours of solar PEC water oxidation, without any surface protection. Abstract Halide perovskites show incredible photovoltaic power conversion efficiency coupled with several hundreds of hours of device stability. However, their stability is poor in aqueous electrolyte media. Reported here is a vacancy ordered halide perovskite, Cs2PtI6, which shows extraordinary stability under ambient conditions (1 year), in aqueous media of extreme acidic (pH 1), basic (pH 13), and under electrochemical reduction conditions. It was employed as an electrocatalyst and photoanode for hydrogen production and water oxidation, respectively. The catalyst remains intact for at least 100 cycles of electrochemical cycling and six hours of hydrogen production at pH 1. Cs2PtI6 was employed as a photoanode for PEC water oxidation, and the material displayed a photocurrent of 0.8 mA cm−2 at 1.23 V (vs. RHE) under simulated AM1.5G sunlight. Using constant voltage measurement, Cs2PtI6 exhibited over 12 hours of PEC stability without loss of performance.

Heteroatom Dopants Promote Two‐Electron O2 Reduction for Photocatalytic Production of H2O2 on Polymeric Carbon Nitride

By Peng Zhang, Yawen Tong, Yong Liu, Junie Jhon M. Vequizo, Hongwei Sun, Can Yang, Akira Yamakata, Fengtao Fan, Wei Lin, Xinchen Wang, Wonyong Choi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 29, 2020.

Heptazine‐based C3N4 photocatalysts with heteroatom dopants exhibit potassium‐induced interlayer charge separation and local charge polarization on sulfur sites. This facilitates O2 adsorption and the subsequent two‐electron reduction of dioxygen to achieve highly efficient and selective production of H2O2 up to a millimolar level per hour and 100 % apparent quantum yield at 420 nm. Abstract Polymeric carbon nitride modified with selected heteroatom dopants was prepared and used as a model photocatalyst to identify and understand the key mechanisms required for efficient photoproduction of H2O2 via selective oxygen reduction reaction (ORR). The photochemical production of H2O2 was achieved at a millimolar level per hour under visible‐light irradiation along with 100 % apparent quantum yield (in 360–450 nm region) and 96 % selectivity in an electrochemical system (0.1 V vs. RHE). Spectroscopic analysis in spatiotemporal resolution and theoretical calculations revealed that the synergistic association of alkali and sulfur dopants in the polymeric matrix promoted the interlayer charge separation and polarization of trapped electrons for preferable oxygen capture and reduction in ORR kinetics. This work highlights the key features that are responsible for controlling the photocatalytic activity and selectivity toward the two‐electron ORR, which should be the basis of further development of solar H2O2 production.

[ASAP] Controlled Cavity-Free, Single-Photon Emission and Bipartite Entanglement of Near-Field-Excited Quantum Emitters

By Frank Bello*†, Nuttawut Kongsuwan‡§?, John F. Donegan†, and Ortwin Hess*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01705

[ASAP] Low-Voltage Domain-Wall LiNbO3 Memristors

By P. Chaudhary†, H. Lu†, A. Lipatov‡, Z. Ahmadi§, J. P. V. McConville#, A. Sokolov†, J. E. Shield§, A. Sinitskii‡, J. M. Gregg#, and A. Gruverman*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01836

[ASAP] Scalable Ti3C2Tx MXene Interlayered Forward Osmosis Membranes for Enhanced Water Purification and Organic Solvent Recovery

By Xing Wu†, Mingmei Ding‡†, Hang Xu‡, Wen Yang‡, Kaisong Zhang§, Huali Tian§, Huanting Wang?, and Zongli Xie*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04471

[ASAP] Layer-Selective Synthesis of MoS2 and WS2 Structures under Ambient Conditions for Customized Electronics

By Seoungwoong Park†‡?, Aram Lee†?, Kwang-Hun Choi†, Seok-Ki Hyeong†, Sukang Bae†, Jae-Min Hong†, Tae-Wook Kim§, Byung Hee Hong*‡, and Seoung-Ki Lee*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02745

[ASAP] Nanotechnology for COVID-19: Therapeutics and Vaccine Research

By Gaurav Chauhan*†, Marc J. Madou*†‡, Sourav Kalra§, Vianni Chopra?, Deepa Ghosh?, and Sergio O. Martinez-Chapa*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04006

[ASAP] Photoactivated H2 Nanogenerator for Enhanced Chemotherapy of Bladder Cancer

By Rui Sun†, Xiaocen Liu†, Guangzhi Li†, Hui Wang†‡, Yongxiang Luo†, Guixiao Huang†, Xisheng Wang§, Guohua Zeng?, Zhuang Liu*?, and Song Wu*†# from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01300

[ASAP] Revealing Factors Influencing the Operational Stability of Perovskite Light-Emitting Diodes

By Jonathan H. Warby, Bernard Wenger, Alexandra J. Ramadan, Robert D. J. Oliver, Harry C. Sansom, Ashley R. Marshall, and Henry J. Snaith* from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03516

[ASAP] Lysosomal Proton Buffering of Poly(ethylenimine) Measured In Situ by Fluorescent pH-Sensor Microcapsules

By Sathi Roy†, Dingcheng Zhu†, Wolfgang J. Parak†‡, and Neus Feliu*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.9b10219

[ASAP] Voltage Control of Magnetism above Room Temperature in Epitaxial SrCo1–xFexO3-d

By Shuai Ning*†, Qiqi Zhang‡, Connor Occhialini§, Riccardo Comin§, Xiaoyan Zhong‡??, and Caroline A. Ross*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03750

[ASAP] Plasmon-Enhanced Resonant Photoemission Using Atomically Thick Dielectric Coatings

By Xiao Xiong†#, Yang Zhou‡#, Yi Luo‡, Xiang Li¶, Michel Bosman§?, Lay Kee Ang?, Peng Zhang*‡, and Lin Wu*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03406

[ASAP] Molecular Beam Epitaxy of Transition Metal (Ti-, V-, and Cr-) Tellurides: From Monolayer Ditellurides to Multilayer Self-Intercalation Compounds

By Kinga Lasek†, Paula Mariel Coelho†, Krzysztof Zberecki‡, Yan Xin§, Sadhu K. Kolekar†, Jingfeng Li†, and Matthias Batzill*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02712

[ASAP] Quantification of Multivalent Interactions between Sialic Acid and Influenza A Virus Spike Proteins by Single-Molecule Force Spectroscopy

By Jose Luis Cuellar-Camacho*†, Sumati Bhatia*†, Valentin Reiter-Scherer‡, Daniel Lauster†§, Susanne Liese?, Ju¨rgen P. Rabe‡, Andreas Herrmann§, and Rainer Haag† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c02852

[ASAP] Correction to “Observation of Resonant Quantum Magnetoelectric Effect in a Multiferroic Metal–Organic Framework”

By Ying Tian, Shipeng Shen, Junzhuang Cong, Liqin Yan, Shouguo Wang, and Young Sun* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 29, 2020.

Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06670

[ASAP] Shallow Distance Dependence for Proton-Coupled Tyrosine Oxidation in Oligoproline Peptides

By Brian Koronkiewicz*‡, John Swierk†, Kevin Regan, and James M. Mayer* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c01429

[ASAP] Aptamers as Versatile Molecular Tools for Antibody Production Monitoring and Quality Control

By Kaiming Chen†, Jie Zhou‡, Zhentao Shao†, Jia Liu†, Jia Song†, Ruowen Wang*†, Juan Li*†‡, and Weihong Tan*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.9b13370

[ASAP] Spotlights on Recent JACS Publications

By ACS Contributing Correspondents from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 29, 2020.

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Journal of the American Chemical Society
DOI: 10.1021/jacs.0c06867

In situ electrochemical generation of nitric oxide for neuronal modulation

By Polina Anikeeva from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Nanotechnology, Published online: 29 June 2020; doi:10.1038/s41565-020-0701-x

Iron sulfide nanoclusters enable on-demand and local generation of nitric oxide, an important lipophilic messenger in the brain, allowing the modulation and investigation of nitric oxide-triggered neural signalling events.

High oscillator strength interlayer excitons in two-dimensional heterostructures for mid-infrared photodetection

By Jinghua Teng from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Nanotechnology, Published online: 29 June 2020; doi:10.1038/s41565-020-0717-2

Formation of interlayer excitons with high oscillator strength in a WS2/HfS2 heterostructure enables the realization of high-responsivity room-temperature mid- and long-wavelength infrared photodetectors.

Quantum Hall effect of Weyl fermions in n-type semiconducting tellurene

By Peide D. Ye from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Nanotechnology, Published online: 29 June 2020; doi:10.1038/s41565-020-0715-4

The accidental band-crossing origin of Weyl nodes paired with the absence of sizeable band gaps hampers the exploitation of low-energy relativistic quasiparticles in Weyl semimetals. In a gate-tunable high-quality tellurene film, quantum Hall measurements unveil a topologically non-trivial π Berry phase caused by unconventional Weyl nodes in these tellurium two-dimensional sheets.

Power-efficient neural network with artificial dendrites

By Huaqiang Wu from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Nanotechnology, Published online: 29 June 2020; doi:10.1038/s41565-020-0722-5

A memristor-based artificial dendrite enables the neural network to perform high-accuracy computation tasks with reduced power consumption.

Subretinally injected semiconducting polymer nanoparticles rescue vision in a rat model of retinal dystrophy

By Fabio Benfenati from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Nanotechnology, Published online: 29 June 2020; doi:10.1038/s41565-020-0696-3

Semiconducting polymer nanoparticles can act as light-sensitive interfaces with retinal neurons, and on microinjection in the eye, rescue vision in retinas affected by photoreceptor degeneration, offering a potential new treatment option for inherited retinal dystrophies and late-stage age-related macular degeneration.

Electrochemical cell in the brain

By Sunghak Park from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Nanotechnology, Published online: 29 June 2020; doi:10.1038/s41565-020-0711-8

Nitric oxide, a gaseous neurotransmitter, can be electrochemically generated inside the brain to activate calcium ion channels, paving the way for implantable neurotransmitter probes.

Chirality-induced relaxor properties in ferroelectric polymers

By Qing Wang from Nature Materials - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Materials, Published online: 29 June 2020; doi:10.1038/s41563-020-0724-6

Relaxor ferroelectric polymers are a material of choice for applications such as electrostrictive actuators or electrocaloric cooling. Here, the origin of relaxor behaviour at the molecular level is investigated and found to arise from conformational disorder.

Distinct handedness of spin wave across the compensation temperatures of ferrimagnets

By Chanyong Hwang from Nature Materials - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Materials, Published online: 29 June 2020; doi:10.1038/s41563-020-0722-8

Right- and left-handed spin-wave modes are identified in ferrimagnets, and their dynamics are revealed.

Exchange magnetostriction in two-dimensional antiferromagnets

By Kin Fai Mak from Nature Materials - Issue - nature.com science feeds. Published on Jun 29, 2020.

Nature Materials, Published online: 29 June 2020; doi:10.1038/s41563-020-0712-x

A coupling of mechanical vibrations and magnetism and strain-tuning of the exchange interactions, is demonstrated for few-layer CrI3.

Supramolecular assembly of DNA-constructed vesicles

By Robert Häner from RSC - Nanoscale latest articles. Published on Jun 29, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR04103C, Communication
Open Access Open Access
Simon Rothenbühler, Ioan Iacovache, Simon M. Langenegger, Benoît Zuber, Robert Häner
The self-assembly of DNA hybrids with tetraphenylethylene sticky ends into vesicular architectures is demonstrated.
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Holistically Engineered Polymer–Polymer and Polymer–Ion Interactions in Biocompatible Polyvinyl Alcohol Blends for High‐Performance Triboelectric Devices in Self‐Powered Wearable Cardiovascular Monitorings

By Ruoxing Wang, Liwen Mu, Yukai Bao, Han Lin, Tuo Ji, Yijun Shi, Jiahua Zhu, Wenzhuo Wu from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

The impact of molecular/ionic fillers on polyvinyl alcohol (PVA) blends’ triboelectric performance is investigated through systematic material engineering, and characterization of PVA blends at different structure levels. Self‐powered devices built with optimized PVA–gelatin composite films are capable of detecting the imperceptible degree of skin deformation induced by the human pulse and capture the cardiovascular information encoded in the pulse signals. Abstract The capability of sensor systems to efficiently scavenge their operational power from stray, weak environmental energies through sustainable pathways could enable viable schemes for self‐powered health diagnostics and therapeutics. Triboelectric nanogenerators (TENG) can effectively transform the otherwise wasted environmental, mechanical energy into electrical power. Recent advances in TENGs have resulted in a significant boost in output performance. However, obstacles hindering the development of efficient triboelectric devices based on biocompatible materials continue to prevail. Being one of the most widely used polymers for biomedical applications, polyvinyl alcohol (PVA) presents exciting opportunities for biocompatible, wearable TENGs. Here, the holistic engineering and systematic characterization of the impact of molecular and ionic fillers on PVA blends’ triboelectric performance is presented for the first time. Triboelectric devices built with optimized PVA‐gelatin composite films exhibit stable and robust triboelectricity outputs. Such wearable devices can detect the imperceptible skin deformation induced by the human pulse and capture the cardiovascular information encoded in the pulse signals with high fidelity. The gained fundamental understanding and demonstrated capabilities enable the rational design and holistic engineering of novel materials for more capable biocompatible triboelectric devices that can continuously monitor vital physiological signals for self‐powered health diagnostics and therapeutics.

Gradient‐Concentration Design of Stable Core–Shell Nanostructure for Acidic Oxygen Reduction Electrocatalysis

By Xiao Lyu, Yi Jia, Xin Mao, Daohao Li, Gen Li, Linzhou Zhuang, Xin Wang, Dongjiang Yang, Qiang Wang, Aijun Du, Xiangdong Yao from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

Highly active Pt–Ni@PtD/G catalysts with extraordinary stability for acidic oxygen reduction reaction (ORR) are synthesized by a gradient‐concentration strategy (i.e., starting with facile galvanic replacement followed by partial dealloying). The optimal “armor” with active and dense locally concave Pt atomic sites is responsible for the enhanced catalytic activity and stability in acidic ORR. Abstract Manipulating the surface structure of electrocatalysts at the atomic level is of primary importance to simultaneously achieve the activity and stability dual‐criteria in oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, a durable acidic ORR electrocatalyst with the “defective‐armored” structure of Pt shell and Pt–Ni core nanoparticle decorated on graphene (Pt–Ni@PtD/G) using a facile and controllable galvanic replacement reaction to generate gradient distribution of Pt–Ni composition from surface to interior, followed by a partial dealloying approach, leaching the minor nickel atoms on the surface to generate defective Pt skeleton shell, is reported. The Pt–Ni@PtD/G catalyst shows impressive performance for ORR in acidic (0.1 m HClO4) electrolyte, with a high mass activity of threefold higher than that of Pt/C catalyst owing to the tuned electronic structure of locally concave Pt surface sites through synergetic contributions of Pt–Ni core and defective Pt shell. More importantly, the electrochemically active surface areas still retain 96% after 20 000 potential cycles, attributing to the Pt atomic shell acting as the protective “armor” to prevent interior Ni atoms from further dissolution during the long‐term operation.

Highly Efficient Persistent Room‐Temperature Phosphorescence from Heavy Atom‐Free Molecules Triggered by Hidden Long Phosphorescent Antenna

By Indranil Bhattacharjee, Shuzo Hirata from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

The extension of the conjugated antenna units relating transition from high order singlet excited states in heavy atom‐free chromophores greatly enhances the phosphorescence rate (kp) without a large increase of vibration‐based radiationless transition rate (knr(RT)) with large triplet yield, which results in the room‐temperature phosphorescence (RTP) yield (Φp(RT)) of 50% as well as the RTP lifetime (τp(RT)) of 1.0 s. Abstract Persistent (lifetime > 100 ms) room‐temperature phosphorescence (pRTP) is important for state‐of‐the‐art security and bioimaging applications. An unclear relationship between chromophores and physical parameters relating to pRTP has prevented obtaining an RTP yield of over 50% and a lifetime over 1 s. Here highly efficient pRTP is reported under ambient conditions from heavy atom‐free chromophores. A heavy atom‐free aromatic core substituted with a long‐conjugated amino group considerably accelerates the phosphorescence rate independent of the intramolecular vibration‐based nonradiative rate from the lowest excited triplet state. One of the designed heavy atom‐free dopant chromophores presents an RTP yield of 50% with a lifetime of 1 s under ambient conditions. The afterglow brightness under strong excitation is at least 104 times stronger than that of conventional long‐persistent luminescence emitters. Here it is shown that highly efficient pRTP materials allow for high‐resolution gated emission with a size of the diffraction limit using small‐scale and low‐cost photodetectors.

A High‐Efficiency CoSe Electrocatalyst with Hierarchical Porous Polyhedron Nanoarchitecture for Accelerating Polysulfides Conversion in Li–S Batteries

By Zhengqing Ye, Ying Jiang, Li Li, Feng Wu, Renjie Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

A high‐efficiency CoSe electrocatalyst with hierarchical porous polyhedron nanoarchitecture (CS@HPP) is presented as a sulfur host for lithium–sulfur batteries. The CS@HPP with high electrical conductivity and abundant active sites can catalytically accelerate capture/diffusion of polysulfides and precipitation/decomposition of Li2S. Consequently, excellent electrochemical performance is synchronously displayed for both slurry‐bladed and freestanding cathodes. Abstract Lithium–sulfur (Li–S) batteries are recognized as promising candidates for next‐generation electrochemical energy storage systems owing to their high energy density and cost‐effective raw materials. However, the sluggish multielectron sulfur redox reactions are the root cause of most of the issues for Li–S batteries. Herein, a high‐efficiency CoSe electrocatalyst with hierarchical porous nanopolyhedron architecture (CS@HPP) derived from a metal–organic framework is presented as the sulfur host for Li–S batteries. The CS@HPP with high crystal quality and abundant reaction active sites can catalytically accelerate capture/diffusion of polysulfides and precipitation/decomposition of Li2S. Thus, the CS@HPP sulfur cathode exhibits an excellent capacity of 1634.9 mAh g−1, high rate performance, and a long cycle life with a low capacity decay of 0.04% per cycle over 1200 cycles. CoSe nanopolyhedrons are further fabricated on a carbon cloth framework (CC@CS@HPP) to unfold the electrocatalytic activity by its high electrical conductivity and large surface area. A freestanding CC@CS@HPP sulfur cathode with sulfur loading of 8.1 mg cm−2 delivers a high areal capacity of 8.1 mAh cm−2 under a lean electrolyte. This work will enlighten the rational design of structure–catalysis engineering of transition‐metal‐based nanomaterials for diverse applications.

