skip to primary navigationskip to content

NanoManufacturing

Michael De Volder, Engineering Department - IfM

Studying at Cambridge

Nanoscience News

Analyzing fidelity and reproducibility of DNA templated plasmonic nanostructures

By Igor L. Medintz from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR03711J, Paper
Divita Mathur, William P. Klein, Matthew Chiriboga, Hieu Bui, Eunkeu Oh, Rafaela Nita, Jawad Naciri, Paul Johns, Jake Fontana, Sebastián A. Díaz, Igor L. Medintz
Synthetic DNA templated nanostructures offer an excellent platform for the precise spatial and orientational positioning of organic and inorganic nanomaterials.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Exploring antiaromaticity in single-molecule junctions formed from biphenylene derivatives

By Martin R. Bryce from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR05375A, Paper
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Markus Gantenbein, Xiaohui Li, Sara Sangtarash, Jie Bai, Gunnar Olsen, Afaf Alqorashi, Wenjing Hong, Colin J. Lambert, Martin R. Bryce
We report the synthesis of a series of oligophenylene-ethynylene (OPE) derivatives with biphenylene core units, designed to assess the effects of biphenylene antiaromaticity on charge transport in molecular junctions.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Effects of oral exposure to titanium dioxide nanoparticles on gut microbiota and gut-associated metabolism in vivo

By Guang Jia from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07580A, Paper
Zhangjian Chen, Shuo Han, Di Zhou, Shupei Zhou, Guang Jia
The antibacterial activity of titanium dioxide nanoparticles (TiO2 NPs) has been extensively documented and applied to food packaging or environmental protection. Ingestion of TiO2 NPs via dietary and environmental exposure...
The content of this RSS Feed (c) The Royal Society of Chemistry

Honeycomb-shaped carbon nanotube supports for BiVO4 based solar water splitting

By M De Volder from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06737J, Paper
Sarah Jessl, Jan Rongé, Davor Copic, Michael A Jones, Johan Martens, M De Volder
Advances in the synthesis and assembly of nanomaterials offer a unique opportunity to purposefully design structures according to the requirements of the targeted applications. This paper shows a process to...
The content of this RSS Feed (c) The Royal Society of Chemistry

Nanocellulose/Graphene Oxide layered membranes: Elucidating their behaviour during filtration of water and metal ions in real time

By Aji Mathew from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07116D, Paper
Open Access Open Access
Luis Valencia, Susanna Monti, Sugam Kumar, Peng Liu, Chuantao Zhu, Shun Yu, Aji Mathew
TThe deposition of a thin layer of Graphene Oxide (GO) onto Cellulose Nanofibrils (CNF) membranes, to form CNF-GO layered-composite membranes, dramatically enhances their wet-mechanical stability, water flux and adsorptive capacity...
The content of this RSS Feed (c) The Royal Society of Chemistry

Fluorine-Assisted Structural Engineering of Colloidal Anatase TiO2 Hierarchical Nanocrystals for Enhanced Photocatalytic Hydrogen Production

By Yadong Yin from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06595D, Paper
Lan Peng, Yiding Liu, Yongjie Li, Feng Teng, Aiwei Tang, Yadong Yin
Anatase TiO2 materials are well-known for their photocatalytic properties and their structure-performance relationship has been intensively studied during the past few decades. In this study, we report a versatile strategy...
The content of this RSS Feed (c) The Royal Society of Chemistry

Revisit Positive Roles of Liquid Polysulfides in Alkali Metal-Sulfur Electrochemistry: from Electrolyte Additives to Active Catholyte

By Xiong Pu from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07416C, Review Article
Caiyun Chang, Xiong Pu
Polysulfide dissolution and shuttling in liquid organic electrolyte are considered as the most challenging detrimental effects of a Li-S cell, i.e. one of the most promising next-generation high-energy density batteries....
The content of this RSS Feed (c) The Royal Society of Chemistry

In situ Encapsulation of Co-based nanoparticles into Nitrogen-doped Carbon-Nanotubes modified reduced Graphene Oxide as Air Cathode for High-performance Zn–Air Batteries

By Shouhua Feng from RSC - Nanoscale latest articles. Published on Oct 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07270E, Paper
Haocheng Qi, Yingying Feng, Zhenzhen Chi, Yuanyuan Cui, MingHui Wang, Jie Liu, Ziyang Guo, Lei Wang, Shouhua Feng
Exploring high-efficient catalysts for oxygen reduction/evolution reaction (ORR/OER) is very important in rechargeable Zn–air batteries. N-doped carbon coupled with transitional metal-based species should be the most promising cathode catalysts for...
The content of this RSS Feed (c) The Royal Society of Chemistry

Cu,N‐Codoped Carbon Nanodisks with Biomimic Stomata‐Like Interconnected Hierarchical Porous Topology as Efficient Electrocatalyst for Oxygen Reduction Reaction

By Tao Wang, Rui Yang, Naien Shi, Jing Yang, Hongyu Yan, Junyi Wang, Zhen Ding, Wei Huang, Qing Luo, Yue Lin, Jian Gao, Min Han from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

2D Cu,N‐codoped carbon (Cu‐N‐C) nanodisks with stomata‐like interconnected hierarchical porous topology are fabricated by etching Cu‐tetrapyridylporphyrin(TPyP)‐metal–organic frameworks (MOFs) carbonization product (Cu@Cu‐N‐C) along with re‐annealing treatment. Due to their unique porous structures and fully exposed Cu single‐atom sites, such Cu‐N‐C nanodisks manifest exceptional electrocatalytic performance toward oxygen reduction, outperforming Cu@Cu‐N‐C, Cu‐TPyP‐MOFs, Pt/C, and most of other reported metal‐N‐codoped carbon catalysts. Abstract Metal,N‐codoped carbon (M‐N‐C) nanostructures are promising electrocatalysts toward oxygen reduction reaction (ORR) or other gas‐involved energy electrocatalysis. Further creating pores into M‐N‐C nanostructures can increase their surface area, fully expose the active sites, and improve mass transfer and electrocatalytic efficiency. Nonetheless, it remains a challenge to fabricate M‐N‐C nanomaterials with both well‐defined morphology and hierarchical porous structures. Herein, high‐quality 2D Cu‐N‐C nanodisks (NDs) with biomimic stomata‐like interconnected hierarchical porous topology are synthesized via carbonization of Cu‐tetrapyridylporphyrin (TPyP)‐metal–organic frameworks (MOFs) precursors and followed by etching the carbonization product (Cu@Cu‐N‐C) along with re‐annealing treatment. Such hierarchical porous Cu‐N‐C NDs possess high specific surface area (293 m2 g−1) and more exposed Cu single‐atom sites, different from their counterparts (Cu@Cu‐N‐C) and pure N‐C control catalysts. Electrochemical tests in alkaline media reveal that they can efficiently catalyze ORR with a half‐wave potential of 0.85 V (vs reversible hydrogen electrode), comparable to Pt/C and outperforming Cu@Cu‐N‐C, N‐C, Cu‐TPyP‐MOFs, and most other reported M‐N‐C catalysts. Moreover, their stability and methanol‐tolerant capability exceed Pt/C. This work may shed some light on optimizing 2D M‐N‐C nanostructures through bio‐inspired pore structure engineering, and accelerate their applications in fuel cells, artificial photosynthesis, or other advanced technological fields.

Uniform Ag Nanocubes Prepared by AgCl Particle–Mediated Heterogeneous Nucleation and Disassembly and Their Mechanism Study by DFT Calculation

By Hye Ji Han, Ju Hyun Park, Jin Kyoung Park, Imanuel Kristanto, Bum Jun Park, Sang Kyu Kwak, Sang Hyuk Im from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

N,N‐dimethylformamide enables uniform Ag nanocubes to be reproducibly synthesized in polyol solution chemistry because it creates Ag nuclei on the surface of AgCl particles by reduction of AgCl into Ag, and greatly reduces the overall reaction time by promotion of the reduction reaction. Abstract Uniform Ag nanocubes are reproducibly synthesized by a AgCl particle‐mediated heterogeneous nucleation and disassembly process in polyol chemistry. By introducing N,N‐dimethylformamide (DMF) in a conventional polyol method with HCl etchant, Ag nanocrystals (NCs) begin to be nucleated on the surface of AgCl‐precipitated particles due to the promoted reduction reaction by DMF. The nucleated Ag NCs on the AgCl particles are grown to Ag nanocubes in shape by consuming Ag sources from the AgCl mother particles. Eventually the grown Ag nanocubes are disassembled from the mother AgCl particles because the AgCl particles are fully digested by the growing Ag nanocubes. Density functional theory calculation confirms that the Ag atoms can be favorably deposited on the (100) facet of AgCl particles and the Ag nuclei on the AgCl particles tend to reveal (100) facet.

Phospholipid‐Free Small Unilamellar Vesicles for Drug Targeting to Cells in the Liver

By Wunan Zhang, Roland Böttger, Zhu Qin, Jayesh A. Kulkarni, Julian Vogler, Pieter R. Cullis, Shyh‐Dar Li from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Phospholipid‐free small unilamellar vesicles (PFSUVs) containing TWEEN 80 are manufactured for the first time with a high cholesterol content (83 mol%) using microfluidics. Compared to previously reported surfactant‐based formulations, PFSUVs can retain a transmembrane gradient for active loading of doxorubicin. After intravenous administration, PFSUVs‐doxorubicin is delivered to the liver, predominantly targeting hepatocytes via the endogenous apolipoprotein mechanism. Abstract It is reported that cholesterol (Chol) and TWEEN 80 at a molar ratio of 5:1 can form small unilamellar vesicles (SUVs) using a staggered herringbone micromixer. These phospholipid‐free SUVs (PFSUVs) can be actively loaded with a model drug for targeting hepatocytes via the endogenous apolipoprotein mechanism. PFSUVs particles with compositions of Chol:TWEEN 80 ranging between 1.5:1 and 5:1 (mol/mol) can be produced with a mean diameter of ≈80 nm, but only the high‐Chol formulations (3:1 and 5:1) can retain a transmembrane gradient of ammonium sulfate for active loading of doxorubicin (DOX). Under cryo‐transmission electron microscopy, PFSUVs‐DOX displays a unilamellar bilayer structure with DOX molecules forming spindle‐shape aggregates inside the aqueous core. Relative to PEGylated liposomal doxorubicin (PLD) that exhibits little interaction with cells in various conditions, the cellular uptake of PFSUVs‐DOX is dependent on the presence of serum and enhanced with an increased concentration of apolipoproteins. After intravenous injection, the vast majority of PFSUVs‐DOX accumulates in the liver and DOX is detected in all liver cells (predominantly the hepatocytes), while PLD is captured only by the sinusoidal cells (i.e., macrophages). This report discloses an innovative lipid bilayer vesicle for highly efficient and selective hepatocyte targeting.

Bioinspired Peptoid Nanotubes for Targeted Tumor Cell Imaging and Chemo‐Photodynamic Therapy

By Yanan Luo, Yang Song, Mingming Wang, Tengyue Jian, Shichao Ding, Peng Mu, Zhihao Liao, Qiurong Shi, Xiaoli Cai, Haibao Jin, Dan Du, Wen‐Ji Dong, Chun‐Long Chen, Yuehe Lin from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

A new class of uniform 1D peptoid nanotubes with high stability is developed by the assembly of ligand‐tagged Nbpm6Nce6 peptoid oligomers. These nanotubes exhibit a high loading efficiency to doxorubicin. Additionally, the photosensitizer‐conjugated nanotubes induce the generation of singlet oxygen and the activation of cell apoptosis. A chemo‐photodynamic therapy combined killing effect is achieved by the drug‐loaded functional nanotubes. Abstract Substantial progress has been made in applying nanotubes in biomedical applications such as bioimaging and drug delivery due to their unique architecture, characterized by very large internal surface areas and high aspect ratios. However, the biomedical applications of organic nanotubes, especially for those assembled from sequence‐defined molecules, are very uncommon. In this paper, the synthesis of two new peptoid nanotubes (PepTs1 and PepTs2) is reported by using sequence‐defined and ligand‐tagged peptoids as building blocks. These nanotubes are highly robust due to sharing a similar structure to those of nontagged ones, and offer great potential to hold guest molecules for biomedical applications. The findings indicate that peptoid nanotubes loaded with doxorubicin drugs are promising candidates for targeted tumor cell imaging and chemo‐photodynamic therapy.

Boosting High‐Rate Sodium Storage Performance of N‐Doped Carbon‐Encapsulated Na3V2(PO4)3 Nanoparticles Anchoring on Carbon Cloth

By Wei Li, Zhujun Yao, Cheng‐ao Zhou, Xiuli Wang, Xinhui Xia, Changdong Gu, Jiangping Tu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

An integrated NVP@NC flexible electrode is constructed by smart combination of a conductive carbon cloth skeleton and N‐doped carbon shell on Na3V2(PO4)3 nanoparticles with superior Na storage performances. Abstract The further development of high‐power sodium‐ion batteries faces the severe challenge of achieving high‐rate cathode materials. Here, an integrated flexible electrode is constructed by smart combination of a conductive carbon cloth fiber skeleton and N‐doped carbon (NC) shell on Na3V2(PO4)3 (NVP) nanoparticles via a simple impregnation method. In addition to the great electronic conductivity and high flexibility of carbon cloth, the NC shell also promotes ion/electron transport in the electrode. The flexible NVP@NC electrode renders preeminent rate capacities (80.7 mAh g−1 at 50 C for cathode; 48 mAh g−1 at 30 C for anode) and superior cycle performance. A flexible symmetric NVP@NC//NVP@NC full cell is endowed with fairly excellent rate performance as well as good cycle stability. The results demonstrate a powerful polybasic strategy design for fabricating electrodes with optimal performance.

Carbon‐Intercalated 0D/2D Hybrid of Hematite Quantum Dots/Graphitic Carbon Nitride Nanosheets as Superior Catalyst for Advanced Oxidation

By Junhua Xi, Hong Xia, Xingming Ning, Zhen Zhang, Jia Liu, Zijie Mu, Shouting Zhang, Peiyao Du, Xiaoquan Lu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

0D hematite quantum dots/2D ultrathin g‐C3N4 nanosheet hybrids are developed by simple chemical reactions and calcination. Highly exposed active surfaces, charge transfer at the intrinsic interface, and synergy between photocatalysis and H2O2 lead to excellent catalytic performance for degrading p‐nitrophenol. This work provides new insights into the development of heterogeneous catalysis for optoelectronic applications. Abstract Efficient charge separation and sufficiently exposed active sites are important for light‐driving Fenton catalysts. 0D/2D hybrids, especially quantum dots (QDs)/nanosheets (NSs), offer a better opportunity for improving photo‐Fenton activity due to their high charge mobility and more catalytic sites, which is highly desirable but remains a great challenge. Herein, a 0D hematite quantum dots/2D ultrathin g‐C3N4 nanosheets hybrid (Fe2O3 QDs/g‐C3N4 NS) is developed via a facile chemical reaction and subsequent low‐temperature calcination. As expected, the specially designed 0D/2D structure shows remarkable catalytic performance toward the removal of p‐nitrophenol. By virtue of large surface area, adequate active sites, and strong interfacial coupling, the 0D Fe2O3 QDs/2D g‐C3N4 nanosheets establish efficient charge transport paths by local in‐plane carbon species, expediting the separation and transfer of electron/hole pairs. Simultaneously, highly efficient charge mobility can lead to continuous and fast Fe(III)/Fe(II) conversion, promoting a cooperative effect between the photocatalysis and chemical activation of H2O2. The developed carbon‐intercalated 0D/2D hybrid provides a new insight in developing heterogeneous catalysis for a large variety of photoelectronic applications, not limited in photo‐Fenton catalysis.

Anisotropic Excitation Polarization Response from a Single White Light‐Emitting β‐NaYF4:Yb3+,Pr3+ Microcrystal

By Dandan Yang, Zixing Peng, Qiuqiang Zhan, Xiongjian Huang, Xingyun Peng, Xin Guo, Guoping Dong, Jianrong Qiu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Anisotropic white light‐emitting β‐NaYF4:Yb,Pr microcrystals are prepared for new insights into optical and structural anisotropy in individual particles. Different excitation polarization responses and Raman scattering modes observed in different excitation configurations clearly present the optical and structural anisotropy of as‐prepared microcrystals, and the corresponding mechanisms are discussed in detail, suggesting the importance of investigation of single particles. Abstract Precise knowledge about optical and structural performance of individual rare earth (RE)‐doped particles is extremely important for the optimization of luminescent particles and for fully exploiting their capability as multifunctional probes for interdisciplinary applications. In this work, optical and structural anisotropy of individual particles through RE‐doped single fluoride microcrystals with controllable morphology is reported. Unique luminescent phenomena, for example, white light‐emission from Pr3+ at single particle level and different photoluminescent spectra variation dependence on excitation polarization orientation at different excitation direction are observed upon excitation with a 980 nm linearly polarized laser. Based on the analysis of local site symmetry and electron cloud distribution of REs in hexagonal structure by density functional theory calculations, an exciting mechanism of excitation polarization response anisotropy is given for the first time, providing a guidance for emission polarization simultaneously. The structural anisotropy is presented in Raman spectra with obvious differing Raman curves, revealing the reason why there are differences between powder groups. Taking advantage of anisotropic crystals, potential applications in microscopic multi‐information transportation are suggested for the optical and structural performance anisotropy from RE‐doped fluoride single nano/microcrystals to ordered nano/microcrystal arrays, such as local rate probing in a flowing liquid.

Bolometric Effect in Bi2O2Se Photodetectors

By Hang Yang, Congwei Tan, Chuyun Deng, Renyan Zhang, Xiaoming Zheng, Xiangzhe Zhang, Yuze Hu, Xiaoxiao Guo, Guang Wang, Tian Jiang, Yi Zhang, Gang Peng, Hailin Peng, Xueao Zhang, Shiqiao Qin from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

The coexistence of the photoconductive effect and bolometric effect in Bi2O2Se photodetectors is generally observed. Moreover, Bi2O2Se bolometer shows a high temperature coefficient of resistance (−1.6% K−1), high bolometric coefficient (−31 nA K−1), and high bolometric responsivity (>320 A W−1). These findings offer a new approach to develop bolometric photodetectors based on Bi2O2Se layered materials. Abstract Bi2O2Se is emerging as a photosensitive functional material for optoelectronics, and its photodetection mechanism is mostly considered to be a photoconductive regime in previous reports. Here, the bolometric effect is discovered in Bi2O2Se photodetectors. The coexistence of photoconductive effect and bolometric effect is generally observed in multiwavelength photoresponse measurements and then confirmed with microscale local heating experiments. The unique photoresponse of Bi2O2Se photodetectors may arise from a change of hot electrons during temperature rises instead of photoexcited holes and electrons. Direct proof of the bolometric effect is achieved by real‐time temperature tracking of Bi2O2Se photodetectors under time evolution after light excitation. Moreover, the Bi2O2Se bolometer shows a high temperature coefficient of resistance (−1.6% K−1), high bolometric coefficient (−31 nA K−1), and high bolometric responsivity (>320 A W−1). These findings offer a new approach to develop bolometric photodetectors based on Bi2O2Se layered materials.

Profiling of Exosomal Biomarkers for Accurate Cancer Identification: Combining DNA‐PAINT with Machine‐ Learning‐Based Classification

By Chen Chen, Shenfei Zong, Yun Liu, Zhuyuan Wang, Yizhi Zhang, Baoan Chen, Yiping Cui from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

A machine learning algorithm and DNA‐PAINT‐based quantitative analysis platform is developed to implement integrated multiplex detection of several exosomal biomarkers at the single‐exosome level. Using this platform, accurate classification of clinical samples is accomplished, indicating promising potential in cancer diagnosis. This platform provides a new avenue to noninvasive diagnosis of cancers using exosomes as the biomarkers. Abstract Exosomes are endosome‐derived vesicles enriched in body fluids such as urine, blood, and saliva. So far, they have been recognized as potential biomarkers for cancer diagnostics. However, the present single‐variate analysis of exosomes has greatly limited the accuracy and specificity of diagnoses. Besides, most diagnostic approaches focus on bulk analysis using lots of exosomes and tend to be less accurate because they are vulnerable to impure extraction and concentration differences of exosomes. To address these challenges, a quantitative analysis platform is developed to implement a sequential quantification analysis of multiple exosomal surface biomarkers at the single‐exosome level, which utilizes DNA‐PAINT and a machine learning algorithm to automatically analyze the results. As a proof of concept, the profiling of four exosomal surface biomarkers (HER2, GPC‐1, EpCAM, EGFR) is developed to identify exosomes from cancer‐derived blood samples. Then, this technique is further applied to detect pancreatic cancer and breast cancer from unknown samples with 100% accuracy.

Enhancing Oxygen Evolution Reaction through Modulating Electronic Structure of Trimetallic Electrocatalysts Derived from Metal–Organic Frameworks

By Yuwen Li, Tao Zhao, Mengting Lu, Yuhang Wu, Yuanbo Xie, Hui Xu, Junkuo Gao, Juming Yao, Guodong Qian, Qichun Zhang from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Facile synthesis of W/Co/Fe trimetallic carbon nanoflake electrocatalysts which are derived from metal–organic frameworks (MOFs) is reported, and an Fe‐dependent volcano‐type relationship is discovered. Furthermore, the doping content of Fe can accurately modulate the electronic structure of the catalysts. The results highlight the great potential of utilizing multimetallic MOFs as promising templates while realizing electronic structure modulation. Abstract The construction of efficient, durable, and non‐noble metal electrocatalysts for oxygen evolution reaction (OER) is of great value but challenging. Herein, a facile method is developed to synthesize a series of trimetallic (W/Co/Fe) metal–organic frameworks (MOFs)‐derived carbon nanoflakes (CNF) with various Fe content, and an Fe‐dependent volcano‐type plot can be drawn out for WCoFex ‐CNF. The optimized WCoFe0.3‐CNF (when the feed ratio of Fe/Co is 0.3) demonstrates superior electrocatalytic performance with a low overpotential of only 254 mV@10 mA cm−2 and excellent durability of 100 h. Further researches show that appropriate amount of iron doping can regulate the electronic structure, resulting in a favorable synergistic environment. This method may stimulate the exploration of electrocatalysts by utilizing MOFs as precursors while realizing electronic modulation by multimetal doping.

CeO2‐Encapsulated Hollow Ag–Au Nanocage Hybrid Nanostructures as High‐Performance Catalysts for Cascade Reactions

By Lingling Zhang, Jing Pan, Yan Long, Jian Li, Wei Li, Shuyan Song, Zhan Shi, Hongjie Zhang from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

High‐quality Ag–Au NC@CeO2 core–shell nanostructures are successfully prepared by a fast and facile self‐assembly method. They are proved to have activity in glucose oxidation cascade reactions. By using a concentration versus absorbance regression equation, the one‐pot detection of glucose without bio‐enzymes is possible, which has a profound impact in biomedicine and development of biomimetic catalysts. Abstract Inspired by bio‐enzymes, multistep cascade reactions are highly attractive in catalysis. Despite extensive research in recent years, it remains a challenge to promote the stability and activity of catalysts. Here, well‐defined core–shell structured Ag–Au nanocage@CeO2 (Ag–Au NC@CeO2) are designed by a simple and facile self‐assembly method. The results indicate that the Ag–Au NC@CeO2 has glucose oxidase‐like activity and intrinsic peroxidase‐like activity at the same time. As expected, Ag–Au NC@CeO2 hybrid nanomaterials exhibit cascade reactions activity. Moreover, the hybrid materials are promising to detect glucose without bio‐enzymes. This research has potential applications in biomedicine and biomimetic catalysis.

Early Lithium Plating Behavior in Confined Nanospace of 3D Lithiophilic Carbon Matrix for Stable Solid‐State Lithium Metal Batteries

By Shaobo Huang, Hao Yang, Jiangkui Hu, Yongchang Liu, Kexin Wang, Hailin Peng, Hao Zhang, Li‐Zhen Fan from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

A significant early homogeneous lithium plating behavior in the confined nanospace of a 3D carbon matrix is explored. The 3D composite lithium anode presents improved Coulombic efficiency with no dendritic growth. The 3D composite lithium anode is successfully applied in solid‐state lithium metal batteries. Abstract Considerable efforts are devoted to relieve the critical lithium dendritic and volume change problems in the lithium metal anode. Constructing uniform Li+ distribution and lithium “host” are shown to be the most promising strategies to drive practical lithium metal anode development. Herein, a uniform Li nucleation/growth behavior in a confined nanospace is verified by constructing vertical graphene on a 3D commercial copper mesh. The difference of solid‐electrolyte interphase (SEI) composition and lithium growth behavior in the confined nanospace is further demonstrated by in‐depth X‐ray photoelectron spectrometer (XPS) and line‐scan energy dispersive X‐ray spectroscopic (EDS) methods. As a result, a high Columbic efficiency of 97% beyond 250 cycles at a current density of 2 mA cm−2 and a prolonged lifespan of symmetrical cell (500 cycles at 5 mA cm−2) can be easily achieved. More meaningfully, the solid‐state lithium metal cell paired with the composite lithium anode and LiNi0.5Co0.2Mn0.3O2 (NCM) as the cathode also demonstrate reduced polarization and extended cycle. The present confined nanospace–derived hybrid anode can further promote the development of future all solid‐state lithium metal batteries.

On the Chemistry and Diffusion of Hydrogen in the Interstitial Space of Layered Crystals h‐BN, MoS2, and Graphite

By Yun An, Agnieszka Kuc, Petko Petkov, Marcelo Lozada‐Hidalgo, Thomas Heine from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

2D layered materials h‐BN and MoS2 are demonstrated to separate hydrogen isotopes via nuclear quantum effects. The hydrogen diffusion through the interstitial space is explored for protium (H) atoms and protons (H+). In both cases, the diffusion is assisted by shear‐modes, with the free‐energy barrier of 0.08 eV for protium and 0.46 eV for protons in h‐BN. Abstract Recent experiments have demonstrated transport and separation of hydrogen isotopes through the van der Waals gap in hexagonal boron nitride and molybdenum disulfide bulk layered materials. However, the experiments cannot distinguish if the transported particles are protons (H+) or protium (H) atoms. Here, reported are the theoretical studies, which indicate that protium atoms, rather than protons, are transported through the gap. First‐principles calculations combined with well‐tempered metadynamics simulations at finite temperature reveal that for h‐BN and MoS2, the diffusion mechanism of both protons and protium (H) atoms involves a hopping process between adjacent layers. This process is assisted by low‐energy phonon shear modes. The extracted diffusion coefficient of protium matches the experiment, while for protons it is several orders of magnitude smaller. This indicates that protium atoms are responsible for the experimental observations. These results allow for a comprehensive interpretation of experimental results on the transport of hydrogen isotopes through van der Waals gaps and can help identify other materials for hydrogen isotope separation applications.

Oxidase‐Like Fe‐N‐C Single‐Atom Nanozymes for the Detection of Acetylcholinesterase Activity

By Yu Wu, Lei Jiao, Xin Luo, Weiqing Xu, Xiaoqian Wei, Hengjia Wang, Hongye Yan, Wenling Gu, Bo Z. Xu, Dan Du, Yuehe Lin, Chengzhou Zhu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Fe‐N‐C single‐atom nanozymes with distributed FeN2 active sites possessing oxidase‐like activity are reported. Based on the inhibition mode by thiols, the Fe‐N‐C single‐atom nanozymes show promising application for evaluating the activity of acetylcholinesterase and constructing sensitive biosensors to detect mercapto molecules and organophosphorus compounds. Abstract Single‐atom catalysts (SACs) have attracted extensive attention in the catalysis field because of their remarkable catalytic activity, gratifying stability, excellent selectivity, and 100% atom utilization. With atomically dispersed metal active sites, Fe‐N‐C SACs can mimic oxidase by activating O2 into reactive oxygen species, O2−• radicals. Taking advantages of this property, single‐atom nanozymes (SAzymes) can become a great impetus to develop novel biosensors. Herein, the performance of Fe‐N‐C SACs as oxidase‐like nanozymes is explored. Besides, the Fe‐N‐C SAzymes are applied in biosensor areas to evaluate the activity of acetylcholinesterase based on the inhibition toward nanozyme activity by thiols. Moreover, this SAzymes‐based biosensor is further used for monitoring the amounts of organophosphorus compounds.

Deconstructed Microfluidic Bone Marrow On‐A‐Chip to Study Normal and Malignant Hemopoietic Cell–Niche Interactions

By Julio Aleman, Sunil K. George, Samuel Herberg, Mahesh Devarasetty, Christopher D. Porada, Aleksander Skardal, Graça Almeida‐Porada from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Described is the deconstruction of the bone marrow niche cellularly into four distinct 3D niche types (sinusoidal, arterial, mesenchymal, and osteoblastic) within a microfluidic tissue chip. Shown is 1) preservation of niche‐specific markers, 2) the capability to live‐track healthy and malignant hematopoietic stem progenitor cells (HSPC), and 3) evidence that healthy versus malignant HSPC show different predilection for homing/engrafting. Abstract Human hematopoietic niches are complex specialized microenvironments that maintain and regulate hematopoietic stem and progenitor cells (HSPC). Thus far, most of the studies performed investigating alterations of HSPC‐niche dynamic interactions are conducted in animal models. Herein, organ microengineering with microfluidics is combined to develop a human bone marrow (BM)‐on‐a‐chip with an integrated recirculating perfusion system that consolidates a variety of important parameters such as 3D architecture, cell–cell/cell–matrix interactions, and circulation, allowing a better mimicry of in vivo conditions. The complex BM environment is deconvoluted to 4 major distinct, but integrated, tissue‐engineered 3D niche constructs housed within a single, closed, recirculating microfluidic device system, and equipped with cell tracking technology. It is shown that this technology successfully enables the identification and quantification of preferential interactions—homing and retention—of circulating normal and malignant HSPC with distinct niches.

Ultrabroad Band Microwave Absorption of Carbonized Waxberry with Hierarchical Structure

By Xianxian Sun, Minglong Yang, Shuang Yang, Shasha Wang, Weilong Yin, Renchao Che, Yibin Li from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

The waxberry, with unique hierarchical structure, is carbonized. The carbonized waxberry shows radial‐gradient structure. The different components of hierarchical waxberry demonstrate distinct dielectric properties. The carbonized waxberry shows ultrabroad bandwidth ranging from 1 to 40 GHz with good absorption property. Moreover, the reflection loss does not change even though the incident angle increases to 40°. Abstract Developing microwave absorption materials with broadband and lightweight characters is of great significance. However, it is still a great challenge for carbonized biomass without loading magnetic particles to cover the broad microwave frequency. Herein, it is proposed to carbonize freeze‐dried waxberry to make full use of its natural hierarchical gradient structure to target the ultrabroad band microwave absorption. The carbonized freeze‐dried waxberry shows radial‐gradient and hierarchical structure. The different components of hierarchical waxberry demonstrate gradient dielectric properties: the outer component shows anisotropic dielectric constants with smaller value, while the inner core shows higher dielectric constants. This gradient dielectric property is beneficial to the impedance matching and strong polarization. As a result, the bandwidth of carbonized waxberry exhibits an ultrabroad band microwave absorption, ranging from 1 to 40 GHz with the reflection loss value below −8 dB. Meanwhile, the bandwidth can cover from 8 to 40 GHz when the reflection loss is below −15 dB. The ultrabroad microwave absorption is attributed to the hierarchical radial‐gradient structure of carbonized waxberry, which provides good impedance matching with air media. This achievement paves the way for the exploitation of natural hierarchical biomass as a superlight and broadband high‐performance microwave absorption material.