On‐Demand Autophagy Cascade Amplification Nanoparticles Precisely Enhanced Oxaliplatin‐Induced Cancer Immunotherapy

By Xuhui Wang, Man Li, Kebai Ren, Chunyu Xia, Jianping Li, Qianwen Yu, Yue Qiu, Zhengze Lu, Yang Long, Zhirong Zhang, Qin He from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

An on‐demand autophagy cascade amplification nanoparticle (ASN) is established to intelligently boost oxaliplatin (OXA)‐induced immunotherapy of cancer cells. Upon arrival at tumor site, ASN first releases OXA to trigger tumor immunogenic death and stimulates autophagy. Then ASN can respond to the OXA‐induced autophagy and further overactivate autophagy, which not only leads tumor to autophagic death but also enhances immune cell recruitment. Abstract Chemoimmunotherapy‐induced antitumor immune response is highly dependent on tumor autophagy. When tumor cells are treated with chemoimmunotherapy, timely overactivated autophagy can not only lead more tumor cells to death, but also participate in the endogenous antigen presentation and immune stimulators secretion of dying cells, thus plays a vital role. However, timely and accurately overactivated tumor autophagy during chemoimmunotherapy is of great difficulty. Here, an on‐demand autophagy cascade amplification nanoparticle (ASN) is reported to boost oxaliplatin‐induced cancer immunotherapy. ASN is prepared by self‐assemble of autophagy‐responsible C‐TFG micelle and is followed by electrostatic binding of oxaliplatin prodrug (HA‐OXA). After entering tumor cells, the HA‐OXA shell of ASN first responds to the reduction microenvironment and releases oxaliplatin to trigger tumor immunogenic cell death and mildly stimulates tumor autophagy. Then, the exposed C‐TFG micelle can sensitively respond to oxaliplatin‐induced autophagy and release a powerful autophagy inducer STF‐62247, which precisely transforms autophagy to “overactivated” condition, leading tumor cells to autophagic death and enhance subsequent tumor antigen processing of the dying cells. In CT26 tumor‐bearing mice, ASN exhibits optimal immune stimulation and antitumor efficiency due to its on‐demand autophagy induction ability.

Initiating a Reversible Aqueous Zn/Sulfur Battery through a “Liquid Film”

By Yuwei Zhao, Donghong Wang, Xinliang Li, Qi Yang, Ying Guo, Funian Mo, Qing Li, Chengxin Peng, Hongfei Li, Chunyi Zhi from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

The first reliable aqueous Zn/S system is activated by a “liquid film” comprising an ionic liquid (IL) encapsulated within PEDOT:PSS. CF3SO3− anions in the IL operate as Zn2+‐transfer channels. The PEDOT:PSS network renders the polysulfide cathode with enhanced structural stability. The Zn/S system delivers extraordinary capacity of 1148 mAh g−1 and overwhelming energy density of 724.7 Wh kg−1cathode at 0.3 Ag−1. Abstract Sulfur cathodes have been under intensive study in various systems, such as Li/S, Na/S, Mg/S, and Al/S batteries. However, to date, Zn/S chemistry has never been reported. The first reliable aqueous Zn/polysulfide system activated by a “liquid film” comprising 4‐(3‐butyl‐1‐imidazolio)‐1‐butanesulfoni ionic liquid (IL) encapsulated within PEDOT:PSS. CF3SO3− anions in the IL operating as Zn2+‐transfer channels is reported. Moreover, the PEDOT:PSS network retains the IL, which renders Zn2+‐transfer channels and a polysulfide cathode with enhanced structural stability. The Zn/polysulfide system delivers extraordinary capacity of 1148 mAh g−1 and overwhelming energy density of 724.7 Wh kg−1cathode at 0.3 Ag−1. During the discharging phase, S62− is dominantly reduced by Zn to S2− (S6  →  S2−). During the charging phase, these short chains are oxidized to form long‐chain ZnxLiyS3‐6. A further optimized high‐concentrated salt electrolyte is used to improve the reversibility of the battery, demonstrating an extended lifetime over 1600 cycles at 1 Ag−1 with a capacity retention of 204 mAh g−1. This facile approach and the superior performance of the developed aqueous Zn/S chemistry provide a new platform for sulfur‐based battery and potentially solve the problems of other metal/sulfur batteries.

Understanding the Effect of Crystalline Structural Transformation for Lead‐Free Inorganic Halide Perovskites

By Ming Shi, Guanna Li, Wenming Tian, Shengye Jin, Xiaoping Tao, Yiming Jiang, Evgeny A. Pidko, Rengui Li, Can Li from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

Silver atoms incorporated into the inorganic halide perovskite Cs3Bi2Br9 to form Cs2AgBiBr6 eliminates the strong localization of electron–hole pairs and makes the electronic bands distribution more dispersible and further changes the photoelectric properties including band structure, exciton binding energy, charge carrier mobility, and carrier relaxation lifetime, which lead to a remarkable enhancement in photocatalytic hydrogen evolution under visible light. Abstract Lead‐free inorganic halide perovskites have triggered appealing interests in various energy‐related applications including solar cells and photocatalysis. However, why perovskite‐structured materials exhibit excellent photoelectric properties and how the unique crystalline structures affect the charge behaviors are still not well elucidated but essentially desired. Herein, taking inorganic halide perovskite Cs3Bi2Br9 as a prototype, the significant derivation process of silver atoms incorporation to induce the structural transformation from Cs3Bi2Br9 to Cs2AgBiBr6, which brings about dramatic differences in photoelectric properties is unraveled. It is demonstrated that the silver incorporation results in the co‐operated orbitals hybridization, which makes the electronic distributions in conduction and valence bands of Cs2AgBiBr6 more dispersible, eliminating the strong localization of electron–hole pairs. As consequences of the electronic structures derivation, exhilarating changes in photoelectric properties like band structure, exciton binding energy, and charge carrier dynamics are verified experimentally and theoretically. Using photocatalytic hydrogen evolution activity under visible light as a typical evaluation, such crystalline structure transformation contributes to a more than 100‐fold enhancement in photocatalytic performances compared with pristine Cs3Bi2Br9, verifying the significant effect of structural derivations on the exhibited performances. The findings will provide evidences for understanding the origin of photoelectric properties for perovskites semiconductors in solar energy conversion.

A Highly Crystalline Perylene Imide Polymer with the Robust Built‐In Electric Field for Efficient Photocatalytic Water Oxidation

By Zijian Zhang, Xianjie Chen, Hanjie Zhang, Weixu Liu, Wei Zhu, Yongfa Zhu from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

A crystalline perylene imide polymer photocatalyst with the highest oxygen evolution performance is achieved. The polymer can be reused over 100 h without any decrease in performance overcoming the poor stability of the organic photocatalysts. The superior photocatalytic performance comes from the suitable energy band and the robust built‐in electric field contributed by the highly crystallinity and large molecular dipole. Abstract A highly crystalline perylene imide polymer (Urea‐PDI) photocatalyst is successfully constructed. The Urea‐PDI presents a wide spectrum response owing to its large conjugated system. The Urea‐PDI performs so far highest oxygen evolution rate (3223.9 µmol g−1 h−1) without cocatalysts under visible light. The performance is over 107.5 times higher than that of the conventional PDI supramolecular photocatalysts. The strong oxidizing ability comes from the deep valence band (+1.52 eV) which is contributed by the covalent‐bonded conjugated molecules. Besides, the high crystallinity and the large molecular dipoles of the Urea‐PDI contribute to a robust built‐in electric field promoting the separation and transportation of photogenerated carriers. Moreover, the Urea‐PDI is very stable and has no performance attenuation after 100 h continuous irradiation. The Urea‐PDI polymer photocatalyst provides with a new platform for the use of photocatalytic water oxidation, which is expected to contribute to clean energy production.

Novel Skutterudite CoP3–Based Asymmetric Supercapacitor with Super High Energy Density

By Jing Jiang, Zhipeng Li, Xinrui He, Yalin Hu, Fu Li, Pei Huang, Chao Wang from Wiley: Small: Table of Contents. Published on Jun 28, 2020.

A skutterudite structure of Ni‐doped CoP3 nanosheets is designed via etching and coprecipitating at room temperature and subsequent low‐temperature phosphating treatment. The incorporation of Ni ensures higher electrical conductivity and richer electrochemical active sites, which results in ultrahigh high energy density when Ni–CoP3 electrode is assembled into asymmetric supercapacitors. Abstract Skutterudite CoP3 holds a unique structural formation that exhibits much better electronic properties for obtaining high energy density supercapacitors. Herein, novel skutterudite Ni–CoP3 nanosheets are constructed by etching and coprecipitating at room temperature and subsequent low‐temperature phosphorization reaction. Benefiting from the enhanced electrical conductivity and more electroactive sites brought about by adjusting the electronic structure with Ni incorporating the Ni–CoP3 electrode with a battery‐type demonstrates an ultrahigh specific capacity of 0.7 mA h cm−2 and exceptional cycling stability. The asymmetric supercapacitor (ASC) device fabricated by employing Ni–CoP3 and activated carbon (AC) as positive and negative electrodes, resepectively, exhibits a remarkable high energy density of 89.6 Wh kg−1 at 796 W kg−1 and excellent stability of 93% after 10 000 cycles, due to the skutterudite structure. The skutterudite Ni–CoP3 shows a great potential to be an excellent next‐generation electrode candidate for supercapacitors and other energy storage devices.

A Graphdiyne Oxide‐Based Iron Sponge with Photothermally Enhanced Tumor‐Specific Fenton Chemistry

By Huan Min, Yingqiu Qi, Yinlong Zhang, Xuexiang Han, Keman Cheng, Ying Liu, Hiubiao Liu, Jianshe Hu, Guangjun Nie, Yiye Li from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

A tumor targeting iron sponge (TTIS) based on graphdiyne oxide is fabricated with controlled iron release. The TTIS can accumulate in tumor tissue to achieve a photoacoustic‐ and magnetic resonance tumor imaging and simultaneously escort an efficient tumor therapy via photothermally enhanced Fenton chemistry. Abstract Fenton reaction‐mediated oncotherapy is an emerging strategy which uses iron ions to catalytically convert endogenous hydrogen peroxide into hydroxyl radicals, the most reactive oxygen species found in biology, for efficient cancer therapy. However, Fenton reaction efficiency in tumor tissue is typically limited due to restrictive conditions. One strategy to overcome this obstacle is to increase the temperature specifically at the tumor site. Herein, a tumor‐targeting iron sponge (TTIS) nanocomposite based on graphdiyne oxide, which has a high affinity for iron is described. TTIS can accumulate in tumor tissue by decoration with a tumor‐targeting polymer to enable tumor photoacoustic and magnetic resonance imaging. With its excellent photothermal conversion efficiency (37.5%), TTIS is an efficient photothermal therapy (PTT) agent. Moreover, the heat produced in the process of PTT can accelerate the release of iron ions from TTIS and simultaneously enhance the efficiency of the Fenton reaction, thus achieving a combined PTT and Fenton reaction‐mediated cancer therapy. This work introduces a graphdiyne oxide‐based iron sponge that exerts an enhanced antitumor effect through PTT and Fenton chemistry.

Lignin‐Based Direct Ink Printed Structural Scaffolds

By Bo Jiang, Yonggang Yao, Zhiqiang Liang, Jinlong Gao, Gegu Chen, Qinqin Xia, Ruiyu Mi, Miaolun Jiao, Xizheng Wang, Liangbing Hu from Wiley: Small: Table of Contents. Published on Jun 28, 2020.

By developing an aqueous‐based, viscoelastic lignin ink, 3D structures of lignin are constructed via a direct ink printing strategy. The ink design and direct printing strategy exhibit distinct advantages over the fused deposition modeling technique, while the printed scaffolds display superior properties such as wet stability and high stiffness, demonstrating an important strategy for value‐added applications of the abundant lignocellulosic materials. Abstract 3D printing of lignocellulosic biomass (cellulose, hemicellulose, and lignin) has attracted increasing attention by using this abundant, sustainable, and ecofriendly material. While cellulose can be easily tailored into a highly viscous ink for 3D printing, after solvent evaporation, the final printed structures become highly porous, fragile, and easily fall apart in water due to its hydrophilic nature. Lignin, another crucial component of natural lignocellulose, has not yet been reported for ink printing due to its unfavorable rheological behavior. Herein, a low‐cost direct ink printing strategy is developed to fabricate lignin‐based 3D structures with lignin no further refined and a more compact microstructure as well as different functionalities compared with printed cellulose. By using a soft triblock copolymer as the crosslinking agent, the rheology of lignin‐based inks can be adjusted from soft to rigid, and even enables vertical printing which requires stiff and self‐supporting features. The lignin‐based inks contain less water (≈40 wt%) and exhibit a much denser, stiffer structure, resulting in a wet tensile strength of ≈30 MPa, compared to only ≈0.6 MPa for printed cellulose. In addition, the unique macromolecular structure of lignin also demonstrates significantly improved stability in water and under heat, as well as UV‐blocking performance.

Lead‐Free Perovskite Variant Solid Solutions Cs2Sn1–xTexCl6: Bright Luminescence and High Anti‐Water Stability

By Zhifang Tan, Yanmeng Chu, Jinxi Chen, Jinghui Li, Guoqi Ji, Guangda Niu, Liang Gao, Zewen Xiao, Jiang Tang from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

Cs2Sn1−xTexCl6 exhibits excellent moisture and thermal stability (upon 618 oC) and near‐unity photoluminescence quantum yield (95.4%), which is caused by the combination of Te luminescent center and Jahn–Teller‐like self‐trapped excitons. There is no photoluminescence degradation even after 360 min of soaking in water. The good stability is due to the large decomposition enthalpy and formation of amorphous alteration phase. Abstract Underwater lighting is important for the exploration of the underwater world in different areas. It is of great significance for developing underwater emitters with high penetrability, high luminous efficiency, good anti‐water stability, and environmental friendliness. Stable lead‐free perovskite luminescent materials, represented by vacancy‐ordered double perovskites, are worthy of research because they can almost meet the above requirements. Here, lead‐free perovskite variant solid solutions with the formula of Cs2Sn1−xTexCl6 are reported. Upon the exchange of Sn/Te ions, strong Jahn–Teller distortion of octahedra occurs in the lattice structure. The combination of Te luminescent center and Jahn–Teller‐like self‐trapped excitons gives this material yellow‐green luminescence with a wavelength of 580 nm and a high photoluminescence quantum yield of 95.4%. Moreover, these solid solutions can withstand the extreme conditions of immersion in water probably due to the formation of amorphous alteration phase. Such good anti‐water stability is also supported by the molecule dynamics simulation result that no reaction occurs on the water/Cs2SnCl6 interface. The high luminous, suitable wavelength, and good anti‐water stability enable the solid solutions suitable for the application for underwater lighting.

Bulk Spin Torque‐Driven Perpendicular Magnetization Switching in L10 FePt Single Layer

By Meng Tang, Ka Shen, Shijie Xu, Huanglin Yang, Shuai Hu, Weiming Lü, Changjian Li, Mengsha Li, Zhe Yuan, Stephen J. Pennycook, Ke Xia, Aurelien Manchon, Shiming Zhou, Xuepeng Qiu from Wiley: Advanced Materials: Table of Contents. Published on Jun 28, 2020.

Bulk spin torque‐driven perpendicular magnetization switching in an L10 FePt single‐layer arises from an inherent structural gradient and exhibits great potential for removing the fundamental obstacles faced by conventional spin–orbit torque devices, such as thermal stability issues and complexity issues regarding three‐terminal operation. Abstract Due to its inherent superior perpendicular magnetocrystalline anisotropy, the FePt in L10 phase enables magnetic storage and memory devices with ultrahigh capacity. However, reversing the FePt magnetic state, and therefore encoding information, has proven to be extremely difficult. Here, it is demonstrated that an electric current can exert a large spin torque on an L10 FePt magnet, ultimately leading to reversible magnetization switching. The spin torque monotonically increases with increasing FePt thickness, exhibiting a bulk characteristic. Meanwhile, the spin torque effective fields and switching efficiency increase as the FePt approaches higher chemical ordering with stronger spin–orbit coupling. The symmetry breaking that generates spin torque within L10 FePt is shown to arise from an inherent structural gradient along the film normal direction. By artificially reversing the structural gradient, an opposite spin torque effect in L10 FePt is demonstrated. At last, the role of the disorder gradient in generating a substantial torque in a single ferromagnet is supported by theoretical calculations. These results will push forward the frontier of material systems for generating spin torques and will have a transformative impact on magnetic storage and spin memory devices with simple architecture, ultrahigh density, and readily application.

[ASAP] Adaptive Nanoparticle Platforms for High Throughput Expansion and Detection of Antigen-Specific T cells

By John W. Hickey†‡§??¶, Ariel Isser†‡§¶, Sebastian F. Salathe#, Kayla M. Gee†, Meng-Hsuan Hsiao?, Wasamah Shaikh§, Nkechi C. Uzoukwu‡§, Joan Glick Bieler‡§, Hai-Quan Mao†???, and Jonathan P. Schneck*‡§? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 28, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01511

[ASAP] Dual-Mode Avocado-like All-Iron Nanoplatform for Enhanced T1/T2 MRI-Guided Cancer Theranostic Therapy

By Jing Li†, Xincong Li†, Siman Gong†, Cuiting Zhang†, Chenggen Qian†, Hongzhi Qiao‡, and Minjie Sun*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 28, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c00817

[ASAP] Parallel Polarization Illumination with a Multifocal Axicon Metalens for Improved Polarization Imaging

By Chen Chen†‡§?, Yiqun Wang†‡§?, Minwei Jiang†‡§, Jian Wang†‡, Jian Guan‡, Baoshun Zhang§, Lei Wang‡, Jie Lin*†‡, and Peng Jin*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 28, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01877

[ASAP] Three-Dimensional Molybdenum Diselenide Helical Nanorod Arrays for High-Performance Aluminum-Ion Batteries

By Yuanfei Ai†‡?, Shu-Chi Wu‡???, Kuangye Wang‡??, Tzu-Yi Yang‡??, Mingjin Liu‡??, Hsiang-Ju Liao‡??, Jiachen Sun†, Jyun-Hong Chen‡??, Shin-Yi Tang‡, Ding Chou Wu‡, Teng-Yu Su‡??, Yi-Chung Wang†‡, Hsuan-Chu Chen‡??, Shan Zhang‡??, Wen-Wu Liu§, Yu-Ze Chen#, Ling Lee†‡??, Jr-Hau He?, Zhiming M. Wang*†, and Yu-Lun Chueh*‡?? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 28, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02831

Connectivity dependent thermopower of bridged biphenyl molecules in single-molecule junctions

By Colin J. Lambert from RSC - Nanoscale latest articles. Published on Jun 27, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR04001K, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Iain M. Grace, Gunnar Olsen, Juan Hurtado-Gallego, Laura Rincón-García, Gabino Rubio-Bollinger, Martin R. Bryce, Nicolás Agraït, Colin J. Lambert
We report measurements on gold|single-molecule|gold junctions, using a modified scanning tunneling microscope-break junction (STM-BJ) technique, of the Seebeck coefficient and electrical conductance of a series of bridged biphenyl molecules.
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Metal Atom‐Doped Co3O4 Hierarchical Nanoplates for Electrocatalytic Oxygen Evolution

By Song Lin Zhang, Bu Yuan Guan, Xue Feng Lu, Shibo Xi, Yonghua Du, Xiong Wen (David) Lou from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

Metal atom‐doped Co3O4 hierarchical nanoplates constructed by ultrathin nanosheets are synthesized by a cooperative etching−coordination−reorganization approach. The method allows doping of 13 metal elements in total. With the structural and compositional advantages, as an example, the Fe‐doped Co3O4 hierarchical nanoplates exhibit greatly enhanced electrocatalytic performance for oxygen evolution. Abstract Electrocatalysts based on hierarchically structured and heteroatom‐doped non‐noble metal oxide materials are of great importance for efficient and low‐cost electrochemical water splitting systems. Herein, the synthesis of a series of hierarchical hollow nanoplates (NPs) composed of ultrathin Co3O4 nanosheets doped with 13 different metal atoms is reported. The synthesis involves a cooperative etching−coordination−reorganization approach starting from zeolitic imidazolate framework‐67 (ZIF‐67) NPs. First, metal atom decorated ZIF‐67 NPs with unique cross‐channels are formed through a Lewis acid etching and metal species coordination process. Afterward, the composite NPs are converted to hollow Co3O4 hierarchical NPs composed of ultrathin nanosheets through a solvothermal reaction, during which the guest metal species is doped into the octahedral sites of Co3O4. Density functional theory calculations suggest that doping of small amount of Fe atoms near the surface of Co3O4 can greatly enhance the electrocatalytic activity toward the oxygen evolution reaction (OER). Benefiting from the structural and compositional advantages, the obtained Fe‐doped Co3O4 hierarchical NPs manifest superior electrocatalytic performance for OER with an overpotential of 262 mV at 10 mA cm−2, a Tafel slope of 43 mV dec−1, and excellent stability even at a high current density of 100 mA cm−2 for 50 h.

Robust Fabrication of Hybrid Lead‐Free Perovskite Pellets for Stable X‐Ray Detectors with Low Detection Limit

By Shujie Tie, Wei Zhao, Deyu Xin, Min Zhang, Jidong Long, Qi Chen, Xiaojia Zheng, Jianguo Zhu, Wen‐Hua Zhang from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

MA3Bi2I9 polycrystalline pellets (PPs) are fabricated by the robust, cost effective, and scalable cold isostatic‐pressing approach, and X‐ray detectors based on MA3Bi2I9‐PPs reach a limit of detection (LoD) of 9.3 nGyair s−1. The low LoD of the X‐ray detectors can obviously decrease the radiation dose used, thereby reducing health risks in medical diagnostics and security screening. Abstract X‐ray detectors are widely utilized in medical diagnostics and nondestructive product inspection. Halide perovskites are recently demonstrated as excellent candidates for direct X‐ray detection. However, it is still challenging to obtain high quality perovskites with millimeter‐thick over a large area for high performance, stable X‐ray detectors. Here, methylammonium bismuth iodide (MA3Bi2I9) polycrystalline pellets (PPs) are developed by a robust, cost effective, and scalable cold isostatic‐pressing for fabricating X‐ray detectors with low limit of detection (LoD) and superior operational stability. The MA3Bi2I9‐PPs possess a high resistivity of 2.28 × 1011 Ω cm and low dark carrier concentration of ≈107 cm−3, and balanced mobility of ≈2 cm2 V−1 s−1 for electrons and holes. These merits enable a sensitivity of 563 μC Gyair−1 cm−2, a detection efficiency of 28.8%, and an LoD of 9.3 nGyair s−1 for MA3Bi2I9‐PPs detectors, and the LoD is much lower than the dose rate required for X‐ray diagnostics used currently (5.5 μGyair s−1). In addition, the MA3Bi2I9‐PPs detectors work stably under high working bias field up to 2000 V cm−1 after sensing an integrated dose >320 Gyair with continuous X‐ray radiation, demonstrating its competitive advantage in practical application. These findings provide an approach to explore a new generation of low LoD, stable and green X‐ray detectors based on MA3Bi2I9‐PPs.

Perovskite Granular Wire Photodetectors with Ultrahigh Photodetectivity

By Yoon Ho Lee, Inho Song, Su Hwan Kim, Ju Hyun Park, Sung O Park, Jeong Hun Lee, Yousang Won, Kilwon Cho, Sang Kyu Kwak, Joon Hak Oh from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

Perovskite granular wires synthesized by a simple yet effective template‐free self‐assembly exhibit superior photodetecting performance with unprecedentedly high photodetectivity, originating from a low dark current due to band‐edge modulation along the long axis of the granular wires. The “self‐assembled nanograin engineering” strategy provides a viable method for the development of high‐performance perovskite photodetectors and can be extended to other integrated optoelectronic systems. Abstract Control over the morphology and crystallinity of metal halide perovskite materials is of key importance to enable high‐performance optoelectronics. Here, a simple yet effective template‐free self‐assembly synthesis of perovskite granular wires with ultrahigh photodetectivity (3.17 × 1015 Jones) is reported. The 1D self‐assembly of perovskite grains is driven by differences in the surface interaction energies of the granular facets. The superb photodetecting performance originates from extremely low dark current engendered by energetic barriers featuring unique band‐edge modulation along the long axis of wire. Flexible photodetector arrays, fabricated by selectively placing perovskite granular wires onto pre‐patterned electrode arrays on a transparent polymer substrate, show independently addressable photonic signal mapping with remarkably high detectivity, photoconductive gain, and responsivity. The “self‐assembled nanograin engineering” strategy developed in this study provides a viable method for the development of high‐performance perovskite photodetectors and can be extended to other integrated optoelectronic systems.

Nonvolatile Electrically Reconfigurable Integrated Photonic Switch Enabled by a Silicon PIN Diode Heater

By Jiajiu Zheng, Zhuoran Fang, Changming Wu, Shifeng Zhu, Peipeng Xu, Jonathan K. Doylend, Sanchit Deshmukh, Eric Pop, Scott Dunham, Mo Li, Arka Majumdar from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

Nonvolatile electrically reconfigurable photonic switches based on phase‐change material‐clad silicon waveguides and microring resonators are demonstrated via in situ silicon PIN diode heaters. Low‐energy, compact, low‐loss, low‐voltage, and high‐cyclability operations at moderate speeds are obtained in a complementary metal‐oxide‐semiconductor‐compatible process, promising very large‐scale programmable electronic–photonic systems such as optical neural networks and general‐purpose integrated photonic processors. Abstract Reconfigurability of photonic integrated circuits (PICs) has become increasingly important due to the growing demands for electronic–photonic systems on a chip driven by emerging applications, including neuromorphic computing, quantum information, and microwave photonics. Success in these fields usually requires highly scalable photonic switching units as essential building blocks. Current photonic switches, however, mainly rely on materials with weak, volatile thermo‐optic or electro‐optic modulation effects, resulting in large footprints and high energy consumption. As a promising alternative, chalcogenide phase‐change materials (PCMs) exhibit strong optical modulation in a static, self‐holding fashion, but the scalability of present PCM‐integrated photonic applications is still limited by the poor optical or electrical actuation approaches. Here, with phase transitions actuated by in situ silicon PIN diode heaters, scalable nonvolatile electrically reconfigurable photonic switches using PCM‐clad silicon waveguides and microring resonators are demonstrated. As a result, intrinsically compact and energy‐efficient switching units operated with low driving voltages, near‐zero additional loss, and reversible switching with high endurance are obtained in a complementary metal‐oxide‐semiconductor (CMOS)‐compatible process. This work can potentially enable very large‐scale CMOS‐integrated programmable electronic–photonic systems such as optical neural networks and general‐purpose integrated photonic processors.

Thu 19 Nov 13:00: Title to be confirmed **Please note this seminar will take place either online or in person**

From All Talks (aka the CURE list). Published on Jun 26, 2020.

Title to be confirmed

Abstract not available

**Please note this seminar will take place either online or in person**

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2D Inorganic Bimolecular Crystals with Strong In‐Plane Anisotropy for Second‐Order Nonlinear Optics

By Xin Feng, Zongdong Sun, Ke Pei, Wei Han, Fakun Wang, Peng Luo, Jianwei Su, Nian Zuo, Guiheng Liu, Huiqiao Li, Tianyou Zhai from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

For the first time, 2D inorganic bimolecular crystals SbI3·3S8 nanobelts are successfully prepared by a facile vertical microspacing sublimation strategy. The SbI3·3S8 nanobelts show strong in‐plane optical anisotropy with high dichroic ratio up to 3.9 due to the anisotropy of phonon vibrations and intramolecular vibrations. Moreover, the second harmonic generation intensity of SbI3·3S8 nanobelts exhibits a great dependence on excitation wavelength and crystalline orientation. Abstract 2D inorganic bimolecular crystals, consisting of two different inorganic molecules, are expected to possess novel physical and chemical properties due to the synergistic effect of the individual components. However, 2D inorganic bimolecular crystals remain unexploited because of the difficulties in preparation arising from non‐typical layered structures and intricate intermolecular interactions. Here, the synthesis of 2D inorganic bimolecular crystal SbI3·3S8 nanobelts via a facile vertical microspacing sublimation strategy is reported. The as‐synthesized SbI3·3S8 nanobelts exhibit strong in‐plane anisotropy of phonon vibrations and intramolecular vibrations as well as show anisotropic light absorption with a high dichroism ratio of 3.9. Furthermore, it is revealed that the second harmonic generation intensity of SbI3·3S8 nanobelts is highly dependent on the excitation wavelength and crystallographic orientation. This work can inspire the growth of more 2D inorganic bimolecular crystals and excite potential applications for bimolecular optoelectronic devices.

Mechanically Robust, Elastic, and Healable Ionogels for Highly Sensitive Ultra‐Durable Ionic Skins

By Tianqi Li, Yuting Wang, Siheng Li, Xiaokong Liu, Junqi Sun from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

Highly sensitive ultra‐durable ionic skins are fabricated by impregnating ionic liquids into a mechanically robust poly(urea‐urethane) network. Even after being stored in open air for 200 days, the I‐skins exhibit a highly reproducible electrical response over 10 000 uninterrupted strain cycles. The fractured I‐skin can be easily healed to regain their original sensing performance. Abstract The fabrication of highly durable skin‐mimicking sensors remains challenging because of the unavoidable fatigue and physical damage that sensors are subjected to in practical applications. In this study, ultra‐durable ionic skins (I‐skins) with excellent healability and high sensitivity are fabricated by impregnating ionic liquids (ILs) into a mechanically robust poly(urea‐urethane) (PU) network. The PU network is composed of crystallized poly(ε‐caprolactone) and flexible poly(ethylene glycol) that are dynamically cross‐linked with hindered urea bonds and hydrogen bonds. Such a design endows the resultant ionogels with high mechanical strength, good elasticity, Young's modulus similar to that of natural skin, and excellent healability. The ionogel‐based I‐skins exhibit a high sensitivity to a wide range of strains (0.1–300%) and pressures (0.1–20 kPa). Importantly, the I‐skins show a highly reproducible electrical response over 10 000 uninterrupted strain cycles. The sensing performance of the I‐skins stored in open air for 200 days is almost the same as that of the freshly prepared I‐skin. The fractured I‐skins can be easily healed by heating at 65 °C that restores their original ultra‐durable sensing performance. The long‐term durability of the I‐skins is attributed to the combination of non‐volatility of the ILs, excellent healability, and well‐designed mechanical properties.

Heterostructures Built in Metal Hydrides for Advanced Hydrogen Storage Reversibility

By Yanran Wang, Xiaowei Chen, Hongyu Zhang, Guanglin Xia, Dalin Sun, Xuebin Yu from Wiley: Advanced Materials: Table of Contents. Published on Jun 26, 2020.

A facile strategy to effectively improve the reversible hydrogen storage performance of Mg(BH4)2 is realized herein by building heterostructures uniformly inside MgH2 nanoparticles. MgH2 acts as a hydrogen pump, which changes the nature of the initial formation of BH bonds from endothermic to exothermic process via breaking stable B–B bonds and hence thermodynamically improves the reversibility of Mg(BH4)2. Abstract Hydrogen storage is a vital technology for developing on‐board hydrogen fuel cells. While Mg(BH4)2 is widely regarded as a promising hydrogen storage material owing to its extremely high gravimetric and volumetric capacity, its poor reversibility poses a major bottleneck inhibiting its practical applications. Herein, a facile strategy to effectively improve the reversible hydrogen storage performance of Mg(BH4)2 via building heterostructures uniformly inside MgH2 nanoparticles is reported. The in situ reaction between MgH2 nanoparticles and B2H6 not only forms homogeneous heterostructures with controllable particle size but also simultaneously decreases the particle size of the MgH2 nanoparticles inside, which effectively reduces the kinetic barrier that inhibits the reversible hydrogen storage in both Mg(BH4)2 and MgH2. More importantly, density functional theory coupled with ab initio molecular dynamics calculations clearly demonstrates that MgH2 in this heterostructure can act as a hydrogen pump, which drastically changes the enthalpy for the initial formation of BH bonds by breaking stable BB bonds from endothermic to exothermic and hence thermodynamically improves the reversibility of Mg(BH4)2. It is believed that building heterostructures provides a window of opportunity for discovering high‐performance hydrogen storage materials for on‐board applications.

High Throughput Screening of Cell Mechanical Response Using a Stretchable 3D Cellular Microarray Platform

By Kabilan Sakthivel, Hitendra Kumar, Mohamed G. A. Mohamed, Bahram Talebjedi, Justin Shim, Homayoun Najjaran, Mina Hoorfar, Keekyoung Kim from Wiley: Small: Table of Contents. Published on Jun 26, 2020.

A high‐throughput platform composed of an elastic composite substrate bioprinted with a 3D cell‐laden microgel array is developed to apply dynamic strain to the cells. The combinatorial cell analysis, by introducing different microgel stiffnesses, in addition to dynamic strain shows discrete cell responses suggesting that the platform could be a promising solution for screening multiple biomaterial parameters for tissue regeneration. Abstract Cells in vivo are constantly subjected to multiple microenvironmental mechanical stimuli that regulate cell function. Although 2D cell responses to the mechanical stimulation have been established, these methods lack relevance as physiological cell microenvironments are in 3D. Moreover, the existing platforms developed for studying the cell responses to mechanical cues in 3D either offer low‐throughput, involve complex fabrication, or do not allow combinatorial analysis of multiple cues. Considering this, a stretchable high‐throughput (HT) 3D cell microarray platform is presented that can apply dynamic mechanical strain to cells encapsulated in arrayed 3D microgels. The platform uses inkjet‐bioprinting technique for printing cell‐laden gelatin methacrylate (GelMA) microgel array on an elastic composite substrate that is periodically stretched. The developed platform is highly biocompatible and transfers the applied strain from the stretched substrate to the cells. The HT analysis is conducted to analyze cell mechano‐responses throughout the printed microgel array. Also, the combinatorial analysis of distinct cell behaviors is conducted for different GelMA microenvironmental stiffnesses in addition to the dynamic stretch. Considering its throughput and flexibility, the developed platform can readily be scaled up to introduce a wide range of microenvironmental cues and to screen the cell responses in a HT way.

[ASAP] Single-atom Catalytic Materials for Lean-electrolyte Ultrastable Lithium–Sulfur Batteries

By Chao Lu†, Yan Chen†, Yuan Yang‡, and Xi Chen*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02167

[ASAP] Phonon Polaritons in Twisted Double-Layers of Hyperbolic van der Waals Crystals

By Zebo Zheng‡, Fengsheng Sun‡, Wuchao Huang, Jingyao Jiang, Runze Zhan, Yanlin Ke, Huanjun Chen*, and Shaozhi Deng* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01627

[ASAP] Type-I Core–Shell ZnSe/ZnS Quantum Dot-Based Resistive Switching for Implementing Algorithm

By Zhan-Peng Wang†?, Yan Wang‡?, Jinbo Yu‡, Jia-Qin Yang‡, Ye Zhou*†, Jing-Yu Mao†, Ruopeng Wang‡, Xiaojin Zhao§, Wenhan Zheng§, and Su-Ting Han*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02227

[ASAP] Nanoenzyme-Reinforced Injectable Hydrogel for Healing Diabetic Wounds Infected with Multidrug Resistant Bacteria

By Shenqiang Wang†, Hua Zheng†, Li Zhou†, Fang Cheng†, Zhao Liu†, Hepeng Zhang†, Lili Wang§, and Qiuyu Zhang*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01371

[ASAP] Selectively Depopulating Valley-Polarized Excitons in Monolayer MoS2 by Local Chirality in Single Plasmonic Nanocavity

By Jiawei Sun†, Huatian Hu†, Deng Pan§, Shunping Zhang*‡, and Hongxing Xu*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01019

[ASAP] Macromolecular Crowding Enhances the Detection of DNA and Proteins by a Solid-State Nanopore

By Chalmers C. Chau†‡, Sheena E. Radford†, Eric W. Hewitt*†, and Paolo Actis*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02246

[ASAP] Correlated Exciton Fluctuations in a Two-Dimensional Semiconductor on a Metal

By Rasmus H. Godiksen†‡, Shaojun Wang†‡§, T. V. Raziman†‡, Marcos H. D. Guimaraes†?, Jaime Go´mez Rivas†‡§, and Alberto G. Curto*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c00756

[ASAP] pH-Controlled Detachable DNA Circuitry and Its Application in Resettable Self-Assembly of Spherical Nucleic Acids

By Yijun Guo†#, Dongbao Yao*†#, Bin Zheng‡, Xianbao Sun†, Xiang Zhou†, Bing Wei†, Shiyan Xiao†, Miao He†, Chengxu Li†, and Haojun Liang*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02329

[ASAP] Two-Dimensional Metallic NiTe2 with Ultrahigh Environmental Stability, Conductivity, and Electrocatalytic Activity

By Jianping Shi*†‡#, Yahuan Huan†#, Mengmeng Xiao§, Min Hong†, Xiaoxu Zhao?, Yinlu Gao?, Fangfang Cui†, Pengfei Yang†, Stephen John Pennycook?, Jijun Zhao?, and Yanfeng Zhang*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03940

[ASAP] Magnetic Vortex Nanodiscs Enable Remote Magnetomechanical Neural Stimulation

By Danijela Gregurec†‡?, Alexander W. Senko†§?, Andrey Chuvilin||#, Pooja D. Reddy§, Ashwin Sankararaman†, Dekel Rosenfeld†‡, Po-Han Chiang†‡, Francisco Garcia‡§, Ian Tafel?, Georgios Varnavides†§¶, Eugenia Ciocan?, and Polina Anikeeva*†‡§? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c00562

[ASAP] Two-Dimensional Molecular Charge Density Waves in Single-Layer-Thick Islands of a Dirac Fermion System

By Kyaw Zin Latt†, John A. Schlueter‡, Pierre Darancet§, and Saw-Wai Hla*†§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03694

[ASAP] Ultrasensitive Magnetic Tuning of Optical Properties of Films of Cholesteric Cellulose Nanocrystals

By Tianxing Chen†, Qinglan Zhao‡, Xin Meng†, Yao Li†, Hui Peng§, Andrew K. Whittaker§, and Shenmin Zhu*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c00506

[ASAP] Opportunities and Challenges for Biosensors and Nanoscale Analytical Tools for Pandemics: COVID-19

By Nikhil Bhalla*†‡, Yuwei Pan§, Zhugen Yang*§, and Amir Farokh Payam*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04421

[ASAP] Self-Blinking Dyes Unlock High-Order and Multiplane Super-Resolution Optical Fluctuation Imaging

By Kristin Grußmayer*†, Tomas Lukes†, Theo Lasser‡§, and Aleksandra Radenovic*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 26, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04602

News: Black Lives Matter - A statement from Materials Today

From Nano Today. Published on Jun 26, 2020.