The Next Generation of Colloidal Probes: A Universal Approach for Soft and Ultra‐Small Particles

By Andreas Mark, Nicolas Helfricht, Astrid Rauh, Matthias Karg, Georg Papastavrou from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Combining nanofluidics with the colloidal probe technique allows to determine the interaction forces on the base of individual nanoparticles as small as 300 nm. Moreover, even particles with a soft outer shell can be immobilized and used in a reversible manner as probes, such as silica‐PNIPAM core‐shell particles. Abstract The colloidal probe technique, which is based on the atomic force microscope, revolutionizes direct force measurements in many fields, such as interface science or biomechanics. It allows for the first time to determine interaction forces on the single particle or cell level. However, for many applications, important “blind spots” remain, namely, the possibility to probe interaction potentials for nanoparticles or complex colloids with a soft outer shell. Definitely, these are colloidal systems that are currently of major industrial importance and interest from theory. The here‐presented novel approach allows for overcome the aforementioned limitations. Its applicability has been demonstrated for 300 nm sized carboxylate‐modified latex particles as well as sub‐micron core–shell particles with a soft poly‐N‐isopropylacrylamide hydrogel shell and a rigid silica core. For the latter, which until now cannot be studied by the colloidal probe technique, determined is the temperature dependency of electrosteric and adhesion forces has been determined on the single particle level.

Chromophore‐Modified Highly Selective Ratiometric Upconversion Nanoprobes for Detection of ONOO−‐Related Hepatotoxicity In Vivo

By Xiao Liu, Huanhua Lai, Juanjuan Peng, Dan Cheng, Xiao‐Bing Zhang, Lin Yuan from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Highly selective near‐infrared ratiometric fluorescent nanoprobes are designed to track the acute hepatotoxicity‐related reactive nitrogen species (RNS) peroxynitrite ONOO−. The nanosystem can estimate the content of ONOO− based on relative fluorescence intensity, and to further realize the assessment of acute liver injury in vivo. Abstract Acute hepatitis is a major problem affecting public health and has attracted more and more attention. Generally, as the standard means, blood tests are taken for evaluating hepatitis. However, such tests fail to accurately reflect the level of hepatitis in vivo. Herein, two highly selective ratiometric fluorescent probes are designed to track peroxynitrite (ONOO−) as the hepatitis indicator, and further evaluate acute liver injury in vivo through dye‐grafted upconversion nanoparticles (UCNPs). Specifically, upconversion luminescence of nanoprobes at 540 or 660 nm can be quenched by the designed and synthesized chromophore E‐CC or H‐CC, that can be destroyed by ONOO− via energy transfer (ET) process, while the upconversion luminescence intensity at 810 nm remains the same. Thus, the developed nanoprobes can be used for ratiometric detection (I540/I660 or I660/I810) of ONOO−. Moreover, the developed near infrared ratiometric nanoprobes can highly selectively detect ONOO−, which can eliminate the interference of HOCl and SO32−. Finally, it is demonstrated that this highly selective ratiometric nanosystem can achieve effective detection of ONOO− in living cells and CCl4‐induced acute liver injury models. It provides some reference value for clinical detection of hepatotoxicity.

High Spatial Resolution Mapping of Localized Surface Plasmon Resonances in Single Gallium Nanoparticles

By María Mata, Sergio Catalán‐Gómez, Flavio Nucciarelli, José L. Pau, Sergio I. Molina from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Low‐loss electron energy‐loss spectroscopy hyperspectral imaging of single gallium nanoparticles reveals the presence of two localized surface plasmon resonances with uneven spatial distribution. Abstract Plasmonics has emerged as an attractive field driving the development of optical systems in order to control and exploit light–matter interactions. The increasing interest around plasmonic systems is pushing the research of alternative plasmonic materials, spreading the operability range from IR to UV. Within this context, gallium appears as an ideal candidate, potentially active within a broad spectral range (UV–VIS–IR), whose optical properties are scarcely reported. Importantly, the smart design of active plasmonic materials requires their characterization at high spatial and spectral resolution to access the optical fingerprint of individual nanostructures, attainable by transmission electron microscopy techniques (i.e., by means of electron energy‐loss spectroscopy, EELS). Therefore, the optical response of individual Ga nanoparticles (NPs) by means of EELS measurements is analyzed, in order to spread the understanding of the plasmonic response of Ga NPs. The results show that single Ga NPs may support several plasmon modes, whose nature is extensively discussed.

Implantable Organic Electronic Ion Pump Enables ABA Hormone Delivery for Control of Stomata in an Intact Tobacco Plant

By Iwona Bernacka‐Wojcik, Miriam Huerta, Klas Tybrandt, Michal Karady, Mohammad Yusuf Mulla, David J. Poxson, Erik O. Gabrielsson, Karin Ljung, Daniel T. Simon, Magnus Berggren, Eleni Stavrinidou from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

An organic electronic ion pump (OEIP) provides a unique means for electronically controlled, flow‐free delivery of ions at the cellular scale. Here, a capillary‐based OEIP is implanted in the leaf of an intact tobacco plant with no significant wound response and effectively delivers the hormone abscisic acid demonstrating the first example of an implantable bioelectronic device in plants. Abstract Electronic control of biological processes with bioelectronic devices holds promise for sophisticated regulation of physiology, for gaining fundamental understanding of biological systems, providing new therapeutic solutions, and digitally mediating adaptations of organisms to external factors. The organic electronic ion pump (OEIP) provides a unique means for electronically‐controlled, flow‐free delivery of ions, and biomolecules at cellular scale. Here, a miniaturized OEIP device based on glass capillary fibers (c‐OEIP) is implanted in a biological organism. The capillary form factor at the sub‐100 µm scale of the device enables it to be implanted in soft tissue, while its hyperbranched polyelectrolyte channel and addressing protocol allows efficient delivery of a large aromatic molecule. In the first example of an implantable bioelectronic device in plants, the c‐OEIP readily penetrates the leaf of an intact tobacco plant with no significant wound response (evaluated up to 24 h) and effectively delivers the hormone abscisic acid (ABA) into the leaf apoplast. OEIP‐mediated delivery of ABA, the phytohormone that regulates plant's tolerance to stress, induces closure of stomata, the microscopic pores in leaf's epidermis that play a vital role in photosynthesis and transpiration. Efficient and localized ABA delivery reveals previously unreported kinetics of ABA‐induced signal propagation.

Influence of Nanopillar Arrays on Fibroblast Motility, Adhesion, and Migration Mechanisms

By Kai S. Beckwith, Sindre Ullmann, Jakob Vinje, Pawel Sikorski from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Glass surfaces decorated with 1 µm high nanopillars with varying pillar to pillar distance are used to study migration and spreading of embryonic mouse fibroblasts (NIH‐3T3). Quantitative description of the migration process on a range of substrates is provided together with the description of key mechanisms responsible for altering cell migration on these substrates. Abstract Surfaces decorated with high aspect ratio nanostructures are a promising tool to study cellular processes and design novel devices to control cellular behavior. However, little is known about the dynamics of cellular phenomenon such as adhesion, spreading, and migration on such surfaces. In particular, how these are influenced by the surface properties. In this work, fibroblast behavior is investigated on regular arrays of 1 µm high polymer nanopillars with varying pillar to pillar distance. Embryonic mouse fibroblasts (NIH‐3T3) spread on all arrays, and on contact with the substrate engulf nanopillars independently of the array pitch. As the cells start to spread, different behavior is observed. On dense arrays which have a pitch equal or below 1 µm, cells are suspended on top of the nanopillars, making only sporadic contact with the glass support. Cells stay attached to the glass support and fully engulf nanopillars during spreading and migration on the sparse arrays which have a pitch of 2 µm and above. These alternate states have a profound effect on cell migration rates. Dynamic F‐actin puncta colocalize with nanopillars during cell spreading and migration. Strong membrane association with engulfed nanopillars might explain the reduced migration rates on sparse arrays.

In Vivo Environment‐Adaptive Nanocomplex with Tumor Cell–Specific Cytotoxicity Enhances T Cells Infiltration and Improves Cancer Therapy

By Yiran Liu, Tianqun Lang, Zhong Zheng, Hui Cheng, Xin Huang, Guanru Wang, Qi Yin, Yaping Li from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Aspirin‐loaded heparan sulfate‐docetaxel micelles bind to polyethyleneimine‐polyethylene glycol copolymers, forming a nanocomplex that displays long circulation behavior in blood and specific toxicity toward tumor cells but not normal cells. The nanocomplex increases intratumoral T cells infiltration and improves the effect of inhibiting tumor growth and lung metastasis in 4T1 tumor‐bearing mice. Abstract Drug delivery strategies possessing selectivity for cancer cells are eagerly needed in therapy of metastatic breast cancer. In this study, the chemotherapeutic agent, docetaxel (DTX), is conjugated onto heparan sulfate (HS). Aspirin (ASP), which has the activity of anti‐metastasis and enhancing T cells infiltration in tumors, is encapsulated into the HS‐DTX micelle. Then the cationic polyethyleneimine (PEI)‐polyethylene glycol (PEG) copolymer binds to HS via electrostatic force, forming the ASP‐loaded HS‐DTX micelle (AHD)/PEI‐PEG nanocomplex (PAHD). PAHD displays long circulation behavior in blood due to the PEG shell. Under the tumor microenvironment with weakly acidic pH, PEI‐PEG separates from AHD, and the free cationic PEI‐PEG facilitates the cellular uptake of AHD by increasing permeability of cell membranes. Then the overexpressed heparanase degrades HS, releasing ASP and DTX. PAHD shows specific toxicity toward tumor cells but not normal cells, with advanced activity of inhibiting tumor growth and lung metastasis in 4T1 tumor‐bearing mice. The number of CD8+ T cells in tumor tissues is also increased. Therefore, PAHD can become an efficient drug delivery system for breast cancer treatment.

Protonation‐Assisted Exfoliation of N‐Containing 2D Conjugated Polymers

By Xinlei Zhang, Xiao Luo, Xusheng Zheng, Xiaojun Wu, Hangxun Xu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Protonation‐assisted liquid‐phase exfoliation: protonation of the heterocyclic nitrogen sites in bulk nitrogen‐containing 2D polymers is shown to be crucial in forming hydrogen bonding between polymer surfaces and water molecules, resulting in favored delamination of layered polymers into ultrathin nanosheets into the liquid phase under sonication. Consequently, the exfoliation yields are dramatically enhanced. Abstract Ultrathin 2D conjugated polymer nanosheets are an emerging class of photocatalysts for solar‐to‐chemical energy conversion. Until now, the majority of ultrathin 2D polymer photocatalysts are produced through exfoliation of layered polymers. Unfortunately, it still remains a great challenge to exfoliate layered polymers into ultrathin nanosheets with high yields. In this work, a liquid‐phase protonation‐assisted exfoliation is demonstrated to enable remarkably improved exfoliation yields of various 2D N‐containing conjugated polymers such as g‐C3N4, C2N, and aza‐CMP. The exfoliation yields are only 2–15% in pure water whereas they can be substantially improved to 41–56% in 12 m HCl. The exfoliated ultrathin nanosheets possess average thicknesses less than 5 nm and can be easily dispersed in aqueous solutions. More importantly, the exfoliated nanosheets exhibit significantly enhanced photocatalytic activity toward photocatalytic water splitting compared to their bulk counterparts. Further characterizations and computational calculations reveal that protonation of the heterocyclic nitrogen sites in the conjugated polymer frameworks can lead to strong hydrogen bonding between the polymer surfaces and water molecules, resulting in facilitated exfoliation of polymers into the liquid phase. This study unveils an important protocol toward producing ultrathin 2D N‐containing conjugated polymer nanosheets for future solar energy conversion.

Masthead: (Small 43/2019)

By from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

RNA‐Based Immunostimulatory Liposomal Spherical Nucleic Acids as Potent TLR7/8 Modulators

By Chenxia Guan, Natalia Chernyak, Donye Dominguez, Lisa Cole, Bin Zhang, Chad A. Mirkin from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Nanoclusters: Metal Nanoclusters Stabilized by Selenol Ligands (Small 43/2019)

By Xi Kang, Manzhou Zhu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

In article number 1902703, Xi Kang and Manzhou Zhu review recent advances in studying selenol protected nanoclusters, including the synthetic methodology, the structure elucidation, and the property investigation, which provide researchers attempting to study selenolated nanoclusters with a synthetic toolbox and researching fundamentals.

Peptoid Nanotubes: Bioinspired Peptoid Nanotubes for Targeted Tumor Cell Imaging and Chemo‐Photodynamic Therapy (Small 43/2019)

By Yanan Luo, Yang Song, Mingming Wang, Tengyue Jian, Shichao Ding, Peng Mu, Zhihao Liao, Qiurong Shi, Xiaoli Cai, Haibao Jin, Dan Du, Wen‐Ji Dong, Chun‐Long Chen, Yuehe Lin from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

In article number 1902485, Chun‐Long Chen, Yuehe Lin, and co‐workers design and synthesize two types of peptoid nanotubes with precisely controlled functional groups for targeted tumor cell imaging and chem‐photodynamic therapy by co‐assembling ligand‐tagged peptoid oligomers. These nanotubes are highly robust and show a high killing efficiency toward cancer cells by combining chemotherapy and photodynamic therapy.

Implantable Bioelectronics: Implantable Organic Electronic Ion Pump Enables ABA Hormone Delivery for Control of Stomata in an Intact Tobacco Plant (Small 43/2019)

By Iwona Bernacka‐Wojcik, Miriam Huerta, Klas Tybrandt, Michal Karady, Mohammad Yusuf Mulla, David J. Poxson, Erik O. Gabrielsson, Karin Ljung, Daniel T. Simon, Magnus Berggren, Eleni Stavrinidou from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

The organic electronic ion pump (OEIP) provides a unique means for electronically controlled, flow‐free delivery of ions at the cellular scale. In article number 1902189, Eleni Stavrinidou and co‐workers implant a capillary‐based OEIP in a leaf of an intact tobacco plant with no significant wound response and effectively deliver the hormone abscisic acid, which is the first example of an implantable bioelectronic device in plants.

Electrocatalysts: Cu,N‐Codoped Carbon Nanodisks with Biomimic Stomata‐Like Interconnected Hierarchical Porous Topology as Efficient Electrocatalyst for Oxygen Reduction Reaction (Small 43/2019)

By Tao Wang, Rui Yang, Naien Shi, Jing Yang, Hongyu Yan, Junyi Wang, Zhen Ding, Wei Huang, Qing Luo, Yue Lin, Jian Gao, Min Han from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Inspired by the stomata of plant leaves, Naien Shi, Yue Lin, Min Han, and co‐workers fabricate 2D Cu‐N‐C nanodisks with stomata‐like interconnected hierarchical porous topology by etching Cu‐tetrapyridylporphyrin (TPyP)‐metal–organic frameworks carbonization product (Cu@Cu‐N‐C) in article number 1902410. Such nanodiscs manifest superior oxygen reduction reaction performance, outperforming Cu@Cu‐N‐C, Pt/C, and most reported M‐N‐C catalysts. This work may promote the optimization and application of 2D M‐N‐C nanostructures in gas‐involved energy electrocatalysis fields.

Photodetectors: Bolometric Effect in Bi2O2Se Photodetectors (Small 43/2019)

By Hang Yang, Congwei Tan, Chuyun Deng, Renyan Zhang, Xiaoming Zheng, Xiangzhe Zhang, Yuze Hu, Xiaoxiao Guo, Guang Wang, Tian Jiang, Yi Zhang, Gang Peng, Hailin Peng, Xueao Zhang, Shiqiao Qin from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Bolometric photodetectors have been widely investigated and studied since their delicate applications in military, commercial, public, and academic domains. In article number 1904482, Hailin Peng, Xueao Zhang, Shiqiao Qin, and co‐workers report that a Bi2O2Se‐based bolometer shows a high temperature coefficient of resistance (−1.6% K−1), high bolometric coefficient (−31 nA K−1) and high bolometric responsivity (>320 A W−1). These findings offer a new approach to develop bolometric photodetectors based on Bi2O2Se‐layered materials.

Noncovalent Functionalization of Pnictogen Surfaces: From Small Molecules to 2D Heterostructures

By Hanieh Ghodrati, Nikolas Antonatos, Zdeněk Sofer from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

In recent years, functionalization of pnictogen sheets, in particular phosphorene, has received considerable attention. In this Review, noncovalent functionalization of pnictogen surfaces with organic molecules, small molecules, and van der Waals heterostructures is discussed considering theoretical and experimental studies. In this regard, noncovalent modification is an effective approach to improve surface stability and electronic properties of such materials. Abstract Beyond graphene, 2D pnictogen polymers are rapidly growing among the family of 2D materials. Due to their unique properties, this group has received considerable interest in recent years. Those properties include tunable electronic band gaps, high charge carrier mobility, and in‐plane anisotropic properties. This Review covers the noncovalent functionalization of pnictogen surfaces considering experimental and theoretical studies. Noncovalent functionalization is of great importance for effective modulation of the electronic structure of these materials as well as improvement of their stability toward surface oxidation. This Review highlights their noncovalent modification by organic molecules, in which enhanced surface stability of phosphorene and generated functionalized materials for applications in biomedical, supercapacitors, energy storage, and biosensors. Moreover, the noncovalent interactions with small molecules show its significance for sensing applications. Lastly, the interactions of pnictogen sheets with other 2D materials and their applications for van der Waals heterostructure formation are discussed. Current state‐of‐the‐art as well as future perspectives in this field are covered.

Metal Nanoclusters Stabilized by Selenol Ligands

By Xi Kang, Manzhou Zhu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Selenolated nanoclusters are anticipated to display different electronic/geometric structures and distinct chemical/physical properties relative to their thiolated analogues. This review highlights recent advances in studying selenol protected nanoclusters, including the synthetic methodology, the structure elucidation, and the property investigation, which provides researchers attempting to study selenolated nanoclusters with a synthetic toolbox and research fundamentals. Abstract The past decades have witnessed great advances in controllable synthesis, structure determination, and property investigation of metal nanoclusters. Selenolated nanoclusters, a special branch in the nanocluster family, have attracted great interest in these years. The electronegativity and atomic radius of selenium is different from sulfur, and thus the selenolated nanoclusters are anticipated to display different electronic/geometric structures and distinct chemical/physical properties relative to their thiolated analogues. This review covers the syntheses, structures, and properties of selenolated nanoclusters (including Au, Ag, Cu, and alloy nanoclusters). Ligand effects (between SeR and SR) on nanocluster properties, including optical absorption, stability, and electrochemical properties, are disclosed as well. At the end of the review, a scope for improvements and future perspectives of selenolated nanoclusters is highlighted. The review hopefully opens up new horizons for cluster scientists to synthesize more selenolated nanoclusters with novel structures and properties. This review is based on publications available up to May 2019.

Efficient and Divergent Synthesis of a‐Halogenated Amides and Esters by Double Electrophilic Activation of Ynamides

By Pierre Thilmany, Gwilherm Evano from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

An efficient and modular entry to α‐halogenated amides and esters is reported. This reaction is based on an underrated double electrophilic activation of ynamides sequentially involving highly reactive activated keteniminium and iminium ions. Upon simple reaction with HCl and an electrophilic halogenation reagent in the presence of water or an alcohol, a broad range of ynamides can be transformed, in a highly divergent manner, to α‐halo‐amides and esters with high efficiency and under mild conditions.

Direct Identification of Acetaldehyde Formation and Characterization of the Active Site in the [VPO4] · + / C2H4 Couple By Gas‐Phase Vibrational Spectroscopy

By Ya-Ke Li, Sreekanta Debnath, Maria Schlangen, Wieland Schöllkopf, Knut Asmis, Helmut Schwarz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

The gas‐phase reaction of the heteronuclear oxide cluster [VPO4] ·+ with C2H4 is studied under multiple collision conditions at 150 K using cryogenic ion trap vibrational spectroscopy combined with electronic structure calculations. The exclusive formation of acetaldehyde is spectroscopically identified directly and discussed in the context of the underlying reaction mechanism. In line with computational predictions it is the terminal P=O and not the V=O unit which provides the oxygen atom in the barrier‐free thermal C2H4 ‐‐‐> CH3CHO conversion. Interestingly, in the course of the reaction the emerging CH3CHO product undergoes a rather complex intramolecular migration, coordinating eventually to the vanadium center prior to its liberation. Moreover, the spectroscopic structural characterization of neutral C2H4O deserves special mentioning as in most, if not all ion/molecule reactions the neutral product is usually only indirectly identified.

Conversion of a Fleeting Open‐Shell Iron Nitride into an Iron Nitrosyl

By Hao‐Ching Chang, Yen‐Hao Lin, Christophe Werlé, Frank Neese, Way‐Zen Lee, Eckhard Bill, Shengfa Ye from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

In situ EPR and Mössbauer investigations reveal unprecedented oxygenation of a transient paramagnetic iron(V) nitrido intermediate yielding an iron nitrosyl species. Computational studies suggest that the N−O bond formation involves transfer of a formally closed‐shell singlet O atom to the (FeN)2+ core concurrent with synergetic orbital interactions. Abstract Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V) nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, in situ EPR and Mössbauer investigations are presented of unprecedented oxygenation of a paramagnetic iron(V) nitrido intermediate, [FeVN(cyclam‐ac)]+ (2, cyclam‐ac−=1,4,8,11‐tetraazacyclotetradecane‐1‐acetate anion), yielding an iron nitrosyl complex, [Fe(NO)(cyclam‐ac)]+ (3). Further theoretical studies suggest that during the reaction a closed‐shell singlet O atom is transferred to 2. Consequently, the N−O bond formation does not follow a radical coupling mechanism proposed for the N−N bond formation but is accomplished by three mutual electron‐transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2.

A Long‐Lived Azafullerenyl Radical Stabilized by Supramolecular Shielding with a [10]Cycloparaphenylene

By Anastasios Stergiou, Jérémy Rio, Jan H. Griwatz, Denis Arčon, Hermann A. Wegner, Christopher P. Ewels, Nikos Tagmatarchis from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

A radical shielding approach based on supramolecular complexation exploits the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling C59N. to stabilize this radical. The EPR signal of C59N.⊂[10]CPP showing characteristic 14N hyperfine splitting was observed even several weeks after its generation. Abstract A major handicap towards the exploitation of radicals is their inherent instability. In the paramagnetic azafullerenyl radical C59N., the unpaired electron is strongly localized next to the nitrogen atom, which induces dimerization to diamagnetic bis(azafullerene), (C59N)2. Conventional stabilization by introducing steric hindrance around the radical is inapplicable here because of the concave fullerene geometry. Instead, we developed an innovative radical shielding approach based on supramolecular complexation, exploiting the protection offered by a [10]cycloparaphenylene ([10]CPP) nanobelt encircling the C59N. radical. Photoinduced radical generation is increased by a factor of 300. The EPR signal showing characteristic 14N hyperfine splitting of C59N.⊂ [10]CPP was traced even after several weeks, which corresponds to a lifetime increase of >108. The proposed approach can be generalized by tuning the diameter of the employed nanobelts, opening new avenues for the design and exploitation of radical fullerenes.

Structural Evolution of Water on ZnO(10 0): From Isolated Monomers via Anisotropic H‐Bonded 2D and 3D Structures to Isotropic Multilayers

By Xiaojuan Yu, Paul Schwarz, Alexei Nefedov, Bernd Meyer, Yuemin Wang, Christof Wöll from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Hydration of ZnO surfaces: Comprehensive results from IRRAS and theory lead to a fundamental understanding of the surface chemistry of water on ZnO(10 0). The hydration is initiated by the formation of intact water monomers and proceeds by an autocatalytic dissociation of dimers and 2D adlayers, finally leading to the formation of various H‐bonded 3D structures. Abstract The surface chemistry of water on zinc oxides is an important topic in catalysis and photocatalysis. Interaction of D2O with anisotropic ZnO(10 0) surfaces was studied by IR reflection absorption spectroscopy using s‐ and p‐polarized light incident along different directions. Interpretation of the experimental data is aided using isotopologues and DFT calculations. The presence of numerous species is revealed: intact monomers, a mixed 2D D2O/OD adlayer, an anisotropic bilayer, and H‐bonded 3D structures. The isolated water monomers are identified unambiguously at low temperatures. The thermally induced diffusion of water monomers occurs at elevated temperatures, forming dimers that undergo autocatalytic dissociation via proton transfer. Polarization‐ and azimuth‐resolved IR data provide information on the orientation and strength of H‐bonds within the 2D and 3D structures. Ab initio molecular dynamics simulations reveal strong anharmonic couplings within the H‐bond network.

Dopant‐Free Squaraine‐Based Polymeric Hole‐Transporting Materials with Comprehensive Passivation Effects for Efficient All‐Inorganic Perovskite Solar Cells

By Qi Xiao, Jingjing Tian, Qifan Xue, Jing Wang, Bijin Xiong, Mengmeng Han, Zhen Li, Zonglong Zhu, Hin‐Lap Yip, Zhong'an Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Squaring the hole: Using N,N‐diarylanilinosquaraines as the comonomers gives polysquaraine hole‐transporting materials (HTMs) that have very high hole mobility. As a dopant‐free HTM for α‐CsPbI2Br‐based all‐inorganic perovskite solar cells, the power conversion efficiency (PCE) can reach 15.5 %, among the best for all‐inorganic PVSCs. Abstract Development of high‐performance dopant‐free hole‐transporting materials (HTMs) with comprehensive passivation effects is highly desirable for all‐inorganic perovskite solar cells (PVSCs). Squaraines (SQs) could be a candidate for dopant‐free HTMs as they are natural passivators for perovskites. One major limitation of SQs is their relatively low hole mobility. Herein we demonstrate that polymerizing SQs into pseudo two dimensional (2D) p–π conjugated polymers could overcome this problem. By rationally using N,N‐diarylanilinosquaraines as the comonomers, the resulting polysquaraine HTMs not only exhibit suitable energy levels and efficient passivation effects, but also achieve very high hole mobility close to 0.01 cm−2 V−1 s−1. Thus as dopant‐free HTMs for α‐CsPbI2Br‐based all‐inorganic PVSCs, the best PCE reached is 15.5 %, outperforming those of the doped‐Spiro‐OMeTAD (14.4 %) based control devices and among the best for all‐inorganic PVSCs.

Time‐Dependent Photodynamic Therapy for Multiple Targets: A Highly Efficient AIE‐Active Photosensitizer for Selective Bacterial Elimination and Cancer Cell Ablation

By Qiyao Li, Ying Li, Tianliang Min, Junyi Gong, Lili Du, David Lee Phillips, Junkai Liu, Jacky W. Y. Lam, Herman H. Y. Sung, Ian D. Williams, Ryan T. K. Kwok, Chun Loong Ho, Kai Li, Jianguo Wang, Ben Zhong Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Millennium bug: A simple and highly efficient photosensitizer, called 4TPA‐BQ, operates by aggregation‐induced emission. A broad‐spectrum and potent antibacterial activity was attained after incubating 4TPA‐BQ with pathogens for 15 minutes. Upon lengthening of the incubation time to 12 hours, photodynamic therapy with 4TPA‐BQ targeted cancer cells and presented low toxicity to normal cells. Abstract Pathogen infections and cancer are two major human health problems. Herein, we report the synthesis of an organic salt photosensitizer (PS), called 4TPA‐BQ, by a one‐step reaction. 4TPA‐BQ presents aggregation‐induced emission features. Owing to the aggregation‐induced reactive oxygen species generated and a sufficiently small ΔEST, 4TPA‐BQ shows a satisfactorily high 1O2 generation efficiency of 97.8 %. In vitro and in vivo experiments confirmed that 4TPA‐BQ exhibited potent photodynamic antibacterial performance against ampicillin‐resistant Escherichia coli with good biocompatibility in a short time (15 minutes). When the incubation duration persisted long enough (12 hours), cancer cells were ablated efficiently, leaving normal cells essentially unaffected. This is the first reported time‐dependent fluorescence‐guided photodynamic therapy in one individual PS, which achieves ordered and multiple targeting simply by varying the external conditions. 4TPA‐BQ reveals new design principles for the implementation of efficient PSs in clinical applications.

Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics

By Nicolò Ferri, Norah Algethami, Andrea Vezzoli, Sara Sangtarash, Maeve McLaughlin, Hatef Sadeghi, Colin J. Lambert, Richard J. Nichols, Simon J. Higgins from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Molecular junctions with hemilabile contact moieties show enhanced mechanoresistive behaviour. In their Research Article (DOI: 10.1002/anie.201906400), A. Vezzolli, S. Sangtarash, C. J. Lambert, S. J. Higgins, and co‐workers present a system in which the molecule–metal contact is forced to transition from a monodentate to a bidentate configuration as the junction is compressed and stretched, with a resulting modulation in conductance of up to two orders of magnitude.

Ion‐Mobility Spectrometry Can Assign Exact Fucosyl Positions in Glycans and Prevent Misinterpretation of Mass‐Spectrometry Data After Gas‐Phase Rearrangement

By Javier Sastre Toraño, Ivan A. Gagarinov, Gaël M. Vos, Frederik Broszeit, Apoorva D. Srivastava, Martin Palmer, James I. Langridge, Oier Aizpurua‐Olaizola, Victor J. Somovilla, Geert‐Jan Boons from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

A clear case: The determination of glycan fucosyl positions with MS/MS is complicated due to rearrangements in the gas‐phase, leading to erroneous structural assignments. Unique IMS arrival‐time distributions of MS/MS fragments can be used to discriminate between fucosides originating from parent compounds and rearranged fucosyl residues, preventing misinterpretation of MS/MS spectra. Abstract The fucosylation of glycans leads to diverse structures and is associated with many biological and disease processes. The exact determination of fucoside positions by tandem mass spectrometry (MS/MS) is complicated because rearrangements in the gas phase lead to erroneous structural assignments. Here, we demonstrate that the combined use of ion‐mobility MS and well‐defined synthetic glycan standards can prevent misinterpretation of MS/MS spectra and incorrect structural assignments of fucosylated glycans. We show that fucosyl residues do not migrate to hydroxyl groups but to acetamido moieties of N‐acetylneuraminic acid as well as N‐acetylglucosamine residues and nucleophilic sites of an anomeric tag, yielding specific isomeric fragment ions. This mechanistic insight enables the characterization of unique IMS arrival‐time distributions of the isomers which can be used to accurately determine fucosyl positions in glycans.

Facet‐Dependent On‐Surface Reactions in the Growth of CdSe Nanoplatelets

By Chenqi Zhu, Dongdong Chen, Weicheng Cao, Runchen Lai, Chaodan Pu, Jiongzhao Li, Xueqian Kong, Xiaogang Peng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Grow, little platelet: The on‐surface reactions of nanoplatelets between the surface Cd sites and activated Se precursors in the solution is found to be strongly facet‐dependent. The process occurs in two stages—rapid adsorption onto the non‐polar side facets and slow surface reaction on the polar {100} basal facets—as well as one destructive (ripening) stage. Abstract Facet‐dependent on‐surface reactions are systematically studied on zinc‐blende CdSe nanoplatelets with atomically‐flat {001} basal facets and small yet non‐polar side facets. The on‐surface half‐reactions between the surface Se sites and Cd carboxylates in the solution are qualitatively equivalent to those on the spheroidal counterparts. Conversely, the on‐surface half‐reactions between the surface Cd sites and the activated Se precursors in solution show a strong facet‐dependence, which includes three distinguishable stages. In the first stage, the Se precursors adsorb onto the small and non‐polar side facets of the nanoplatelets. The second stage is initiated by the adsorbed Se precursors at the side‐basal plane edges and proceeds from the edges to the center of the basal planes in quasi‐zeroth‐order kinetics. In the third stage, the nanoplatelets are dismantled, which includes the creation of a hole in the middle and a build‐up of thick edges.

Conformational Re‐engineering of Porphyrins as Receptors with Switchable N−H⋅⋅⋅X‐Type Binding Modes

By Karolis Norvaiša, Keith J. Flanagan, Dáire Gibbons, Mathias O. Senge from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

A porphyrin‐based molecular sensor for selective detection of anions is described by M. O. Senge and co‐workers in their Communication (DOI: 10.1002/anie.201907929). The acid‐activated interface between the specially designed binding cavity and corresponding substrates results in distinct spectroscopic alterations with vibrant colorimetric response. The cover picture by Ella Marushchenko illustrates chemically re‐engineered pigments to act like tiny Venus flytraps luring anions disguised as flies.

Tuning the Electrochemical Performance of Titanium Carbide MXene by Controllable In Situ Anodic Oxidation

By Jun Tang, Tyler S. Mathis, Narendra Kurra, Asia Sarycheva, Xu Xiao, Mohamed N. Hedhili, Qiu Jiang, Husam N. Alshareef, Baomin Xu, Feng Pan, Yury Gogotsi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Good made better: Controllable anodic oxidation of 2D Ti3C2Tx improves the rate performance of supercapacitor electrodes. The capacitance retention at 2000 mV s−1 increases gradually from 38 % to 66 % by tuning the degree of anodic oxidation. Abstract MXenes are a class of two‐dimensional (2D) transition metal carbides, nitrides and carbonitrides that have shown promise for high‐rate pseudocapacitive energy storage. However, the effects that irreversible oxidation have on the surface chemistry and electrochemical properties of MXenes are still not understood. Here we report on a controlled anodic oxidation method which improves the rate performance of titanium carbide MXene (Ti3C2Tx, Tx refers to ‐F, =O, ‐Cl and ‐OH) electrodes in acidic electrolytes. The capacitance retention at 2000 mV s−1 (with respect to the lowest scan rate of 5 mV s−1) increases gradually from 38 % to 66 % by tuning the degree of anodic oxidation. At the same time, a loss in the redox behavior of Ti3C2Tx is evident at high anodic potentials after oxidation. Several analysis methods are employed to reveal changes in the structure and surface chemistry while simultaneously introducing defects, without compromising electrochemically active sites, are key factors for improving the rate performance of Ti3C2Tx. This study demonstrates improvement of the electrochemical performance of MXene electrodes by performing a controlled anodic oxidation.

Tuning the Reactivity of Cyclopropenes from Living Ring‐Opening Metathesis Polymerization (ROMP) to Single‐Addition and Alternating ROMP

By Jessica K. Su, Zexin Jin, Rui Zhang, Gang Lu, Peng Liu, Yan Xia from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

A simple change in the substituents on cyclopropene rings elicited strikingly different modes of metathesis reactivity, switching from living homopolymerization to either selective single‐addition or alternating copolymerization. In both cases well‐controlled polymers were obtained. Abstract Ring‐opening metathesis polymerization (ROMP) has become one of the most important living polymerizations. Cyclopropenes (CPEs) remain underexplored for ROMP. Described here is that the simple swap of 1‐methyl to 1‐phenyl on 1‐(benzoyloxymethyl)CPEs elicited strikingly different modes of reactivity, switching from living polymerization to either selective single‐addition or living alternating ROMP. The distinct reactivity stems from differences in steric repulsions at the Ru alkylidene after CPE ring opening. Possible olefin or oxygen chelation from ring‐opened CPE substituents was also observed to significantly affect the rate of propagation. These results demonstrate the versatility of CPEs as a new class of monomers for ROMP, provide mechanistic insights for designing new monomers with rare single‐addition reactivity, and generate a new functionalizable alternating copolymer scaffold with controlled molecular weight and low dispersity.

Eliminating Trap‐States and Functionalizing Vacancies in 2D Semiconductors by Electrochemistry

By Jianjian Shi, Xunhua Zhao, Zhiguo Wang, Yuanyue Liu from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Chalcogen vacancies are harmful to the electronic and optoelectronic performance of 2D metal dichalcogenides due to the creation of trap states for electrons/holes. Here through first‐principles calculations, it is shown by using aqueous electrochemistry that chalcogen vacancies can be passivated and the trap states can be eliminated, suggesting an approach to improve the performance of 2D metal dichalcogenides. Abstract One major challenge that limits the applications of 2D semiconductors is the detrimental electronic trap states caused by vacancies. Here using grand‐canonical density functional theory calculations, a novel approach is demonstrated that uses aqueous electrochemistry to eliminate the trap states of the vacancies in 2D transition metal dichalcogenides while leaving the perfect part of the material intact. The success of this electrochemical approach is based on the selectivity control by the electrode potential and the isovalence between oxygen and chalcogen. Motivated by these results, electrochemical conditions are further identified to functionalize the vacancies by incorporating various single metal atoms, which can bring in magnetism, tune carrier concentration/polarity, and/or activate single‐atom catalysis, enabling a wide range of potential applications. These approaches may be generalized to other 2D materials. The results open up a new avenue for improving the properties and extending the applications of 2D materials.

Peptide Nanotube‐Templated Biomineralization of Cu2−xS Nanoparticles for Combination Treatment of Metastatic Tumor

By Yi Lai, Zhiai Xu, Xianli Hu, Li Lei, Lingling Li, Liang Dong, Haijun Yu, Wen Zhang from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

1D peptide nanotubes are employed as a template for biomineralization of Cu7S4 nanoparticles. An oxaliplatin prodrug is further covalently grafted to construct a versatile nanoplatform. Upon NIR laser illumination, the nanoplatform induces significant hyperthermia effect and elicits reactive oxygen species generation, which dramatically inhibits the tumor growth and lung metastasis of melanoma by combined photo‐ and chemotherapy. Abstract 1D peptide nanostructures (i.e., peptide nanotubes, PNTs) exhibit tunable chemo‐physical properties and functions such as improved tissue adhesion, increased cellular uptake, and elongated blood circulation. In this study, the application of PNTs as a desirable 1D template for biomineralization of Cu2−xS nanoparticles (Cu2−xS NPs, x = 1–2) is reported. Monodisperse Cu2−xS NPs are uniformly coated on the peptide nanotubes owing to the specific high binding affinity of Cu ions to the imidazole groups exposed on the surface of nanotubes. The Cu2−xS NP–coated PNTs are further covalently grafted with an oxaliplatin prodrug (Pt–CuS–PNTs) to construct a versatile nanoplatform for combination cancer therapy. Upon 808 nm laser illumination, the nanoplatform induces significant hyperthermia effect and elicits reactive oxygen species generation through electron transfer and Fenton‐like reaction. It is demonstrated that the versatile nanoplatform dramatically inhibits tumor growth and lung metastasis of melanoma in a B16‐F10 melanoma tumor‐bearing mouse model by combined photo‐ and chemotherapy. This study highlights the ability of PNTs for biomineralization of metal ions and the promising potential of such nanoplatforms for cancer treatment.

Nonconfinement Structure Revealed in Dion–Jacobson Type Quasi‐2D Perovskite Expedites Interlayer Charge Transport

By Shuang Yu, Yajie Yan, Mohamed Abdellah, Tõnu Pullerits, Kaibo Zheng, Ziqi Liang from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

Nonconfinement structure is disclosed in 2D Dion–Jacobson perovskite (p‐xylylenediamine, PDMA)MAn−1PbnI3n+1 (n > 3), which promotes interlayer exciton splitting and charge transport, leading to an impressive power conversion efficiency (PCE) up to 11% in inverted planar solar cells with greatly enhanced stability. Abstract Dion–Jacobson (DJ) type 2D perovskites with a single organic cation layer exhibit a narrower distance between two adjacent inorganic layers compared to the corresponding Ruddlesden–Popper perovskites, which facilitates interlayer charge transport. However, the internal crystal structures in 2D DJ perovskites remain elusive. Herein, in a p‐xylylenediamine (PDMA)‐based DJ perovskite bearing bifunctional NH3+ spacer, the compression from confinement structure (inorganic layer number, n = 1, 2) to nonconfinement structure (n > 3) with the decrease of PDMA molar ratio is unraveled. Remarkably, the nonconfined perovskite displays shorter spacing between 2D quantum wells, which results in a lower exciton binding energy and hence promotes exciton dissociation. The significantly diminishing quantum confinement promotes interlayer charge transport leading to a maximum photovoltaic efficiency of ≈11%. Additionally, the tighter interlayer packing arising from the squeezing of inorganic octahedra gives rise to enhanced ambient stability.

Dynamically Reconfigurable, Multifunctional Emulsions with Controllable Structure and Movement

By Kang Hee Ku, Jie Li, Kosuke Yoshinaga, Timothy M. Swager from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Dynamically reconfigurable, multifunctional emulsions are developed through the controlled assembly of active particles. Dynamic attachment of polymer surfactants to the emulsions afford both shape and configuration transitions of complex Pickering emulsions between encapsulated core/shell and Janus configurations. Finally, the production of bimetallic microcapsules with controlled payload release and the magnetization with the associated directed movement of emulsions are demonstrated. Abstract Dynamically reconfigurable oil‐in‐water (o/w) Pickering emulsions are developed, wherein the assembly of particles (i.e., platinum‐on‐carbon and iron‐on‐carbon particles) can be actively controlled by adjusting interfacial tensions. A balanced adsorption of particles and surfactants at the o/w interface allows for the creation of inhomogeneity of the particle distribution on the emulsion surface. Complex Pickering emulsions with highly controllable and reconfigurable morphologies are produced in a single step by exploiting the temperature‐sensitive miscibility of hydrocarbon and fluorocarbon liquids. Dynamic adsorption/desorption of (polymer) surfactants afford both shape and configuration transitions of multiple Pickering emulsions and encapsulated core/shell structured can be transformed into a Janus configuration. Finally, to demonstrate the intrinsic catalytic or magnetic properties of the particles provided by carbon bound Pt and Fe nanoparticles, two different systems are investigated. Specifically, the creation of a bimetallic microcapsule with controlled payload release and precise modulation of translational and rotational motions of magnetic emulsions are demonstrated, suggesting potential applications for sensing and smart payload delivery.

Multimodal Precision Imaging of Pulmonary Nanoparticle Delivery in Mice: Dynamics of Application, Spatial Distribution, and Dosimetry

By Lin Yang, Regine Gradl, Martin Dierolf, Winfried Möller, David Kutschke, Annette Feuchtinger, Lorenz Hehn, Martin Donnelley, Benedikt Günther, Klaus Achterhold, Axel Walch, Tobias Stoeger, Daniel Razansky, Franz Pfeiffer, Kaye S. Morgan, Otmar Schmid from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

The multimodal in vivo/ex vivo imaging platform established here provides comprehensive insights into the dynamic process of pulmonary nanoparticle delivery with high temporal and quantitative 3D spatial resolution in entire mouse lungs. Abstract Targeted delivery of nanomedicine/nanoparticles (NM/NPs) to the site of disease (e.g., the tumor or lung injury) is of vital importance for improved therapeutic efficacy. Multimodal imaging platforms provide powerful tools for monitoring delivery and tissue distribution of drugs and NM/NPs. This study introduces a preclinical imaging platform combining X‐ray (two modes) and fluorescence imaging (three modes) techniques for time‐resolved in vivo and spatially resolved ex vivo visualization of mouse lungs during pulmonary NP delivery. Liquid mixtures of iodine (contrast agent for X‐ray) and/or (nano)particles (X‐ray absorbing and/or fluorescent) are delivered to different regions of the lung via intratracheal instillation, nasal aspiration, and ventilator‐assisted aerosol inhalation. It is demonstrated that in vivo propagation‐based phase‐contrast X‐ray imaging elucidates the dynamic process of pulmonary NP delivery, while ex vivo fluorescence imaging (e.g., tissue‐cleared light sheet fluorescence microscopy) reveals the quantitative 3D drug/particle distribution throughout the entire lung with cellular resolution. The novel and complementary information from this imaging platform unveils the dynamics and mechanisms of pulmonary NM/NP delivery and deposition for each of the delivery routes, which provides guidance on optimizing pulmonary delivery techniques and novel‐designed NM for targeting and efficacy.

Nanoscale Topotactic Phase Transformation in SrFeOx Epitaxial Thin Films for High‐Density Resistive Switching Memory

By Junjiang Tian, Haijun Wu, Zhen Fan, Yang Zhang, Stephen J. Pennycook, Dongfeng Zheng, Zhengwei Tan, Haizhong Guo, Pu Yu, Xubing Lu, Guofu Zhou, Xingsen Gao, Jun‐Ming Liu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

The resistive switching (RS) mechanism in SrFeOx epitaxial thin films is revealed to be the formation/rupture of perovskite SrFeO3 nanofilaments in the brownmillerite SrFeO2.5 matrix, mediated by the electric field‐induced local topotactic phase transformation. With this mechanism, SrFeOx‐based RS devices can be downscaled to the 100 nm range and exhibit excellent performance. Abstract Resistive switching (RS) memory has stayed at the forefront of next‐generation nonvolatile memory technologies. Recently, a novel class of transition metal oxides (TMOs), which exhibit reversible topotactic phase transformation between insulating brownmillerite (BM) phase and conducting perovskite (PV) phase, has emerged as promising candidate materials for RS memories. Nevertheless, the microscopic mechanism of RS in these TMOs is still unclear. Furthermore, RS devices with simultaneously high density and superior memory performance are yet to be reported. Here, using SrFeOx as a model system, it is directly observed that PV SrFeO3 nanofilaments are formed and extend almost through the BM SrFeO2.5 matrix in the ON state and are ruptured in the OFF state, unambiguously revealing a filamentary RS mechanism. The nanofilaments are ≈10 nm in diameter, enabling to downscale Au/SrFeOx/SrRuO3 RS devices to the 100 nm range for the first time. These nanodevices exhibit good performance including ON/OFF ratio as high as ≈104, retention time over 105 s, and endurance up to 107 cycles. This study significantly advances the understanding of the RS mechanism in TMOs exhibiting topotactic phase transformation, and it also demonstrates the potential of these materials for use in high‐density RS memories.

In‐Plane Potential Gradient Induces Low Frictional Energy Dissipation during the Stick‐Slip Sliding on the Surfaces of 2D Materials

By Feng He, Xiao Yang, Zhengliang Bian, Guoxin Xie, Dan Guo, Jianbin Luo from Wiley: Small: Table of Contents. Published on Oct 22, 2019.

By applying an in‐plane potential gradient across the 2D nanosheets, a reversible reduction of up to ≈30% friction force is achieved. A friction‐reducing mechanism, where high‐friction dissipation processes are inhibited and low‐friction dissipation processes are promoted, is proposed. These results not only help to reveal the origin of friction, but also provide a novel way to electrically manipulate friction. Abstract Understanding the nanoscale friction properties of 2D materials and further manipulating their friction behaviors is of great significance for the development of various micro/nanodevices. Recent studies, taking advantage of the close relationship between friction and surface charges, use an external out‐of‐plane electric field to control the interfacial friction. Nevertheless, friction increases with the application of the out‐of‐plane electric field in most cases. Here, an in‐plane potential gradient is applied for the investigation of the contribution of electric charges to friction on the surfaces of 2D materials. Experimental results show that the friction between an atomic force microscope tip and the flakes of 2D materials decreases with the application of the in‐plane potential gradient, and the higher the potential gradient, the greater the friction decrease. By comparing the in situ atomic‐level stick‐slip maps before and after the application of the in‐plane potential gradient, it is proposed that the promotion of low friction dissipative motion during the stick‐slip process owing to the presence of the potential gradient gives rise to the friction reduction. These results not only help to reveal the origin of friction, but also provide a novel way to manipulate friction through an electrically‐controlled sliding process.

Depth‐Resolved Modulation of Metal–Oxygen Hybridization and Orbital Polarization across Correlated Oxide Interfaces

By Paul C. Rogge, Padraic Shafer, Gilberto Fabbris, Wen Hu, Elke Arenholz, Evguenia Karapetrova, Mark P. M. Dean, Robert J. Green, Steven J. May from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Resonant X‐ray reflectivity is used to quantitatively measure changes in band hybridization across transition metal oxide interfaces. Spatially determining the degree of metal versus oxygen character in a superlattice of SrFeO3/CaFeO3 reveals how interfaces can alter the orbital character of valence electrons and further reveal a new class of oxide interfacial reconstructions, that of metal–oxygen hybridization. Abstract Interface‐induced modifications of the electronic, magnetic, and lattice degrees of freedom drive an array of novel physical properties in oxide heterostructures. Here, large changes in metal–oxygen band hybridization, as measured in the oxygen ligand hole density, are induced as a result of interfacing two isovalent correlated oxides. Using resonant X‐ray reflectivity, a superlattice of SrFeO3 and CaFeO3 is shown to exhibit an electronic character that spatially evolves from strongly O‐like in SrFeO3 to strongly Fe‐like in CaFeO3. This alternating degree of Fe electronic character is correlated with a modulation of an Fe 3d orbital polarization, giving rise to an orbital superstructure. At the SrFeO3/CaFeO3 interfaces, the ligand hole density and orbital polarization reconstruct in a single unit cell of CaFeO3, demonstrating how the mismatch in these electronic parameters is accommodated at the interface. These results provide new insight into how the orbital character of electrons is altered by correlated oxide interfaces and lays out a broadly applicable approach for depth‐resolving band hybridization.

Fast Gelation of Ti3C2Tx MXene Initiated by Metal Ions

By Yaqian Deng, Tongxin Shang, Zhitan Wu, Ying Tao, Chong Luo, Jiachen Liang, Daliang Han, Ruiyang Lyu, Changsheng Qi, Wei Lv, Feiyu Kang, Quan‐Hong Yang from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Fast gelation of Ti3C2Tx MXenes is initiated by divalent metal ions in aquesous solution. Typically, Fe2+ ions eliminate the electrostatic repulsion, networking MXene nanosheets into a 3D structured hydrogel. The wet hydrogel avoids nanosheet restacking and is ideal for applications highlighting the surface utilization, especially as freestanding electrodes for high‐rate supercapacitors. Abstract Gelation is an effective way to realize the self‐assembly of nanomaterials into different macrostructures, and in a typical use, the gelation of graphene oxide (GO) produces various graphene‐based carbon materials with different applications. However, the gelation of MXenes, another important type of 2D materials that have different surface chemistry from GO, is difficult to achieve. Here, the first gelation of MXenes in an aqueous dispersion that is initiated by divalent metal ions is reported, where the strong interaction between these ions and OH groups on the MXene surface plays a key role. Typically, Fe2+ ions are introduced in the MXene dispersion which destroys the electrostatic repulsion force between the MXene nanosheets in the dispersion and acts as linkers to bond the nanosheets together, forming a 3D MXene network. The obtained hydrogel effectively avoids the restacking of the MXene nanosheets and greatly improves their surface utilization, resulting in a high rate performance when used as a supercapacitor electrode (≈226 F g−1 at 1 V s−1). It is believed that the gelation of MXenes indicates a new way to build various tunable MXene‐based structures and develop different applications.

Development of an In Situ Cancer Vaccine via Combinational Radiation and Bacterial‐Membrane‐Coated Nanoparticles

By Ravi B. Patel, Mingzhou Ye, Peter M. Carlson, Abigail Jaquish, Luke Zangl, Ben Ma, Yuyuan Wang, Ian Arthur, Ruosen Xie, Ryan J. Brown, Xing Wang, Raghava Sriramaneni, KyungMann Kim, Shaoqin Gong, Zachary S. Morris from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Tumor‐directed radiation therapy can result in immunogenic cell death and neoantigen release, yet on its own, it rarely induces a long‐term antitumor immune response. Therefore, a bacterial membrane nanoparticle is designed to bridge innate and adaptive immune activation after radiation therapy and results in improved tumor responses in immunologically “cold” tumors. Abstract Neoantigens induced by random mutations and specific to an individual's cancer are the most important tumor antigens recognized by T cells. Among immunologically “cold” tumors, limited recognition of tumor neoantigens results in the absence of a de novo antitumor immune response. These “cold” tumors present a clinical challenge as they are poorly responsive to most immunotherapies, including immune checkpoint inhibitors (ICIs). Radiation therapy (RT) can enhance immune recognition of “cold” tumors, resulting in a more diversified antitumor T‐cell response, yet RT alone rarely results in a systemic antitumor immune response. Therefore, a multifunctional bacterial membrane‐coated nanoparticle (BNP) composed of an immune activating PC7A/CpG polyplex core coated with bacterial membrane and imide groups to enhance antigen retrieval is developed. This BNP can capture cancer neoantigens following RT, enhance their uptake in dendritic cells (DCs), and facilitate their cross presentation to stimulate an antitumor T‐cell response. In mice bearing syngeneic melanoma or neuroblastoma, treatment with BNP+RT results in activation of DCs and effector T cells, marked tumor regression, and tumor‐specific antitumor immune memory. This BNP facilitates in situ immune recognition of a radiated tumor, enabling a novel personalized approach to cancer immunotherapy using off‐the‐shelf therapeutics.

Understanding the Structure and Properties of Sesqui‐Chalcogenides (i.e., V2VI3 or Pn2Ch3 (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective

By Yudong Cheng, Oana Cojocaru‐Mirédin, Jens Keutgen, Yuan Yu, Michael Küpers, Mathias Schumacher, Pavlo Golub, Jean‐Yves Raty, Richard Dronskowski, Matthias Wuttig from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

V2VI3 compounds including Bi2Te3, Bi2Se3, Sb2Te3 and β‐As2Te3 exhibit a remarkable property portfolio. These properties can be related to a special bonding mechanism termed metavalent bonding, where σ‐bonds between adjacent atoms are formed by half‐filled p‐bands. Metavalent bonding is characterized by modest levels of charge transfer and sharing of about one electron between adjacent atoms. Abstract A number of sesqui‐chalcogenides show remarkable properties, which make them attractive for applications as thermoelectrics, topological insulators, and phase‐change materials. To see if these properties can be related to a special bonding mechanism, seven sesqui‐chalcogenides (Bi2Te3, Bi2Se3, Bi2S3, Sb2Te3, Sb2Se3, Sb2S3, and β‐As2Te3) and GaSe are investigated. Atom probe tomography studies reveal that four of the seven sesqui‐chalcogenides (Bi2Te3, Bi2Se3, Sb2Te3, and β‐As2Te3) show an unconventional bond‐breaking mechanism. The same four compounds evidence a remarkable property portfolio in density functional theory calculations including large Born effective charges, high optical dielectric constants, low Debye temperatures and an almost metal‐like electrical conductivity. These results are indicative for unconventional bonding leading to physical properties distinctively different from those caused by covalent, metallic, or ionic bonding. The experiments reveal that this bonding mechanism prevails in four sesqui‐chalcogenides, characterized by rather short interlayer distances at the van der Waals like gaps, suggestive of significant interlayer coupling. These conclusions are further supported by a subsequent quantum‐chemistry‐based bonding analysis employing charge partitioning, which reveals that the four sesqui‐chalcogenides with unconventional properties are characterized by modest levels of charge transfer and sharing of about one electron between adjacent atoms. Finally, the 3D maps for different properties reveal discernible property trends and enable material design.

An Interfacial Solar‐Driven Atmospheric Water Generator Based on a Liquid Sorbent with Simultaneous Adsorption–Desorption

By Heshan Qi, Tianqi Wei, Wei Zhao, Bin Zhu, Guoliang Liu, Pingping Wang, Zhenhui Lin, Xueyang Wang, Xiuqiang Li, Xiaowei Zhang, Jia Zhu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A novel interfacial solar‐driven atmospheric water generator can simultaneously adsorb and desorb water based on a liquid sorbent, 1‐ethyl‐3‐methyl‐imidazolium acetate. With enhanced desorption capability and continuous water supplement in the sorbent, this atmospheric water generator can achieve a high rate of water production (≈0.5 L m−2 h−1) and 2.8 L m−2 d−1 for the outdoor environment. Abstract Water scarcity is one of the greatest challenges facing human society. Because of the abundant amount of water present in the atmosphere, there are significant efforts to harvest water from air. Particularly, solar‐driven atmospheric water generators based on sequential adsorption–desorption processes are attracting much attention. However, incomplete daytime desorption is the limiting factor for final water production, as the rate of water desorption typically decreases very quickly with decreased water content in the sorbents. Hereby combining tailored interfacial solar absorbers with an ionic‐liquid‐based sorbent, an atmospheric water generator with a simultaneous adsorption–desorption process is generated. With enhanced desorption capability and stabilized water content in the sorbent, this interfacial solar‐driven atmospheric water generator enables a high rate of water production (≈0.5 L m−2 h−1) and 2.8 L m−2 d−1 for the outdoor environment. It is expected that this interfacial solar‐driven atmospheric water generator, based on the liquid sorbent with a simultaneous adsorption–desorption process opens up a promising pathway to effectively harvest water from air.

A Highly Responsive Organic Image Sensor Based on a Two‐Terminal Organic Photodetector with Photomultiplication

By Yi‐Lin Wu, Kenjiro Fukuda, Tomoyuki Yokota, Takao Someya from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A highly responsive organic image sensor based on vertically stacked two‐terminal pixels is achieved with pixels of a diode‐type organic photodetector through photomultiplication. With an optimized injection electrode and additionally stacked rectifying layers, the organic image sensor with an extremely simple architecture exhibits a high pixel photoresponse and demonstrates a weak‐light imaging capability at 1 µW cm−2. Abstract Highly responsive organic image sensors are crucial for medical imaging applications. To enhance the pixelwise photoresponse in an organic image sensor, the integration of an organic photodetector with amplifiers, or the use of a highly responsive organic photodetector without an additional amplifying component, is required. The use of vertically stacked, two‐terminal organic photodetectors with photomultiplication is a promising approach for highly responsive organic image sensors owing to their simple two‐terminal structure and intrinsically large responsivity. However, there are no demonstrations of an imaging sensor array using organic photomultiplication photodetectors. The main obstacle to a sensor array is the weak‐light sensitivity, which is limited by a relatively large dark current. Herein, a highly responsive organic image sensor based on monolithic, vertically stacked two‐terminal pixels is presented. This is achieved using pixels of a vertically stacked diode‐type organic photodetector with photomultiplication. Furthermore, applying an optimized injection electrode and additionally stacked rectifying layers, this two‐terminal device simultaneously demonstrates a high responsivity (>40 A W−1), low dark current, and high rectification under illumination. An organic image sensor based on this device with an extremely simple architecture exhibits a high pixel photoresponse, demonstrating a weak‐light imaging capability even at 1 µW cm−2.

Fast Photoelectric Conversion in the Near‐Infrared Enabled by Plasmon‐Induced Hot‐Electron Transfer

By Yuanfang Yu, Yue Sun, Zhenliang Hu, Xuhong An, Dongming Zhou, Hongzhi Zhou, Wenhui Wang, Kaiyang Liu, Jie Jiang, Dandan Yang, Zainab Zafar, Haibo Zeng, Fengqiu Wang, Haiming Zhu, Junpeng Lu, Zhenhua Ni from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Interfacial charge transfer is a crucial process in photoelectric conversion. Plasmon‐induced hot‐electron transfer is demonstrated as a sufficiently fast charge‐transfer process to realize high‐speed photoelectric conversion. A near‐infrared photodetector with fast detection speed and extended spectral response to the communication band (1550 nm) is achieved built on a tungsten suboxide nanocrystal arrays–graphene heterostructure. Abstract Interfacial charge transfer is a fundamental and crucial process in photoelectric conversion. If charge transfer is not fast enough, carrier harvesting can compromise with competitive relaxation pathways, e.g., cooling, trapping, and recombination. Some of these processes can strongly affect the speed and efficiency of photoelectric conversion. In this work, it is elaborated that plasmon‐induced hot‐electron transfer (HET) from tungsten suboxide to graphene is a sufficiently fast process to prevent carrier cooling and trapping processes. A fast near‐infrared detector empowered by HET is demonstrated, and the response time is three orders of magnitude faster than that based on common band‐edge electron transfer. Moreover, HET can overcome the spectral limit of the bandgap of tungsten suboxide (≈2.8 eV) to extent the photoresponse to the communication band of 1550 nm (≈0.8 eV). These results indicate that plasmon‐induced HET is a new strategy for implementation of efficient and high‐speed photoelectric devices.

Controllable High‐Speed Electrostatic Manipulation of Water Droplets on a Superhydrophobic Surface

By Haoyu Dai, Can Gao, Junhan Sun, Chuxin Li, Ning Li, Lei Wu, Zhichao Dong, Lei Jiang from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A revolution to the microfluidic device commonly used in biological processes and technological applications is demonstrated. The new approach, which moves drops at a high speed with low adhesion or retention by electrostatic attraction or repulsion on a superhydrophobic surface, can enable microfluidic experiments to be conducted more efficiently, cost‐effectively, and at larger scales. Abstract Biological processes and technological applications cannot work without liquid control, where versatile water droplet manipulation is a significant issue. Droplet motion is conventionally manipulated by functionalizing the target surface or by utilizing additives in the droplet, still, with uncontrolled limitation on superhydrophobic surfaces since droplets are either unable to move fast or are difficult to stop while moving. A controllable high‐speed “all‐in‐one” no‐loss droplet manipulation, that is, in‐plane moving and stopping/pinning in any direction on a superhydrophobic surface, with electrostatic charging is demonstrated. The experimental results reveal that the transport speed can vary from zero to several hundreds of millimeters per second. Controlled dynamic switching between the onset moving state and the offset pinning state of a water droplet can be achieved by out‐of‐plane electrostatic charging. This work opens the possibility of droplet control techniques in various applications, such as combinatory chemistry, biochemical, and medical detection.