The killings of George Floyd, Breonna Taylor, Rayshard Brooks, and many others, has rightfully shaken the world and once again shined a light on ongoing and systematic racism and racial bias. Like many others, we are overwhelmed by feelings of sadness, anger, frustration - and disappointment that we have not done more. It has made many of us reflect on our role in society. We strongly denounce racism in all forms, and we commit to do better for the Black community.

News: Black Lives Matter - A statement from Materials Today

From Carbon. Published on Jun 26, 2020.

The killings of George Floyd, Breonna Taylor, Rayshard Brooks, and many others, has rightfully shaken the world and once again shined a light on ongoing and systematic racism and racial bias. Like many others, we are overwhelmed by feelings of sadness, anger, frustration - and disappointment that we have not done more. It has made many of us reflect on our role in society. We strongly denounce racism in all forms, and we commit to do better for the Black community.

Semiconductor-to-conductor transition in 2D copper(II) oxide nanosheets through surface sulfur-functionalization

By Lisa D. Pfefferle from RSC - Nanoscale latest articles. Published on Jun 26, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR02208J, Paper
Matthew J. Montgomery, Nikita V. Sugak, Ke R. Yang, James M. Rogers, Sebastian A. Kube, Anthony C. Ratinov, Jan Schroers, Victor S. Batista, Lisa D. Pfefferle
Sulfur-functionalization leads to surface modification of CuO nanosheets by Cu–S structures, which imparts conductive behavior to the material.
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Tue 14 Jul 16:00: Xenon 1T

From All Talks (aka the CURE list). Published on Jun 25, 2020.

Xenon 1T

Abstract not available

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Fiber‐Reinforced Viscoelastomers Show Extraordinary Crack Resistance That Exceeds Metals

By Wei Cui, Daniel R. King, Yiwan Huang, Liang Chen, Tao Lin Sun, Yunzhou Guo, Yoshiyuki Saruwatari, Chung‐Yuen Hui, Takayuki Kurokawa, Jian Ping Gong from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Novel soft fiber‐reinforced polymers (FRPs) are developed by using viscoelastic polymers that are adhesive, soft, and tough as matrices. The unique combination of these properties in the matrices ensures a strong component interface, which consequently maximizes the energy dissipation density and gives rise to a large force transfer length enabled by the extremely high fiber/matrix modulus ratio. As a result, the soft FRPs can achieve toughness of up to 2500 kJ m−2, exceeding any existing best‐in‐class materials. Abstract Soft fiber‐reinforced polymers (FRPs), consisting of rubbery matrices and rigid fabrics, are widely utilized in industry because they possess high specific strength in tension while allowing flexural deformation under bending or twisting. Nevertheless, existing soft FRPs are relatively weak against crack propagation due to interfacial delamination, which substantially increases their risk of failure during use. In this work, a class of soft FRPs that possess high specific strength while simultaneously showing extraordinary crack resistance are developed. The strategy is to synthesize tough viscoelastic matrices from acrylate monomers in the presence of woven fabrics, which generates soft composites with a strong interface and interlocking structure. Such composites exhibit fracture energy, Γ, of up to 2500 kJ m−2, exceeding the toughest existing materials. Experimental elucidation shows that the fracture energy obeys a simple relation, Γ = W · lT, where W is the volume‐weighted average of work of extension at fracture of the two components and lT is the force transfer length that scales with the square root of fiber/matrix modulus ratio. Superior Γ is achieved through a combination of extraordinarily large lT (10–100 mm), resulting from the extremely high fiber/matrix modulus ratios (104–105), and the maximized energy dissipation density, W. The elucidated quantitative relationship provides guidance toward the design of extremely tough soft composites.

Interfacial Molecular Doping of Metal Halide Perovskites for Highly Efficient Solar Cells

By Qi Jiang, Zhenyi Ni, Guiying Xu, Yun Lin, Peter N. Rudd, Rongming Xue, Yaowen Li, Yongfang Li, Yongli Gao, Jinsong Huang from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

A small molecule of 4,4′,4″,4′″‐(pyrazine‐2,3,5,6‐tetrayl) tetrakis (N,N‐bis(4‐methoxyphenyl) aniline) (PT‐TPA) is applied to effectively p‐dope the FAxMA1−xPbI3 (FA:HC(NH2)2; MA:CH3NH3) perovskite surface, with obvious conductivity and carrier concentration increase. After applying PT‐TPA into perovskite solar cells, the doping‐induced band bending at perovskite surface facilitates hole extraction to hole transport layer and expels electrons toward cathode, which reduces the surface charge recombination. The optimized devices demonstrate a stabilized efficiency of 22.9%. Abstract Tailoring the doping of semiconductors in heterojunction solar cells shows tremendous success in enhancing the performance of many types of inorganic solar cells, while it is found challenging in perovskite solar cells because of the difficulty in doping perovskites in a controllable way. Here, a small molecule of 4,4′,4″,4″′‐(pyrazine‐2,3,5,6‐tetrayl) tetrakis (N,N‐bis(4‐methoxyphenyl) aniline) (PT‐TPA) which can effectively p‐dope the surface of FAxMA1−xPbI3 (FA: HC(NH2)2; MA: CH3NH3) perovskite films is reported. The intermolecular charge transfer property of PT‐TPA forms a stabilized resonance structure to accept electrons from perovskites. The doping effect increases perovskite dark conductivity and carrier concentration by up to 4737 times. Computation shows that electrons in the first two layers of octahedral cages in perovskites are transferred to PT‐TPA. After applying PT‐TPA into perovskite solar cells, the doping‐induced band bending in perovskite effectively facilitates hole extraction to hole transport layer and expels electrons toward cathode side, which reduces the charge recombination there. The optimized devices demonstrate an increased photovoltage from 1.12 to 1.17 V and an efficiency of 23.4% from photocurrent scanning with a stabilized efficiency of 22.9%. The findings demonstrate that molecular doping is an effective route to control the interfacial charge recombination in perovskite solar cells which is in complimentary to broadly applied defect passivation techniques.

Consolidating Lithiothermic‐Ready Transition Metals for Li2S‐Based Cathodes

By Zhenyu Xing, Guoqiang Tan, Yifei Yuan, Bao Wang, Lu Ma, Jing Xie, Zesheng Li, Tianpin Wu, Yang Ren, Reza Shahbazian‐Yassar, Jun Lu, Xiulei Ji, Zhongwei Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

A series of Li2S/transition metal nanocomposites is synthesized by lithiothermic reduction reaction. On one hand, incorporation of W, Mo, or Ti greatly increases electronic and ionic conductivity, decreased activation potential, and inhibited polysulfide dissolution of Li2S. On the other hand, integrating Co, Mn, and Zn turns Li2S into prelithiation agents. Abstract Li2S holds a promising role as a high‐capacity Li‐containing cathode, circumventing use of metallic lithium in constructing next‐generation batteries to replace current Li‐ion batteries. However, progress of Li2S cathode has been plagued by its intrinsic drawbacks, including high activation potentials, poor rate performance, and rapid capacity fading during long cycling. Herein, a series of Li2S/transition metal (TM) nanocomposites are synthesized via a lithiothermic reduction reaction, and it is realized that the presence of TMs in Li2S matrix can transform electrochemical behaviors of Li2S. On the one hand, the incorporation of W, Mo, or Ti greatly increases electronic and ionic conductivity of Li2S composites and inhibits the polysulfide dissolution via the TMS bond, effectively addressing the drawbacks of Li2S cathodes. In particular, Li2S/W and Li2S/Mo exhibit the highest ionic conductivity of solid‐phase Li‐ion conductors ever‐reported: 5.44 × 10−2 and 3.62 × 10−2 S m−1, respectively. On the other hand, integrating Co, Mn, and Zn turns Li2S into a prelithiation agent, forming metal sulfides rather than S8 after the full charge. These interesting findings may shed light on the design of Li2S‐based cathode materials.

Low‐Bandgap Porphyrins for Highly Efficient Organic Solar Cells: Materials, Morphology, and Applications

By Ke Gao, Yuanyuan Kan, Xuebin Chen, Feng Liu, Bin Kan, Li Nian, Xiangjian Wan, Yongsheng Chen, Xiaobin Peng, Thomas P. Russell, Yong Cao, Alex K.‐Y. Jen from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Porphyrin is a very promising unit to construct low‐bandgap materials to harness solar photons in the near‐infrared region. This can help organic solar cells (OSCs) maximize solar energy utilization. Recent progress of porphyrin‐based materials, design and synthesis routes, morphology, and applications in OSCs is summarized, and future perspective and endeavors are discussed to facilitate higher performance for OSCs. Abstract With developments in materials, thin‐film processing, fine‐tuning of morphology, and optimization of device fabrication, the performance of organic solar cells (OSCs) has improved markedly in recent years. Designing low‐bandgap materials has been a focus in order to maximize solar energy conversion. However, there are only a few successful low‐bandgap donor materials developed with near‐infrared (NIR) absorption that are well matched to the existing efficient acceptors. Porphyrin has shown great potential as a useful building block for constructing low‐bandgap donor materials due to its large conjugated plane and strong absorption. Porphyrin‐based donor materials have been shown to contribute to many record‐high device efficiencies in small molecule, tandem, ternary, flexible, and OSC/perovskite hybrid solar cells. Specifically, non‐fullerene small‐molecule solar cells have recently shown a high power conversion efficiency of 12% using low‐bandgap porphyrin. All these have validated the great potential of porphyrin derivatives as effective donor materials and made DPPEZnP‐TRs a family of best low‐bandgap donor materials in the OSC field so far. Here, recent progress in the rational design, morphology, dynamics, and multi‐functional applications starting from 2015 will be highlighted to deepen understanding of the structure–property relationship. Finally, some future directions of porphyrin‐based OSCs are presented.

Biodegradable Materials and Green Processing for Green Electronics

By Wenhui Li, Qian Liu, Yuniu Zhang, Chang'an Li, Zhenfei He, Wallace C. H. Choy, Paul J. Low, Prashant Sonar, Aung Ko Ko Kyaw from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Recent research progress of biodegradable materials and green processing for green electronics is comprehensively reviewed. The biodegradable materials used for different functional layers and green/non‐toxic processing for solar cells, organic field‐effect transistors, light‐emitting diodes, and other devices are discussed in detail. Future development and perspective of green electronics are also proposed and presented. Abstract There is little question that the “electronic revolution” of the 20th century has impacted almost every aspect of human life. However, the emergence of solid‐state electronics as a ubiquitous feature of an advanced modern society is posing new challenges such as the management of electronic waste (e‐waste) that will remain through the 21st century. In addition to developing strategies to manage such e‐waste, further challenges can be identified concerning the conservation and recycling of scarce elements, reducing the use of toxic materials and solvents in electronics processing, and lowering energy usage during fabrication methods. In response to these issues, the construction of electronic devices from renewable or biodegradable materials that decompose to harmless by‐products is becoming a topic of great interest. Such “green” electronic devices need to be fabricated on industrial scale through low‐energy and low‐cost methods that involve low/non‐toxic functional materials or solvents. This review highlights recent advances in the development of biodegradable materials and processing strategies for electronics with an emphasis on areas where green electronic devices show the greatest promise, including solar cells, organic field‐effect transistors, light‐emitting diodes, and other electronic devices.

Cellular Interactions of Liposomes and PISA Nanoparticles during Human Blood Flow in a Microvascular Network

By Mai N. Vu, Hannah G. Kelly, Adam K. Wheatley, Scott Peng, Emily H. Pilkington, Nicholas A. Veldhuis, Thomas P. Davis, Stephen J. Kent, Nghia P. Truong from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

An innovative methodology to characterize cellular interactions of nanomaterials under human blood flow conditions is developed. Fresh whole human blood and an artificial microvascular network are employed for the first time. This platform is easy to set up in any lab and can be applied to future studies of any type of nanoparticles. Abstract A key concept in nanomedicine is encapsulating therapeutic or diagnostic agents inside nanoparticles to prolong blood circulation time and to enhance interactions with targeted cells. During circulation and depending on the selected application (e.g., cancer drug delivery or immune modulators), nanoparticles are required to possess low or high interactions with cells in human blood and blood vessels to minimize side effects or maximize delivery efficiency. However, analysis of cellular interactions in blood vessels is challenging and is not yet realized due to the diverse components of human blood and hemodynamic flow in blood vessels. Here, the first comprehensive method to analyze cellular interactions of both synthetic and commercially available nanoparticles under human blood flow conditions in a microvascular network is developed. Importantly, this method allows to unravel the complex interplay of size, charge, and type of nanoparticles on their cellular associations under the dynamic flow of human blood. This method offers a unique platform to study complex interactions of any type of nanoparticles in human blood flow conditions and serves as a useful guideline for the rational design of liposomes and polymer nanoparticles for diverse applications in nanomedicine.

Thu 06 Aug 15:00: Systematic Rateless Coding for Efficient Data Transport in Data Centres

From All Talks (aka the CURE list). Published on Jun 25, 2020.

Systematic Rateless Coding for Efficient Data Transport in Data Centres

The talk describes SCDP , a novel, general purpose data transport protocol for data centres that, in contrast to all other protocols proposed to date, natively supports one-to-many and many-to-one data communication, which is extremely common in modern data centres. SCDP does so without compromising on efficiency for short and long unicast flows. SCDP achieves this by integrating RaptorQ codes with receiver-driven data transport, in-network packet trimming and Multi-Level Feedback Queuing (MLFQ); (1) RaptorQ codes enable efficient one-to-many and many-to-one data transport; (2) on top of RaptorQ codes, receiver-driven flow control, in combination with in-network packet trimming, enable efficient usage of network resources as well as multi-path transport and packet spraying for all transport modes. Incast and Outcast are eliminated; (3) the systematic nature of RaptorQ codes, in combination with MLFQ , enable fast, decoding-free completion of short flows. We extensively evaluate SCDP in a wide range of simulated scenarios with realistic data centre workloads. For one-to-many and many-to-one transport sessions, SCDP performs significantly better compared to NDP . For short and long unicast flows, SCDP performs equally well or better compared to NDP ”

Bio:

Mohammed Alasmar received his Ph.D from the Department of Informatics, University of Sussex, in October 2019. His research is about designing and implementing robust data transport in data centres, with a focus on distributed storage systems. Since November 2018, he has been working as a Network Engineer at MAVIS Broadcast Ltd in Brighton, UK.

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Boosting Neutral Water Oxidation through Surface Oxygen Modulation

By Longsheng Zhang, Liping Wang, Yunzhou Wen, Fenglou Ni, Bo Zhang, Huisheng Peng from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

A novel design of efficient neutral oxygen evolution reaction catalyst is demonstrated by incorporating hydrated metal cations (Ca2+) into Ru–Ir binary oxide. The obtained Ru–Ir–Ca oxide catalyst on glassy carbon electrode achieves 10 mA cm−2 at a low overpotential of 250 mV, and its turnover frequency is about 2‐, 7‐, and 45‐times higher than those of Ru–Ir oxide, RuO2, and IrO2 catalysts, respectively. Abstract Developing efficient electrocatalysts for oxygen evolution reaction (OER) in pH‐neutral electrolyte is crucial for microbial electrolysis cells and electrochemical CO2 reduction. Unfortunately, the OER kinetics in neutral electrolyte is sluggish due to the low concentration of adsorbed reactants, with overpotentials of neutral OER at present much higher than that in acidic or alkaline electrolyte. Here, hydrated metal cations (Ca2+) are sought to be incorporated into the state‐of‐the‐art Ru–Ir binary oxide to tailor the surface oxygen environments (lattice‐oxygen and adsorbed oxygen species) for efficient neutral OER. Using a sol–gel method, ternary Ru–Ir–Ca oxides are synthesized in atomically homogenous manner, and the obtained catalyst on glassy carbon electrode achieves 10 mA cm−2 at a low overpotential of 250 mV, with no degradation for 200 h of operation. In situ X‐ray absorption spectroscopy, in situ 18O isotope‐labeling differential electrochemical mass spectrometry, and 18O isotope‐labeling secondary ion mass spectroscopy studies are carried out. The results reveal that incorporation of Ca2+ can enhance the covalency of metal–oxygen bonds and the electrophilic nature of surface metal‐bonded oxygen sites; and simultaneously facilitate the adsorption of water molecules on catalyst surface, which accelerates the lattice‐oxygen‐involved reaction, thus improving the overall OER performance of RuIrCaOx catalyst.

High‐Performance and Reliable Lead‐Free Layered‐Perovskite Transistors

By Huihui Zhu, Ao Liu, Kyu In Shim, Jisu Hong, Jeong Woo Han, Yong‐Young Noh from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Universal approaches for high‐performance and reliable p‐channel lead‐free phenethylammonium tin iodide perovskite‐based transistors are developed, including self‐passivation for grain boundary by excess phenethylammonium iodide, crystallization control by adduct, and iodide vacancy passivation through oxygen treatment. The first complementary inverter is also demonstrated combined with n‐channel indium gallium zinc oxide transistors. Abstract Perovskites have been intensively investigated for their use in solar cells and light‐emitting diodes. However, research on their applications in thin‐film transistors (TFTs) has drawn less attention despite their high intrinsic charge carrier mobility. In this study, the universal approaches for high‐performance and reliable p‐channel lead‐free phenethylammonium tin iodide TFTs are reported. These include self‐passivation for grain boundary by excess phenethylammonium iodide, grain crystallization control by adduct, and iodide vacancy passivation through oxygen treatment. It is found that the grain boundary passivation can increase TFT reproducibility and reliability, and the grain size enlargement can hike the TFT performance, thus, enabling the first perovskite‐based complementary inverter demonstration with n‐channel indium gallium zinc oxide TFTs. The inverter exhibits a high gain over 30 with an excellent noise margin. This work aims to provide widely applicable and repeatable methods to make the gate more open for intensive efforts toward high‐performance printed perovskite TFTs.