Chasing the “Killer” Phonon Mode for the Rational Design of Low‐Disorder, High‐Mobility Molecular Semiconductors

By Guillaume Schweicher, Gabriele D'Avino, Michael T. Ruggiero, David J. Harkin, Katharina Broch, Deepak Venkateshvaran, Guoming Liu, Audrey Richard, Christian Ruzié, Jeff Armstrong, Alan R. Kennedy, Kenneth Shankland, Kazuo Takimiya, Yves H. Geerts, J. Axel Zeitler, Simone Fratini, Henning Sirringhaus from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Molecular vibrations strongly impact the charge transport properties of weakly van der Waals bonded organic semiconductors. Quantum mechanical simulations, combined with low‐frequency vibrational spectroscopy, enable resolution of vibrational modes and ensuing electron–phonon coupling constants. The long‐axis sliding motion of molecular subunits is identified as a “killer” phonon mode, which in some materials contributes more than 80% to the total thermal disorder. Abstract Molecular vibrations play a critical role in the charge transport properties of weakly van der Waals bonded organic semiconductors. To understand which specific phonon modes contribute most strongly to the electron–phonon coupling and ensuing thermal energetic disorder in some of the most widely studied high‐mobility molecular semiconductors, state‐of‐the‐art quantum mechanical simulations of the vibrational modes and the ensuing electron–phonon coupling constants are combined with experimental measurements of the low‐frequency vibrations using inelastic neutron scattering and terahertz time‐domain spectroscopy. In this way, the long‐axis sliding motion is identified as a “killer” phonon mode, which in some molecules contributes more than 80% to the total thermal disorder. Based on this insight, a way to rationalize mobility trends between different materials and derive important molecular design guidelines for new high‐mobility molecular semiconductors is suggested.

Direct Synthesis of a Self‐Assembled WSe2/MoS2 Heterostructure Array and its Optoelectrical Properties

By Jae‐Bok Lee, Yi Rang Lim, Ajit K. Katiyar, Wooseok Song, Jongsun Lim, Sukang Bae, Tae‐Wook Kim, Seoung‐Ki Lee, Jong‐Hyun Ahn from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A WSe2/MoS2‐based p–n heterostructure array is realized by a solution‐based direct growth method. WSe2 wires are selectively stacked over the MoS2 wires at the desired angle to form parallel‐ or cross‐aligned heterostructures over a large area. The p–n heterojunction array has a clean interface, resulting in outstanding rectification. Additionally, a prototype photosensing device with good photoresponsivity and response time is demonstrated. Abstract Functional van der Waals heterojunctions of transition metal dichalcogenides are emerging as a potential candidate for the basis of next‐generation logic devices and optoelectronics. However, the complexity of synthesis processes so far has delayed the successful integration of the heterostructure device array within a large scale, which is necessary for practical applications. Here, a direct synthesis method is introduced to fabricate an array of self‐assembled WSe2/MoS2 heterostructures through facile solution‐based directional precipitation. By manipulating the internal convection flow (i.e., Marangoni flow) of the solution, the WSe2 wires are selectively stacked over the MoS2 wires at a specific angle, which enables the formation of parallel‐ and cross‐aligned heterostructures. The realized WSe2/MoS2‐based p–n heterojunction shows not only high rectification (ideality factor: 1.18) but also promising optoelectrical properties with a high responsivity of 5.39 A W−1 and response speed of 16 µs. As a feasible application, a WSe2/MoS2‐based photodiode array (10 × 10) is demonstrated, which proves that the photosensing system can detect the position and intensity of an external light source. The solution‐based growth of hierarchical structures with various alignments could offer a method for the further development of large‐area electronic and optoelectronic applications.

Fully Integrated Design of a Stretchable Solid‐State Lithium‐Ion Full Battery

By Xi Chen, Haijian Huang, Long Pan, Tian Liu, Markus Niederberger from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A solid‐state lithium‐ion battery, in which all components (current collector, anode and cathode, electrolyte, and packaging) are stretchable, is designed and fabricated. The thin‐film full cell can be stretched up to 50% of its original length during the charge and discharge process. Abstract A solid‐state lithium‐ion battery, in which all components (current collector, anode and cathode, electrolyte, and packaging) are stretchable, is introduced, giving rise to a battery design with mechanical properties that are compliant with flexible electronic devices and elastic wearable systems. By depositing Ag microflakes as a conductive layer on a stretchable carbon–polymer composite, a current collector with a low sheet resistance of ≈2.7 Ω □−1 at 100% strain is obtained. Stretchable electrodes are fabricated by integrating active materials with the elastic current collector. A polyacrylamide–“water‐in‐salt” electrolyte is developed, offering high ionic conductivity of 10−3 to 10−2 S cm−1 at room temperature and outstanding stretchability up to ≈300% of its original length. Finally, all these components are assembled into a solid‐state lithium‐ion full cell in thin‐film configuration. Thanks to the deformable individual components, the full cell functions when stretched, bent, or even twisted. For example, after stretching the battery to 50%, a reversible capacity of 28 mAh g−1 and an average energy density of 20 Wh kg−1 can still be obtained after 50 cycles at 120 mA g−1, confirming the functionality of the battery under extreme mechanical stress.

Rational Tuning of Molecular Interaction and Energy Level Alignment Enables High‐Performance Organic Photovoltaics

By Rui Wang, Jun Yuan, Rui Wang, Guangchao Han, Tianyi Huang, Wenchao Huang, Jingjing Xue, Hao‐Cheng Wang, Chunfeng Zhang, Chenhui Zhu, Pei Cheng, Dong Meng, Yuanping Yi, Kung‐Hwa Wei, Yingping Zou, Yang Yang from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

By rationally tuning the molecular interaction and energy level alignments of the donors and acceptors, when both donor and acceptor are fluorinated or both are not fluorinated, high‐performance organic photovoltaics can be realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit power conversion efficiencies as high as 14.8% and 15.9%, respectively. Abstract The performance of organic photovoltaics (OPVs) has rapidly improved over the past years. Recent work in material design has primarily focused on developing near‐infrared nonfullerene acceptors with broadening absorption that pair with commercialized donor polymers; in the meanwhile, the influence of the morphology of the blend film and the energy level alignment on the efficiency of charge separation needs to be synthetically considered. Herein, the selection rule of the donor/acceptor blend is demonstrated by rationally considering the molecular interaction and energy level alignment, and highly efficient OPV devices using both‐fluorinated or both‐nonfluorinated donor/acceptor blends are realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, the devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit champion power conversion efficiencies as high as 14.8% and 15.9%, respectively.

Beyond Gold: Spin‐Coated Ti3C2‐Based MXene Photodetectors

By Kiana Montazeri, Marc Currie, Louisiane Verger, Pouya Dianat, Michel W. Barsoum, Bahram Nabet from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Ti3C2‐based MXene contacts—spin‐coated from an aqueous colloidal suspension onto a GaAs substrate—are compared with vacuum‐deposited titanium/gold electrodes for the photodetection of light. Such an MXene‐based device has better detectivity, quantum efficiency, and a higher dynamic range as compared to the conventional Au‐based metal–semiconductor–metal devices. Abstract 2D transition metal carbides, known as MXenes, are transparent when the samples are thin enough. They are also excellent electrical conductors with metal‐like carrier concentrations. Herein, these characteristics are exploited to replace gold (Au) in GaAs photodetectors. By simply spin‐coating transparent Ti3C2‐based MXene electrodes from aqueous suspensions onto GaAs patterned with a photoresist and lifted off with acetone, photodetectors that outperform more standard Au electrodes are fabricated. Both the Au‐ and MXene‐based devices show rectifying contacts with comparable Schottky barrier heights and internal electric fields. The latter, however, exhibit significantly higher responsivities and quantum efficiencies, with similar dark currents, hence showing better dynamic range and detectivity, and similar sub‐nanosecond response speeds compared to the Au‐based devices. The simple fabrication process is readily integratable into microelectronic, photonic‐integrated circuits and silicon photonics processes, with a wide range of applications from optical sensing to light detection and ranging and telecommunications.

Do Zinc Dendrites Exist in Neutral Zinc Batteries: A Developed Electrohealing Strategy to In Situ Rescue In‐Service Batteries

By Qi Yang, Guojin Liang, Ying Guo, Zhuoxin Liu, Boxun Yan, Donghong Wang, Zhaodong Huang, Xinliang Li, Jun Fan, Chunyi Zhi from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A first‐in‐class electrohealing methodology is developed to tackle Zn dendrites and prolong the lifespan of zinc‐ion batteries (ZBs) by 410%, benefitting from the passivation of the initially sharp dendrite tips. This electrohealing strategy may promote research on metal dendrites in various batteries, evolving from passive prevention to active elimination, rescuing in‐service batteries in situ to achieve elongated lifetime. Abstract The dendritic issue in aqueous zinc‐ion batteries (ZBs) using neutral/mild electrolytes has remained an intensive controversy for a long time: some researchers assert that dendrites severely exist while others claim great cycling stability without any protection. This issue is clarified by investigating charge/discharge‐condition‐dependent formation of Zn dendrites. Lifespan degradation (120 to 1.2 h) and voltage hysteresis deterioration (134 to 380 mV) are observed with increased current densities due to the formation of Zn dendrites (edge size: 0.69–4.37 µm). In addition, the capacity is also found to remarkably affect the appearance of the dendrites as well. Therefore, at small current densities or loading mass, Zn dendrites might not be an issue, while the large conditions may rapidly ruin batteries. Based on this discovery, a first‐in‐class electrohealing methodology is developed to eliminate already‐formed dendrites, generating extremely prolonged lifespans by 410% at 7.5 mA cm–2 and 516% at 10 mA cm–2. Morphological analysis reveals that vertically aligned Zn dendrites with sharp tips gradually become passivated and finally generate a smooth surface. This developed electrohealing strategy may promote research on metal dendrites in various batteries evolving from passive prevention to active elimination, rescuing in‐service batteries in situ to achieve elongated lifetime.

A Force‐Engineered Lint Roller for Superclean Graphene

By Luzhao Sun, Li Lin, Zihao Wang, Dingran Rui, Zhiwei Yu, Jincan Zhang, Yanglizhi Li, Xiaoting Liu, Kaicheng Jia, Kexin Wang, Liming Zheng, Bing Deng, Tianbao Ma, Ning Kang, Hongqi Xu, Konstantin S. Novoselov, Hailin Peng, Zhongfan Liu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A new approach to clean the surface of graphene is reported by using a force‐engineered “lint roller”, which is enabled by selectively removing intrinsic surface contaminants on graphene. The as‐obtained superclean graphene can be transferred to dielectric substrates with significantly reduced polymer residues and exhibits superior electronic and optical properties such as ultrahigh carrier mobility and low contact resistance. Abstract Contamination is a major concern in surface and interface technologies. Given that graphene is a 2D monolayer material with an extremely large surface area, surface contamination may seriously degrade its intrinsic properties and strongly hinder its applicability in surface and interfacial regions. However, large‐scale and facile treatment methods for producing clean graphene films that preserve its excellent properties have not yet been achieved. Herein, an efficient postgrowth treatment method for selectively removing surface contamination to achieve a large‐area superclean graphene surface is reported. The as‐obtained superclean graphene, with surface cleanness exceeding 99%, can be transferred to dielectric substrates with significantly reduced polymer residues, yielding ultrahigh carrier mobility of 500 000 cm2 V−1 s−1 and low contact resistance of 118 Ω µm. The successful removal of contamination is enabled by the strong adhesive force of the activated‐carbon‐based lint roller on graphene contaminants.

An Ordered Ni6‐Ring Superstructure Enables a Highly Stable Sodium Oxide Cathode

By Peng‐Fei Wang, Mouyi Weng, Yao Xiao, Zongxiang Hu, Qinghao Li, Meng Li, Yi‐Ding Wang, Xin Chen, Xinan Yang, Yuren Wen, Ya‐Xia Yin, Xiqian Yu, Yinguo Xiao, Jiaxin Zheng, Li‐Jun Wan, Feng Pan, Yu‐Guo Guo from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Two ions with very different MO bond energy are selected to construct a highly ordered Ni6‐ring superstructure within transition metal layers in a model compound (NaNi2/3Sb1/3O2). The formed Ni6‐rings with super‐exchange interaction by Ni/Sb ordering can greatly enhance the air stability and thermal stability of layered cathodes, increase the redox potential, and simplify the phase‐transition process during battery cycling. Abstract Sodium‐based layered oxides are among the leading cathode candidates for sodium‐ion batteries, toward potential grid energy storage, having large specific capacity, good ionic conductivity, and feasible synthesis. Despite their excellent prospects, the performance of layered intercalation materials is affected by both a phase transition induced by the gliding of the transition metal slabs and air‐exposure degradation within the Na layers. Here, this problem is significantly mitigated by selecting two ions with very different MO bond energies to construct a highly ordered Ni6‐ring superstructure within the transition metal layers in a model compound (NaNi2/3Sb1/3O2). By virtue of substitution of 1/3 nickel with antimony in NaNiO2, the existence of these ordered Ni6‐rings with super‐exchange interaction to form a symmetric atomic configuration and degenerate electronic orbital in layered oxides can not only largely enhance their air stability and thermal stability, but also increase the redox potential and simplify the phase‐transition process during battery cycling. The findings reveal that the ordered Ni6‐ring superstructure is beneficial for constructing highly stable layered cathodes and calls for new paradigms for better design of layered materials.

A Probiotic Spore‐Based Oral Autonomous Nanoparticles Generator for Cancer Therapy

By Qingling Song, Cuixia Zheng, Jiajia Jia, Hongjuan Zhao, Qianhua Feng, Hongling Zhang, Lei Wang, Zhenzhong Zhang, Yun Zhang from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Inspired by the natural physiological process of spores, a probiotic spore‐based oral autonomous nanoparticles generator is developed for cancer therapy. This smart generator can not only germinate and colonize in the intestine but also form nanoparticles in the intestinal environment, enhancing the stability of drugs in the gastrointestinal tract, and overcome the multibiological barriers of the intestinal epithelium. Abstract Spores, the dormant life forms of probiotics, can germinate to metabolically active vegetative cells with the disintegration of their hydrophobic protein coat in the intestinal microenvironment, which provides the possibility for the formation of nanoparticles (NPs) in vivo. Inspired by the natural physiological process of spores, herein, an oral autonomous NPs generator is developed to overcome the spatially variable gastrointestinal tract environment and multibiological barriers. Spores modified with deoxycholic acid (DA) and loaded with chemotherapeutic drugs (doxorubicin and sorafenib, DOX/SOR) serve as an autonomous production line of NPs, which can efficaciously protect the drugs passing through the rugged environment of the stomach and furthermore can be transported to the intestinal environment and colonized rapidly. Subsequently, the DOX/SOR/Spore‐DA NPs are produced by the autonomous NPs generator in the intestinal regions based on the disintegrated hydrophobic protein and the hydrophilic DA, and they can efficiently penetrate the epithelial cells via the bile acid pathway, increasing basolateral drug release. In vitro and in vivo studies confirm that this biological nanogenerator can autonomously produce substantial NPs in the intestine, providing a promising strategy for cancer therapy.

Implanting Atomic Cobalt within Mesoporous Carbon toward Highly Stable Lithium–Sulfur Batteries

By Jin Xie, Bo‐Quan Li, Hong‐Jie Peng, Yun‐Wei Song, Meng Zhao, Xiao Chen, Qiang Zhang, Jia‐Qi Huang from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Atomic cobalt implantation to mesoporous carbon enhances the sulfur kinetics in Li–S batteries. Atomic cobalt dopants with high polarity endow the mesoporous carbon (represented by the apes) with high affinity with polysulfides (represented by the bananas). Therefore, the shuttle effect is eliminated and the sulfur kinetics is improved, facilitating highly stable Li–S batteries. Abstract Lithium–sulfur (Li–S) batteries hold great promise to serve as next‐generation energy storage devices. However, the practical performances of Li–S batteries are severely limited by the sulfur cathode regarding its low conductivity, huge volume change, and the polysulfide shuttle effect. The first two issues have been well addressed by introducing mesoporous carbon hosts to the sulfur cathode. Unfortunately, the nonpolar nature of carbon materials renders poor affinity to polar polysulfides, leaving the shuttling issue unaddressed. In this contribution, atomic cobalt is implanted within the skeleton of mesoporous carbon via a supramolecular self‐templating strategy, which simultaneously improves the interaction with polysulfides and maintains the mesoporous structure. Moreover, the atomic cobalt dopants serve as active sites to improve the kinetics of the sulfur redox reactions. With the atomic‐cobalt‐decorated mesoporous carbon host, a high capacity of 1130 mAh gS−1 at 0.5 C and a high stability with a retention of 74.1% after 300 cycles are realized. Implanting atomic metal in mesoporous carbon demonstrates a feasible strategy to endow nanomaterials with targeted functions for Li–S batteries and broad applications.

Artificial Natural Killer Cells for Specific Tumor Inhibition and Renegade Macrophage Re‐Education

By Mei‐Zhen Zou, Wen‐Long Liu, Fan Gao, Xue‐Feng Bai, Han‐Shi Chen, Xuan Zeng, Xian‐Zheng Zhang from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Artificial natural killer (NK) cells are constructed with minor limitations of the immunosuppressive tumor microenvironment for specific tumor killing and renegade macrophage re‐education. The artificial NK cells exhibit efficient tumor inhibition and immune activation as a new sight to overcome tumors by simulating the functions of immune cells. Abstract Natural killer (NK) cells can not only recognize and eliminate abnormal cells but also recruit and re‐educate immune cells to protect the host. However, the functions of NK cells are often limited in the immunosuppressive tumor microenvironment (TME). Here, artificial NK cells (designated as aNK) with minor limitations of TME for specific tumor killing and renegade macrophage re‐education are created. The red blood cell membrane (RBCM) cloaks perfluorohexane (PFC) and glucose oxidase (GOX) to construct the aNK. The aNK can directly kill tumor cells by exhausting glucose and generating hydrogen peroxide (H2O2). The generated H2O2 is also similar to cytokines and chemokines for recruiting immune cells and re‐educating survived macrophages to attack tumor cells. In addition, the oxygen‐carried PFC can strengthen the catalytic reaction of GOX and normalize the hypoxic TME. In vitro and in vivo experiments display that aNK with slight TME limitations exhibit efficient tumor inhibition and immune activation. The aNK will provide a new sight to treat tumor as the supplement of aggressive NK cells.

Universal Strategy for Efficient Electron Injection into Organic Semiconductors Utilizing Hydrogen Bonds

By Hirohiko Fukagawa, Munehiro Hasegawa, Katsuyuki Morii, Kazuma Suzuki, Tsubasa Sasaki, Takahisa Shimizu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Efficient electron injection into organic semiconductors is achieved by hydrogen bond formation between the host materials and bases that are commonly used in organic synthesis as catalysts. The electron‐injection efficiency in inverted organic light‐emitting diodes, the electron‐injection layer of which consists of the host and bases, is found to be almost proportional to the basicity of the bases. Abstract Molecular n‐dopants that can lower the electron injection barrier between organic semiconductors and electrodes are essential in present‐day organic electronics. However, the development of stable molecular n‐dopants remains difficult owing to their low ionization potential, which generally renders them unstable. It is shown that the stable bases widely used in organic synthesis as catalysts can lower the electron injection barrier similar to that in conventional n‐doping in organic optoelectronic devices. In contrast to conventional n‐doping, which is based on the electron transfer from dopants with low ionization potential, the reduction of the injection barrier caused by adding bases is determined by the formation of hydrogen bonds between the hosts and the bases, providing energy‐level‐independent electron injection. The observation of the efficient electron injection induced by hydrogen bonding affords new perspectives on the method for controlling the behavior of electrons unique to organic semiconductors.

Dynamic Fluid‐Like Graphene with Ultralow Frictional Molecular Bearing

By Intak Jeon, Gee Hoon Park, Pan Wang, Ju Li, Ian W. Hunter, Timothy M. Swager from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Fluid‐like graphene shows macroscopic lubricity reaching a coefficient of friction of 0.01. The rigid 3D molecular interlocking groups (molecular bearing: triaminotriptycene, additive) create nanostructures by bonding (stabilizer: Meisenheimer complexation) to the 3,5‐dinitrophenyl‐functionalized graphene. Mechanical shearing converts these graphene composites into highly stable surface‐bound tribolayers with a coefficient of friction (COF) of ≈0.01. Abstract Fluid‐like sliding graphenes but with solid‐like out‐of‐plane compressive rigidity offer unique opportunities for achieving unusual physical and chemical properties for next‐generation interfacial technologies. Of particular interest in the present study are graphenes with specific chemical functionalization that can predictably promote adhesion and wetting to substrate and ultralow frictional sliding structures. Lubricity between stainless steel (SS) and diamond‐like carbon (DLC) is experimentally demonstrated with densely functionalized graphenes displaying dynamic intersheet bonds that mechanically transform into stable tribolayers. The macroscopic lubricity evolves through the formation of a thin film of an interconnected graphene matrix that provides a coefficient of friction (COF) of 0.01. Mechanical sliding generates complex folded graphene structures wherein equilibrated covalent chemical linkages impart rigidity and stability to the films examined in macroscopic friction tests. This new approach to frictional reduction has broad implications for manufacturing, transportation, and aerospace.

3D Honeycomb Architecture Enables a High‐Rate and Long‐Life Iron (III) Fluoride–Lithium Battery

By Feixiang Wu, Vesna Srot, Shuangqiang Chen, Simon Lorger, Peter A. Aken, Joachim Maier, Yan Yu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

FeF3 nanoparticles (10–50 nm) are uniformly embedded in a 3D honeycomb architecture where the honeycomb walls and hexagonal‐like channels provide sufficient pathways for fast electron and Li‐ion diffusion, respectively. As a result, the as‐produced 3D honeycomb FeF3@C composite cathodes offer unprecedented rate capability up to 100C and remarkable cycle stability within 1000 cycles. Abstract Metal fluoride–lithium batteries with potentially high energy densities, even higher than lithium–sulfur batteries, are viewed as very promising candidates for next‐generation lightweight and low‐cost rechargeable batteries. However, so far, metal fluoride cathodes have suffered from poor electronic conductivity, sluggish reaction kinetics and side reactions causing high voltage hysteresis, poor rate capability, and rapid capacity degradation upon cycling. Herein, it is reported that an FeF3@C composite having a 3D honeycomb architecture synthesized by a simple method may overcome these issues. The FeF3 nanoparticles (10–50 nm) are uniformly embedded in the 3D honeycomb carbon framework where the honeycomb walls and hexagonal‐like channels provide sufficient pathways for the fast electron and Li‐ion diffusion, respectively. As a result, the as‐produced 3D honeycomb FeF3@C composite cathodes even with high areal FeF3 loadings of 2.2 and 5.3 mg cm−2 offer unprecedented rate capability up to 100 C and remarkable cycle stability within 1000 cycles, displaying capacity retentions of 95%–100% within 200 cycles at various C rates, and ≈85% at 2C within 1000 cycles. The reported results demonstrate that the 3D honeycomb architecture is a powerful composite design for conversion‐type metal fluorides to achieve excellent electrochemical performance in metal fluoride–lithium batteries.

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution

By Daming Zhao, Chung‐Li Dong, Bin Wang, Chao Chen, Yu‐Cheng Huang, Zhidan Diao, Shuzhou Li, Liejin Guo, Shaohua Shen from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Boron dopants and nitrogen defects are simultaneously introduced into g‐C3N4 through a simple NaBH4 thermal treatment approach. With exceptionally modulated band structures for effective optical absorption and increased water‐oxidation driving force, as well as engineered electronic structure for efficient electron excitation and facilitated charge transport, the resultant boron‐doped and nitrogen‐deficient g‐C3N4 exhibits excellent activity for photocatalytic oxygen evolution. Abstract Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g‐C3N4) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g‐C3N4. The resultant boron‐doped and nitrogen‐deficient g‐C3N4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h−1 g−1, much higher than previously reported g‐C3N4. It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g‐C3N4, the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C–N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g‐C3N4 with simultaneous introduction of dopants and defects for high‐performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.

Anomalous Defect Dependence of Thermal Conductivity in Epitaxial WO3 Thin Films

By Shuai Ning, Samuel C. Huberman, Zhiwei Ding, Ho‐Hyun Nahm, Yong‐Hyun Kim, Hyun‐Suk Kim, Gang Chen, Caroline A. Ross from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

An anomalous dependence of thermal conductivity on point defects is observed in epitaxial WO3 thin films. In particular, an increase of the lattice thermal conductivity found in WO3/YAO is accompanied by a lattice contraction upon the introduction of point defects, suggesting that the lattice volume rather than defect concentration plays the dominant role in determining the thermal conductivity. Abstract Lattice defects typically reduce lattice thermal conductivity, which has been widely exploited in applications such as thermoelectric energy conversion. Here, an anomalous dependence of the lattice thermal conductivity on point defects is demonstrated in epitaxial WO3 thin films. Depending on the substrate, the lattice of epitaxial WO3 expands or contracts as protons are intercalated by electrolyte gating or oxygen vacancies are introduced by adjusting growth conditions. Surprisingly, the observed lattice volume, instead of the defect concentration, plays the dominant role in determining the thermal conductivity. In particular, the thermal conductivity increases significantly with proton intercalation, which is contrary to the expectation that point defects typically lower the lattice thermal conductivity. The thermal conductivity can be dynamically varied by a factor of ≈1.7 via electrolyte gating, and tuned over a larger range, from 7.8 to 1.1 W m−1 K−1, by adjusting the oxygen pressure during film growth. The electrolyte‐gating‐induced changes in thermal conductivity and lattice dimensions are reversible through multiple cycles. These findings not only expand the basic understanding of thermal transport in complex oxides, but also provide a path to dynamically control the thermal conductivity.

Masthead: (Adv. Mater. 43/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Concurrent Drug Unplugging and Permeabilization of Polyprodrug‐Gated Crosslinked Vesicles for Cancer Combination Chemotherapy

By Xianglong Hu, Shaodong Zhai, Guhuan Liu, Da Xing, Haojun Liang, Shiyong Liu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Contents: (Adv. Mater. 43/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Clean Graphene Surfaces: A Force‐Engineered Lint Roller for Superclean Graphene (Adv. Mater. 43/2019)

By Luzhao Sun, Li Lin, Zihao Wang, Dingran Rui, Zhiwei Yu, Jincan Zhang, Yanglizhi Li, Xiaoting Liu, Kaicheng Jia, Kexin Wang, Liming Zheng, Bing Deng, Tianbao Ma, Ning Kang, Hongqi Xu, Konstantin S. Novoselov, Hailin Peng, Zhongfan Liu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

A new approach to clean the surface of graphene is reported by Hailin Peng, Zhongfan Liu, and co‐workers in article number 1902978, who use a force‐engineered “lint roller” to selectively removing the graphene's intrinsic surface contaminants. The as‐obtained super‐clean graphene can be transferred to dielectric substrates with significantly reduced polymer residues, and it exhibits superior electronic and optical properties such as ultrahigh carrier mobility and low contact resistance.

Metal Fluoride–Lithium Batteries: 3D Honeycomb Architecture Enables a High‐Rate and Long‐Life Iron (III) Fluoride–Lithium Battery (Adv. Mater. 43/2019)

By Feixiang Wu, Vesna Srot, Shuangqiang Chen, Simon Lorger, Peter A. Aken, Joachim Maier, Yan Yu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Metal fluoride–lithium batteries are promising for the fabrication of lighter, thinner, and cheaper next‐generation rechargeable batteries. In article number 1905146, Feixiang Wu, Yan Yu, and co‐workers develop a 3D honeycomb architecture to synchronously achieve fast electron and Li+ transport in an FeF3@C cathode. The produced FeF3@C composite cathodes offer unprecedented rate capability up to 100C and remarkable cycle stability within 1000 cycles.

Mxene Photodetectors: Beyond Gold: Spin‐Coated Ti3C2‐Based MXene Photodetectors (Adv. Mater. 43/2019)

By Kiana Montazeri, Marc Currie, Louisiane Verger, Pouya Dianat, Michel W. Barsoum, Bahram Nabet from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

“As good as gold” is a seldom true adage, but in article number 1903271, Bahram Nabet and co‐workers show that using a Ti3C2Tz (MXene) aqueous suspension, a table‐top spinner, and acetone, GaAs photodetectors that outperform conventional ones using Ti/Au can be fabricated. This ambient condition process is promising for integration into microelectronics, photonic integrated circuits, and silicon photonics technologies.

Organic Electronics: Universal Strategy for Efficient Electron Injection into Organic Semiconductors Utilizing Hydrogen Bonds (Adv. Mater. 43/2019)

By Hirohiko Fukagawa, Munehiro Hasegawa, Katsuyuki Morii, Kazuma Suzuki, Tsubasa Sasaki, Takahisa Shimizu from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

In article number 1904201, Hirohiko Fukagawa and co‐workers report a novel strategy for efficient electron injection into organic semiconductors, which is realized by forming hydrogen bonds between host semiconductors and bases. Both the operational stability and moisture resistance of devices fabricated employing this technique are higher than those of devices fabricated employing the conventional electron‐injection technique using typical n‐dopants.

Heterostructure Arrays: Direct Synthesis of a Self‐Assembled WSe2/MoS2 Heterostructure Array and its Optoelectrical Properties (Adv. Mater. 43/2019)

By Jae‐Bok Lee, Yi Rang Lim, Ajit K. Katiyar, Wooseok Song, Jongsun Lim, Sukang Bae, Tae‐Wook Kim, Seoung‐Ki Lee, Jong‐Hyun Ahn from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

In article number 1904194, Seoung‐Ki Lee, Jong‐Hyun Ahn, and co‐workers demonstrate a heterostructure array based on transition‐metal dichalcogenides, via a solution‐based self‐assembly method. The heterostructure is composed of p‐WSe2 wires and n‐MoS2 wires in parallel‐ or cross‐aligned structure. This WSe2/MoS2 p–n junction array exhibits outstanding electrical and optoelectrical properties, including high rectifying behavior and photoresponsivity with fast response time.

Using Large Datasets to Understand Nanotechnology

By Kalina Paunovska, David Loughrey, Cory D. Sago, Robert Langer, James E. Dahlman from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Studying biological processes with genomics, transcriptomics, and proteomics has become commonplace. Omics‐based approaches can help study the vast nanomaterial chemical space as well as biological factors that affect the safety, toxicity, and efficacy of nanotechnologies. The generation and analysis of large datasets and their application to answer fundamental questions in nanotechnology‐based drug delivery are reviewed. Abstract Advances in sequencing technologies have made studying biological processes with genomics, transcriptomics, and proteomics commonplace. As a result, this suite of increasingly integrated techniques is well positioned to study drug delivery, a process that is influenced by many biomolecules working in concert. Omics‐based approaches can be used to study the vast nanomaterial chemical space as well as the biological factors that affect the safety, toxicity, and efficacy of nanotechnologies. The generation and analysis of large datasets, methods to interpret them, and dataset applications to nanomaterials to date, are demonstrated here. Finally, new approaches for how sequencing‐generated datasets can answer fundamental questions in nanotechnology based drug delivery are proposed.