Atomic‐Distributed Coordination State of Metal‐Phenolic Compounds Enabled Low Temperature Graphitization for High‐Performance Multioriented Graphite Anode

By Min Chang Shin, Jae Ho Kim, Seunghoon Nam, Yun Ji Oh, Hyoung‐Joon Jin, Chong Rae Park, Qiang Zhang, Seung Jae Yang from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Low‐temperature pyrolysis of a non‐graphitizable precursor is enabled by the coordination of tannic acid with atomically distributed nickel ion. The resulting 3D graphite nanoballs (GNBs) possess unprecedented nanostructures with multioriented graphite domain. The GNBs exhibit outstanding rate capability and highly stable cycling performance when evaluated as an anode material for lithium ion batteries. Abstract Continuous efforts have been made to achieve nanostructured carbon materials with highly ordered graphitic structures using facile synthetic methods. 3D graphite nanoballs (GNBs) are synthesized by the low‐temperature pyrolysis of a non‐graphitizable precursor, tannic acid (TA). Abundant phenol groups on TA bind to Ni2+ to form metal‐phenolic coordination, which renders each Ni cation to be atomically distributed by the TA ligands. Even at low temperatures (1000 °C), highly ordered graphitic structure is promoted by the distributed Ni nanoparticles that act as a graphitization catalyzer. The crystallinity of the GNB is fully corroborated by the intense 2D peak observed in Raman spectroscopy. In particular, the graphitic layers have orientations pointing toward multidirections, which are beneficial for the rapid transport of Li‐ions into graphite grains. The resulting materials exhibit outstanding electrochemical performance (120 mAh g−1 at 5 C and 282 mAh g−1 at 0.5 C after 500 cycles) when evaluated as a fast‐chargeable negative electrode for lithium ion batteries.

2D Metal–Organic Frameworks (MOFs) for High‐Performance BatCap Hybrid Devices

By Kuaibing Wang, Qingqing Li, Zhujuan Ren, Chao Li, Yang Chu, Zikai Wang, Mingdao Zhang, Hua Wu, Qichun Zhang from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Flexible pillar‐supported layered metal–organic frameworks (MOFs) with non‐square interlayer pores, namely, CoFRS and NiFRS, are prepared and serve as active electrode elements in supercapacitors. After coupling them with activated carbon as negative electrodes, the hybrid NiFRS//activated carbon (AC) battery‐supercapacitor (BatCap) device delivers better electrochemical performances (i.e., capacity, energy density, and cycling life) than the CoFRS//AC device. Abstract Two identical layered metal–organic frameworks (MOFs) (CoFRS and NiFRS) are constructed by using flexible 1,10‐bis(1,2,4‐triazol‐1‐yl)decane as pillars and 1,4‐benzenedicarboxylic acid as rigid linkers. The single‐crystal structure analysis indicates that the as‐synthesized MOFs possess fluctuant 2D networks with large interlayer lattices. Serving as active electrode elements in supercapacitors, both MOFs deliver excellent rate capabilities, high capacities, and longstanding endurances. Moreover, the new intermediates in two electrodes before and after long‐lifespan cycling are also examined, which cannot be identified as metal hydroxides in the peer reports. After assembled into battery‐supercapacitor (BatCap) hybrid devices, the NiFRS//activated carbon (AC) device displays better electrochemical results in terms of gravimetric capacitance and cycling performance than CoFRS//AC devices, and a higher energy‐density value of 28.7 Wh kg−1 compared to other peer references with MOFs‐based electrodes. Furthermore, the possible factors to support the distinct performances are discussed and analyzed.

Self‐Assembled Biomimetic Capsules for Self‐Preservation

By Lei Zhang, Guo‐Hong Tao, Chun‐Mei Xu, Guo‐Hao Zhang, Ling He from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Self‐protection silver chloride (AgCl) capsules are self‐assembled inspired by the pomegranate. The AgCl particles inside the shell maintain their morphology and structure well after 6 months light‐treatment. They exhibit excellent photocatalytic activity, same as newly prepared AgCl particles for degradation of six conventional organic dye pollutants. A probable assembling mechanism is proposed based on the electrostatic potential investigation. Abstract The inorganic semiconductor is an attractive material in sewage disposal and solar power generation. The main challenges associated with environment‐sensitive semiconductors are structural degradation and deactivation caused by the unfavorable environment. Here, inspired by the pomegranate, a self‐protection strategy based on the self‐assembly of silver chloride (AgCl) particles is reported. The distributed photosensitive AgCl particles can be encapsulated by themselves through mixing aqueous silver nitrate and protic ionic liquids (PILs). A probable assembling mechanism is proposed based on the electrostatic potential investigation of PILs cations. The AgCl particles inside the shell maintain their morphology and structure well after 6 months light‐treatment. Moreover, they exhibit excellent photocatalytic activity, same as newly prepared AgCl particles, for degradation of methyl orange (MO), neutral red (NR), bromocresol green (BG), rhodamine B (RhB), Congo red (CR), and crystal violet (CV).

Alchemy‐Inspired Green Paper for Spontaneous Recovery of Noble Metals

By Yao Yao, Lingyi Lan, Xunjia Li, Xiaoxue Liu, Yibin Ying, Jianfeng Ping from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Metallic transition metal dichalcogenide papers are used as Alchemy‐inspired templates to recover noble metals (Au, Pd, Pt, Ag, and Ru) in an efficient and green way without any auxiliary condition. Excellent performance could be obtained in extracting noble metals from e‐waste and spent catalysts, which provides a blueprint for the design of a next‐generation platform for noble metal regeneration. Abstract Recycling of noble metal from waste materials, namely from electronic wastes (e‐waste), spent catalyst, and industrial wastewater, is attracting growing attention due to the scarcity, economic importance, and criticality of those noble metals. Traditional techniques reported to date require toxic reagent and strict extraction conditions, which deeply hinders the development of precious metal recovery in complex environments. Here, an approach is proposed that uses flexible metallic transition metal dichalcogenide (TMD) paper, which provides abundant active sites for spontaneous adsorption and reduction of noble metal ions, as an Alchemy‐inspired template to recover noble metal in an efficient and green way without the aid of reductant and heating. The metallic TMD (MoS2, WS2) paper is shown to rapidly extract five noble metal ions (Au, Pd, Pt, Ag, and Ru) from complex samples containing various interferents. This unique property endows the metallic TMD paper with gifted ability in extracting gold from e‐waste, and recovering platinum group metals (palladium and platinum) from spent catalysts, which provides a blueprint for the design of next‐generation green platforms for noble metal regeneration.

Photoactivatable RNA N6‐Methyladenosine Editing with CRISPR‐Cas13

By Jie Zhao, Bing Li, Jianxiong Ma, Weilin Jin, Xinlong Ma from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

The photoactivatable RNA m6A editing system using CRISPR‐dCas13 (PAMEC) provides an optogenetic toolbox to study biological processes at the epitranscriptome level. Further engineering of the PAMEC system results in more efficient RNA editing and multi‐targeting capability. By coupling with upconversion nanotechnology, the spectral sensitivity of RNA editors is greatly extended, thus offering a powerful approach to remotely manipulate RNA editing. Abstract RNA has important and diverse biological roles, but the molecular methods to manipulate it spatiotemporally are limited. Here, an engineered photoactivatable RNA N6‐methyladenosine (m6A) editing system with CRISPR‐Cas13 is designed to direct specific m6A editing. Light‐inducible heterodimerizing proteins CIBN and CRY2PHR are fused to catalytically inactive PguCas13 (dCas13) and m6A effectors, respectively. This system, referred to as PAMEC, enables the spatiotemporal control of m6A editing in response to blue light. Further optimization of this system to create a highly efficient version, known as PAMECR, allows the manipulation of multiple genes robustly and simultaneously. When coupled with an upconversion nanoparticle film, the optogenetic operation window is extended from the visible range to tissue‐penetrable near‐infrared wavelengths, which offers an appealing avenue to remotely control RNA editing. These results show that PAMEC is a promising optogenetic platform for flexible and efficient targeting of RNA, with broad applicability for epitranscriptome engineering, imaging, and future therapeutic development.

Efficient Laser‐Induced Construction of Oxygen‐Vacancy Abundant Nano‐ZnCo2O4/Porous Reduced Graphene Oxide Hybrids toward Exceptional Capacitive Lithium Storage

By Li Li, Zhengjun Xie, Gaoxue Jiang, Yijing Wang, Bingqiang Cao, Changzhou Yuan from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Oxygen‐vacancy abundant nano‐ZnCo2O4/porous reduced graphene oxide hybrids are efficiently prepared through the laser irradiation involved methodology, and exhibit exceptional Li‐storage properties for Li‐ion batteries as competitive anodes. Abstract Recently, binary ZnCo2O4 has drawn enormous attention for lithium‐ion batteries (LIBs) as attractive anode owing to its large theoretical capacity and good environmental benignity. However, the modest electrical conductivity and serious volumetric effect/particle agglomeration over cycling hinder its extensive applications. To address the concerns, herein, a rapid laser‐irradiation methodology is firstly devised toward efficient synthesis of oxygen‐vacancy abundant nano‐ZnCo2O4/porous reduced graphene oxide (rGO) hybrids as anodes for LIBs. The synergistic contributions from nano‐dimensional ZnCo2O4 with rich oxygen vacancies and flexible rGO guarantee abundant active sites, fast electron/ion transport, and robust structural stability, and inhibit the agglomeration of nanoscale ZnCo2O4, favoring for superb electrochemical lithium‐storage performance. More encouragingly, the optimal L‐ZCO@rGO‐30 anode exhibits a large reversible capacity of ≈1053 mAh g−1 at 0.05 A g−1, excellent cycling stability (≈746 mAh g−1 at 1.0 A g−1 after 250 cycles), and preeminent rate capability (≈686 mAh g−1 at 3.2 A g−1). Further kinetic analysis corroborates that the capacitive‐controlled process dominates the involved electrochemical reactions of hybrid anodes. More significantly, this rational design holds the promise of being extended for smart fabrication of other oxygen‐vacancy abundant metal oxide/porous rGO hybrids toward advanced LIBs and beyond.

Direct Synthesis of Ultrathin Pt Nanowire Arrays as Catalysts for Methanol Oxidation

By Hongyan Li, Xuesong Wu, Xiaolin Tao, Yan Lu, Yawen Wang from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Arrays of ultrathin Pt nanowires are directly synthesized on substrate under ambient conditions. Mechanism study reveals that surface functionalization and control of reduction kinetics are of critical importance for the 1D growth. The nanowire arrays grown on conductive substrate can be directly applied as the catalyst for methanol electrooxidation and exhibit enhanced catalytic activity. Abstract High‐performance electrocatalysts are of critical importance for fuel cells. Morphological modulation of the catalyst materials is a rare but feasible strategy to improve their performance. In this work, Pt nanowire arrays are directly synthesized with a template‐less wet chemical method. The effects of surface functionalization and the reduction kinetics are revealed to be vital to the nanowire growth. The growth mechanism of the Pt nanowires is studied. By adjusting the concentration of the organic ligands, Pt nanowire arrays with tunable surface roughness can be obtained on various substrate surfaces. Such arrays avoid the contact resistance of randomly packed particles and allow open diffusion channels for reactants and products alike, making them excellent electrocatalysts for the methanol oxidation reaction. In particular, Pt nanowire arrays with rough surface have a mass activity of 1.24 A mgPt−1 at 1.12 V (vs Ag/AgCl), 3.18‐fold higher than that of the commercial Pt/C catalysts. It also shows more resistant against poisoning, as indicated by the higher If/Ib ratio (2.06), in comparison to the Pt/C catalysts (1.30).

Controlling Enamel Remineralization by Amyloid‐Like Amelogenin Mimics

By Dong Wang, Jingjing Deng, Xuliang Deng, Changqing Fang, Xu Zhang, Peng Yang from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

The amyloid‐like proteinaceous nanofilm entrapping peptide can mimic amelogenin matrix in nature, mediating the oriented array of amorphous calcium phosphate nanoparticles and their transformation to ordered enamel‐like hydroxyapatite (HAp) crystals. This technology can reproduce the growth of ordered HAp crystals, with the nearly identical mechanical strength to natural enamel, thus providing a promising strategy for treating dental caries. Abstract In situ regeneration of the enamel‐like structure of hydroxyapatite (HAp) crystals under oral conditions is significant for dental caries treatment. However, it is still a challenge for dentists to duplicate the elegant and well‐aligned apatite structure bonding to the surface of demineralized enamel. A biocompatible amelogenin‐inspired matrix, a phasetransited lysozyme (PTL) film mimicking an N‐terminal amelogenin with central domain (N‐Ame) combined with synthetic peptide (C‐AMG) based on the functional domains of C‐terminal telopeptide (C‐Ame) is shown here, which is formed by amyloid‐like lysozyme aggregation at the enamel interface through a rapid one‐step aqueous coating process. In the PTL/C‐AMG matrix, C‐AMG facilitated the oriented arrangement of amorphous calcium phosphate (ACP) nanoparticles and their transformation to ordered enamel‐like HAp crystals, while PTL served as a strong interfacial anchor to immobilize the C‐AMG peptide and PTL/C‐AMG matrix on versatile substrate surfaces. PTL/C‐AMG film‐coated enamel induced both of the in vivo and in vitro synthesis of HAp crystals, facilitated epitaxial growth of HAp crystals and recovered the highly oriented structure and mechanical properties to levels nearly identical to those of natural enamel. This work underlines the importance of amyloid‐like protein aggregates in the biomineralization of enamel, providing a promising strategy for treating dental caries.

Self‐Repairing Tin‐Based Perovskite Solar Cells with a Breakthrough Efficiency Over 11%

By Chengbo Wang, Feidan Gu, Ziran Zhao, Haixia Rao, Yaming Qiu, Zelun Cai, Ge Zhan, Xiaoyue Li, Boxun Sun, Xiao Yu, Boqin Zhao, Zhiwei Liu, Zuqiang Bian, Chunhui Huang from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Phenylhydrazine hydrochloride is introduced into FASnI3 (FA = NH2CH = NH2+)‐based perovskite solar cells in order to reduce the existing Sn4+ and prevent the further degradation of FASnI3. Consequently, the champion device shows a high power conversion efficiency up to 11.4%, a long‐term storage stability over 2300 h, and an efficiency recovery capability after being exposed to air. Abstract The development of tin (Sn)‐based perovskite solar cells (PSCs) is hindered by their lower power conversion efficiency and poorer stability compared to the lead‐based ones, which arise from the easy oxidation of Sn2+ to Sn4+. Herein, phenylhydrazine hydrochloride (PHCl) is introduced into FASnI3 (FA = NH2CH = NH2+) perovskite films to reduce the existing Sn4+ and prevent the further degradation of FASnI3, since PHCl has a reductive hydrazino group and a hydrophobic phenyl group. Consequently, the device achieves a record power conversion efficiency of 11.4% for lead‐free PSCs. Besides, the unencapsulated device displays almost no efficiency reduction in a glove box over 110 days and shows efficiency recovery after being exposed to air, due to a proposed self‐repairing trap state passivation process.

Stable and Biocompatible Carbon Nanotube Ink Mediated by Silk Protein for Printed Electronics

By Xiaoping Liang, Haifang Li, Jinxin Dou, Qi Wang, Wenya He, Chunya Wang, Donghang Li, Jin‐Ming Lin, Yingying Zhang from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

A highly stable and biocompatible conductive ink is developed based on carbon nanotubes and natural silk sericin. Owing to its high electrical conductivity, high colloidal stability, and good biocompatibility, this ink holds great potential in flexible and wearable electronics. Abstract Ink‐based processes, which enable scalable fabrication of flexible devices based on nanomaterials, are one of the practical approaches for the production of wearable electronics. However, carbon nanotubes (CNTs), which possess great potential for flexible electronics, are facing challenges for use in inks due to their low dispersity in most solvents and suspicious cytotoxicity. Here, a stable and biocompatible CNT ink, which is stabilized by sustainable silk sericin and free from any artificial chemicals, is reported. The ink shows stability up to months, which can be attributed to the formation of sericin–CNT (SSCNT) hybrid through non‐covalent interactions. It is demonstrated that the SSCNT ink can be used for fabricating versatile circuits on textile, paper, and plastic films through various techniques. As proofs of concept, electrocardiogram electrodes, breath sensors, and electrochemical sensors for monitoring human health and activity are fabricated, demonstrating the great potential of the SSCNT ink for smart wearables.

Unveiling the Fine Structural Distortion of Atomically Thin Bi2O2Se by Third‐Harmonic Generation

By Jing Liang, Teng Tu, Guanchu Chen, Yuanwei Sun, Ruixi Qiao, He Ma, Wentao Yu, Xu Zhou, Chaojie Ma, Peng Gao, Hailin Peng, Kaihui Liu, Dapeng Yu from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Unveiling fine structural distortions, especially the oxygen rotation/tilt, is important to in‐depth understanding of the physical properties of complex oxides. However, most available techniques are either time consuming or requiring tedious sample treatment. This work reports a noninvasive and highly‐sensitive method based on third‐harmonic generation to successfully reveal the oxygen square rotation

Air‐Stable Organic Radicals: New‐Generation Materials for Flexible Electronics?

By Lei Ji, Junqing Shi, Juan Wei, Tao Yu, Wei Huang from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

Newly developed organic air‐stable radicals and radical polymers, as well as their properties and applications in flexible electronic devices, are reviewed. Recently, these materials have shown high performance in batteries, photovoltaics, transistors, light‐emitting diodes, and photothermal devices. A short perspective is also given. Abstract In the last few years, air‐stable organic radicals and radical polymers have attracted tremendous attention due to their outstanding performance in flexible electronic devices, including transistors, batteries, light‐emitting diodes, thermoelectric and photothermal conversion devices, and among many others. The main issue of radicals from laboratory studies to real‐world applications is that the number of known air‐stable radicals is very limited, and the radicals that have been used as materials are even less. Here, the known and newly developed air‐stable organic radicals are summarized, generalizing the way of observing air‐stable radicals. The special electric and photophysical properties of organic radicals and radical polymers are interpreted, which give radicals a wide scope for various of potential applications. Finally, the exciting applications of radicals that have been achieved in flexible electronic devices are summarized. The aim herein is to highlight the recent achievements in radicals in chemistry, materials science, and flexible electronics, and further bridge the gap between these three disciplines.

Crystallization in Confinement

By Fiona C. Meldrum, Cedrick O'Shaughnessy from Wiley: Advanced Materials: Table of Contents. Published on Jun 25, 2020.

The influence of confinement on crystallization processes, where effects on features including the crystal polymorph, morphology, and orientation are observed in environments with different length scales and geometries, is described. Understanding this phenomenon will therefore enable confinement to be used to control crystallization in multiple applications and to provide superior insight into crystallization in many real‐world environments. Abstract Many crystallization processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small volumes rather than bulk solution. Here, the influence of confinement on crystallization processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystallization, and geochemistry. Experiments are principally conducted within confining systems that offer well‐defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes. Dramatic effects are observed, including a stabilization of metastable polymorphs, a depression of freezing points, and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk. Confinement is also shown to influence crystallization processes over length scales ranging from the atomic to hundreds of micrometers, and to originate from a wide range of mechanisms. The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystallization processes in many real‐world environments, but will also enable this phenomenon to be used to control crystallization in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering.