Mutual Insight on Ferroelectrics and Hybrid Halide Perovskites: A Platform for Future Multifunctional Energy Conversion

By Richa Pandey, Gaurav Vats, Jae Yun, Chris R. Bowen, Anita W. Y. Ho‐Baillie, Jan Seidel, Keith Tobias Butler, Sang Il Seok from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Hybrid halide perovskites and ferroelectric perovskites are two different classes of materials with analogies in their structure. Such analogies and state‐of‐the‐art technologies based on these materials are reviewed so that future multisource energy conversion devices (which are capable of utilizing piezoelectric, pyroelectric, photovoltaic, and thermoelectric effects simultaneously) and storage devices can be created in a holistic manner. Abstract An insight into the analogies, state‐of‐the‐art technologies, concepts, and prospects under the umbrella of perovskite materials (both inorganic–organic hybrid halide perovskites and ferroelectric perovskites) for future multifunctional energy conversion and storage devices is provided. Often, these are considered entirely different branches of research; however, considering them simultaneously and holistically can provide several new opportunities. Recent advancements have highlighted the potential of hybrid perovskites for high‐efficiency solar cells. The intrinsic polar properties of these materials, including the potential for ferroelectricity, provide additional possibilities for simultaneously exploiting several energy conversion mechanisms such as the piezoelectric, pyroelectric, and thermoelectric effect and electrical energy storage. The presence of these phenomena can support the performance of perovskite solar cells. The energy conversion using these effects (piezo‐, pyro‐, and thermoelectric effect) can also be enhanced by a change in the light intensity. Thus, there lies a range of possibilities for tuning the structural, electronic, optical, and magnetic properties of perovskites to simultaneously harvest energy using more than one mechanism to realize an improved efficiency. This requires a basic understanding of concepts, mechanisms, corresponding material properties, and the underlying physics involved with these effects.

Multiscale Toughening Mechanisms in Biological Materials and Bioinspired Designs

By Wei Huang, David Restrepo, Jae‐Young Jung, Frances Y. Su, Zengqian Liu, Robert O. Ritchie, Joanna McKittrick, Pablo Zavattieri, David Kisailus from Wiley: Advanced Materials: Table of Contents. Published on Oct 22, 2019.

Toughening mechanisms of light weight, strong, and tough biological materials constructed from the atomic‐ to macroscale are reviewed. The multiscale toughening mechanisms are validated via computational modeling, and subsequently translated to engineering materials through bioinspired processing such as freeze casting and additive manufacturing. Abstract Biological materials found in Nature such as nacre and bone are well recognized as light‐weight, strong, and tough structural materials. The remarkable toughness and damage tolerance of such biological materials are conferred through hierarchical assembly of their multiscale (i.e., atomic‐ to macroscale) architectures and components. Herein, the toughening mechanisms of different organisms at multilength scales are identified and summarized: macromolecular deformation, chemical bond breakage, and biomineral crystal imperfections at the atomic scale; biopolymer fibril reconfiguration/deformation and biomineral nanoparticle/nanoplatelet/nanorod translation, and crack reorientation at the nanoscale; crack deflection and twisting by characteristic features such as tubules and lamellae at the microscale; and structure and morphology optimization at the macroscale. In addition, the actual loading conditions of the natural organisms are different, leading to energy dissipation occurring at different time scales. These toughening mechanisms are further illustrated by comparing the experimental results with computational modeling. Modeling methods at different length and time scales are reviewed. Examples of biomimetic designs that realize the multiscale toughening mechanisms in engineering materials are introduced. Indeed, there is still plenty of room mimicking the strong and tough biological designs at the multilength and time scale in Nature.

Hybrid Plasmonic‐Aerogel Materials as Optical Superheaters with Engineered Resonances

By Benjamin Klemmed, Lucas Besteiro, Albrecht Benad, Maximilian Georgi, Zhiming Wang, Alexander O. Govorov, Alexander Eychmüller from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Solar radiation is a versatile source of energy, convertible to different useful forms of power. A direct path to exploit it is the generation of heat, for applications including passive building heating, but it can also drive secondary energy conversion steps. We present a novel concept for a hybrid material which is both strongly photo‐absorbing and with superior characteristics for the insulation of heat. The combination of that two properties is rather unique, and make of this material an optical superheater. To realize such material, we are combining plasmonic nanoheaters with alumina aerogel. In our hybrid material, the aerogel has the double function of providing structural support for plasmonic nanocrystal, which serve as nanoheaters, and reducing the diffusion rate of the heat generated by them, resulting in large local temperature increases under a relatively low radiation intensity. Alongside their optical and photothermal properties, this work includes theoretical discussion on the physical mechanisms impacting the system’s balanced thermal equilibrium.

Identifying Copper Vacancies and Their Role in the CuO Based Photocathode for Water Splitting

By Zhiliang Wang, Lei Zhang, Tobias U. Schülli, Yang Bai, Sabiha Akter Monny, Aiju Du, Lianzhou Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Pretty vacant: Copper vacancies induced in the CuO photocathode facilitates charge separation and transfer, leading to remarkably improved photoelectrochemcial performance. A simple O2 treatment on the CuO photocathode leads to the formation of copper vacancies. Abstract Metal oxides are an important family of semiconductors for effective photoelectrodes in solar‐to‐chemical energy conversion. Defect engineering, such as modification of oxygen vacancy density, has been extensively applied in tailoring the optoelectric properties of photoelectrodes. Very limited attention has been paid to the influence of metal vacancies. Herein, we study metal vacancies in a typical CuO photocathode for photoelectrochemical (PEC) water splitting. The Cu vacancies can improve the charge carrier concentration, and facilitate the charge separation and transfer in the CuO photocathode. By changing the O2 partial pressure, the density of Cu vacancies can be tuned, which leads to improved PEC performance. The CuO photocathode prepared in pure O2 exhibits a 100 % photocurrent increase compared to that prepared in air. The promotion effect of Cu vacancies on the PEC is also observed in other Cu based photocathodes, showing the generic role of metal vacancies in efficient photocathodes.

Hybrid Halide Perovskites: Discussions on Terminology and Materials

By Nicolas Mercier from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

What′s my name? In this Viewpoint, a critical discussion about the use of the word “perovskite” and some acronyms (DJ, RP, ACI, d‐HP, hollow perovskites) is proposed, and a description of perovskite networks through an elimination/substitution process from the ABX3 structure is compared to the known dimensional reduction concept. Abstract Hybrid halide perovskites (HP) have emerged in the last decade as a new class of semiconductors with superior performances in photovoltaic and electronic devices. The literature about these halide semiconductors is abundant and a lot of names/expressions are used to define networks, structures, or materials. In this context, there is a need to offer some discussions about the relevance of using the word “perovskite” and the associated expressions (“RP” (Ruddlesden–Popper), “DJ” (Dion–Jacobson), “ACI” (alternating cations in the interlayer space), “hexagonal perovskites”, “hollow perovskites”, “d‐HP” (deficient 3D HP),…). Moreover, the description of perovskite networks through elimination/substitution processes from the ABX3 structure will be compared to the known dimensional reduction concept.

Controlled Growth of CH3NH3PbBr3 Perovskite Nanocrystals via a Water–Oil Interfacial Synthesis Method

By Fangfang Li, Liya Cao, Shuangshuang Shi, Heng Gao, Li Song, Chong Geng, Wengang Bi, Shu Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Growth on the water: A comprehensive kinetic study of the growth mechanism of MAPbBr3 nanocrystals (NCs; MA=CH3NH3+) is made possible through the water–oil interfacial synthesis method. The overall reaction time of MAPbBr3 NCs is thereby prolonged to tens of minutes by reducing the formation rate of PbBr64− octahedra and the diffusion rate of MA. Abstract Fundamental insights into the reaction kinetics of organic–inorganic lead halide perovskite nanocrystals (LHP NCs) are still limited due to their ultrafast formation rate. Herein, we develop a water–oil interfacial synthesis of MAPbBr3 NCs (MA=CH3NH3+), which prolongs the reaction time to tens of minutes. This method makes it possible to monitor in situ the formation process of MAPbBr3 NCs and observe successive spectral evolutions from 438 to 534 nm in a single reaction by extending reaction time. The implementation of this method depends on reducing the formation rate of PbBr64− octahedra and the diffusion rate of MA. The formation of PbBr64− is a rate‐determining step, and the biphasic system offers a favorable reaction condition to control the mass transfer of MA. The effects of temperature and concentration of precursor and ligand are investigated in detail.

Reprocessable Thermoset Soft Actuators

By Yang Yang, Eugene M. Terentjev, Yubai Zhang, Qiaomei Chen, Yuan Zhao, Yen Wei, Yan Ji from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Liquid crystalline epoxy thermosets (LCETs) can be reprocessed into various complex 3D soft actuators by reconfiguring, reprogramming, and welding their structures. The slow transesterification reaction of LCETs is, nonetheless, fast enough to allow topology rearrangement and subsequent reprocessing when the transesterification time is prolonged according to the time–temperature equivalence principle. Abstract Widely used traditional thermosets are good candidates for construction of 3D soft actuators because of their excellent stability; however, it is generally acknowledged that they cannot be reprocessed. The time–temperature equivalence principle enables reprocessing of traditional liquid crystalline epoxy thermosets (LCETs) into 3D soft actuators. Even though the transesterification reaction of LCETs is extremely slow, it is fast enough to induce a topology rearrangement and subsequent reprocessing when prolonging the transesterification time according to aforementioned principle. Therefore, LCETs can be aligned by a simple procedure. The alignment is quite stable at high temperature and remains after more than 1000 heating–cooling actuation cycles. The resulting 3D soft actuators are remouldable, reprogrammable, reconfigurable, weldable, self‐healable, recyclable, and stable, which is impossible for any traditional thermosets and is therefore a compelling advance in terms of the applications open to 3D soft actuators.

Construction of Covalent‐Organic Frameworks (COFs) from Amorphous Covalent Organic Polymers via Linkage Replacement

By Yufeng Zhai, Guiyan Liu, Fenchun Jin, Yingying Zhang, Xuefang Gong, Zhuang Miao, Jinheng Li, Mengyao Zhang, Yumeng Cui, Lingyan Zhang, Yu Liu, Huixin Zhang, Yanli Zhao, Yongfei Zeng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Good COP good COF strategy: The facile construction of highly crystalline and porous covalent‐organic frameworks (COFs) from amorphous covalent organic polymers (COPs) via linkage replacement is possible using a conversion strategy. Four COFs with high crystallinity and porosity are constructed. Abstract Covalent‐organic frameworks (COFs) as porous crystalline materials show promising potential applications. However, developing facile strategies for the construction of COFs directly from amorphous covalent organic polymers (COPs) is still a great challenge. To this end, we report a novel approach for easy preparation of COFs from amorphous COPs through the linkage replacement under different types of reactions. Four COFs with high crystallinity and porosity were constructed via the linkage substitution of polyimide‐linked COPs to imine‐linked COFs as well as imine‐linked COPs to polyimide‐linked COFs. The realization of the linkage substitution would significantly expand the research scope of COFs.

Concise Synthesis of Open‐Cage Fullerenes for Oxygen Delivery

By Zishuo Zhou, Hongfei Han, Zijing Chen, Rui Gao, Zhen Liu, Jie Su, Nana Xin, Xiaobing Yang, Liangbing Gan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Open‐cage fullerenes with a 19‐membered orifice were prepared in three steps from C60. Encapsulation of oxygen was achieved at room temperature under moderate pressure (50 atm), and the oxygen could be released slowly under ambient conditions. The activation energy of the oxygen‐releasing process is 18.8 kcal mol−1 and the half‐life at 37 °C was 73 min, which makes this a potential oxygen‐delivery material. Abstract Open‐cage fullerenes with a 19‐membered orifice were prepared in three steps from C60. The key step for cage‐opening is aniline mediated ring expansion of a fullerene‐mixed peroxide with a ketolactone moiety on the orifice. Release of ring strain on the spherical fullerene cage served as the main driving force for the efficient cage‐opening sequence. Encapsulation of oxygen could be achieved at room temperature under moderate pressure (50 atm) and the encapsulated oxygen could be released slowly under ambient conditions. The activation energy of the oxygen‐releasing process is 18.8 kcal mol−1 and the half‐life at 37 °C was 73 min, which makes this open‐cage fullerene derivative a potential oxygen‐delivery material.

Response‐Retaliation Behavior in Synthetic Protocell Communities

By Yan Qiao, Mei Li, Dong Qiu, Stephen Mann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

An eye for an eye: Two artificial predation strategies are spatially and temporally coupled to generate rudimentary tit‐for‐tat behavior in a ternary community of chemically interacting synthetic protocells. Abstract Two different artificial predation strategies are spatially and temporally coupled to generate a simple tit‐for‐tat mechanism in a ternary protocell network capable of antagonistic enzyme‐mediated interactions. The consortium initially consists of protease‐sensitive glucose‐oxidase‐containing proteinosomes (1), non‐interacting pH‐sensitive polypeptide/mononucleotide coacervate droplets containing proteinase K (2), and proteinosome‐adhered pH‐resistant polymer/polysaccharide coacervate droplets (3). On receiving a glucose signal, secretion of protons from 1 triggers the disassembly of 2 and the released protease is transferred to 3 to initiate a delayed contact‐dependent killing of the proteinosomes and cessation of glucose oxidase activity. Our results provide a step towards complex mesoscale dynamics based on programmable response‐retaliation behavior in artificial protocell consortia.

Stabilization of Classical [B2H5]−: Structure and Bonding of [(Cp*Ta)2(B2H5)(μ‐H)L2] (Cp*=η5‐C5Me5; L=SCH2S)

By Koushik Saha, Sagar Ghorai, Sourav Kar, Suvam Saha, Rajarshi Halder, Beesam Raghavendra, Eluvathingal D. Jemmis, Sundargopal Ghosh from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Isolation of a classical diborane(5) complex of tantalum was achieved by the room‐temperature reaction of [Cp*TaCl4] with LiBH4⋅THF followed by addition of S2CPPh3. Reactivity with metal carbonyls was also explored. Abstract The room‐temperature reaction of [Cp*TaCl4] with LiBH4⋅THF followed by addition of S2CPPh3 results in pentahydridodiborate species [(Cp*Ta)2(μ,η2:η2‐B2H5)(μ‐H)(κ2,μ‐S2CH2)2] (1), a classical [B2H5]− ion stabilized by the binuclear tantalum template. Theoretical studies and bonding analysis established that the unusual stability of [B2H5]− in 1 is mainly due to the stabilization of sp2‐B center by electron donation from tantalum. Reactions to replace the hydrogens attached to the diborane moiety in 1 with a 2 e {M(CO)4} fragment (M=Mo or W) resulted in simple adducts, [{(Cp*Ta)(CH2S2)}2(B2H5)(H){M(CO)3}] (6: M=Mo and 7: M=W), that retained the diborane(5) unit.

Direct Conversion of Methane with Carbon Dioxide Mediated by RhVO3− Cluster Anions

By Yuan Yang, Bin Yang, Yan‐Xia Zhao, Li‐Xue Jiang, Zi‐Yu Li, Yi Ren, Hong‐Guang Xu, Wei‐Jun Zheng, Sheng‐Gui He from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Both on board: A dinuclear species (RhVO3−) that can mediate co‐conversion of CH4 and CO2 has been identified. The Rh atom is the active site to activate both of the molecules. Abstract Direct conversion of methane with carbon dioxide to value‐added chemicals is attractive but extremely challenging because of the thermodynamic stability and kinetic inertness of both molecules. Herein, the first dinuclear cluster species, RhVO3−, has been designed to mediate the co‐conversion of CH4 and CO2 to oxygenated products, CH3OH and CH2O, in the temperature range of 393–600 K. The resulting cluster ions RhVO3CO− after CH3OH formation can further desorb the [CO] unit to regenerate the RhVO3− cluster, leading to the successful establishment of a catalytic cycle for methanol production from CH4 and CO2 (CH4+CO2→CH3OH+CO). The exceptional activity of Rh‐V dinuclear oxide cluster (RhVO3−) identified herein provides a new mechanism for co‐conversion of two very stable molecules CH4 and CO2.

Identification of Key Reversible Intermediates in Self‐Reconstructed Nickel‐Based Hybrid Electrocatalysts for Oxygen Evolution

By Jianwen Huang, Yaoyao Li, Yadong Zhang, Gaofeng Rao, Chunyang Wu, Yin Hu, Xianfu Wang, Ruifeng Lu, Yanrong Li, Jie Xiong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

An irreversible phase transformation was tracked in situ from NiNPS to α‐Ni(OH)2. This result and potential‐dependent reversible conversion between α‐Ni(OH)2 and γ‐NiOOH prior to OER unveil the real active species of γ‐NiOOH in self‐reconstructed Ni‐based catalysts. Abstract The oxygen evolution reaction (OER) has been explored extensively for reliable hydrogen supply to boost the energy conversion efficiency. The superior OER performance of newly developed non‐noble metal electrocatalysts has concealed the identification of the real active species of the catalysts. Now, the critical active phase in nickel‐based materials (represented by NiNPS) was directly identified by observing the dynamic surface reconstruction during the harsh OER process via combining in situ Raman tracking and ex situ microscopy and spectroscopy analyses. The irreversible phase transformation from NiNPS to α‐Ni(OH)2 and reversible phase transition between α‐Ni(OH)2 and γ‐NiOOH prior to OER demonstrate γ‐NiOOH as the key active species for OER. The hybrid catalyst exhibits 48‐fold enhanced catalytic current at 300 mV and remarkably reduced Tafel slope to 46 mV dec−1, indicating the greatly accelerated catalytic kinetics after surface evolution.

Engaging Aldehydes in CuH‐Catalyzed Reductive Coupling Reactions: Stereoselective Allylation with Unactivated 1,3‐Diene Pronucleophiles

By Chengxi Li, Kwangmin Shin, Richard Y. Liu, Stephen L. Buchwald from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Concentration matters: CuH‐catalyzed stereoselective reductive coupling of aldehydes with 1,3‐dienes was achieved by employing a suitable chiral ligand system and metered addition of aldehyde substrates. This method enables direct access to a variety of functionalized homoallylic alcohols. DFT and kinetic studies provide mechanistic insights into the effect of the relative concentrations of aldehyde and diene on the chemoselectivity. Abstract Recently, CuH‐catalyzed reductive coupling processes involving carbonyl compounds and imines have become attractive alternatives to traditional methods for stereoselective addition because of their ability to use readily accessible and stable olefins as surrogates for organometallic nucleophiles. However, the inability to use aldehydes, which usually reduce too rapidly in the presence of copper hydride complexes to be viable substrates, has been a major limitation. Shown here is that by exploiting relative concentration effects through kinetic control, this intrinsic reactivity can be inverted and the reductive coupling of 1,3‐dienes with aldehydes achieved. Using this method, both aromatic and aliphatic aldehydes can be transformed into synthetically valuable homoallylic alcohols with high levels of diastereo‐ and enantioselectivities, and in the presence of many useful functional groups. Furthermore, using a combination of theoretical (DFT) and experimental methods, important mechanistic features of this reaction related to stereo‐ and chemoselectivities were uncovered.

Multiple Anti‐Counterfeiting Guarantees from a Simple Tetraphenylethylene Derivative – High‐Contrasted and Multi‐State Mechanochromism and Photochromism

By Guangxi Huang, Qing Xia, Wenbin Huang, Jianwu Tian, Zikai He, Bing Shi Li, Ben Zhong Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Forgery‐proof: The novel AIE molecule 1 is designed with high‐contrasted and multi‐state mechanochromic and photochromic properties. Based on these properties, 1 shows great potential for application in advanced multidimensional anti‐counterfeiting, which was demonstrated by fabrication of a model banknote. Abstract Herein the novel tetraphenylethylene (TPE) derivative 1 was designed with an integration of aggregation‐induced emission (AIE), multi‐state mechanochromism and self‐recovery photochromism. The molecule was susceptible to grinding, heating and vapor fuming and showed corresponding transition of its emission colors. The heated powder or single crystal of 1 exhibited reversible photochromism. After a short period of UV irradiation, it showed a bright red color, but recovered to its original white appearance within 1 min. The photochromism is due to the formation of photocyclization intermediates upon UV irradiation, while the eversible mechanochromism is attributed to the weak molecular interactions derived from head‐to‐tail stacking of the molecules. This reversible multi‐state, high‐contrasted and rapid responsive mechanochromic and photochromic property cooperatively provide double enhancement of a multimode guarantee in advanced anti‐counterfeiting.

Rb4Li2TiOGe4O12: A Titanyl Nonlinear Optical Material with the Widest Transparency Range

By Mingjun Xia, Chuan Tang, Rukang Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Crystal clear: A germanate Rb4Li2TiOGe4O12 mid‐infrared (MIR) nonlinear optical (NLO) crystal, containing well‐aligned compressed TiO5 groups and distorted GeO4 tetrahedra, shows a strong second‐harmonic generation (SHG) response. It exhibits concurrently short ultraviolet and long IR cutoffs, fully covering the atmospheric window spectral range of 3–5 μm. Abstract Practical mid‐infrared (MIR) coherent light beams generated by frequency conversion in nonlinear optical (NLO) crystals are indispensable in time‐resolved infrared vibrational spectroscopy, remote light detection and ranging, and free‐space communications. Herein, a new titanyl germanate Rb4Li2TiOGe4O12 (RLTG) MIR NLO crystal was obtained by heavier element substitution. It features a complicated structure network composed of compressed TiO5 square pyramids and distorted GeO4 tetrahedra, separated by Rb+ and Li+ cations. More importantly, RLTG exhibits concurrently short ultraviolet (0.28 μm) and long IR (5.58 μm) transmittance cutoffs, fully covering the atmospheric transparent window of 3–5 μm. Related to the short UV cutoff, it shows a higher laser‐induced damage threshold in comparison to commercial MIR NLO crystals, about twice that of KTiOPO4 (KTP) and 50 times that of AgGaS2 (AGS).

Vinyl Cation Stabilization by Silicon Enables a Formal Metal‐Free α‐Arylation of Alkyl Ketones

By Amandine Pons, Jean Michalland, Wojciech Zawodny, Yong Chen, Veronica Tona, Nuno Maulide from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

I can Si clearly now: The ability of silicon to stabilize vinyl cationic species enables a redox arylation of alkynes whereby the poor reactivity and regioselectivity of alkyl‐substituted alkynes are lifted. This enables the synthesis of a range of α‐silyl‐α′‐arylketones under mild conditions in good to excellent yields. The silicon moiety of the products can either be removed or harnessed for additional C−C bond formation. Abstract The ability of silicon to stabilize vinyl cationic species leads to a redox arylation of alkynes whereby the stringent limitations of reactivity and regioselectivity of alkyl‐substituted alkynes are lifted. This allows the synthesis of a range of α‐silyl‐α′‐arylketones under mild conditions in good to excellent yields and with high functional group tolerance, whereby the silicon moiety in the final products can either be removed for a formal acetone monoarylation transform, or capitalized upon for subsequent electrophilic substitutions at either side of the carbonyl group.

Artificial Enzyme Catalyzed Cascade Reactions: Antitumor Immunotherapy Reinforced by NIR‐II Light

By Mei Wen, Jiang Ouyang, Chuanwan Wei, Hui Li, Wansong Chen, You‐Nian Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Stressed out: Cu2−xTe nanoparticles are presented as a new artificial multienzyme with enzymatic activity reinforced by near‐infrared‐II (NIR‐II) light. Cu2−xTe catalyzes cascade reactions continuously and elevates intratumor oxidative stress, which not only eradicates primary tumors, but also reverses the tumor immunosuppressive (cold) state into a proinflammatory (hot) state to combat tumor metastasis and recurrence. Abstract Current cancer therapy is seriously challenged by tumor metastasis and recurrence. One promising solution to these problems is to build antitumor immunity. However, immunotherapeutic efficacy is highly impeded by the immunosuppressive state of the tumors. Here a new strategy is presented, catalytic immunotherapy based on artificial enzymes. Cu2−xTe nanoparticles exhibit tunable enzyme‐mimicking activity (including glutathione oxidase and peroxidase) under near‐infrared‐II (NIR‐II) light. The cascade reactions catalyzed by the Cu2−xTe artificial enzyme gradually elevates intratumor oxidative stress to induce immunogenic cell death. Meanwhile, the continuously generated oxidative stress by the Cu2−xTe artificial enzyme reverses the immunosuppressive tumor microenvironment, and boosts antitumor immune responses to eradicate both primary and distant metastatic tumors. Moreover, immunological memory effect is successfully acquired after treatment with the Cu2−xTe artificial enzyme to suppress tumor relapse.

Artificial‐Intelligence‐Driven Organic Synthesis—En Route towards Autonomous Synthesis?

By Claire Empel, Rene M. Koenigs from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

AI for chemistry: Automated synthesis can now be performed using an artificial intelligence algorithm to propose the synthetic route and a robotic microfluidic platform to execute the synthesis. The Highlight describes this approach towards small‐molecule synthesis and reflects on the significance of this milestone in chemistry.

Atroposelective Arene Formation by Carbene‐Catalyzed Formal [4+2] Cycloaddition

By Ke Xu, Wenchang Li, Shaoheng Zhu, Tingshun Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Atroposelective [4+2]: A new organocatalyzed atroposelective arene formation reaction involves a carbene‐catalyzed formal [4+2] cycloaddition of conjugated enals and α‐aryl ketones. This study expands the synthetic potential of N‐heterocyclic carbene (NHC) organocatalysis and provides a competitive pathway for the synthesis of axially chiral ligands, catalysts, and other functional molecules. Abstract Atroposelective arene formation is an efficient method to build axially chiral molecules with multi‐substituted arenes. Reported here is an organocatalyzed atroposelective arene formation reaction by an N‐heterocyclic carbene (NHC) catalyzed formal [4+2] cycloaddition of conjugated dienals and α‐aryl ketones. This study expands the synthetic potential of NHC organocatalysis and provides a competitive pathway for the synthesis of axially chiral ligands, catalysts, and other functional molecules.

Organic Room‐Temperature Phosphorescence with Strong Circularly Polarized Luminescence Based on Paracyclophanes

By Xiao Liang, Ting‐Ting Liu, Zhi‐Ping Yan, Yan Zhou, Jian Su, Xu‐Feng Luo, Zheng‐Guang Wu, Yi Wang, You‐Xuan Zheng, Jing‐Lin Zuo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

A series of organic phosphors based on paracyclophanes (PCPs) exhibit both strong room‐temperature phosphorescence (RTP) and excellent circularly polarized luminescence. Modulating the PCP core with non‐halogen‐containing electron‐withdrawing units elongates the RTP lifetime to 313.59 and 528.00 ms. The afterglow is visible for several seconds under ambient conditions. Abstract Pure organic materials with intrinsic room‐temperature phosphorescence typically rely on heavy atoms or heteroatoms. Two different strategies towards constructing organic room‐temperature phosphorescence (RTP) species based upon the through‐space charge transfer (TSCT) unit of [2.2]paracyclophane (PCP) were demonstrated. Materials with bromine atoms, PCP‐BrCz and PPCP‐BrCz, exhibit RTP lifetime of around 100 ms. Modulating the PCP core with non‐halogen‐containing electron‐withdrawing units, PCP‐TNTCz and PCP‐PyCNCz, successfully elongate the RTP lifetime to 313.59 and 528.00 ms, respectively, the afterglow of which is visible for several seconds under ambient conditions. The PCP‐TNTCz and PCP‐PyCNCz enantiomers display excellent circular polarized luminescence with dissymmetry factors as high as −1.2×10−2 in toluene solutions, and decent RTP lifetime of around 300 ms for PCP‐TNTCz enantiomers in crystalline state.

Anionic Dopant Delocalization through p‐Band Modulation to Endow Metal Oxides with Enhanced Visible‐Light Photoactivity

By Xianyin Song, Dong He, Wenqing Li, Zunjian Ke, Jiangchao Liu, Chongyang Tang, Li Cheng, Changzhong Jiang, Ziyu Wang, Xiangheng Xiao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

A typical N‐doped TiO2 model reveals the anions activation mechanism based on the fundamental delocalized orbital hybridization modulation through O‐vacancy incorporation and demonstrated its necessity and usefulness for pre‐evaluating the role of dopants according to systematically experimental and theoretical studies. Abstract An N‐doped TiO2 model reveals a conceptually different mechanism for activating the N dopant based on delocalized orbital hybridization through O vacancy incorporation. Synchrotron‐based X‐ray absorption spectroscopy, time‐resolved fluorescence, and DFT studies revealed that O vacancy incorporation can effectively stimulate the delocalization of N impurity states through p‐band orbital modulation, which leads to a significant enhancement in photocarrier lifetime. Consequently, this effect also results in a remarkable increase in the incident photon‐to‐electron conversion efficiency in the range of 400–550 nm compared to that of conventional N‐incorporated TiO2 (15 % versus 1 % at 450 nm). This work reveals the fundamental necessity of orbital modulation in the band engineering of metal oxides for driving solar water splitting and beyond.

Catalytic Asymmetric Conjugate Addition of a Borylalkyl Copper Complex for Chiral Organoboronate Synthesis

By Won Jun Jang, Jaesook Yun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Neat as a new Bpin: Asymmetric catalytic conjugate addition of a borylalkyl copper nucleophile generated in situ from a 1,1‐diborylmethane to α,β‐unsaturated diesters enabled the enantioselective incorporation of a CH2Bpin moiety at the β‐position of the diesters. The resulting β‐chiral alkylboronates were obtained in up to 86 % yield with high enantioselectivity (see scheme). Abstract We report the catalytic enantioselective conjugate addition of a borylalkyl copper nucleophile generated in situ from a 1,1‐diborylmethane derivative to α,β‐unsaturated diesters. In the presence of a chiral N‐heterocyclic carbene (NHC)–copper catalyst, this method facilitated the enantioselective incorporation of a CH2Bpin moiety at the β‐position of the diesters to yield β‐chiral alkyl boronates in up to 86 % yield with high enantioselectivity. The alkylboron moiety in the resulting chiral diester products was converted into various functional groups by organic transformation of the C−B bond.

Volatile Organic Compound Based Probe for Induced Volatolomics of Cancers

By Justin Lange, Balkis Eddhif, Mehrad Tarighi, Théa Garandeau, Elodie Péraudeau, Jonathan Clarhaut, Brigitte Renoux, Sébastien Papot, Pauline Poinot from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Induced volatolomics: A volatile organic compound (VOC) based probe is selectively converted by tumours into a VOC that diffuses into the blood stream and is then released in exhaled breath. The VOC in the exhaled breath can be detected and used as a diagnostic tool for cancer. This approach was used in the detection of several different tumours in mice, and for monitoring tumour growth and tumour response to chemotherapy. Abstract The development of efficient protocols for cancer diagnosis remains highly challenging. An emerging approach relies on the detection in exhaled breath of volatile organic compounds (VOC) produced by tumours. In this context, described here is a novel strategy in which a VOC‐based probe is converted selectively in malignant tissues, by a tumour‐associated enzyme, for releasing the corresponding VOC. The latter is then detected in the exhaled breath as a tumour marker for cancer diagnosis. This approach allows the detection of several different tumours in mice, the monitoring of tumour growth and tumour response to chemotherapy. Thus, the concept of “induced volatolomics” provides a new way to explore biological processes using VOC‐based probes that could be adapted to many biomedical applications.