Dendritic Cell‐Inspired Designed Architectures toward Highly Efficient Electrocatalysts for Nitrate Reduction Reaction

By Hui Xu, Jing Wu, Wei Luo, Qin Li, Weixian Zhang, Jianping Yang from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

All‐carbon dendritic cell‐like (DCL) architecture with CuPd nanoparticles anchoring through stringing mesoporous carbon spheres (MCS) with carbon nanotubes (CNTs) is elaborately fabricated. The CuPd@DCL‐MCS/CNTs electrocatalyst presents an impressive nitrate removal capacity (22500 mg N/g CuPd) and nitrogen selectivity (> 95 %) in nitrate reduction process. Abstract Electrocatalysis for nitrate reduction reaction (NRR) has recently been recognized as a promising technology to convert nitrate to nitrogen. Catalyst support plays an important role in electrocatalytic process. Although porous carbon and metal oxides are considered as common supports for metal‐based catalysts, fabrication of such architecture with high electric conductivity, uniform dispersion of nanoparticles, and long‐term catalytic stability through a simple and feasible approach still remains a significant challenge. Herein, inspired by the signal transfer mode of dendritic cell, an all‐carbon dendritic cell‐like (DCL) architecture comprising mesoporous carbon spheres (MCS) connected by tethered carbon nanotubes (CNTs) with CuPd nanoparticles dispersed throughout (CuPd@DCL‐MCS/CNTs) is reported. An impressive removal capacity as high as 22 500 mg N g−1 CuPd (≈12 times superior to Fe‐based catalysts), high nitrate conversion (>95%) and nitrogen selectivity (>95%) are achieved under a low initial concentration of nitrate (100 mg L−1) when using an optimized‐NRR electrocatalyst (4CuPd@DCL‐MCS/CNTs). Remarkably, nitrate conversion and nitrogen selectivity are both close to 100% in an ultralow concentration of 10 mg L−1, meeting drinking water standard. The present work not only provides high electrocatalytic performance for NRR but also introduces new inspiration for the preparation of other DCL‐based architectures.

Ratiometric Nanoparticle Probe Based on FRET‐Amplified Phosphorescence for Oxygen Sensing with Minimal Phototoxicity

By Pichandi Ashokkumar, Nagappanpillai Adarsh, Andrey S. Klymchenko from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Luminescent oxygen‐sensing nanoparticles are developed based on a light‐harvesting principle that ensures efficient FRET from thousands of donor fluorescent dyes to few oxygen‐sensitive phosphorescent acceptors. Owing to high brightness, ratiometric response to dissolved oxygen, and low phototoxicity, the developed nanoprobe is applied to imaging of microfluidics‐generated oxygen gradients in cancer cells. Abstract Luminescent oxygen probes enable direct imaging of hypoxic conditions in cells and tissues, which are associated with a variety of diseases, including cancer. Here, a nanoparticle probe that addresses key challenges in the field is developed, it: i) strongly amplifies room temperature phosphorescence of encapsulated oxygen‐sensitive dyes; ii) provides ratiometric response to oxygen; and iii) solves the fundamental problem of phototoxicity of phosphorescent sensors. The nanoprobe is based on 40 nm polymeric nanoparticles, encapsulating ≈2000 blue‐emitting cyanine dyes with fluorinated tetraphenylborate counterions, which are as bright as 70 quantum dots (QD525). It functions as a light‐harvesting nanoantenna that undergoes efficient Förster resonance energy transfer to ≈20 phosphorescent oxygen‐sensitive platinum octaethylporphyrin (PtOEP) acceptor dyes. The obtained nanoprobe emits stable blue fluorescence and oxygen‐sensitive red phosphorescence, providing ratiometric response to dissolved oxygen. The light harvesting leads to ≈60‐fold phosphorescence amplification and makes the single nanoprobe particle as bright as ≈1200 PtOEP dyes. This high brightness enables oxygen detection at a single‐particle level and in cells at ultra‐low nanoprobe concentration with no sign of phototoxicity, in contrast to PtOEP dye. The developed nanoprobe is successfully applied to the imaging of a microfluidics‐generated oxygen gradient in cancer cells. It constitutes a promising tool for bioimaging of hypoxia.

High‐Performance Al/PDMS TENG with Novel Complex Morphology of Two‐Height Microneedles Array for High‐Sensitivity Force‐Sensor and Self‐Powered Application

By Kai‐Hong Ke, Chen‐Kuei Chung from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

Here, a high‐performance Al/PDMS‐TENG with a complex morphology of overlapped deep two‐height microneedles (OL‐DTH‐MN) is proposed. It is fabricated by integrating low‐cost CO2 laser ablation and PDMS casting processes for the self‐powered devices and high‐sensitivity force/pressure sensors. It not only exhibits the energy storage capability but also activates various self‐powered devices and lights colorful 226 LEDs. Abstract Triboelectric nanogenerators (TENGs) are widely applied to self‐powered devices and force sensors. TENGs consist of the electrode‐layer frequently made of high‐cost conductors (Ag, Au, ITO) and the tribo‐layer of rigid negative‐triboelectricity fluoropolymers (PTFE, FEP). The surface morpholoy is studied for enhancing performance. Here, a high‐performance Al/PDMS‐TENG is proposed with a complex morphology of overlapped deep two‐height microneedles (OL‐DTH‐MN) fabricated by the integrated process of low‐cost CO2 laser ablation and PDMS casting for self‐powered devices and high‐sensitivity force/pressure sensors. The high open‐circuit voltage and short‐circuit current of the OL‐DTH‐MN‐TENG are 167 V and 129.3 µA. Also, the sensitivity of the force/pressure sensor of the OL‐DTH‐MN‐TENG is very high, 1.03 V N−1 and about 3.11 V kPa−1, at an area of 30 cm2 that is much higher than the sensitivity of about 0.18–0.414 V N−1 and 0.013–0.29 V kPa−1 of conventional TENG sensors. Meanwhile, the high‐performance OL‐DTH‐MN‐TENG not only exhibits the energy storage capability of charging a 0.1 µF capacitor to 2.75 V at 1.19 s, to maximum 3.22 V, but also activates various self‐powered devices including lighting colorful 226 LEDs connected in series, the “2020‐ME‐NCKU” advertising board, a calculator and a temperature sensor. Numerical simulation is also performed to support the experiments.

High Performance Quasi‐2D Perovskite Sky‐Blue Light‐Emitting Diodes Using a Dual‐Ligand Strategy

By Fuzhi Wang, Zhenye Wang, Wenda Sun, Zhibin Wang, Yiming Bai, Tasawar Hayat, Ahmed Alsaedi, Zhan’ao Tan from Wiley: Small: Table of Contents. Published on Jun 25, 2020.

High‐performance blue perovskite light‐emitting diodes (PeLEDs) are fabricated by forming quasi‐2D perovskite with a dual‐ligand strategy. By using an appropriate ratio of i‐butylammonium (iBA) and phenylethylammonium (PEA) as capping ligands, the electric and luminescent properties of the perovskite films are improved. Sky‐blue PeLEDs are achieved with a maximum luminance up to 1130 cd m−2 and a maximum external quantum efficiency (EQE) up to 7.84%. Abstract For quasi‐2D perovskite light‐emitting diodes, the introduction of insulating bulky cation reduces the charge transport property, leading to lowered brightness and increased turn‐on voltage. Herein, a dual‐ligand strategy is adopted to prepare perovskite films by using an appropriate ratio of i‐butylammonium (iBA) and phenylethylammonium (PEA) as capping ligands. The introduction of iBA enhances the binding energy of the ligands on the surface of the quasi‐2D perovskite, and effectively controls the proportion of 2D perovskite to allow more efficient energy transfer, resulting in the great enhancement of the electric and luminescent properties of the perovskite. The photoluminescence (PL) mapping of the perovskite films exhibits that enhanced photoluminescence performance with better uniformity and stronger intensity can be achieved with this dual‐ligand strategy. By adjusting the proportion of the two ligands, sky‐blue perovskite light‐emitting diodes (PeLEDs) with electroluminescence (EL) peak located 485 nm are achieved with a maximum luminance up to 1130 cd m−2 and a maximum external quantum efficiency (EQE) up to 7.84%. In addition, the color stability and device stability are significantly enhanced by using a dual‐ligand strategy. This simple and feasible method paves the way for improving the performance of quasi‐2D PeLEDs.

[ASAP] Optical Potential-Well Array for High-Selectivity, Massive Trapping and Sorting at Nanoscale

By Yuzhi Shi†, Haitao Zhao†, Lip Ket Chin†, Yi Zhang‡, Peng Huat Yap§, Wee Ser†, Cheng-Wei Qiu*?, and Ai Qun Liu*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01464

[ASAP] Designing Kagome Lattice from Potassium Atoms on Phosphorus–Gold Surface Alloy

By Shuo Sun†‡?, Songtao Zhao§?, Yong Zheng Luo†?, Xingyu Gu†, Xu Lian‡, Anton Tadich?, Dong-Chen Qi?#, Zhirui Ma‡, Yue Zheng†, Chengding Gu‡, Jia Lin Zhang*†‡, Zhenyu Li*¶, and Wei Chen*†‡?? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02426

[ASAP] Manipulating Relative Permittivity for High-Performance Wearable Triboelectric Nanogenerators

By Long Jin†, Xiao Xiao‡, Weili Deng†, Ardo Nashalian‡, Daren He‡, Vidhur Raveendran‡, Cheng Yan†, Hai Su†, Xiang Chu†, Tao Yang†, Wen Li†, Weiqing Yang*†§, and Jun Chen*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01987

[ASAP] Mechanochemical Activation of Class-B G-Protein-Coupled Receptor upon Peptide–Ligand Binding

By Cristina Lo Giudice†, Haonan Zhang‡, Beili Wu‡, and David Alsteens*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02333

[ASAP] Depletion Effect-mediated Association of Carbon Nanotube–Polymer Composites and Their Application as Inexpensive Electrode Support Materials

By Zhangjun Huang and Paul J. Dyson* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01718

[ASAP] Continuous Label-Free Electronic Discrimination of T Cells by Activation State

By Patrick Han†#, Shari Yosinski‡#, Zachary A. Kobos§#, Rabib Chaudhury†, Jung Seok Lee‡, Tarek M. Fahmy†‡, and Mark A. Reed*§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03018

[ASAP] Versatile Triboiontronic Transistor via Proton Conductor

By Xixi Yang†‡??, Jing Han†‡?, Jinran Yu†‡?, Youhui Chen†‡, Huai Zhang†‡, Mei Ding§, Chuankun Jia§, Jia Sun?, Qijun Sun*†‡#, and Zhong Lin Wang*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03030

[ASAP] Network Topology in Water Nanoconfined between Phospholipid Membranes

By Fausto Martelli*†, Jason Crain†‡, and Giancarlo Franzese§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02984

[ASAP] Biodegradable and Insoluble Cellulose Photonic Crystals and Metasurfaces

By Vincenzo Caligiuri*†‡§, Giacomo Tedeschi†, Milan Palei†?, Mario Miscuglio?, Beatriz Martin-Garcia†?, Susana Guzman-Puyol†?, Mehdi Keshavarz Hedayati¶, Anders Kristensen?, Athanassia Athanassiou†, Roberto Cingolani†, Volker J. Sorger?, Marco Salerno?, Francesco Bonaccorso†?, Roman Krahne†, and Jose´ Alejandro Heredia-Guerrero*†? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03224

[ASAP] Wafer-Scale Uniform Carbon Nanotube Transistors for Ultrasensitive and Label-Free Detection of Disease Biomarkers

By Yuqi Liang†+, Mengmeng Xiao‡+, Ding Wu§, Yanxia Lin‡, Lijun Liu‡, Jianping He†, Guojun Zhang§, Lian-Mao Peng†‡, and Zhiyong Zhang*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 25, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03523

Combined plasmonic Au-nanoparticle and conducting metal oxide high-temperature optical sensing with LSTO

By Paul R. Ohodnicki Jr. from RSC - Nanoscale latest articles. Published on Jun 25, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR03306E, Paper
Jeffrey K. Wuenschell, Youngseok Jee, Derek K. Lau, Yang Yu, Paul R. Ohodnicki Jr.
Coupled plasmonic and Drude response of gold-nanoparticle incorporated LSTO demonstrates visible and NIR fiber-based sensing of hydrogen at high-temperature (600–800 °C).
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2D Transition Metal Dichalcogenides: Design, Modulation, and Challenges in Electrocatalysis

By Qiang Fu, Jiecai Han, Xianjie Wang, Ping Xu, Tai Yao, Jun Zhong, Wenwu Zhong, Shengwei Liu, Tangling Gao, Zhihua Zhang, Lingling Xu, Bo Song from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2020.

Transition metal dichalcogenides (TMDs) are considered to be promising candidates over noble metal catalysts for their electrochemical hydrogen production. The basic mechanism for the hydrogen evolution reaction (HER) is introduced, followed by a description of the different synthesis methods and modulation approaches to enhance the catalytic performance of TMD‐based catalysts toward HER. Abstract Hydrogen has been deemed as an ideal substitute fuel to fossil energy because of its renewability and the highest energy density among all chemical fuels. One of the most economical, ecofriendly, and high‐performance ways of hydrogen production is electrochemical water splitting. Recently, 2D transition metal dichalcogenides (also known as 2D TMDs) showed their utilization potentiality as cost‐effective hydrogen evolution reaction (HER) catalysts in water electrolysis. Herein, recent representative research efforts and systematic progress made in 2D TMDs are reviewed, and future opportunities and challenges are discussed. Furthermore, general methods of synthesizing 2D TMDs materials are introduced in detail and the advantages and disadvantages for some specific methods are provided. This explanation includes several important regulation strategies of creating more active sites, heteroatoms doping, phase engineering, construction of heterostructures, and synergistic modulation which are capable of optimizing the electrical conductivity, exposure to the catalytic active sites, and reaction energy barrier of the electrode material to boost the HER kinetics. In the last section, the current obstacles and future chances for the development of 2D TMDs electrocatalysts are proposed to provide insight into and valuable guidelines for fabricating effective HER electrocatalysts.

Biomedical Micro‐/Nanomotors: From Overcoming Biological Barriers to In Vivo Imaging

By Changyong Gao, Yong Wang, Zihan Ye, Zhihua Lin, Xing Ma, Qiang He from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2020.

Synthetic micro‐/nanomotors (MNMs) with efficient autonomous motion and drug‐transport capabilities are recognized as the next generation of diagnostic and therapeutic systems. Recent progress of MNMs in overcoming biological barriers and in vivo motion‐tracking imaging technologies are summarized. The challenges and perspectives for developing biomedical MNMs are presented. Abstract Self‐propelled micro‐ and nanomotors (MNMs) have shown great potential for applications in the biomedical field, such as active targeted delivery, detoxification, minimally invasive diagnostics, and nanosurgery, owing to their tiny size, autonomous motion, and navigation capacities. To enter the clinic, biomedical MNMs request the biodegradability of their manufacturing materials, the biocompatibility of chemical fuels or externally physical fields, the capability of overcoming various biological barriers (e.g., biofouling, blood flow, blood–brain barrier, cell membrane), and the in vivo visual positioning for autonomous navigation. Herein, the recent advances of synthetic MNMs in overcoming biological barriers and in vivo motion‐tracking imaging techniques are highlighted. The challenges and future research priorities are also addressed. With continued attention and innovation, it is believed that, in the future, biomedical MNMs will pave the way to improve the targeted drug delivery efficiency.

Guiding Cell Network Assembly using Shape‐Morphing Hydrogels

By John M. Viola, Catherine M. Porter, Ananya Gupta, Mariia Alibekova, Louis S. Prahl, Alex J. Hughes from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2020.

Choreographed movement of cells and extracellular matrix (ECM) is a common, yet under‐engineered tissue‐building process. Shape‐changing metamaterials (“kinomorphs”) made from precisely patterned cells in ECM are introduced. These cells program strains and trigger shape‐morphing dynamics, leading to multi‐scale kidney cell network assembly and maturation as tubules. The kinomorphs advance emerging tissue model systems by directing cell assembly over centimeters. Abstract Forces and relative movement between cells and extracellular matrix (ECM) are crucial to the self‐organization of tissues during development. However, the spatial range over which these dynamics can be controlled in engineering approaches is limited, impeding progress toward the construction of large, structurally mature tissues. Herein, shape‐morphing materials called “kinomorphs” that rationally control the shape and size of multicellular networks are described. Kinomorphs are sheets of ECM that change their shape, size, and density depending on patterns of cell contractility within them. It is shown that these changes can manipulate structure‐forming behaviors of epithelial cells in many spatial locations at once. Kinomorphs are built using a new photolithographic technology to pattern single cells into ECM sheets that are >10× larger than previously described. These patterns are designed to partially mimic the branch geometry of the embryonic kidney epithelial network. Origami‐inspired simulations are then used to predict changes in kinomorph shapes. Last, kinomorph dynamics are shown to provide a centimeter‐scale program that sets specific spatial locations in which ≈50 µm‐diameter epithelial tubules form by cell coalescence and structural maturation. The kinomorphs may significantly advance organ‐scale tissue construction by extending the spatial range of cell self‐organization in emerging model systems such as organoids.

Nanopore Targeted Sequencing for the Accurate and Comprehensive Detection of SARS‐CoV‐2 and Other Respiratory Viruses

By Ming Wang, Aisi Fu, Ben Hu, Yongqing Tong, Ran Liu, Zhen Liu, Jiashuang Gu, Bin Xiang, Jianghao Liu, Wen Jiang, Gaigai Shen, Wanxu Zhao, Dong Men, Zixin Deng, Lilei Yu, Wu Wei, Yan Li, Tiangang Liu from Wiley: Small: Table of Contents. Published on Jun 24, 2020.

A detection technology, nanopore targeted sequencing (NTS), for the accurate and comprehensive detection of SARS‐CoV‐2 and other respiratory viruses within 6–10 h is developed, which is suitable for the identification of suspected cases and used as a supplementary technique for the SARS‐CoV‐2 test. NTS can also monitor mutations in the virus and the type of virus. Abstract The ongoing global novel coronavirus pneumonia COVID‐19 outbreak has engendered numerous cases of infection and death. COVID‐19 diagnosis relies upon nucleic acid detection; however, currently recommended methods exhibit high false‐negative rates and are unable to identify other respiratory virus infections, thereby resulting in patient misdiagnosis and impeding epidemic containment. Combining the advantages of targeted amplification and long‐read, real‐time nanopore sequencing, herein, nanopore targeted sequencing (NTS) is developed to detect SARS‐CoV‐2 and other respiratory viruses simultaneously within 6–10 h, with a limit of detection of ten standard plasmid copies per reaction. Compared with its specificity for five common respiratory viruses, the specificity of NTS for SARS‐CoV‐2 reaches 100%. Parallel testing with approved real‐time reverse transcription‐polymerase chain reaction kits for SARS‐CoV‐2 and NTS using 61 nucleic acid samples from suspected COVID‐19 cases show that NTS identifies more infected patients (22/61) as positive, while also effectively monitoring for mutated nucleic acid sequences, categorizing types of SARS‐CoV‐2, and detecting other respiratory viruses in the test sample. NTS is thus suitable for COVID‐19 diagnosis; moreover, this platform can be further extended for diagnosing other viruses and pathogens.