Mechanoluminescence or Room‐Temperature Phosphorescence: Molecular Packing‐Dependent Emission Response

By Jinfeng Wang, Zhaofei Chai, Jiaqiang Wang, Can Wang, Mengmeng Han, Qiuyan Liao, Arui Huang, Peixuan Lin, Conggang Li, Qianqian Li, Zhen Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Mechanoluminescence and room‐temperature phosphorescence were separated in polymorphisms with varied molecular packing. This afforded crucial information to deeply understand the packing–function relationship and the internal mechanism of different emission properties. Abstract Mechanoluminescence (ML) and room‐temperature photophosphorescence (RTP) were achieved in polymorphisms of a triphenylamine derivative with ortho‐substitution. This molecular packing‐dependent emission afforded crucial information to deeply understand the intrinsic mechanism of different emission forms and the possible packing–function relationship. With the incorporation of solid‐state 13C NMR spectra of single crystals, as well as the analysis of crystal structures, the preferred packing modes for ML and/or RTP were investigated in detail, which can guide the reasonable design of organic molecules with special light‐emission properties.

Metal–Organic Gels from Silver Nanoclusters with Aggregation‐Induced Emission and Fluorescence‐to‐Phosphorescence Switching

By Zengchun Xie, Panpan Sun, Zhi Wang, Hongguang Li, Longyue Yu, Di Sun, Mengjun Chen, Yuting Bi, Xia Xin, Jingcheng Hao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Solvent‐induced gelation of Ag nanoclusters with atomic precision has been achieved. The metal–organic gel exhibits aggregation‐induced emission with fluorescence‐to‐phosphorescence switching and reversible changes upon heating‐cooling cycles. Abstract Luminescent metal nanoclusters (NCs) are emerging as a new class of functional materials that have rich physicochemical properties and wide potential applications. In recent years, it has been found that some metal NCs undergo aggregation‐induced emission (AIE) and an interesting fluorescence‐to‐phosphorescence (F‐P) switching in solutions. However, insights of both the AIE and the F‐P switching remain largely unknown. Now, gelation of water soluble, atomically precise Ag9 NCs is achieved by the addition of antisolvent. Self‐assembly of Ag9 NCs into entangled fibers was confirmed, during which AIE was observed together with an F‐P switching occurring within a narrow time scale. Structural evaluation indicates the fibers are highly ordered. The self‐assembly of Ag9 NCs and their photoluminescent property are thermally reversible, making the metal–organic gels good candidates for luminescent ratiometric thermometers.

Photoelectrochemical CO2 Reduction with a Rhenium Organometallic Redox Mediator at Semiconductor/Aqueous Liquid Junction Interfaces

By Sang Youn Chae, Ja Youn Choi, Yoolim Kim, Dang Le Tri Nguyen, Oh‐Shim Joo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

The selectivity control between hydrogen evolution and CO2 reduction at the interface of a semiconductor/electrolyte junction is described by O. S. Joo et al. in their Communication (DOI: 10.1002/anie.201908398). Competition between CO2 reduction and hydrogen evolution was observed on (photo)electrodes under electrochemical conditions. However, hydrogen evolution was suppressed under photoelectrochemical conditions, showing a high selectivity for CO2 reduction using an identical electrode/electrolyte system.

Live‐Cell Localization Microscopy with a Fluorogenic and Self‐Blinking Tetrazine Probe

By Philipp Werther, Klaus Yserentant, Felix Braun, Nicolai Kaltwasser, Christoph Popp, Mathis Baalmann, Dirk-Peter Herten, Richard Wombacher from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Recent developments in fluorescence microscopy call for novel small molecule‐based labels with multiple functionalities to satisfy different experimental requirements. A current limitation in the advancement of live‐cell single‐molecule localization microscopy, is the high excitation power required to induce blinking. This is in marked contrast to the minimal phototoxicity required in live‐cell experiments. At the same time, quality of super‐resolution imaging depends on high label specificity, making removal of excess dye essential. Approaching both hurdles, we present a rational design and synthetic route for a novel type of small molecule label comprising both fluorogenic and self‐blinking features. Bioorthogonal “click” chemistry ensures fast and highly selective attachment onto a variety of biomolecular targets. Along with spectroscopic characterization, we demonstrate that the probe overall improves quality and conditions for regular and single‐molecule localization microscopy on live‐cell samples. The fluorescent probe is tailor‐made for advanced live‐cell microscopy technologies with molecular features that go far beyond the usual requirements of spectral and photophysical properties for small‐molecule labels.

Unpaired 3d Electron on Atomically Dispersed Cobalt Centre in Coordination Polymers to Regulate both ORR Activity and Selectivity

By Yuebin Lian, Wenjuan Yang, Chufeng Zhang, Hao Sun, Zhao Deng, Wenjie Xu, Li Song, Zhongwen Ouyang, Zhenxing Wang, Jun Guo, Yang Peng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 22, 2019.

Reversible oxygen conversion is of vital importance for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP = 2, 3, 6, 7, 10, 11‐hexaiminotriphenylene) as the ligand, with the aim to interrogate the role of metal centers in modulating the activity of oxygen reduction reaction (ORR). The differences in crystallographic structure, spin character, electric conductivity, and coordination states are elaborately compared for both Co3HITP2 and Ni3HITP2 , revealing the former with unpaired 3d electrons possessing less coplanarity but more radical features. As a result, despite of a reduced crystallinity and conductivity, the best ORR activity comparable to 20% Pt/C is obtained for Co3HITP2 , signifying the 3d orbital configuration of the metal center in promoting ORR. More importantly, both experimental and DFT investigations unveil a transition of ORR pathway from four‐electron for Co3HITP2 to two‐electron for Ni3HITP2 owing to different intermediate binding energetics. Further in conjunction with the considerable OER activities, rechargeable zinc‐air batteries using Co3HITP2 as the air cathode catalyst demonstrate excellent energy efficiency and operation stability.

[ASAP] Quasi-line Spectral Emissions from Highly Crystalline One-Dimensional Organic Nanowires

By Ankur Sharma†, Ahmed Khan†, Yi Zhu, Robert Halbich, Wendi Ma, Yilin Tang, Bowen Wang, and Yuerui Lu* from Nano Letters: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02943

[ASAP] Competitive Binding Study Revealing the Influence of Fluorophore Labels on Biomolecular Interactions

By Marina S. Dietz†, S. Sophia Wehrheim†, Marie-Lena I. E. Harwardt†, Hartmut H. Niemann§, and Mike Heilemann*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03736

[ASAP] Direct-Ink-Write 3D Printing of Hydrogels into Biomimetic Soft Robots

By Yin Cheng, Kwok Hoe Chan, Xiao-Qiao Wang, Tianpeng Ding, Tongtao Li, Xin Lu, and Ghim Wei Ho* from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06144

[ASAP] Tailoring Cu+ for Ga3+ Cation Exchange in Cu2–xS and CuInS2 Nanocrystals by Controlling the Ga Precursor Chemistry

By Stijn O. M. Hinterding†?, Anne C. Berends†¶, Mert Kurttepeli‡#, Marc-Etienne Moret§, Johannes D. Meeldijk?, Sara Bals‡, Ward van der Stam†?, and Celso de Mello Donega*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05337

[ASAP] Classifying the Electronic and Optical Properties of Janus Monolayers

By Anders C. Riis-Jensen*†, Thorsten Deilmann*†‡, Thomas Olsen†, and Kristian S. Thygesen†§ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06698

[ASAP] Direct Epitaxial Synthesis of Selective Two-Dimensional Lateral Heterostructures

By Juwon Lee†¶, Sangyeon Pak‡¶, Young-Woo Lee§, Youngsin Park?, A-Rang Jang†?, John Hong†, Yuljae Cho†#, Bo Hou†#, Sanghyo Lee†#, Hu Young Jeong?, Hyeon Suk Shin?, Stephen M. Morris†, SeungNam Cha*‡, Jung Inn Sohn*†?, and Jong Min Kim# from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05722

[ASAP] Three-Dimensional-Ordered Porous Nanostructures for Lithium–Sulfur Battery Anodes and Cathodes Confer Superior Energy Storage Performance

By Shengxuan Lin, M. Khizar Shafique, Zihe Cai, Jiajia Xiao, Yuhang Chen, Yifan Wang, and Xiaobin Hu* from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05718

[ASAP] Co-delivery of Bee Venom Melittin and a Photosensitizer with an Organic–Inorganic Hybrid Nanocarrier for Photodynamic Therapy and Immunotherapy

By Haojie Liu†?, Yan Hu‡?, Yajie Sun‡?, Chao Wan‡, Zhanjie Zhang‡, Xiaomeng Dai‡, Zihan Lin†, Qianyuan He†, Zhe Yang†, Piao Huang†, Yuxuan Xiong†, Jinguo Cao†, Xu Chen†, Qi Chen†, Jonathan F. Lovell§, Zushun Xu*†, Honglin Jin*‡, and Kunyu Yang*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04181

[ASAP] Effect of Airborne Hydrocarbons on the Wettability of Phase Change Nanoparticle Decorated Surfaces

By Weiteng Guo†, Bin Chen†, Van Lam Do†, Gert H. ten Brink†, Bart J. Kooi†, Vitaly B. Svetovoy†‡, and George Palasantzas*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06909

[ASAP] Supramolecular Tessellations by a Rigid Naphthalene Diimide Triangle

By Yassine Beldjoudi†, Ashwin Narayanan‡?, Indranil Roy†, Tyler J. Pearson†, M. Mustafa Cetin†, Minh T. Nguyen†, Matthew D. Krzyaniak†§, Fehaid M. Alsubaie#, Michael R. Wasielewski†§, Samuel I. Stupp†‡??, and J. Fraser Stoddart*†¶? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08758

[ASAP] Selection of DNA-Encoded Libraries to Protein Targets within and on Living Cells

By Bo Cai, Dongwook Kim†, Saeed Akhand, Yixing Sun, Robert J. Cassell, Aktan Alpsoy, Emily C. Dykhuizen, Richard M. Van Rijn, Michael K. Wendt, and Casey J. Krusemark* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08085

[ASAP] Homogenous Synthesis of Monodisperse High Oligomers of 3-Hexylthiophene by Temperature Cycling

By George R. McKeown†, Shuyang Ye†, Susan Cheng†, and Dwight S. Seferos*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08240

[ASAP] Engineering Structural Dynamics of Zirconium Metal–Organic Frameworks Based on Natural C4 Linkers

By Sujing Wang†‡, Nertil Xhaferaj†, Mohammad Wahiduzzaman§, Kolade Oyekan?, Xiao Li?, Kevin Wei?, Bin Zheng§, Antoine Tissot†, Je´ro^me Marrot#, William Shepard?, Charlotte Martineau-Corcos#?, Yaroslav Filinchuk?, Kui Tan*?, Guillaume Maurin*§, and Christian Serre*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07816

[ASAP] Enhanced Gas Uptake in a Microporous Metal–Organic Framework via a Sorbate Induced-Fit Mechanism

By Mei-Hui Yu†, Brian Space§, Douglas Franz§, Wei Zhou?, Chaohui He?, Libo Li?, Rajamani Krishna#, Ze Chang†, Wei Li†, Tong-Liang Hu*†, and Xian-He Bu*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07807

[ASAP] Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules

By Michael Rauch, Zack Strater, and Gerard Parkin* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08342

[ASAP] Ensemble-Based Modeling of the NMR Spectra of Solid Solutions: Cation Disorder in Y2(Sn,Ti)2O7

By Robert F. Moran†, David McKay†, Paulynne C. Tornstrom‡, Alex Aziz‡, Arantxa Fernandes†, Ricardo Grau-Crespo*‡, and Sharon E. Ashbrook*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09036

[ASAP] Lithium Thiophosphate Functionalized Zirconium MOFs for Li–S Batteries with Enhanced Rate Capabilities

By Avery E. Baumann†, Xu Han†, Megan M. Butala‡§, and V. Sara Thoi*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09538

[ASAP] Spotlights on Recent JACS Publications

By ACS Contributing Correspondents from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b11333

[ASAP] Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters

By Sangmin Kim†, Florian Loose†, Ma´te´ J. Bezdek†, Xiaoping Wang‡, and Paul J. Chirik*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09540

[ASAP] A Unified Description of Intrinsically Disordered Protein Dynamics under Physiological Conditions Using NMR Spectroscopy

By Wiktor Adamski, Nicola Salvi, Damien Maurin, Justine Magnat, Sigrid Milles, Malene Ringkjøbing Jensen, Anton Abyzov, Christophe J. Moreau, and Martin Blackledge* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09002

[ASAP] Installation of Minimal Tetrazines through Silver-Mediated Liebeskind–Srogl Coupling with Arylboronic Acids

By William D. Lambert†, Yinzhi Fang†, Subham Mahapatra‡, Zhen Huang§, Christopher W. am Ende*‡, and Joseph M. Fox*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08677

[ASAP] Stereocontrolled Syntheses of Functionalized cis- and trans-Siladecalins

By Eric A. Marro, Carlton P. Folster, Eric M. Press, Hoyeon Im, John T. Ferguson, Maxime A. Siegler, and Rebekka S. Klausen* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09902

Co-feeding copper catalysts couple carbon

By Peidong Yang from Nature Nanotechnology - Issue - nature.com science feeds. Published on Oct 22, 2019.

Nature Nanotechnology, Published online: 22 October 2019; doi:10.1038/s41565-019-0575-y

The mechanistic electrochemical mass spectrometry study of ethylene production on Cu-based nanocatalysts under CO2/CO co-feeds indicates the existence of separate, reactant-specific surface adsorption sites for CO2 and CO, which guided the design of a multi-component CO2RR electrocatalyst.

How nanoscale surface steps promote ice growth on feldspar: microscopy observation of morphology-enhanced condensation and freezing

By Konrad Thürmer from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08729J, Paper
Ray Friddle, Konrad Thürmer
Ice in the atmosphere affects Earth’s radiative properties and initiates most precipitation. Growing ice often requires a solid surface, either to catalyze freezing of supercooled cloud droplets or to serve...
The content of this RSS Feed (c) The Royal Society of Chemistry

Effect of nanotube coupling on exciton transport in polymer-free monochiral semiconducting carbon nanotube networks

By Andrew J Ferguson from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07821E, Paper
Dylan H. Arias, Dana B. Sulas-Kern, Stephanie M. Hart, Hyun Suk Kang, Ji Hao, Rachelle Ihly, Justin C. Johnson, Jeffrey Blackburn, Andrew J Ferguson
Semiconducting single-walled carbon nanotubes (s-SWCNTs) are attractive light-harvesting components for solar photoconversion schemes and architectures, and selective polymer extraction has emerged as a powerful route to obtain highly pure s-SWCNT...
The content of this RSS Feed (c) The Royal Society of Chemistry

Thiourea additive based quadruple cation lead halide perovskite with ultra large grain size for efficient perovskite solar cells

By Chang Kook Hong from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07377A, Paper
Jyoti V Patil, Sawanta S. Mali, Chang Kook Hong
The quadruple cation based perovskite solar cell (PVSC) is now crossing 25.2 % power conversion efficiency (PCE) because of its effective light harvesting ability. The perovskite materials and type of...
The content of this RSS Feed (c) The Royal Society of Chemistry

Core-shell tecto dendrimers formed via host-guest supramolecular assembly as a pH-responsive intelligent carrier for enhanced anticancer drug delivery

By Xiangyang Shi from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08309J, Paper
Jianhong Wang, Du Li, Yu Fan, Menghan Shi, yunxia yang, Le Wang, Yitian Peng, Mingwu Shen, Xiangyang Shi
Design of pH-sensitive supramolecular drug delivery systems for efficient antineoplastic drug delivery has been remaining a huge challenge. Herein, we describe the development of pH-responsive core-shell tecto dendrimers (CSTDs) formed...
The content of this RSS Feed (c) The Royal Society of Chemistry

Palladium / Cobalt Nanowires with Improved Hydrogen Sensing Stability at Ultra-Low Temperatures

By Dachi Yang from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07834G, Communication
Lingling Du, Dongliang Feng, Xiaxia Xing, Yang Fu, Luis F F Fonseca, Dachi Yang
The metallic dopants in palladium (Pd) sensing materials enable a modification to the d-band electrons of Pd, which is expected to tune the α-β phase transitions of PdHx intermediate, and...
The content of this RSS Feed (c) The Royal Society of Chemistry

Ru nanoclusters confined in porous organic cages for catalytic hydrolysis of ammonia borane and tandem hydrogenation reaction

By Zhengping Dong from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08483E, Paper
Qiang Song, Wei David Wang, Xiwei Hu, Zhengping Dong
The fabrication of narrow-sized metal nanoclusters for heterogeneous catalysis has attracted widespread research attention. Nevertheless, it is still a significant challenge to fabricate highly dispersed metal-nanocluster-based catalysts with high activity...
The content of this RSS Feed (c) The Royal Society of Chemistry

Vertically Aligned Laser Sliced MWCNTs

By Colin L Raston from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08715J, Paper
Thaar Alharbi, Kasturi Vimalanathan, Ibrahim Alsulami, Colin L Raston
Applications of multi-walled carbon nanotubes (MWCNTs) can benefit with the availability of specific lengths of the material while keeping the outer walls pristine, for example, for applications requiring vertically alignment...
The content of this RSS Feed (c) The Royal Society of Chemistry

Proton irradiation of graphene: insights from atomistic modeling

By Igor Jovanovic from RSC - Nanoscale latest articles. Published on Oct 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06502D, Paper
Tan Shi, Qing Peng, Zhitong Bai, Fei Gao, Igor Jovanovic
Various types of topological defects are produced during proton irradiation, which are crucial in functionalizing graphene, but the mechanisms of the defect generation process and the structure change are still...
The content of this RSS Feed (c) The Royal Society of Chemistry

“HOT” Alkaline Hydrolysis of Amorphous MOF Microspheres to Produce Ultrastable Bimetal Hydroxide Electrode with Boosted Cycling Stability

By Haobing Zhang, Ben Xu, Hao Mei, Yingjie Mei, Shiyu Zhang, Zhendong Yang, Zhenyu Xiao, Wenpei Kang, Daofeng Sun from Wiley: Small: Table of Contents. Published on Oct 21, 2019.

An amorphous metal–organic framework template/precursor and KOH aqueous solution are separately heated and mixed until 120 °C to produce hydroxide electrodes. The electrode obtained through this unique “HOT” alkaline is extremely stable during cycling. Furthermore, the low KOH concentration of 0.2 m and recycled ligands during the unique “HOT” alkaline treatment are preferable for practical applications. Abstract Nickel/cobalt hydroxide is a promising battery‐type electrode material for supercapacitors. However, its low cycle stability hinders further applications. Herein, Ni0.7Co0.3(OH)2 core–shell microspheres exhibiting extreme‐prolonged cycling life are successfully synthesized, employing Ni‐Co‐metal–organic framework (MOF) as the precursor/template and a specific hydrolysis strategy. The Ni‐Co‐MOF and KOH aqueous solution are separated and heated to 120 °C before mixing, rather than mixing before heating. Through this hydrolysis strategy, no MOF residual exists in the product, contributing to close stacking of the hydroxide nanoflakes to generate Ni0.7Co0.3(OH)2 microspheres with a robust core–shell structure. The electrode material exhibits high specific capacity (945 C g−1 at 0.5 A g−1) and unprecedented cycling performance (100% after 10 000 cycles). The fabricated asymmetric supercapacitor delivers an energy density of 40.14 Wh kg−1 at a power density of 400.56 W kg−1 and excellent cycling stability (100% after 20 000 cycles). As far as is known, it is the best cycling performance for pure Ni/Co(OH)2.

Bidirectional Transport of Nanoparticles and Cells with a Bio‐Conveyor Belt

By Xiaoshuai Liu, You Wu, Xiaohao Xu, Yuchao Li, Yao Zhang, Baojun Li from Wiley: Small: Table of Contents. Published on Oct 21, 2019.

A bio‐conveyor belt with adjustable length is assembled from biological cells and applied for the bidirectional transport of nanoparticles and cells. The impacts of cell size and particle properties on transport capability are analyzed using numerical simulations. The bio‐conveyor belt can also be assembled with mammalian cells and then devoted to the transport of cells in vivo. Abstract The bidirectional transport of nanoparticles and biological cells is of great significance in efficient biological assays and precision cell screening, and can be achieved with optical conveyor belts in a noncontact and noninvasive manner. However, implantation of these belts into biological systems can present significant challenges owing to the incompatibility of the artificial materials. In this work, an optical conveyor belt assembled from natural biological cells is proposed. The diameter of the belt (500 nm) is smaller than the laser wavelength (980 nm) and, therefore, the evanescent wave stably traps the nanoparticles and cells on the belt surface. By adjusting the relative power of the lasers injected into the belt, the particles or cells can be bidirectionally transported along the bio‐conveyor belt. The experimental results are numerically interpreted and the transport velocities are investigated based on simulations. Further experiments show that the bio‐conveyor belt can also be assembled with mammalian cells and then applied to dynamic cell transport in vivo. The bio‐conveyor belt might provide a noninvasive and biocompatible tool for biomedical assays, drug delivery, and biological nanoarchitectonics.

The Fundamental Mechanism Behind Colossal Permittivity in Oxides

By Ned T. Taylor, Francis H. Davies, Shane G. Davies, Conor J. Price, Steven P. Hepplestone from Wiley: Advanced Materials: Table of Contents. Published on Oct 21, 2019.

The atomic‐scale origin of colossal permittivity in CaCu3Ti4O12 is shown to be the result of a metallic interface between its grains and the intergrain material, CuxO. When under an applied electric field, interface charges respond by flowing within the grain edge, resulting in a large polarization of the electronic charge that gives rise to colossal permittivity. Abstract Colossal permittivity materials exhibit extreme polarization in an applied electric field, providing applications in electronics and energy transmission. Understanding the atomic‐scale mechanism behind colossal permittivity remains a challenging task and is key to optimizing materials with this property. The fundamental mechanism of colossal permittivity is reported and, using CaCu3Ti4O12 as an example, it is attributed to the formation of an unusual metallic interface between the grain and grain boundary materials (CaCu3Ti4O12 and CuxO (x = 1, 2), respectively), not created by oxygen vacancies as is normally the case in oxide materials. This metallic layer around the grain forms confined shells of charge that pool on one side when under an applied field, which results in colossal permittivity. A route towards enhancing colossal permittivity is explained by means of manipulating the interface properties, as well as altering sample geometries. A methodology to artificially engineer colossal permittivity metamaterials is also shown.

Cesium Lead Inorganic Solar Cell with Efficiency beyond 18% via Reduced Charge Recombination

By Qiufeng Ye, Yang Zhao, Shaiqiang Mu, Fei Ma, Feng Gao, Zema Chu, Zhigang Yin, Pingqi Gao, Xingwang Zhang, Jingbi You from Wiley: Advanced Materials: Table of Contents. Published on Oct 21, 2019.

The power conversion efficiency of inorganic perovskite solar cells (PSCs) is still low compared with hybrid PSCs. The use of lithium fluoride on SnO2 and PbCl2 additive in perovskite is reported for reducing the charge recombination, 18.64% efficiency of CsPbI3–xBrx solar cells is demonstrated, and the devices show over than 1000 h light soaking stability. Abstract Cesium‐based inorganic perovskite solar cells (PSCs) are promising due to their potential for improving device stability. However, the power conversion efficiency of the inorganic PSCs is still low compared with the hybrid PSCs due to the large open‐circuit voltage (VOC) loss possibly caused by charge recombination. The use of an insulated shunt‐blocking layer lithium fluoride on electron transport layer SnO2 for better energy level alignment with the conduction band minimum of the CsPbI3‐xBrx and also for interface defect passivation is reported. In addition, by incorporating lead chloride in CsPbI3‐xBrx precursor, the perovskite film crystallinity is significantly enhanced and the charge recombination in perovksite is suppressed. As a result, optimized CsPbI3‐xBrx PSCs with a band gap of 1.77 eV exhibit excellent performance with the best VOC as high as 1.25 V and an efficiency of 18.64%. Meanwhile, a high photostability with a less than 6% efficiency drop is achieved for CsPbI3‐xBrx PSCs under continuous 1 sun equivalent illumination over 1000 h.

Colloidal Single‐Layer Photocatalysts for Methanol‐Storable Solar H2 Fuel

By Yingping Pang, Md Nasir Uddin, Wei Chen, Shaghraf Javaid, Emily Barker, Yunguo Li, Alexandra Suvorova, Martin Saunders, Zongyou Yin, Guohua Jia from Wiley: Advanced Materials: Table of Contents. Published on Oct 21, 2019.

A scalable stacking‐hinderable strategy is developed to enable exclusive single‐layer growth mode for transition metal dichalcogenides selectively sandwiched by surfactant molecules. These can act as efficient solar‐driven photocatalysts for solar H2 fuel production from hydrogen‐stored liquid carrier—methanol. Abstract Molecular surfactants are widely used to control low‐dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single‐layer growth for 2D materials. A scalable stacking‐hinderable strategy to not only enable exclusive single‐layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single‐layer TMDs' photoredox activities is developed. The single‐layer growth mechanism is well explained by theoretical calculation. Three types of single‐layer TMDs, including MoS2, WS2, and ReS2, are successfully synthesized and demonstrated in solar H2 fuel production from hydrogen‐stored liquid carrier—methanol. Such H2 fuel production from single‐layer MoS2 nanosheets is COx‐free and reliably workable under room temperature and normal pressure with the generation rate reaching ≈617 µmole g−1 h−1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol‐storable solar H2 fuel with facile chemical rebonding actualized by 2D single‐layer photocatalysts.

Nonradiative Recombination in Perovskite Solar Cells: The Role of Interfaces

By Christian M. Wolff, Pietro Caprioglio, Martin Stolterfoht, Dieter Neher from Wiley: Advanced Materials: Table of Contents. Published on Oct 21, 2019.

Perovskite solar cells have reached certified efficiencies of 25.2% within just ten years due to their excellent optoelectronic properties. Nonradiative recombination at the interface between the perovskite absorber and charge‐transporting layers is identified as the major source of open‐circuit‐voltage losses in state‐of‐the‐art devices, requiring advanced strategies to study and to control efficiency‐limiting interfacial processes. Abstract Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their VOC to values well below the Shockley–Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi‐Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the VOC of operational devices. These measurements prove that in state‐of‐the‐art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump‐probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome—paving the way to the thermodynamic efficiency limit.

Regulating Nonclassical Pathways of Silicalite‐1 Crystallization through Controlled Evolution of Amorphous Precursors

By Madhuresh K. Choudhary, Manjesh Kumar, Jeffrey D. Rimer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

An evolutionary idea: Organic molecules in zeolite synthesis switch the predominant mode of silicalite‐1 growth between classical and nonclassical pathways by mediating the degree to which silica nanoparticle precursors undergo microstructural evolution. Abstract Differentiating mechanisms of zeolite crystallization is challenging owing to the vast number of species in growth solutions. The presence of amorphous colloidal particles is ubiquitous in many zeolite syntheses, and has led to extensive efforts to understand the driving force(s) for their self‐assembly and putative roles in processes of nucleation and growth. In this study, we use a combination of in situ scanning probe microscopy, particle dissolution measurements, and colloidal stability assays to elucidate the degree to which silica nanoparticles evolve in their structure during the early stages of silicalite‐1 synthesis. We show how changes in precursor structure are mediated by the presence of organics, and demonstrate how these changes lead to significant differences in precursor–crystal interactions that alter preferred modes of crystal growth. Our findings provide guidelines for selectively controlling silicalite‐1 growth by particle attachment or monomer addition, thus allowing for the manipulation of anisotropic rates of crystallization. In doing so, we also address a longstanding question regarding what factors are at our disposal to switch from a nonclassical to classical mechanism.

Near‐Infrared Optogenetic Genome Engineering Based on Photon‐Upconversion Hydrogels

By Yoichi Sasaki, Mio Oshikawa, Pankaj Bharmoria, Hironori Kouno, Akiko Hayashi‐Takagi, Moritoshi Sato, Itsuki Ajioka, Nobuhiro Yanai, Nobuo Kimizuka from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Near‐infrared (NIR) light‐triggered optogenetics with triplet–triplet annihilation‐based photon upconversion (TTA‐UC) is demonstrated. Triplet‐lifetime extension by the covalent conjugation of donor and acceptor and a heat‐induced conformational change of the hydrogel that prevents oxygen diffusion enables the formation of dendritic‐spine‐like structures by hippocampal neurons, induced by NIR‐to‐blue TTA‐UC. Abstract Photon upconversion (UC) from near‐infrared (NIR) light to visible light has enabled optogenetic manipulations in deep tissues. However, materials for NIR optogenetics have been limited to inorganic UC nanoparticles. Herein, NIR‐light‐triggered optogenetics using biocompatible, organic TTA‐UC hydrogels is reported. To achieve triplet sensitization even in highly viscous hydrogel matrices, a NIR‐absorbing complex is covalently linked with energy‐pooling acceptor chromophores, which significantly elongates the donor triplet lifetime. The donor and acceptor are solubilized in hydrogels formed from biocompatible Pluronic F127 micelles, and heat treatment endows the excited triplets in the hydrogel with remarkable oxygen tolerance. Combined with photoactivatable Cre recombinase technology, NIR‐light stimulation successfully performs genome engineering resulting in the formation of dendritic‐spine‐like structures of hippocampal neurons.

Direct Visualization and Semi‐Quantitative Analysis of Payload Loading in the Case of Gold Nanocages

By Miaoxin Yang, Wenxia Wang, Jichuan Qiu, Meng‐Yi Bai, Younan Xia from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Seeing is believing: A method capable of directly visualizing the loading of payload into the cavity of a gold nanocage was demonstrated. Pyrrole was used as a model, which could be polymerized to give solid polypyrrole deposited on the inner and outer surfaces of the nanocage. Abstract Upon incubation with Au nanocages, pyrrole (Py) molecules can enter the cavities by diffusing through the porous walls and then be polymerized to generate a polypyrrole (PPy) coating on the inner surface. The thicknesses of the PPy coating can serve as a direct indicator for the amount of Py molecules that diffuse into the cavity. Py molecules are able to diffuse into the cavities throughout the polymerization process, while a prolonged incubation time increases the amount of Py accumulated on both inner and outer surfaces of the nanocages. Furthermore, it is demonstrated that the dimensions of the cavity and the size of the pores in the wall are not critical parameters in determining the loading efficiency, as they do not affect the thickness of the PPy coating on the inner surface. These findings offer direct evidence to support the applications of Au nanocages as carriers for drug delivery and controlled release.

Combinatorial Immunophenotyping of Cell Populations with an Electronic Antibody Microarray

By Ruxiu Liu, Chia‐Heng Chu, Ningquan Wang, Tevhide Ozkaya‐Ahmadov, Ozgun Civelekoglu, Dohwan Lee, A K M Arifuzzman, A. Fatih Sarioglu from Wiley: Small: Table of Contents. Published on Oct 21, 2019.

An electrically readable microfluidic antibody microarray for the combinatorial immunophenotyping of cell populations is demonstrated. The cell capture statistics across the whole device are acquired from a single electrical output without any loss of information. The ability to electrically screen cell immunophenotypes on a disposable microfluidic chip can be transformative in cell‐based diagnostics at the point‐of‐care and resource‐limited scenarios. Abstract Immunophenotyping is widely used to characterize cell populations in basic research and to diagnose diseases from surface biomarkers in the clinic. This process usually requires complex instruments such as flow cytometers or fluorescence microscopes, which are typically housed in centralized laboratories. Microfluidics are combined with an integrated electrical sensor network to create an antibody microarray for label‐free cell immunophenotyping against multiple antigens. The device works by fractionating the sample via capturing target subpopulations in an array of microfluidic chambers functionalized against different antigens and by electrically quantifying the cell capture statistics through a network of code‐multiplexed electrical sensors. Through a combinatorial arrangement of antibody sequences along different microfluidic paths, the device can measure the prevalence of different cell subpopulations in a sample from computational analysis of the electrical output signal. The device performance is characterized by analyzing heterogeneous samples of mixed tumor cell populations and then the technique is applied to determine leukocyte subpopulations in blood samples and the results are validated against complete blood cell count and flow cytometry results. Label‐free immunophenotyping of cell populations against multiple targets on a disposable electronic chip presents opportunities in global health and telemedicine applications for cell‐based diagnostics and health monitoring.

Welch Award in Chemistry / And also in the News

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Synthesis of Gb3 Glycosphingolipids with Labeled Head Groups: Distribution in Phase‐Separated Giant Unilamellar Vesicles

By Jeremias Sibold, Katharina Kettelhoit, Loan Vuong, Fangyuan Liu, Daniel B. Werz, Claudia Steinem from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Making the invisible visible: Shiga toxin B subunits (STxB) bind to liquid‐ordered (lo) domains in model membranes, implying that its receptor Gb3 is localized in these lo domains. The synthetic access to Gb3 glycosphingolipids with labeled head groups allows quantification of their partitioning in coexisting lo/ld (liquid‐disordered) phase giant unilamellar vesicles prior to STxB binding. The data clearly indicate an impact of the fatty acid (un)saturation and α‐hydroxylation on the partitioning between phases. Abstract The receptor lipid Gb3 is responsible for the specific internalization of Shiga toxin (STx) into cells. The head group of Gb3 defines the specificity of STx binding, and the backbone with different fatty acids is expected to influence its localization within membranes impacting membrane organization and protein internalization. To investigate this influence, a set of Gb3 glycosphingolipids labeled with a BODIPY fluorophore attached to the head group was synthesized. C24 fatty acids, saturated, unsaturated, α‐hydroxylated derivatives, and a combination thereof, were attached to the sphingosine backbone. The synthetic Gb3 glycosphingolipids were reconstituted into coexisting liquid‐ordered (lo)/liquid‐disordered (ld) giant unilamellar vesicles (GUVs), and STx binding was verified by fluorescence microscopy. Gb3 with the C24:0 fatty acid partitioned mostly in the lo phase, while the unsaturated C24:1 fatty acid distributes more into the ld phase. The α‐hydroxylation does not influence its partitioning.

A Simple Organic Molecule Realizing Simultaneous TADF, RTP, AIE, and Mechanoluminescence: Understanding the Mechanism Behind the Multifunctional Emitter

By Lisi Zhan, Zhanxiang Chen, Shaolong Gong, Yepeng Xiang, Fan Ni, Xuan Zeng, Guohua Xie, Chuluo Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Multifunctional organic emitter: One simple organic molecule exhibits aggregation‐induced emission (AIE), thermally activated delayed fluorescence (TADF), room‐temperature phosphorescence (RTP), and mechanoluminescence (ML) simultaneously. Abstract Aggregation‐induced emission (AIE), thermally activated delayed fluorescence (TADF), room‐temperature phosphorescence (RTP), and mechanoluminescence (ML) have attracted widespread interest. However, a multifunctional organic emitter exhibiting simultaneous AIE, TADF, RTP, and ML has not been reported. Now, two multifunctional blue emitters with very simple structures, mono‐DMACDPS and Me‐DMACDPS, exhibit typical AIE, TADF, and RTP properties but different behavior in mechanoluminescence. Crystal structure analysis reveals that large dipole moment and multiple intermolecular interactions with tight packing mode endow mono‐DMACDPS with strong ML. Combined with the data of crystal analysis and theoretical calculation, the separated monomer and dimer in the crystal lead to the typical TADF and RTP properties, respectively. Simple‐structure mono‐DMACDPS is the first example realizing TADF, RTP, AIE, and ML simultaneously.

Free‐Standing CoO‐POM Janus‐like Ultrathin Nanosheets

By Bilal Akram, Wenxiong Shi, Hao Zhang, Shaheed Ullah, Muhammad Khurram, Xun Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Van der Waals integration of ultrathin Janus‐like 2D heterostructures can also be achieved in a single step through a solution‐based approach. The structural configuration can be simply changed by proper selection of solvents. Such a heteromaterial has tunable properties and can be used as an advanced oxidation catalyst. Abstract A single‐step solution‐based strategy is used to obtain 2D Janus‐like free‐standing ultrathin nanosheets build from two structurally unrelated species, that is, polyoxomolybdate (POM) and CoO. A controlled 2D‐to‐1D morphological transition was achieved by judiciously adjusting the solvent choice. These POM‐CoO heterostructures can behave as an ideal catalyst for the epoxidation of styrene. Benefiting from their amphiphilic nature, these 2D POM‐CoO nanosheets have also been used as surfactant to emulsify immiscible solvents. It is anticipated that structurally diverse polyoxometalates will offer promise as design elements for variety of structurally and compositionally tunable van der Waals integrated heteromaterials having a broad range applications.

Thermal Oxidation of Carbonaceous Nanomaterials Revisited: Evidence of Mechanism Changes

By Emmanuel Picheau, Ferdinand Hof, Alain Derré, Barbara Daffos, Alain Pénicaud from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Despite 450 000 years of human use, carbon combustion still holds secrets. In their Communication (DOI: 10.1002/anie.201906026), A. Pénicaud et al. report a new method to study the kinetics of solid/gas reactions under thermogravimetric analysis. This method was applied to carbon combustion and demonstrates why this reaction still challenges scientists, suggesting exciting further studies.

Radical Monofluoroalkylative Alkynylation of Olefins by a Docking–Migration Strategy

By Min Wang, Huihui Zhang, Jige Liu, Xinxin Wu, Chen Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Docking and migration: Both activated and unactivated alkenes can be modified by a radical‐mediated monofluoroalkylative alkynylation, generating valuable products in a docking–migration process. Many complex natural products and drug derivatives can be readily functionalized with this approach. Abstract A radical‐mediated monofluoroalkylative alkynylation of alkenes is disclosed for the first time. The reaction demonstrates a remarkably broad substrate scope in which both activated and unactivated alkenes are suitable starting materials. The concurrent addition of an alkynyl and a monofluoroalkyl group onto an alkene proceeds through a docking–migration sequence, affording a vast array of valuable fluoroalkyl‐substituted alkynes. Many complex natural products and drug derivatives are readily functionalized, demonstrating that this method can be used for late‐stage alkynylation.

S‐Adenosyl Methionine Cofactor Modifications Enhance the Biocatalytic Repertoire of Small Molecule C‐Alkylation

By Iain J. W. McKean, Joanna C. Sadler, Anibal Cuetos, Amina Frese, Luke D. Humphreys, Gideon Grogan, Paul A. Hoskisson, Glenn A. Burley from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

A tandem enzymatic strategy to enhance the scope of C‐alkylation of small molecules via coupling the production of S‐adenosyl methionine (SAM) cofactor analogues with C‐(m)ethyl transfer to coumarin substrates, catalyzed by the methyltransferase (MTase) NovO, is described. This forms C‐(m)ethylated coumarins in superior yield and greater substrate scope relative to that obtained using cofactors lacking nucleobase modifications. Abstract A tandem enzymatic strategy to enhance the scope of C‐alkylation of small molecules via the in situ formation of S‐adenosyl methionine (SAM) cofactor analogues is described. A solvent‐exposed channel present in the SAM‐forming enzyme SalL tolerates 5′‐chloro‐5′‐deoxyadenosine (ClDA) analogues modified at the 2‐position of the adenine nucleobase. Coupling SalL‐catalyzed cofactor production with C‐(m)ethyl transfer to coumarin substrates catalyzed by the methyltransferase (MTase) NovO forms C‐(m)ethylated coumarins in superior yield and greater substrate scope relative to that obtained using cofactors lacking nucleobase modifications. Establishing the molecular determinants that influence C‐alkylation provides the basis to develop a late‐stage enzymatic platform for the preparation of high value small molecules.

Electrochemically tunable proton coupled electron transfer in Pd‐catalyzed benzaldehyde hydrogenation

By Katherine Koh, Udishnu Sanyal, Mal-Soon Lee, Guanhua Cheng, Miao Song, Vassiliki-Alexandra Glezakou, Yue Liu, Dongsheng Li, Roger Rousseau, Oliver Y. Gutiérrez, Abhijeet Karkamkar, Miroslaw Derewinski, Johannes Lercher from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Acid‐functionalization of carbon support allows enhancing the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol in proportion to the concentration of Brønsted acid sites. In contrast, the hydrogenation rate is not affected when H 2 is used as reduction equivalent. The different response to catalyst properties is shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H 2 induced hydrogenation pathways. The enhancement of the electrocatalytic reduction is realized by the participation of support generated hydronium ions at the perimeter of metal particles.

Hydration‐Facilitated Fine‐Tuning the Color of AIE Amphiphile and It’s Application as Erasable Materials with Hot/Cold Dual Writing‐Modes

By Hongjun Jin, Hongpeng Li, Zhiyang Zhu, Jianbin Huang, Yunlong Xiao, Yun Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

It has long been recognized that hydration water greatly impacts the color of inorganic crystals, but it is still unknown whether hydration water can be utilized to systematically manipulate the emission color of organic luminescent groups. Herein, we report that metal ions with different hydration ability allow fine‐tuning the emission color of a fluorescent group displaying aggregation induced emission (AIE). Because the hydration water can be removed facilely by gentle heating or mechanical grinding and re‐gained by solvent fuming, rewritable materials can be fabricated both in the hot‐writing and cold‐writing modes. This hydration‐facilitated strategy will open up a new vista in fine‐tuning the emission color of AIE molecules based on one synthesis and in the design of smart luminescent devices.

Thermally Driven Structure and Performance Evolution of Atomically Dispersed Fe‐N4 Sites for Oxygen Reduction

By Jianzhan Li, Hanguang Zhang, Widitha Samarakoon, Weitao Shan, David Cullen, Stavros Karakalos, Mengjie Chen, Daming Gu, Karren More, Guofeng Wang, Zhenxing Feng, Zhenbo Wang, Gang Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

FeN 4 moieties embedded in partially graphitized carbon are the most efficient platinum group metal‐free active sites for oxygen reduction reaction in acidic proton exchange membrane fuel cells. However, their formation mechanisms have been remaining elusive for decades. Because the Fe‐N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high‐temperature treatments. Here, we elucidate the Fe‐N 4 site formation mechanisms through hosting Fe ions into a nitrogen‐doped carbon followed by a controlled thermal activation. Among studied hosts, the ZIF‐8‐dervied nitrogen‐doped carbon is an ideal model with well‐defined nitrogen doping and porosity. This approach is able to deconvolute Fe‐N bond formation from complex carbonization and nitrogen doping, which correlates Fe‐N bond properties with activity and stability of FeN 4 sites as a function of thermal activation temperatures. The evolution of catalyst performance of FeN 4 sites driven by thermal activation is associate with two main factors: (i) the increase of active site density due to the transformation of ultra‐fine FeO x particles to atomically dispersed FeN 4 sites; (ii) the intrinsic change of atomistic Fe‐N bonds with enhanced strength and shortened length.

Slow Dynamics of the Spin‐Crossover Process in an Apparent High‐Spin Mononuclear Fe(II) Complex

By Yi Shan Ye, Xiu Qin Chen, You De Cai, Bin Fei, Pierre Dechambenoit, Mathieu Rouzières, Corine Mathonière, Xin Bao, Rodolphe Clerac from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

A mononuclear Fe(II) complex, that shows a high‐spin (S = 2) paramagnetic behavior at all temperatures (with standard temperature scan‐rates, of about 1 Kmin −1 ), has indeed a low‐spin (S = 0) ground state below 100 K. This low‐spin state is not easily accessible due to the extremely slow dynamics of the spin‐crossover process. Indeed, a full relaxation of the metastable high‐spin state to the low‐spin ground state takes more than five hours below 80 K. Bidirectional photoswitching of the Fe(II) state is achieved reproducibly by two selective irradiations (at 530‐590 and 830‐850 nm). The slow dynamics of spin‐crossover and the strong structural cooperativity result in in a remarkably wide 95‐K hysteresis loop induced by both temperature and selected light stimuli.

Carbon‐Nanoplated CoS@TiO2 Nanofibrous Membrane: An Interface‐Engineered Heterojunction for High‐Efficiency Electrocatalytic Nitrogen Reduction

By Bin Ding, Yi-Tao Liu, Xingxing Chen, Jianyong Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Developing noble‐metal‐free electrocatalysts is of utmost importance to industrially viable ammonia synthesis through nitrogen reduction reaction (NRR). However, the present transition metal electrocatalysts still suffer from low activity and Faradaic efficiency due to poor interfacial reaction kinetics. Herein, an interface‐engineered heterojunction, composed of CoS nanosheets anchored on a TiO2 nanofibrous membrane, is developed. As an active matrix, the TiO2 nanofibrous membrane can uniformly confine the CoS nanosheets against agglomeration, and contribute substantially to the NRR performance. The intimate coupling between CoS and TiO2 enables easy carrier transport in between, resulting in fast reaction kinetics at the heterointerface. Moreover, the conductivity and structural integrity of the heterojunction are further enhanced by carbon nanoplating. Profited by this interfacial design, the resulting C@CoS@TiO2 electrocatalyst achieves strikingly high ammonia yield (8.09×10–10 mol s–1 cm–2) and Faradaic efficiency (28.6%), as well as superior long‐term durability.

Catalytic Enantioselective Cyclopropenation of Internal Alkynes: Access to Difluoromethylated Three‐Membered Carbocycles

By Zhi-Qi Zhang, Meng-Meng Zheng, Xiao-Song Xue, Ilan Marek, Fa-Guang Zhang, Jun-An Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Herein we described an expeditious Rh(II)‐catalysed enantioselective cyclopropenation reaction of internal alkynes with a masked difluorodiazoethane reagent (PhSO2CF2CHN2,Ps‐DFA). This asymmetric transformation offers efficient access to a broad range of enantioenriched difluoromethylated cyclopropenes (40 examples, up to 99% yield, 97% ee). The synthetic utility of obtained strained carbocycles is demonstrated by subsequent stereo‐defined processes including cross‐couplings, hydrogenation, Diels‐Alder reaction, and Pauson−Khand reaction.

Alwin Mittasch Prize: P. van Leeuwen / BioTrans Prizes: D. B. Janssen and D. Rother / Tetrahedron Prize for Creativity: P. G. Schultz

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Corrigendum: The cis‐Diammineplatinum(II) Complex of Curcumin: A Dual Action DNA Crosslinking and Photochemotherapeutic Agent

By Koushambi Mitra, Srishti Gautam, Paturu Kondaiah, Akhil R. Chakravarty from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Graphical Abstract: Angew. Chem. Int. Ed. 44/2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Inside Cover: Enantiospecific Desorption Triggered by Circularly Polarized Light (Angew. Chem. Int. Ed. 44/2019)

By Farinaz Mortaheb, Katrin Oberhofer, Johann Riemensberger, Florian Ristow, Reinhard Kienberger, Ulrich Heiz, Hristo Iglev, Aras Kartouzian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Exposing racemic samples of 1,1′‐bi‐2‐naphthol (BINOL) coated onto achiral glass substrates to right or left circularly polarized light leads to preferential desorption of one or the other enantiomer. In their Communication on page 15685 ff., H. Iglev, A. Kartouzian and co‐workers show how this effect can be exploited for contamination‐free enantioenrichment. A simplified phenomenological model suggests that the contribution of quantum mechanical processes should be explored.

Cover Picture: The Three‐Dimensional Dendrite‐Free Zinc Anode on a Copper Mesh with a Zinc‐Oriented Polyacrylamide Electrolyte Additive (Angew. Chem. Int. Ed. 44/2019)

By Qi Zhang, Jingyi Luan, Liang Fu, Shengan Wu, Yougen Tang, Xiaobo Ji, Haiyan Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

A combination of a Cu–Zn solid solution interface on copper mesh with good zinc affinity and a polyacrylamide electrolyte additive (PAM) is developed to modify the zinc anode. As shown by H. Wang et al. in their Communication on page 15841 ff., the Cu–Zn solid solution formed in the initial process can regulate zinc nucleation and PAM can suppress the growth of zinc dendrites in the subsequent cycles. The prepared zinc anodes show a dendrite‐free behavior.

Frontispiece: Molecular Semiconductor Surfactants with Fullerenol Heads and Colored Tails for Carbon Dioxide Photoconversion

By Marius Kunkel, Sebastian Sutter, Sebastian Polarz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Artificial Photosynthesis In their Communication on page 15620 ff., S. Polarz et al. present surfactants consisting of dye molecules and a polyhydroxylated fullerene, which self‐assemble into bilayer vesicles that mimic key functions of photosystems II and I.

Frontispiece: A Polymer Solution To Prevent Nanoclustering and Improve the Selectivity of Metal Nanoparticles for Electrocatalytic CO2 Reduction

By Lei Zhang, Zichao Wei, Srinivas Thanneeru, Michael Meng, Megan Kruzyk, Gaël Ung, Ben Liu, Jie He from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

CO2 Reduction. Polymeric N‐heterocyclic carbene (NHC) ligands are demonstrated to improve catalytic efficiency and lifetime of Au and Pd nanocatalysts for CO2 electroreduction by B. Liu, J. He et al. in their Research Article on page 15834 ff.

Inside Back Cover: Exploiting Coordination Isomerism for Controlled Self‐Assembly (Angew. Chem. Int. Ed. 44/2019)

By Nils Bäumer, Kalathil K. Kartha, Naveen Kumar Allampally, Shiki Yagai, Rodrigo Q. Albuquerque, Gustavo Fernández from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Coordination isomerism can be used to control the morphology of a supramolecular polymer, as G. Fernández et al. show in their Communication on page 15626. Tuning the coordination isomerism of a PtII complex leads to tunable coordination isomerism, which in turn allows fully reversible switching between two distinct aggregate species (1D fibers↔2D lamellae) with different photoresponsive behavior. These observations pave the way for novel stimuli‐responsive materials and offer a new approach for size control in self‐assembled systems.

Back Cover: [UF6]2−: A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments (Angew. Chem. Int. Ed. 44/2019)

By Kasper S. Pedersen, Katie R. Meihaus, Andrei Rogalev, Fabrice Wilhelm, Daniel Aravena, Martín Amoza, Eliseo Ruiz, Jeffrey R. Long, Jesper Bendix, Rodolphe Clérac from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Insights into the electronic properties of actinide ions can be obtained by using X‐ray magnetic circular dichroism spectroscopy. In their Communication on page 15650 ff., K. S. Pedersen, R. Clérac, and co‐workers present the first structurally characterized hexafluorido complex of a tetravalent actinide ion, [UF6]2–. Its non‐magnetic ground state results from an almost perfect cancellation of spin and orbital magnetic moments, which are virtually identical in magnitude but opposite in sign.

Oxysulfide Semiconductors for Photocatalytic Overall Water Splitting with Visible Light

By Guigang Zhang, Xinchen Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

A Y2Ti2O5S2 oxysulfide photocatalyst that is activated and stabilized by Rh/Cr2O3 and IrO2 co‐catalysts achieves efficient photocatalytic overall water splitting when irradiated with 600 nm visible light. The band gap of Y2Ti2O5S2 is a narrow 1.9 eV because Y 3d contributes to the valence band maximum. This Highlight discusses this recent innovation in sulfide‐based photocatalytic materials. Key: conduction (CB) and valence (VB) bands, hydrogen (HEC) and oxygen (OEC) evolution co‐catalysts. Abstract Photocatalytic overall water splitting by sulfide‐based materials is a great challenge because of the poor resilience of such materials against hole oxidation. In a recent study, Domen and co‐workers developed an innovative strategy to stabilize sulfide‐based photocatalysts by hybridizing S 3p with O 2p orbitals to produce oxysulfides in which S2− is stable. Further surface engineering of the oxysulfides with dual co‐catalysts promoted charge separation and interface transfer, thus reducing the charge build‐up that inhibits photocorrosion. The pH value of the reaction mixture is a critical consideration for achieving efficient stoichiometric H2 and O2 evolution by these oxysulfide photocatalysts.

Guiding Drugs to Target‐Harboring Organelles: Stretching Drug‐Delivery to a Higher Level of Resolution

By Sivan Louzoun‐Zada, Qais Z. Jaber, Micha Fridman from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The highest resolution of drug delivery is achieved by targeting molecules to specific subcellular compartments through chemical modifications. This approach can lead to improved clinical efficacy and reduced side effects and to essential chemical probes for cell biology research. Abstract The ratio between the dose of drug required for optimal efficacy and the dose that causes toxicity is referred to as the therapeutic window. This ratio can be increased by directing the drug to the diseased tissue or pathogenic cell. For drugs targeting fungi and malignant cells, the therapeutic window can be further improved by increasing the resolution of drug delivery to the specific organelle that harbors the drug's target. Organelle targeting is challenging and is, therefore, an under‐exploited strategy. Here we provide an overview of recent advances in control of the subcellular distribution of small molecules with the focus on chemical modifications. Highlighted are recent examples of active and passive organelle‐specific targeting by incorporation of organelle‐directing molecular determinants or by chemical modifications of the pharmacophore. The outstanding potential that lies in the development of organelle‐specific drugs is becoming increasingly apparent.

All‐Inorganic CsPbX3 Perovskite Solar Cells: Progress and Prospects

By Jingru Zhang, Gary Hodes, Zhiwen Jin, Shengzhong (Frank) Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Thermally stable and able: All‐inorganic CsPbX3 perovskites (X is halide) have attracted attention owing to their thermally stability for photovoltaic applications. This Review presents the various CsPbX3 materials and the challenges as well as perspectives for the future development of CsPbX3 solar cells. Abstract Recently, lead halide‐based perovskites have become one of the hottest topics in photovoltaic research because of their excellent optoelectronic properties. Among them, organic‐inorganic hybrid perovskite solar cells (PSCs) have made very rapid progress with their power conversion efficiency (PCE) now at 23.7 %. However, the intrinsically unstable nature of these materials, particularly to moisture and heat, may be a problem for their long‐term stability. Replacing the fragile organic group with more robust inorganic Cs+ cations forms the cesium lead halide system (CsPbX3, X is halide) as all‐inorganic perovskites which are much more thermally stable and often more stable to other factors. From the first report in 2015 to now, the PCE of CsPbX3‐based PSCs has abruptly increased from 2.9 % to 17.1 % with much enhanced stability. In this Review, we summarize the field up to now, propose solutions in terms of development bottlenecks, and attempt to boost further research in CsPbX3 PSCs.

Molecular Design Strategy for Ordered Mesoporous Stoichiometric Metal Oxide

By Changyao Wang, Xiaoyue Wan, Linlin Duan, Peiyuan Zeng, Liangliang Liu, Dingyi Guo, Yuan Xia, Ahmed A. Elzatahry, Yongyao Xia, Wei Li, Dongyuan Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Well‐coordinated: Ordered mesoporous Ti3+‐doped Li4Ti5O12 nanocrystal frameworks were synthesized by the stoichiometric cationic coordination assembly process. Abstract A molecular design strategy is used to construct ordered mesoporous Ti3+‐doped Li4Ti5O12 nanocrystal frameworks (OM‐Ti3+‐Li4Ti5O12) by the stoichiometric cationic coordination assembly process. Ti4+/Li+‐citrate chelate is designed as a new molecular precursor, in which the citrate can not only stoichiometrically coordinate Ti4+ with Li+ homogeneously at the atomic scale, but also interact strongly with the PEO segments in the Pluronic F127. These features make the co‐assembly and crystallization process more controllable, thus benefiting for the formation of the ordered mesostructures. The resultant OM‐Ti3+‐Li4Ti5O12 shows excellent rate (143 mAh g−1 at 30 C) and cycling performances (

Polyethylene Aerogels with Combined Physical and Chemical Crosslinking: Improved Mechanical Resilience and Shape‐Memory Properties

By Douriya Khedaioui, Christophe Boisson, Franck D'Agosto, Damien Montarnal from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Taking shape: Polyethylene aerogels with low density and excellent mechanical resilience were obtained by combining and maximizing physical crosslinking, by crystallization, and chemical crosslinking, controlled by hydrosilylation reactions. These materials display remarkable shape‐memory properties. Abstract While the introduction of polymers into aerogels strongly enhances their toughness, truly elastic monolithic aerogels which restore their dimensions upon extensive compression are still challenging to synthesize. In this context hydrophobic semi‐crystalline polymers with low glass transition temperatures, and combined stiffness and flexibility, have only recently attracted attention. Shown here is that polyethylene aerogels with a low density, and combined chemical crosslinking and high crystallinity, display high moduli and excellent mechanical resilience. To maximize the crystallinity of these aerogels while maintaining a high crosslinking density, polyethylene networks with well‐defined segments were synthesized by hydrosilylation crosslinking of telechelic, vinyl‐functionalized oligomers obtained from catalyzed chain‐growth polymerization. Recoverable deformations both above and below the melting temperature of polyethylene affords remarkable shape‐memory properties.

Photo‐induced and Rapid Labeling of Tetrazine‐Bearing Proteins via Cyclopropenone‐Caged Bicyclononynes

By Susanne V. Mayer, Anton Murnauer, Marie‐Kristin Wrisberg, Marie‐Lena Jokisch, Kathrin Lang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Light‐induced protein labeling: Cyclopropenone‐caged dibenzoannulated bicyclononynes (photo‐DMBO) are photo‐activatable dienophiles that engage in rapid inverse electron‐demand Diels–Alder cycloadditions with tetrazines upon light‐induced decarbonylation. Site‐specific incorporation of methyl‐tetrazine amino acids allows photo‐induced protein labeling in living cells with spatio‐temporal control using photo‐DMBO fluorophore conjugates. Abstract Inverse electron‐demand Diels–Alder cycloadditions (iEDDAC) between tetrazines and strained alkenes/alkynes have emerged as essential tools for studying and manipulating biomolecules. A light‐triggered version of iEDDAC (photo‐iEDDAC) is presented that confers spatio‐temporal control to bioorthogonal labeling in vitro and in cellulo. A cyclopropenone‐caged dibenzoannulated bicyclo[6.1.0]nonyne probe (photo‐DMBO) was designed that is unreactive towards tetrazines before light‐activation, but engages in iEDDAC after irradiation at 365 nm. Aminoacyl tRNA synthetase/tRNA pairs were discovered for efficient site‐specific incorporation of tetrazine‐containing amino acids into proteins in living cells. In situ light activation of photo‐DMBO conjugates allows labeling of tetrazine‐modified proteins in living E. coli. This allows proteins in living cells to be modified in a spatio‐temporally controlled manner and may be extended to photo‐induced and site‐specific protein labeling in animals.

Electrochemical Oxidation of 5‐Hydroxymethylfurfural on Nickel Nitride/Carbon Nanosheets: Reaction Pathway Determined by In Situ Sum Frequency Generation Vibrational Spectroscopy

By Nana Zhang, Yuqin Zou, Li Tao, Wei Chen, Ling Zhou, Zhijuan Liu, Bo Zhou, Gen Huang, Hongzhen Lin, Shuangyin Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

To sum up: A carbon‐coupled nickel nitride nanosheet was employed as an efficient electrocatalyst for 5‐hydroxymethylfurfural (HMF) oxidation. In situ sum frequency generation (SFG) spectroscopy was used to explore the HMF electrooxidation process, and confirmed that the oxidation pathway proceeds via 5‐hydroxymethyl‐2‐furancarboxylic acid (HMFCA). Abstract 2,5‐Furandicarboxylic acid was obtained from the electrooxidation of 5‐hydroxymethylfurfural (HMF) with non‐noble metal‐based catalysts. Moreover, combining the biomass oxidation with the hydrogen evolution reaction (HER) increased the energy conversion efficiency of an electrolyzer and also generated value‐added products at both electrodes. Here, the reaction pathway on the surface of a carbon‐coupled nickel nitride nanosheet (Ni3N@C) electrode was evaluated by surface‐selective vibrational spectroscopy using sum frequency generation (SFG) during the electrochemical oxidation. The Ni3N@C electrode shows catalytic activities for HMF oxidation and the HER. As the first in situ SFG study on transition‐metal nitride for the electrooxidation upgrade of HMF, this work not only demonstrates that the reaction pathway of electrochemical oxidation but also provides an opportunity for nonprecious metal nitrides to simultaneously upgrade biomass and produce H2 under ambient conditions.

Real‐Time In‐Situ Monitoring of a Tunable Pentapeptide Gel–Crystal Transition

By Tom Guterman, Maayan Levin, Sofiya Kolusheva, Davide Levy, Nadav Noor, Yael Roichman, Ehud Gazit from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Unusual phase tester: An accessible pentapeptide system for studying gel–crystal phase transitions in supramolecular gels is introduced. The system allows to continuously measure the kinetics and visualize the dynamics of this common gel‐destabilizing phase‐transition process in situ using non‐destructive microscopy‐based methodology. Abstract Supramolecular gels often become destabilized by the transition of the gelator into a more stable crystalline phase, but often the long timescale and sporadic localization of the crystalline phase preclude a persistent observation of this process. We present a pentapeptide gel–crystal phase transition amenable for continuous visualization and quantification by common microscopic methods, allowing the extraction of kinetics and visualization of the dynamics of the transition. Using optical microscopy and microrheology, we show that the transition is a sporadic event in which gel dissolution is associated with microcrystalline growth that follows a sigmoidal rate profile. The two phases are based on β‐sheets of similar yet distinct configuration. We also demonstrate that the transition kinetics and crystal morphology can be modulated by extrinsic factors, including temperature, solvent composition, and mechanical perturbation. This work introduces an accessible model system and methodology for studying phase transitions in supramolecular gels.