Wed 08 Jul 10:00: Influences of Melt Water from Sea Ice/Ice Shelf in Polar Oceans The talk will be online. Contact the host to get Zoom details.

From All Talks (aka the CURE list). Published on Jun 24, 2020.

Influences of Melt Water from Sea Ice/Ice Shelf in Polar Oceans

Fresh melt water from sea ice and ice shelf is not only essential to the ocean hydrography but the mesoscale dynamics due to the induced baroclinicity. Warm intrusions from the Bering Strait transport heat and nutrients via baroclinic eddies vertically beneath the sea ice and laterally across structural fronts near the ice edge in the eastern Chukchi Sea. Numerical models using the Regional Ocean Model System (ROMS) are integrated to systematically investigate the importance of the baroclinic eddy field and the factors that affect its dynamics, specifically on the stratifications determined by the fresh water volume. Model results show a noticeable effect of strong wind events on ice edge displacement. The advection of ice away from or toward the inflow changes the ice melt rate and the salinity of the melt water plume, both are the factors that important to the heat transported by baroclinic instability and further feedback to the ice melt rate. Similar mechanisms can be found elsewhere around the ice fronts of sea ice and ice shelves,it is worth studying with more systematically models of the other regional oceans to explore the coincidences and dissimilarities.

The talk will be online. Contact the host to get Zoom details.

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Tubulin‐Based Nanotubes as Delivery Platform for Microtubule‐Targeting Agents

By Jinjoo Kim, Juncheol Lee, Jimin Lee, Hyeongseop Keum, Yumi Kim, Yujin Kim, Byeongjun Yu, Sang Yeop Lee, Junichi Tanaka, Sangyong Jon, Myung Chul Choi from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2020.

Tubulin‐based nanotubes are developed as novel delivery carriers for microtubule‐targeting agents. This work proposes a new strategy of using a drug's target protein as a drug carrier. Upon loading microtubule‐stabilizing/destabilizing agents, the drug‐driven structural/functional transformations and anticancer effects in vitro and in vivo are investigated. Abstract Tubulin‐based nanotubes (TNTs) to deliver microtubule‐targeting agents (MTAs) for clinical oncology are reported. Three MTAs, docetaxel (DTX), laulimalide (LMD), and monomethyl auristatin E (MMAE), which attach to different binding sites in a tubulin, are loaded onto TNTs and cause structural changes in them, including shape anisotropy and tubulin layering. This drug‐driven carrier transformation leads to changes in the drug‐loading efficiency and stability characteristics of the carrier. TNTs coloaded with DTX and LMD efficiently deliver dual drug cargoes to cellular tubulins by the endolysosomal pathway, and results in synergistic anticancer and antiangiogenic action of the drugs in vitro. In in vivo tests, TNTs loaded with a microtubule‐destabilizing agent MMAE suppress the growth of tumors with much higher efficacy than free MMAE did. This work suggests a new concept of using a drug's target protein as a carrier. The findings demonstrate that the TNTs developed here can be used universally as a delivery platform for many MTAs.

Enhanced Thermoelectric Performance of N‐Type Organic Semiconductor via Electric Field Modulated Photo‐Thermoelectric Effect

By Wenrui Zhao, Fengjiao Zhang, Xiaojuan Dai, Wenlong Jin, Lanyi Xiang, Jiamin Ding, Xian Wang, Yan Wan, Hongguang Shen, Zihan He, Juan Wang, Xike Gao, Ye Zou, Chong‐an Di, Daoben Zhu from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2020.

The electric field is demonstrated to enhance the photo‐thermoelectric effect by promoting the exciton separation efficiency with a coupled modulation process. The increased photoinduced carrier concentration and abnormal trade‐off relationship of the TE parameters together lead to a more than 500% enhancement in the PF to 11.2 µW m−1 K−2. Abstract Modulating photophysical processes is a fundamental way for tuning performance of many organic devices. However, it has not been explored as an effective strategy to manipulate the thermoelectric (TE) conversion of organic semiconductors (OSCs) owing to their critical requirement to carrier concentration (>1018 cm−3) and the fact of low exciton separation efficiency in single element OSCs. Here, an electric field modulated photo‐thermoelectric (P‐TE) effect in an n‐type OSC is demonstrated to realize a significant improvement of TE performance. The electrical and spectroscopy characterizations reveal that the electric field gating generates combined modulation of exciton separation, charge screening, and carrier recombination, which produces a more than ten times improvement of photoinduced carrier concentration. These coupled processes contribute to the unconventional Seebeck coefficient (S)‐electrical conductivity (σ) trade‐off relationship of the photoexcited films, therefore leading to a more than 500% enhancement in the power factor for n‐type OTE semiconductors. This work opens a unique way toward state‐of‐the‐art organic P‐TE materials for energy harvesting applications.

Mon 17 Aug 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 24, 2020.

Title to be confirmed

Abstract: TBD

Bio: After completing an MSc from Scuola Normale Superiore and a PhD in theoretical particle physics from SISSA , Dr Ferretti moved to Barcelona, Cologne and Paris to focus on population genomics. In 2015, he moved to the Pirbright Institute (UK) to study dynamics of pathogens and viral-host interactions. His current research at the Big Data Institute involves an interplay of epidemiology, genetics, evolution and within-host dynamics of HIV and other viral pathogens such as FMDV and ASF .

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Homogeneous 2D MoTe2 CMOS Inverters and p–n Junctions Formed by Laser‐Irradiation‐Induced p‐Type Doping

By Jing Chen, Junqiang Zhu, Qiyuan Wang, Jing Wan, Ran Liu from Wiley: Small: Table of Contents. Published on Jun 24, 2020.

In this work, stable CMOS inverters and p–n junctions are simultaneously prepared in a single MoTe2 nanoflake using selective laser‐irradiation‐induced p‐type doping. The p‐type doping effect is ascribed to intended production MoOx. This work demonstrates the advantage of the selective doping technique in MoTe2 film by using laser scan, and its great potential application in CMOS circuits’ fabrication. Abstract Among all typical transition‐metal dichalcogenides (TMDs), the bandgap of α‐MoTe2 is smallest and is close to that of conventional 3D Si. The properties of α‐MoTe2 make it a favorable candidate for future electronic devices. Even though there are a few reports regarding fabrication of complementary metal–oxide‐semiconductor (CMOS) inverters or p–n junction by controlling the charge‐carrier polarity of TMDs, the fabrication process is complicated. Here, a straightforward selective doping technique is demonstrated to fabricate a 2D p–n junction diode and CMOS inverter on a single α‐MoTe2 nanoflake. The n‐doped channel of a single α‐MoTe2 nanoflake is selectively converted to a p‐doped region via laser‐irradiation‐induced MoOx doping. The homogeneous 2D MoTe2 CMOS inverter has a high DC voltage gain of 28, desirable noise margin (NMH = 0.52 VDD, NML = 0.40 VDD), and an AC gain of 4 at 10 kHz. The results show that the doping technique by laser scan can be potentially used for future larger‐scale MoTe2 CMOS circuits.

Dislocation‐Free and Atomically Flat GaN Hexagonal Microprisms for Device Applications

By Maryam Khalilian, Zhaoxia Bi, Jonas Johansson, Filip Lenrick, Olof Hultin, Jovana Colvin, Rainer Timm, Reine Wallenberg, Jonas Ohlsson, Mats‐Erik Pistol, Anders Gustafsson, Lars Samuelson from Wiley: Small: Table of Contents. Published on Jun 24, 2020.

Dislocation‐free and atomically smooth 3D GaN microprisms are realized via two key epitaxial steps: growth from masked holes to eliminate threading dislocations from the substrate, followed by a crucial reformation step to achieve prisms with six parallel and equivalent side facets, with a micrometer‐sized top surface. The image shows 30° tilted‐view and side‐view SEM images of the GaN microprisms. Abstract III‐nitrides are considered the material of choice for light‐emitting diodes (LEDs) and lasers in the visible to ultraviolet spectral range. The development is hampered by lattice and thermal mismatch between the nitride layers and the growth substrate leading to high dislocation densities. In order to overcome the issue, efforts have gone into selected area growth of nanowires (NWs), using their small footprint in the substrate to grow virtually dislocation‐free material. Their geometry is defined by six tall side‐facets and a pointed tip which limits the design of optoelectronic devices. Growth of dislocation‐free and atomically smooth 3D hexagonal GaN micro‐prisms with a flat, micrometer‐sized top‐surface is presented. These self‐forming structures are suitable for optical devices such as low‐loss optical cavities for high‐efficiency LEDs. The structures are made by annealing GaN NWs with a thick radial shell, reforming them into hexagonal flat‐top prisms with six equivalents either m‐ or s‐facets depending on the initial heights of the top pyramid and m‐facets of the NWs. This shape is kinetically controlled and the reformation can be explained with a phenomenological model based on Wulff construction that have been developed. It is expected that the results will inspire further research into micron‐sized III‐nitride‐based devices.

[ASAP] Triboelectric Nanogenerator Enhanced Schottky Nanowire Sensor for Highly Sensitive Ethanol Detection

By Jianping Meng†?, Hu Li†§?, Luming Zhao†‡, Junfeng Lu†, Caofeng Pan†‡?, Yan Zhang†?, and Zhou Li*†‡? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01063

[ASAP] Exciton Dipole Orientation of Strain-Induced Quantum Emitters in WSe2

By Yue Luo*†‡§?, Na Liu†‡, Bumho Kim?, James Hone?, and Stefan Strauf*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01358

[ASAP] Self-Confined Nucleation of Iron Oxide Nanoparticles in a Nanostructured Amorphous Precursor

By Jens Baumgartner†?, Raj Kumar Ramamoorthy‡#, Alexy P. Freitas‡§, Marie-Alexandra Neouze§, Mathieu Bennet†, Damien Faivre*†?, and David Carriere*‡? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01125

[ASAP] Low Tortuous, Highly Conductive, and High-Areal-Capacity Battery Electrodes Enabled by Through-thickness Aligned Carbon Fiber Framework

By Baohui Shi†#, Yuanyuan Shang†#, Yong Pei‡, Shaopeng Pei†, Liyun Wang†, Dirk Heider§?, Yong Y. Zhao?, Chaolun Zheng‡, Bao Yang‡, Shridhar Yarlagadda*§?, Tsu-Wei Chou†§, and Kun Kelvin Fu*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c02053

[ASAP] Signature of Large-Gap Quantum Spin Hall State in the Layered Mineral Jacutingaite

By Konra´d Kandrai†, Pe´ter Vancso´†, Gergo? Kukucska‡, Ja´nos Koltai‡, Gyo¨rgy Baranka†, A´kos Hoffmann†, A´ron Pekker¶, Katalin Kamara´s¶, Zsolt E. Horva´th†, Anna Vymazalova´§, Levente Tapaszto´†, and Pe´ter Nemes-Incze*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01499

[ASAP] Room Temperature Terahertz Electroabsorption Modulation by Excitons in Monolayer Transition Metal Dichalcogenides

By Jiaojian Shi?†, Edoardo Baldini?‡, Simone Latini¶, Shunsuke A. Sato§¶, Yaqing Zhang†, Brandt C. Pein†, Pin-Chun Shen?, Jing Kong?, Angel Rubio¶?#, Nuh Gedik‡, and Keith A. Nelson*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01134

[ASAP] All-Dielectric Nanophotonics Enables Tunable Excitation of the Exchange Spin Waves

By Alexander I. Chernov*†‡§, Mikhail A. Kozhaev†§?, Daria O. Ignatyeva†§?, Evgeniy N. Beginin#, Alexandr V. Sadovnikov#, Andrey A. Voronov†?, Dolendra Karki?, Miguel Levy?, and Vladimir I. Belotelov†§? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01528

[ASAP] Exchange Bias in Magnetic Topological Insulator Superlattices

By Jieyi Liu*†¶, Angadjit Singh‡§, Yu Yang Fredrik Liu‡, Adrian Ionescu‡, Balati Kuerbanjiang†, Crispin H. W. Barnes‡, and Thorsten Hesjedal*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c01666

[ASAP] A Mechanically Tunable Quantum Dot in a Graphene Break Junction

By Sabina Caneva†#, Matthijs Hermans†?, Martin Lee†, Amador Garci´a-Fuente‡§, Kenji Watanabe?, Takashi Taniguchi?, Cees Dekker†, Jaime Ferrer‡§, Herre S. J. van der Zant†, and Pascal Gehring*†? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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Nano Letters
DOI: 10.1021/acs.nanolett.0c00984

[ASAP] Interactions between Ultrastable Na4Ag44(SR)30 Nanoclusters and Coordinating Solvents: Uncovering the Atomic-Scale Mechanism

By Daniel M. Chevrier†?, Brian E. Conn‡, Bo Li§, De-en Jiang§, Terry P. Bigioni‡, Amares Chatt†, and Peng Zhang*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02615

[ASAP] Nanotunnels within Poly(3,4-ethylenedioxythiophene)-Carbon Nanotube Composite for Highly Sensitive Neural Interfacing

By Nuan Chen†‡§, Baiwen Luo§, Anoop C. Patil‡§, Jiahui Wang§, Gil Gerald Lasam Gammad§, Zhigao Yi?, Xiaogang Liu§?, Shih-Cheng Yen§?, Seeram Ramakrishna*†, and Nitish V. Thakor*‡§?# from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c00672

[ASAP] Prospects for Functionalizing Elemental 2D Pnictogens: A Study of Molecular Models

By Cameron Jellett†, Jan Plutnar†, and Martin Pumera*†‡§? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01005

[ASAP] 2-D Materials for Ultrascaled Field-Effect Transistors: One Hundred Candidates under the Ab Initio Microscope

By Cedric Klinkert†, A´ron Szabo´†, Christian Stieger†, Davide Campi‡, Nicola Marzari‡, and Mathieu Luisier*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02983

[ASAP] Engineering Nanoscale Interfaces of Metal/Oxide Nanowires to Control Catalytic Activity

By Hee Chan Song†‡§, Gyu Rac Lee?§, Kiung Jeon?, Hyunhwa Lee†‡, Si Woo Lee†‡, Yeon Sik Jung*?, and Jeong Young Park*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02347

[ASAP] Transport and Durability of Energy Storage Materials Operating at High Temperatures

By Puritut Nakhanivej†, Harpalsinh H. Rana†, Haejin Kim§, Bao Yu Xia?, and Ho Seok Park*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04402

[ASAP] In Situ Monitoring of the Seeding and Growth of Silver Metal–Organic Nanotubes by Liquid-Cell Transmission Electron Microscopy

By Karthikeyan Gnanasekaran†, Kristina M. Vailonis‡, David M. Jenkins*‡, and Nathan C. Gianneschi*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03209

[ASAP] Enhanced Polysulfide Regulation via Porous Catalytic V2O3/V8C7 Heterostructures Derived from Metal–Organic Frameworks toward High-Performance Li–S Batteries

By Long Zhang†‡?, Yicheng Liu†?, Zedong Zhao†, Peilu Jiang†, Teng Zhang‡, Mengxiong Li†, Shaoxue Pan†, Tianyu Tang‡, Tianqi Wu†, Peiying Liu†, Yanglong Hou*‡, and Hongbin Lu*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c02762

[ASAP] Spiranthes sinensis-Inspired Circular Polarized Luminescence in a Solid Block Copolymer Film with a Controllable Helix

By Qingxiang Li†, Jianan Yuan‡, Hongyu Liang†, Feng Zheng‡, Xuemin Lu*†, Chunyang Yu†, and Qinghua Lu†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03734

[ASAP] Assembling Carbon Nanotube Architectures

By Michael Dasbach†, Markus Pyschik†, Viktor Lehmann†, Kristian Parey‡, Daniel Rhinow†‡, Hendrik M. Reinhardt†, and Norbert A. Hampp*†§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c01606

[ASAP] Plasmonic and Superhydrophobic Self-Decontaminating N95 Respirators

By Hong Zhong†, Zhaoran Zhu†, Peng You‡, Jing Lin†, Chi Fai Cheung†, Vivien L. Lu§, Feng Yan‡, Ching-Yuen Chan†, and Guijun Li*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c03504

[ASAP] Highly Efficient Electrochemical Reduction of Nitrogen to Ammonia on Surface Termination Modified Ti3C2Tx MXene Nanosheets

By Ying Guo†, Tairan Wang†, Qi Yang†, Xinliang Li†, Hongfei Li‡, Yukun Wang†, Tianpeng Jiao†, Zhaodong Huang†, Binbin Dong§, Wenjun Zhang†, Jun Fan†, and Chunyi Zhi*†? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2020.

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ACS Nano
DOI: 10.1021/acsnano.0c04284

Masters of disguise

By Philip Ball from Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2020.

Nature Materials, Published online: 24 June 2020; doi:10.1038/s41563-020-0714-8

Masters of disguise

Increasingly complex DNA assemblies

From Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2020.

Nature Materials, Published online: 24 June 2020; doi:10.1038/s41563-020-0727-3

Prompted by advances in the programmability of DNA nanostructures and their hybridization, the complexity of nanomaterial lattices guided by DNA continues to increase.

Oncogenetic engagement with mechanosensing

By Wanjin Hong from Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2020.

Nature Materials, Published online: 24 June 2020; doi:10.1038/s41563-020-0700-1

Reprogramming normal cells into tumour precursors involves complex reconditioning of the tissue microenvironment. Cumulative integration of genetic drivers with extrinsic mechanical inputs is now shown to engage YAP/TAZ to rewire cell mechanics and initiate tumorigenic reprogramming.

A selective ionic rectifier

By Shuhei Furukawa from Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2020.

Nature Materials, Published online: 24 June 2020; doi:10.1038/s41563-020-0686-8

Creation of bioinspired ion channels that separate ions without compromising selectivity, conductivity or rectification ability has long been a challenge. Integration of metal–organic frameworks into asymmetric nanopore membranes overcomes this limitation.

De novo nanomaterial crystals from DNA frameworks

By Mauri A. Kostiainen from Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2020.

Nature Materials, Published online: 24 June 2020; doi:10.1038/s41563-020-0709-5

Programmable DNA building blocks hosting diverse nano-objects assemble into three-dimensional nanoparticle lattices whose geometry is determined by the shape and valence of the DNA block.

A mesoporous encapsulated nanozyme for decontaminating two kinds of wastewater and avoiding secondary pollution

By Xiaogang Qu from RSC - Nanoscale latest articles. Published on Jun 24, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR03217D, Communication
Faming Wang, Yan Zhang, Zhengwei Liu, Jinsong Ren, Xiaogang Qu
A complex nanozyme with dual enzyme mimic activities has been constructed by confining Au/Pt/Co tri-metal in a macroporous silica scaffold. The nanozyme has a huge advantage in treating different sewages in one system.
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Cobalt doping of FePS3 promotes intrinsic active sites for the efficient hydrogen evolution reaction

By Wenwu Zhong from RSC - Nanoscale latest articles. Published on Jun 24, 2020.

Nanoscale, 2020, Advance Article
DOI: 10.1039/D0NR03819A, Communication
Shuang Wang, Beibei Xiao, Shijie Shen, Kai Song, Zhiping Lin, Zongpeng Wang, Yuchao Chen, Wenwu Zhong
High HER activity FePS3 was constructed by doping of cobalt based on theoretical calculations that Co dopants improve H affinity on P sites and electrical conductivity.
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In Situ TEM Study on Conversion‐Type Electrodes for Rechargeable Ion Batteries

By Jiang Cui, Hongkui Zheng, Kai He from Wiley: Advanced Materials: Table of Contents. Published on Jun 23, 2020.

In situ transmission electron microscopy is a powerful tool to study rechargeable battery materials, providing mechanistic insights into understanding phase transformation and associated structural and chemical evolution upon charge and discharge. The recent progress on reaction mechanism, kinetics, and degradation of conversion‐type electrode materials, especially metal oxides and chalcogenides, is systematically reviewed; the challenges and prospects are also discussed. Abstract Conversion‐type materials have been considered as potentially high‐energy‐density alternatives to commercially dominant intercalation‐based electrodes for rechargeable ion batteries and have attracted tremendous research effort to meet the performance for viable energy‐storage technologies. In situ transmission electron microscopy (TEM) has been extensively employed to provide mechanistic insights into understanding the behavior of battery materials. Noticeably, a great portion of previous in situ TEM studies has been focused on conversion‐type materials, but a dedicated review for this group of materials is missing in the literature. Herein, recent developments of in situ TEM techniques for investigation of dynamic phase transformation and associated structural, morphological, and chemical evolutions during conversion reactions with alkali ions in secondary batteries are comprehensively summarized. The materials of interest broadly cover metal oxides, chalcogenides, fluorides, phosphides, nitrides, and silicates with specific emphasis on spinel metal oxides and recently emerged 2D metal chalcogenides. Special focus is placed on the scientific findings that are uniquely obtained by in situ TEM to address fundamental questions and practical issues regarding phase transformation, structural evolution, electrochemical redox, reaction mechanism, kinetics, and degradation. Critical challenges and perspectives are discussed for advancing new knowledge that can bridge the gap between prototype materials and real‐world applications.

Recent Advances in Perovskite‐Based Building‐Integrated Photovoltaics

By Munkhbayar Batmunkh, Yu Lin Zhong, Huijun Zhao from Wiley: Advanced Materials: Table of Contents. Published on Jun 23, 2020.

The recent advances achieved in building‐integrated photovoltaics based on perovskite materials for four areas of applications, namely semitransparent windows, colorful wall facades, electrochromic windows, and thermochromic windows, are presented. Critical roadmaps on future developments of this cutting‐edge research field are provided. Abstract Perovskite‐based solar cells have attracted great attention due to their low cost and high photovoltaic (PV) performance. In addition to their success in the PV sector, there has been growing interest in employing perovskites in energy‐efficient smart windows and other building technologies owing to their large absorption coefficient and color tunability. The major challenge lies in integrating perovskite materials into windows and building facades and combining them with added functionalities while maintaining their remarkable power conversion efficiencies. Herein, advances that have been made in the application of perovskites to building‐integrated photovoltaics (BIPVs) in four areas are highlighted: semitransparent windows, colorful wall facades, electrochromic windows, and thermochromic windows. In addition, the opportunities and challenges of this cutting‐edge research area and important roadmaps for the future use of perovskites in BIPVs are discussed.

Water‐Pillared Sodium Vanadium Bronze Nanowires for Enhanced Rechargeable Magnesium Ion Storage

By Ruimin Sun, Xiao Ji, Chao Luo, Singyuk Hou, Ping Hu, Xiangjun Pu, Longsheng Cao, Liqiang Mai, Chunsheng Wang from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

Magnesium‐ion batteries with high safety, low cost, and high volumetric capacity have been extensively investigated. However, lack of suitable cathode is the biggest challenge. Here, water‐pillared layered Na2V6O16·1.63H2O nanowires are reported, which show great electrochemical performance and reversibility of Mg2+ insertion. This work aims at bringing new insights to develop Mg battery cathodes for large‐scale energy storage. Abstract Owing to the advantages of high safety, low cost, high theoretical volumetric capacities, and environmental friendliness, magnesium‐ion batteries (MIBs) have more feasibility for large‐scale energy storage compared to lithium‐ion batteries. However, lack of suitable cathode materials due to sluggish kinetics of magnesium ion is one of the biggest challenges. Herein, water‐pillared sodium vanadium bronze nanowires (Na2V6O16·1.63H2O) are reported as cathode material for MIBs, which display high performance in magnesium storage. The hydrated sodium ions provide excellent structural stability. The charge shielding effect of lattice water enables fast Mg2+ diffusion. It exhibits high specific capacity of 175 mAh g−1, long cycle life (450 cycles), and high coulombic efficiency (≈100%). At high current density of 200 mA g−1, the capacity retention is up to 71% even after 450 cycles (compared to the highest capacity), demonstrating excellent long‐term cycling performance. The nature of charge storage kinetics is explored. Furthermore, a highly reversible structure change during the electrochemical process is proved by comprehensive electrochemical analysis. The remarkable electrochemical performance makes Na2V6O16·1.63H2O a promising cathode material for low‐cost and safe MIBs.

Active Encapsulation in Biocompatible Nanocapsules

By Baiheng Wu, Chenjing Yang, Bo Li, Leyun Feng, Mingtan Hai, Chun‐Xia Zhao, Dong Chen, Kai Liu, David A. Weitz from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

Hierarchical core–shell nanocapsules are developed by controlled co‐precipitation and phase separation. The core–shell nanocapsules serve as excellent delivery vehicles and possess tunable shell thickness, high encapsulation efficiency, high loading capacity, good dispersity in water, improved stability, and pH‐triggered release, which opens a door to a range of new applications in food, cosmetic, and drug delivery. Abstract Co‐precipitation is generally refers to the co‐precipitation of two solids and is widely used to prepare active‐loaded nanoparticles. Here, it is demonstrated that liquid and solid can precipitate simultaneously to produce hierarchical core–shell nanocapsules that encapsulate an oil core in a polymer shell. During the co‐precipitation process, the polymer preferentially deposits at the oil/water interface, wetting both the oil and water phases; the behavior is determined by the spreading coefficients and driven by the energy minimization. The technique is applicable to directly encapsulate various oil actives and avoid the use of toxic solvent or surfactant during the preparation process. The obtained core–shell nanocapsules harness the advantage of biocompatibility, precise control over the shell thickness, high loading capacity, high encapsulation efficiency, good dispersity in water, and improved stability against oxidation. The applications of the nanocapsules as delivery vehicles are demonstrated by the excellent performances of natural colorant and anti‐cancer drug‐loaded nanocapsules. The core–shell nanocapsules with a controlled hierarchical structure are, therefore, ideal carriers for practical applications in food, cosmetics, and drug delivery.

Solar‐Driven Carbon Nanoreactor Coupling Gold and Platinum Nanocatalysts for Alcohol Oxidations

By Wenjie Yang, Jinhui Zhao, Hao Tian, Lizhuo Wang, Xinyao Wang, Sheng Ye, Jian Liu, Jun Huang from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

A solar‐driven carbon nanoreactor incorporated with gold and platinum nanoparticles is synthesized. The surface plasmons of gold nanoparticles resonate with visible light, generate hot electrons, and transfer to the nearby Pt surface. The cooperative effect of platinum and gold nanoparticles utilized in this work largely increases the efficiency of harvesting solar energy to enhance the oxidation of alcohols. Abstract This research reports gold (Au) and platinum (Pt) nanocatalysts spatially confined in a porous carbon nanosphere as a new solar‐driven carbon nanoreactor (CNR). The CNRs have confined size (≈100 nm), high specific surface area, and high thermal and electrical conductivity. The black color of CNR can improve the energy harvest efficiency of the solar irradiation to thermal energy within each nanoreactor. The localized surface plasmon resonance (LSPR) on Au nanocatalysts‐induced electron oscillation causes the localized heating effect inside each CNR. Therefore, the heat will be accumulated in the confined space of CNR and transferred to reaction energy to drive the alcohol oxidation on uniformly dispersed Au and Pt nanoparticles inside the nanoreactor. The energetic electrons induced by LSPR effect on the surface of Au nanoparticles are transferred to the nearby and more active Pt surface via the conductive CNR, which strongly enhances the conversion of cinnamyl alcohol from 14% on Pt‐CNR up to 100% on AuPt‐CNR after a 3 h reaction. Therefore, the cooperative effect of Au and Pt nanoparticles confined in the CNRs utilized in this work can largely increase the efficiency of harvesting solar energy to drive the important chemical processes.

Ion Reservoir Enabled by Hierarchical Bimetallic Sulfides Nanocages Toward Highly Effective Sodium Storage

By Jin Yuan, Baihua Qu, Qingfei Zhang, Wei He, Qingshui Xie, Dong‐Liang Peng from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

Zinc–tin sulfide nanocages (ZnS‐NC/SnS2) collaboratively create the unique hierarchical hollow structure and bimetallic‐ions pseudocapacitance effect. Which amazingly accelerate the electrochemical performance in sodium‐ion batteries. Abstract Designing and constructing bimetallic hierarchical structures is vital for the conversion‐alloy reaction anode of sodium‐ion batteries (SIBs). Particularly, the rationally designed hetero‐interface engineering can offer fast diffusion kinetics in the interface, leading to the improved high‐power surface pseudocapacitance and cycling stability for SIBs. Herein, the hierarchical zinc–tin sulfide nanocages (ZnS‐NC/SnS2) are constructed through hydrothermal and sulfuration reactions. The unconventional hierarchical design with internal void space greatly optimizes the structure stability, and bimetallic sulfide brings a bimetallic composite interface and N heteroatom doping, which are devoted to high electrochemical activity and improved interfacial charge transfer rate for Na+ storage. Remarkably, the ZnS‐NC/SnS2 composite anode exhibits a delightful reversible capacity of 595 mAh g−1 after 100 cycles at 0.2 A g−1, and long cycling capability for 500 cycles with a low capacity loss of 0.08% per cycle at 1 A g−1. This study opens up a new route for rationally constructing hierarchical heterogeneous interfaces and sheds new light on efficient anode material for SIBs.

Engineering Protein Nanoparticles Out from Components of the Human Microbiome

By Hèctor López‐Laguna, Laura Sánchez‐García, Naroa Serna, Eric Voltà‐Durán, Julieta M. Sánchez, Alejandro Sánchez‐Chardi, Ugutz Unzueta, Marcin Łoś, Antonio Villaverde, Esther Vázquez from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

The human microbiome is a source of structural proteins useful as protein materials for clinical uses by exploiting their self‐assembling tendencies and the limited interactivity with human molecules. Two phages and one bacterial protein are used to explore this concept, through the controlled formation of regular protein nanoparticles, stable under physiological conditions and suitable for further functionalization. Abstract Nanoscale protein materials are highly convenient as vehicles for targeted drug delivery because of their structural and functional versatility. Selective binding to specific cell surface receptors and penetration into target cells require the use of targeting peptides. Such homing stretches should be incorporated to larger proteins that do not interact with body components, to prevent undesired drug release into nontarget organs. Because of their low interactivity with human body components and their tolerated immunogenicity, proteins derived from the human microbiome are appealing and fully biocompatible building blocks for the biofabrication of nonreactive, inert protein materials within the nanoscale. Several phage and phage‐like bacterial proteins with natural structural roles are produced in Escherichia coli as polyhistidine‐tagged recombinant proteins, looking for their organization as discrete, nanoscale particulate materials. While all of them self‐assemble in a variety of sizes, the stability of the resulting constructs at 37 °C is found to be severely compromised. However, the fine adjustment of temperature and Zn2+ concentration allows the formation of robust nanomaterials, fully stable in complex media and under physiological conditions. Then, microbiome‐derived proteins show promise for the regulatable construction of scaffold protein nanomaterials, which can be tailored and strengthened by simple physicochemical approaches.

Bottom‐Up Design of Composite Supraparticles for Powder‐Based Additive Manufacturing

By Herbert Canziani, Salvatore Chiera, Thomas Schuffenhauer, Sebastian‐Paul Kopp, Florian Metzger, Andreas Bück, Michael Schmidt, Nicolas Vogel from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

A bottom‐up process is presented for the production of micrometer‐sized polystyrene and polystyrene silica composite supraparticles from colloidal building blocks, with precise composition, morphology, and surface properties for powder‐based additive manufacturing. The controlled surface properties allow tailoring the powder flowability. It is demonstrated that composite materials with homogeneously distributed nanoscale additives can be produced by selective laser sintering. Abstract Additive manufacturing promises high flexibility and customized product design. Powder bed fusion processes use a laser to melt a polymer powder at predefined locations and iterate the scheme to build 3D objects. The design of flowable powders is a critical parameter for a successful fabrication process that currently limits the choice of available materials. Here, a bottom‐up process is introduced to fabricate tailored polymer‐ and composite supraparticles for powder‐based additive manufacturing processes by controlled aggregation of colloidal primary particles. These supraparticles exhibit a near‐spherical shape and tailored composition, morphology, and surface roughness. These parameters can be precisely controlled by the mixing and size ratio of the primary particles. Polystyrene/silica composite particles are chosen as a model system to establish structure–property relations connecting shape, morphology, and surface roughness to the adhesion within the powder, which is accessed by tensile strength measurements. The adhesive properties are then connected to powder flowability and it is shown that the resulting powders allow the formation of dense powder films with uniform coverage. Finally, successful powder bed fusion is demonstrated by producing macroscopic single layer specimens with uniform distribution of nanoscale silica additives.

Wood‐Derived Functional Polymeric Materials

By Jifu Wang, Daihui Zhang, Fuxiang Chu from Wiley: Advanced Materials: Table of Contents. Published on Jun 23, 2020.

Wood components are considered as important feedstocks to fabricate functional materials. An insightful summary of recent wood‐derived functional polymeric materials is provided from the perspective of macromolecular engineering, including the structural characteristics of cellulose and lignin, molecular modification, and subsequent assembly behavior to generate distinctive functional materials. Abstract In recent years, tremendous efforts have been dedicated to developing wood‐derived functional polymeric materials due to their distinctive properties, including environmental friendliness, renewability, and biodegradability. Thus, the uniqueness of the main components in wood (cellulose and lignin) has attracted enormous interest for both fundamental research and practical applications. Herein, the emerging field of wood‐derived functional polymeric materials fabricated by means of macromolecular engineering is reviewed, covering the basic structures and properties of the main components, the design principle to utilize these main components, and the resulting wood‐derived functional polymeric materials in terms of elastomers, hydrogels, aerogels, and nanoparticles. In detail, the natural features of wood components and their significant roles in the fabrication of materials are emphasized. Furthermore, the utilization of controlled/living polymerization, click chemistry, dynamic bonds chemistry, etc., for the modification is specifically discussed from the perspective of molecular design, together with their sequential assembly into different morphologies. The functionalities of wood‐derived polymeric materials are mainly focused on self‐healing and shape‐memory abilities, adsorption, conduction, etc. Finally, the main challenges of wood‐derived functional polymeric materials fabricated by macromolecular engineering are presented, as well as the potential solutions or directions to develop green and scalable wood‐derived functional polymeric materials.

Bioactive‐Tissue‐Derived Nanocomposite Hydrogel for Permanent Arterial Embolization and Enhanced Vascular Healing

By Jingjie Hu, Izzet Altun, Zefu Zhang, Hassan Albadawi, Marcela A. Salomao, Joseph L. Mayer, L. P. Madhubhani P. Hemachandra, Suliman Rehman, Rahmi Oklu from Wiley: Advanced Materials: Table of Contents. Published on Jun 23, 2020.

A biohybrid hydrogel composed of cardiac‐derived extracellular matrix (ECM) and nanoclay (NC) is developed as a multifunctional embolic biomaterial that offers both the biological activity and the mechanical support necessary for successful arterial embolization. The shear‐thinning ECM–NC hydrogel exhibits excellent transcatheter injectability, retrievability, and proangiogenic characteristics to serve as a catheter‐directed bioactive embolic agent for the treatment of a variety of vascular diseases. Abstract Transcatheter embolization is a minimally invasive procedure that uses embolic agents to intentionally block diseased or injured blood vessels for therapeutic purposes. Embolic agents in clinical practice are limited by recanalization, risk of non‐target embolization, failure in coagulopathic patients, high cost, and toxicity. Here, a decellularized cardiac extracellular matrix (ECM)‐based nanocomposite hydrogel is developed to provide superior mechanical stability, catheter injectability, retrievability, antibacterial properties, and biological activity to prevent recanalization. The embolic efficacy of the shear‐thinning ECM‐based hydrogel is shown in a porcine survival model of embolization in the iliac artery and the renal artery. The ECM‐based hydrogel promotes arterial vessel wall remodeling and a fibroinflammatory response while undergoing significant biodegradation such that only 25% of the embolic material remains at 14 days. With its unprecedented proregenerative, antibacterial properties coupled with favorable mechanical properties, and its superior performance in anticoagulated blood, the ECM‐based hydrogel has the potential to be a next‐generation biofunctional embolic agent that can successfully treat a wide range of vascular diseases.

Modular Molecular Self‐Assembly for Diversified Chiroptical Systems

By Zhuoer Wang, Heng Zhang, Aiyou Hao, Yanli Zhao, Pengyao Xing from Wiley: Small: Table of Contents. Published on Jun 23, 2020.

A modularized ternary molecular assembly strategy is developed to generate chiroptically active materials at diverse hierarchical levels based on N‐terminated aromatic amino acids containing charge transfer and hydrogen bonding sites. These assemblies show unique handedness, emission color, and abundant circular polarized luminescence. Ternary coassemblies facilitate the hydrogel formation constituted by super‐helical nanostructures, demonstrating interesting topological evolution. Abstract Bottom‐up multicomponent molecular self‐assembly is an efficient approach to fabricate and manipulate chiral nanostructures and their chiroptical activities such as the Cotton effect and circular polarized luminescence (CPL). However, the integrated coassembly suffers from spontaneous and inherent systematic pathway complexity with low yield and poor fidelity. Consequently, a rational design of chiral self‐assembled systems with more than two components remains a significant challenge. Herein, a modularized, ternary molecular self‐assembly strategy that generates chiroptically active materials at diverse hierarchical levels is reported. N‐terminated aromatic amino acids appended with binding sites for charge transfer and multiple hydrogen bonds undergo the evolution of supramolecular chirality with unique handedness and luminescent color, generating abundant CPL emission with high luminescence dissymmetry factor values in precisely controlled modalities. Ternary coassembly facilitates high‐water‐content hydrogel formation constituted by super‐helical nanostructures, demonstrating a helix to toroid topological transition. This discovery would shed light on developing complicated multicomponent systems in mimicking biological coassembly events.