Interplay of Atomic Interactions in the Intermetallic Semiconductor Be5Pt

By Alfred Amon, Eteri Svanidze, Alim Ormeci, Marcus König, Deepa Kasinathan, Daisuke Takegami, Yurii Prots, Yen‐Fa Liao, Ku‐Ding Tsuei, Liu Hao Tjeng, Andreas Leithe‐Jasper, Yuri Grin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Progressive metals: Be5Pt is a rare representative of semiconductors that are formed by metallic elements only. The gap in the band structure appears due to both relativistic effects and a unique chemical‐bonding situation with polar two‐atom and multi‐atom Pt–Be interactions. Abstract Semiconducting substances form one of the most important families of functional materials. However, semiconductors containing only metals are very rare. The chemical mechanisms behind their ground‐state properties are only partially understood. Our investigations have rather unexpectedly revealed the semiconducting behaviour (band gap of 190 meV) for the intermetallic compound Be5Pt formed at a very low valence‐electron count. Quantum‐chemical analysis shows strong charge transfer from Be to Pt and reveals a three‐dimensional entity of vertex‐condensed empty Be4 tetrahedrons with multi‐atomic cluster bonds interpenetrated by the framework of Pt‐filled vertex‐condensed Be4 tetrahedrons with two‐atomic polar Be−Pt bonds. The combination of strong Coulomb interactions with relativistic effects results in a band gap.

High‐Precision Size Recognition and Separation in Synthetic 1D Nanochannels

By Ping Wang, Xinyi Chen, Qiuhong Jiang, Matthew Addicoat, Ning Huang, Sasanka Dalapati, Thomas Heine, Fengwei Huo, Donglin Jiang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The right channel: Open 1D channels were able to recognize differences in molecular size when the pores were designed with a triangular shape and discrete size in covalent organic frameworks. This finding introduces the possibility of using 1D channels for selective transport and instant molecular separation with infinite selectivity (see picture). Abstract Covalent organic frameworks (COFs) allow elaborate manufacture of ordered one‐dimensional channels in the crystal. We defined a superlattice of COFs by engineering channels with a persistent triangular shape and discrete pore size. We observed a size‐recognition regime that is different from the characteristic adsorption of COFs, whereby pore windows and walls were cooperative so that triangular apertures sorted molecules of one‐atom difference and notch nanogrooves confined them into single‐file molecular chains. The recognition and confinement were accurately described by sensitive spectroscopy and femtosecond dynamic simulations. The resulting COFs enabled instantaneous separation of mixtures at ambient temperature and pressure. This study offers an approach to merge precise recognition, selective transport, and instant separation in synthetic 1D channels.

Particle‐in‐a‐Frame Nanostructures with Interior Nanogaps

By Seunghoon Lee, Jaeyoung Kim, Hyunwoo Yang, Emiliano Cortés, Seungwoo Kang, Sang Woo Han from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Particle in a frame: Gold particle‐in‐a‐frame nanostructures with well‐defined interior nanogaps were successfully generated through fine control over the galvanic replacement reaction of Ag nanoprisms with Au precursors. The prepared nanostructures exhibited enhanced plasmonic performance owing to their interior nanogaps, which strongly promote the plasmonic field. Abstract Designing plasmonic hollow colloids with small interior nanogaps would allow structural properties to be exploited that are normally linked to an ensemble of particles but within a single nanoparticle. Now, a synthetic approach for constructing a new class of frame nanostructures is presented. Fine control over the galvanic replacement reaction of Ag nanoprisms with Au precursors gave unprecedented Au particle‐in‐a‐frame nanostructures with well‐defined sub‐2 nm interior nanogaps. The prepared nanostructures exhibited superior performance in applications, such as plasmonic sensing and surface‐enhanced Raman scattering, over their solid nanostructure and nanoframe counterparts. This highlights the benefit of their interior hot spots, which can highly promote and maximize the electric field confinement within a single nanostructure.

Programmable Exposure of Pt Active Facets for Efficient Oxygen Reduction

By Guanzhi Wang, Zhenzhong Yang, Yingge Du, Yang Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The unique dynamic oxygen‐bubble template (DOBT) programmably controlled by a square‐wave potential was utilized to tune catalyst morphology and expose Pt active facets in PtNi PFs. PtNi PFs with enriched Pt(111) facets can be obtained by affecting the surface‐adsorbed OH* through adjusting the anodic voltage. Abstract To produce efficient ORR catalysts with low Pt content, PtNi porous films (PFs) with sufficiently exposed Pt active sites were designed by an approach combining electrochemical bottom‐up (electrodeposition) and top‐down (anodization) processes. The dynamic oxygen‐bubble template (DOBT) programmably controlled by a square‐wave potential was used to tune the catalyst morphology and expose Pt active facets in PtNi PFs. Surface‐bounded species, such as hydroxyl (OH*, *=surface site) on the exposed PtNi PFs surfaces were adjusted by the applied anodic voltage, further affecting the dynamic oxygen (O2) bubbles adsorption on Pt. As a result, PtNi PF with enriched Pt(111) facets (denoted as Pt3.5 %Ni PF) was obtained, showing prominent ORR activity with an onset potential of 0.92 V (vs. RHE) at an ultra‐low Pt loading (0.015 mg cm−2).

A Polymer Solution To Prevent Nanoclustering and Improve the Selectivity of Metal Nanoparticles for Electrocatalytic CO2 Reduction

By Lei Zhang, Zichao Wei, Srinivas Thanneeru, Michael Meng, Megan Kruzyk, Gaël Ung, Ben Liu, Jie He from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Ligands for nanocatalysts: Polymeric N‐heterocyclic carbene (NHC) ligands are demonstrated to stabilize Au and Pd nanoparticles for CO2 electroreduction while simultaneously enhancing their selectivity over competitive proton reduction. Abstract The stability of metal nanocatalysts for electrocatalytic CO2 reduction is of key importance for practical application. We report the use of two polymeric N‐heterocyclic carbenes (NHC) (polydentate and monodentate) to stabilize metal nanocatalysts (Au and Pd) for efficient CO2 electroreduction. Compared with other conventional ligands including thiols and amines, metal–carbene bonds that are stable under reductive potentials prevent the nanoclustering of nanoparticles. Au nanocatalysts modified by polymeric NHC ligands show an activity retention of 86 % after CO2 reduction at −0.9 V for 11 h, while it is less than 10 % for unmodified Au. We demonstrate that the hydrophobicity of polymer ligands and the enriched surface electron density of metal NPs through σ‐donation of NHCs substantially improve the selectivity for CO2 reduction over proton.

A Genetically Encoded, Phage‐Displayed Cyclic‐Peptide Library

By Xiaoshan Shayna Wang, Peng‐Hsun Chase Chen, J. Trae Hampton, Jeffery M. Tharp, Catrina A. Reed, Sukant K. Das, Duen‐Shian Wang, Hamed S. Hayatshahi, Yang Shen, Jin Liu, Wenshe Ray Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Using amber‐codon suppression, Nϵ‐acryloyl‐lysine was genetically encoded in a phage‐displayed peptide library for cyclization with a pre‐installed cysteine. Selection from this phage‐display library afforded cyclic peptides that bind TEV protease and histone deacetylase, HDAC8, much more strongly than their linear counterparts. Abstract Superior to linear peptides in biological activities, cyclic peptides are considered to have great potential as therapeutic agents. To identify cyclic‐peptide ligands for therapeutic targets, phage‐displayed peptide libraries in which cyclization is achieved by the covalent conjugation of cysteines have been widely used. To resolve drawbacks related to cysteine conjugation, we have invented a phage‐display technique in which its displayed peptides are cyclized through a proximity‐driven Michael addition reaction between a cysteine and an amber‐codon‐encoded Nϵ‐acryloyl‐lysine (AcrK). Using a randomized 6‐mer library in which peptides were cyclized at two ends through a cysteine–AcrK linker, we demonstrated the successful selection of potent ligands for TEV protease and HDAC8. All selected cyclic peptide ligands showed 4‐ to 6‐fold stronger affinity to their protein targets than their linear counterparts. We believe this approach will find broad applications in drug discovery.

Organocatalytic Enantioselective Functionalization of Unactivated Indole C(sp3)−H Bonds

By Dengke Ma, Zhihan Zhang, Min Chen, Zhenyang Lin, Jianwei Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Not just one, but two: An organocatalytic asymmetric functionalization of unactivated benzylic C(sp3)−H bonds of alkyl indoles with trifluoropyruvates was developed with high enantioselectivity. Mechanistic studies and DFT calculations show an unusual mechanism, including the first installation of a trifluoropyruvate electrophile at C3 of indoles, towards the formation of the key enamine nucleophile, followed by the addition of the second trifluoropyruvate. Abstract Described here is a direct catalytic asymmetric functionalization of unactivated alkyl indoles using organocatalysis. In the presence of an effective chiral urea catalyst and a phosphoric acid additive, the intermolecular C−C bond formation between alkyl indoles and trifluoropyruvates proceeded with high efficiency and enantiocontrol. Unlike previous asymmetric C(sp3−H) functionalizations of α‐azaarenes, this process does not require the use of either a strong base or an electron‐deficient substrate. The excellent enantiocontrol is particularly noteworthy in view of the severe background reaction as well as the complete inability of other types of catalysts evaluated. Control experiments, kinetic studies, and DFT calculations provided important insights into the mechanism.

The Three‐Dimensional Dendrite‐Free Zinc Anode on a Copper Mesh with a Zinc‐Oriented Polyacrylamide Electrolyte Additive

By Qi Zhang, Jingyi Luan, Liang Fu, Shengan Wu, Yougen Tang, Xiaobo Ji, Haiyan Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

A dendrite‐free zinc plating behavior was achieved by combining a Cu‐Zn solid solution interface on a copper mesh skeleton and polyacrylamide electrolyte additive. The zinc ion has strong selective adsorption on the acyl group of polyacrylamide and can be transferred along the polymer chains, leading to the homogeneous zinc distribution. Abstract Rechargeable aqueous zinc‐ion batteries have been considered as a promising candidate for next‐generation batteries. However, the formation of zinc dendrites are the most severe problems limiting their practical applications. To develop stable zinc metal anodes, a synergistic method is presented that combines the Cu‐Zn solid solution interface on a copper mesh skeleton with good zinc affinity and a polyacrylamide electrolyte additive to modify the zinc anode, which can greatly reduce the overpotential of the zinc nucleation and increase the stability of zinc deposition. The as‐prepared zinc anodes show a dendrite‐free plating/stripping behavior over a wide range of current densities. The symmetric cell using this dendrite‐free anode can be cycled for more than 280 h with a very low voltage hysteresis (93.1 mV) at a discharge depth of 80 %. The high capacity retention and low polarization are also realized in Zn/MnO2 full cells.

Computationally Driven Discovery of a Family of Layered LiNiB Polymorphs

By Volodymyr Gvozdetskyi, Gourab Bhaskar, Maria Batuk, Xin Zhao, Renhai Wang, Scott L. Carnahan, Michael P. Hanrahan, Raquel A. Ribeiro, Paul C. Canfield, Aaron J. Rossini, Cai‐Zhuang Wang, Kai‐Ming Ho, Joke Hadermann, Julia V. Zaikina from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

By design: Novel lithium nickel borides with unique layered structures were theoretically predicted and synthesized. Their structures are composed of [NiB] layers with different topologies alternating with layers of Li cations (see picture). These compounds are ultimate precursors for further exfoliation to generate 2D transition‐metal borides, known as MBenes. Abstract Two novel lithium nickel boride polymorphs, RT‐LiNiB and HT‐LiNiB, with layered crystal structures are reported. This family of compounds was theoretically predicted by using the adaptive genetic algorithm (AGA) and subsequently synthesized by a hydride route with LiH as the lithium source. Unique among the known ternary transition‐metal borides, the LiNiB structures feature Li layers alternating with nearly planar [NiB] layers composed of Ni hexagonal rings with a B–B pair at the center. A comprehensive study using a combination of single crystal/synchrotron powder X‐ray diffraction, solid‐state 7Li and 11B NMR spectroscopy, scanning transmission electron microscopy, quantum‐chemical calculations, and magnetism has shed light on the intrinsic features of these polymorphic compounds. The unique layered structures of LiNiB compounds make them ultimate precursors for exfoliation studies, thus paving a way toward two‐dimensional transition‐metal borides, MBenes.

A Dual Plating Battery with the Iodine/[ZnIx(OH2)4−x]2−x Cathode

By Jessica J. Hong, Liangdong Zhu, Cheng Chen, Longteng Tang, Heng Jiang, Bei Jin, Trenton C. Gallagher, Qiubo Guo, Chong Fang, Xiulei Ji from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

A highly reversible iodine plating cathode is presented that operates on the redox couples of I2/[ZnIx(OH2)4−x]2−x in a water‐in‐salt electrolyte. The iodine plating cathode with the theoretical capacity of 211 mAh g−1 plates on carbon fiber paper as the current collector, delivering a large areal capacity of 4 mAh cm−2. Abstract Plating battery electrodes typically deliver higher specific capacity values than insertion or conversion electrodes because the ion charge carriers represent the sole electrode active mass, and a host electrode is unnecessary. However, reversible plating electrodes are rare for electronically insulating nonmetals. Now, a highly reversible iodine plating cathode is presented that operates on the redox couples of I2/[ZnIx(OH2)4−x]2−x in a water‐in‐salt electrolyte. The iodine plating cathode with the theoretical capacity of 211 mAh g−1 plates on carbon fiber paper as the current collector, delivering a large areal capacity of 4 mAh cm−2. Tunable femtosecond stimulated Raman spectroscopy coupled with DFT calculations elucidate a series of [ZnIx(OH2)4−x]2−x superhalide ions serving as iodide vehicles in the electrolyte, which eliminates most free iodide ions, thus preventing the consequent dissolution of the cathode‐plated iodine as triiodides.

Designed Negative Feedback from Transiently Formed Catalytic Nanostructures

By Syed Pavel Afrose, Subhajit Bal, Ayan Chatterjee, Krishnendu Das, Dibyendu Das from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Burst catalysis: A substrate‐induced transient helical morphology was accessed as a self‐assembled state. Critically, burst hydrolytic rates of substrates result in disassembly, thus mimicking the dynamic instability of microtubules. Abstract Highly dynamic and complex systems of microtubules undergo a substrate‐induced change of conformation that leads to polymerization. Owing to the augmented catalytic potential at the polymerized state, rapid hydrolysis of the substrate is observed, leading to catastrophe, thus realizing the out‐of‐equilibrium state. A simple synthetic mimic of these dynamic natural systems is presented, where similar substrate induced conformational change is observed and a transient helical morphology is accessed. Further, augmented catalytic potential of these helical nanostructures leads to rapid hydrolysis of the substrate providing negative feedback on the stability of the nanostructures and realization of an out‐of‐equilibrium state. This simple system, made from amino acid functionalized lipids, demonstrates a substrate‐induced self‐assembled state, where the fuel‐to‐waste conversion leads to the temporal presence of helical nanostructures.

Crosslinking Allosteric Sites on the Nucleosome

By Lucinda K. Batchelor, Louis De Falco, Thibaud Erlach, Deepti Sharma, Zenita Adhireksan, Ursula Roethlisberger, Curt A. Davey, Paul J. Dyson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Nucleosomal allostery: Inspired by the binding of RAPTA‐T on the nucleosome core, which triggers a cascade of allosteric modifications to allow auranofin to bind at a distant site, a hetero‐bimetallic compound was designed that bridges the two sites and impacts the activity of nucleosomes. Abstract Targeting defined histone protein sites in chromatin is an emerging therapeutic approach that can potentially be enhanced by allosteric effects within the nucleosome. Here we characterized a novel hetero‐bimetallic compound with a design based on a nucleosomal allostery effect observed earlier for two unrelated drugs—the RuII antimetastasis/antitumor RAPTA‐T and the AuI anti‐arthritic auranofin. The RuII moiety binds specifically to two H2A glutamate residues on the nucleosome acidic patch, allosterically triggering a cascade of structural changes that promote binding of the AuI moiety to selective histidine residues on H3, resulting in cross‐linking sites that are over 35 Å distant. By tethering the H2A‐H2B dimers to the H3‐H4 tetramer, the hetero‐bimetallic compound significantly increases stability of the nucleosome, illustrating its utility as a site‐selective cross‐linking agent.

Tuning the Chemistry of Organonitrogen Compounds for Promoting All‐Organic Anionic Rechargeable Batteries

By Alia Jouhara, Eric Quarez, Franck Dolhem, Michel Armand, Nicolas Dupré, Philippe Poizot from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Charging ahead: The development of anion–ion batteries is possible by combining the benefits of p‐type organic redox‐active materials and molecular engineering to tune their working potentials. The pairing of an aromatic diamine as the positive electrode with a zwitterionic bipyridinium carboxylate compound as the negative electrode resulted in the assembly of an all‐organic anionic battery. Abstract The ever‐increasing demand for rechargeable batteries induces significant pressure on the worldwide metal supply, depleting resources and increasing costs and environmental concerns. In this context, developing the chemistry of anion‐inserting electrode organic materials could promote the fabrication of molecular (metal‐free) rechargeable batteries. However, few examples have been reported because little effort has been made to develop such anionic‐ion batteries. Here we show the design of two anionic host electrode materials based on the N‐substituted salts of azaaromatics (zwitterions). A combination of NMR, EDS, FTIR spectroscopies coupled with thermal analyses and single‐crystal XRD allowed a thorough structural and chemical characterization of the compounds. Thanks to a reversible electrochemical activity located at an average potential of 2.2 V vs. Li+/Li, the coupling with dilithium 2,5‐(dianilino)terephthalate (Li2DAnT) as the positive electrode enabled the fabrication of the first all‐organic anionic rechargeable batteries based on crystallized host electrode materials capable of delivering a specific capacity of ≈27 mAh/gelectrodes with a stable cycling over dozens of cycles (≈24 Wh/kgelectrodes).

Preparation of Polyfunctional Biaryl Derivatives by Cyclolanthanation of 2‐Bromobiaryls and Heterocyclic Analogues Using nBu2LaCl⋅4 LiCl

By Baosheng Wei, Dongchao Zhang, Yi‐Hung Chen, Aiwen Lei, Paul Knochel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

One stone, four birds: Various 2‐bromobiaryl derivatives undergo a smooth cyclolanthanation upon reaction with nBu2LaCl⋅4 LiCl. The resulting cyclometalated lanthanum reagents are versatile intermediates for the facile preparation of valuable polyfunctional biaryl derivatives. X‐ray absorption fine structure (XAFS) measurements rationalize the proposed structures of the involved organolanthanum species. Abstract Various aryl‐ and heteroaryl‐substituted 2‐bromobiaryls are converted to cyclometalated lanthanum intermediates by reaction with nBu2LaCl⋅4 LiCl. These resulting lanthanum heterocycles are key intermediates for the facile preparation of functionalized 2,2′‐diiodobiaryls, silafluorenes, fluoren‐9‐ones, phenanthrenes, and their related heterocyclic analogues. X‐ray absorption fine structure (XAFS) spectroscopy was used to rationalize the proposed structures of the involved organolanthanum species.

Transition‐Metal‐Free Reductive Hydroxymethylation of Isoquinolines

By Benjamin M. Reeves, Hamish B. Hepburn, Alexandru Grozavu, Peter J. Lindsay‐Scott, Timothy J. Donohoe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Reductive Functionalization: The transition‐metal‐free synthesis of tetrahydroisoquinolines that bear a quaternary center through a reductive hydroxymethylation process is reported. It is a simple and robust method using cheap and accessible reagents to prepare complex heterocyclic motifs. Abstract A transition‐metal‐free reductive hydroxymethylation reaction has been developed, enabling the preparation of tetrahydroisoquinolines bearing C4‐quaternary centers from the corresponding isoquinolines. Deuterium labelling studies and control experiments enable a potential mechanism to be elucidated which features a key Cannizzaro‐type reduction followed by an Evans–Tishchenko reaction. When isoquinolines featuring a proton at the 4‐position are used, a tandem methylation‐hydroxymethylation occurs, leading to the formation of 2 new C−C bonds in one pot.

The Surface Activity of the Hydrated Proton Is Substantially Higher than That of the Hydroxide Ion

By Sudipta Das, Mischa Bonn, Ellen H. G. Backus from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

At the border: The relative surface propensity of hydrated proton and hydroxide at the D2O–air interface in the presence of excess D3O+/OD− was determined by probing the stretching vibration of interfacial water with sum‐frequency generation spectroscopy. The hydrated proton is found to be orders of magnitude more surface active than the hydroxide ion. Abstract The behavior of hydroxide and hydrated protons, the auto‐ionization products of water, at surfaces is important for a wide range of applications and disciplines. However, it is unknown at which bulk concentration these ions start to become surface active at the water–air interface. Here, we report changes in the D2O–air interface in the presence of excess D+hyd/OD−hyd determined using surface‐sensitive vibrational sum‐frequency generation (SFG) spectroscopy. The onset of the perturbation of the D2O surface occurs at a bulk concentration as low as 2.7±0.2 mm D+hyd. In contrast, a concentration of several hundred mm OD−hyd is required to change the D2O surface. The hydrated proton is thus orders of magnitude more surface‐active than hydroxide at the water–air interface.

[UF6]2−: A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments

By Kasper S. Pedersen, Katie R. Meihaus, Andrei Rogalev, Fabrice Wilhelm, Daniel Aravena, Martín Amoza, Eliseo Ruiz, Jeffrey R. Long, Jesper Bendix, Rodolphe Clérac from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The electronic ground state of the weakly magnetic UIV was studied in great detail for the simple structurally characterized [UF6]2− anion, combining X‐ray absorption spectroscopy, magnetometry, and quantum‐chemical calculations. The decomposition and quantification of the relatively large spin and orbital magnetic moments provide key information for an improved understanding of the complex electronic structures of actinide ions. Abstract The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6]2− anion, is reported in the (NEt4)2[UF6]⋅2 H2O salt (1). The weak magnetic response of 1 results from both UIV spin and orbital contributions, as established by combining X‐ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non‐magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.

Modular Approach to Degradable Acetal Polymers Using Cascade Enyne Metathesis Polymerization

By Liangbing Fu, Xuelin Sui, Alex E. Crolais, Will R. Gutekunst from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Well‐defined polyacetals are designed that readily degrade in aqueous environments through the use of enyne metathesis polymerization. This approach permits modular design of the monomer scaffolds, and post‐polymerization functionalization with triazolinediones modulates the rate of hydrolytic degradation. Abstract A modular synthetic approach to degradable metathesis polymers is presented using acetal‐containing enyne monomers. The monomers are prepared in a short and divergent synthetic sequence that features two points of modification to tune polymerization behavior and introduce molecular cargo. Steric and stereochemical elements are critical in the monomer design in order to provide rapid and living polymerizations capable of generating block polymers. The developed polyacetal materials readily undergo pH‐dependent degradation in aqueous mixtures, and the rate of hydrolysis can be tuned through post‐polymerization modification with triazolinedione click chemistry. This presents a new scaffold for responsive metathesis polymers that may find use in applications that requires controllable breakdown and release of small molecules.

Stable 2D Heteroporous Covalent Organic Frameworks for Efficient Ionic Conduction

By Zhen Xie, Bo Wang, Zongfan Yang, Xiao Yang, Xiang Yu, Guolong Xing, Yinghui Zhang, Long Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Planarization‐enhanced stability: Dibenzo[g,p]chrysene (DBC), a “closed” version of tetraphenylethene (4PE), was integrated into a 2D heteroporous imine covalent organic framework (COF). The resulting DBC‐COF exhibited much better crystallinity and stability than its counterpart 4PE‐COF, and is a promising host material for ionic conduction. Abstract Two‐dimensional (2D) covalent organic frameworks (COFs) feature open and ordered one‐dimensional column nanochannels which offer immense possibilities for incorporation of various guests for specific functions. However, the relatively low chemical stability of most COFs originating from the dynamic covalent linkages hinders their practical application. In this work, a highly crystalline and heteroporous dibenzo[g,p]chrysene‐based COF (DBC‐2P) was synthesized and served as a host material for ionic conduction. DBC‐2P exhibits excellent stability both in strong acid and base due to the large conjugated DBC‐based knot that reinforces the interlayer interactions. Subsequent encapsulation of linear polyethylene glycol (PEG) and PEG‐LiBF4 salt into the nanochannels of DBC‐2P affords a hybrid material with a high ionic conductivity of 2.31×10−3 S cm−1. This work demonstrates an efficient post‐synthetic strategy for the development of new COF–polymer composites with intriguing properties.

A Chalcogen‐Bonding Cascade Switch for Planarizable Push–Pull Probes

By Mariano Macchione, Antoine Goujon, Karolina Strakova, Heorhii V. Humeniuk, Giuseppe Licari, Emad Tajkhorshid, Naomi Sakai, Stefan Matile from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

For the demonstration of physical forces in biology, a general concept in supramolecular chemistry that focuses on chalcogen bonds is introduced to access the desired stable, evolvable mechanochemistry tools. The source of inspiration of their rational design is illustrated in freeze–thaw cycles in DMSO. Abstract Planarizable push–pull probes have been introduced to demonstrate physical forces in biology. However, the donors and acceptors needed to polarize mechanically planarized probes are incompatible with their twisted resting state. The objective of this study was to overcome this “flipper dilemma” with chalcogen‐bonding cascade switches that turn on donors and acceptors only in response to mechanical planarization of the probe. This concept is explored by molecular dynamics simulations as well as chemical double‐mutant cycle analysis. Cascade switched flipper probes turn out to excel with chemical stability, red shifts adding up to high significance, and focused mechanosensitivity. Most important, however, is the introduction of a new, general and fundamental concept that operates with non‐trivial supramolecular chemistry, solves an important practical problem and opens a wide chemical space.

Scaled‐Up Synthesis of Amorphous NiFeMo Oxides and Their Rapid Surface Reconstruction for Superior Oxygen Evolution Catalysis

By Yu Duan, Zi‐You Yu, Shao‐Jin Hu, Xu‐Sheng Zheng, Chu‐Tian Zhang, Hong‐He Ding, Bi‐Cheng Hu, Qi‐Qi Fu, Zhi‐Long Yu, Xiao Zheng, Jun‐Fa Zhu, Min‐Rui Gao, Shu‐Hong Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Amorphous NiFeMo oxide (up to 515 g one batch) with homogeneous elemental distribution was synthesized through a facile supersaturated co‐precipitation method. The amorphous NiFeMo oxide undergoes rapid surface self‐reconstruction during OER that forms a metal oxy(hydroxide) active layer with oxygen vacancies, enabling efficient OER catalysis. Abstract The anode oxygen evolution reaction (OER) is known to largely limit the efficiency of electrolyzers owing to its sluggish kinetics. While crystalline metal oxides are promising as OER catalysts, their amorphous phases also show high activities. Efforts to produce amorphous metal oxides have progressed slowly, and how an amorphous structure benefits the catalytic performances remains elusive. Now the first scalable synthesis of amorphous NiFeMo oxide (up to 515 g in one batch) is presented with homogeneous elemental distribution via a facile supersaturated co‐precipitation method. In contrast to its crystalline counterpart, amorphous NiFeMo oxide undergoes a faster surface self‐reconstruction process during OER, forming a metal oxy(hydroxide) active layer with rich oxygen vacancies, leading to superior OER activity (280 mV overpotential at 10 mA cm−2 in 0.1 m KOH). This opens up the potential of fast, facile, and scale‐up production of amorphous metal oxides for high‐performance OER catalysts.

Exploring Lead‐Free Hybrid Double Perovskite Crystals of (BA)2CsAgBiBr7 with Large Mobility‐Lifetime Product toward X‐Ray Detection

By Zhiyun Xu, Xin Liu, Yaobin Li, Xitao Liu, Tao Yang, Chengmin Ji, Shiguo Han, Yadong Xu, Junhua Luo, Zhihua Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Finding X‐rays: Single crystals of a lead‐free hybrid double perovskite, (BA)2CsAgBiBr7 (BA+: n‐Butylammonium), adopting a unique 2D multilayered quantum‐confined motif, can serve as a potential X‐ray detecting material. This promise stems from the large μτ product of 1.21×10−3 cm2 V−1, high bulk resistivity, low trap density, and efficient X‐ray attenuation. Abstract Halide double perovskites have recently bloomed as the green candidates for optoelectronic applications, such as X‐ray detection. Despite great efforts, the exploration of promising organic–inorganic hybrid double perovskites toward X‐ray detection remains unsuccessful. Now, single crystals of the lead‐free hybrid double perovskite, (BA)2CsAgBiBr7 (BA+ is n‐butylammonium), featuring the unique 2D multilayered quantum‐confined motif, enable quite large μτ (mobility‐lifetime) product up to 1.21×10−3 cm2 V−1. This figure‐of‐merit realized in 2D hybrid double perovskites is unprecedented and comparable with that of CH3NH3PbI3 wafers. (BA)2CsAgBiBr7 crystals also exhibit other intriguing attributes for X‐ray detection, including high bulk resistivity, low density of defects and traps, and large X‐ray attenuation coefficient. Consequently, a vertical‐structure crystal device under X‐ray source yields a superior sensitivity of 4.2 μC Gyair−1 cm−2.

Carbene‐Catalyzed Desymmetrization and Direct Construction of Arenes with All‐Carbon Quaternary Chiral Center

By Tingshun Zhu, Yingguo Liu, Marie Smetankova, Shitian Zhuo, Chengli Mou, Huifang Chai, Zhichao Jin, Yonggui Robin Chi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Indane formation: A one‐step organic catalytic strategy for enantioselective access to indanes with an all‐carbon quaternary center is disclosed. The reaction involves an N‐heterocyclic carbene (NHC) catalyzed process for direct arene construction, indane formation, remote‐carbon desymmetrization, and excellent chirality control. This approach enables the concise synthesis of arene‐containing molecules, including those having complex structures and challenging chiral centers. Abstract Multisubstituted arenes such as indanes with attached all‐carbon quaternary centers are unique scaffolds in synthetic functional molecules and sophisticated natural products. A key challenge in preparing such molecules lies in the enantioselective installation of the quaternary carbon centers. Conventional methods in this direction include asymmetric substitution reactions and substrate‐controlled cyclization reactions. These reactions lead to poor stereoselectivities and/or require long and tedious synthetic steps. Disclosed here is a one‐step organic catalytic strategy for enantioselective access to this class of molecules. The reaction involves an N‐heterocyclic carbene catalyzed process for direct benzene construction, indane formation, remote‐carbon desymmetrization, and excellent chirality control. This approach will enable the concise synthesis of arene‐containing molecules, including those with complex structures and challenging chiral centers.

Supported Intermetallic PdZn Nanoparticles as Bifunctional Catalysts for the Direct Synthesis of Dimethyl Ether from CO‐Rich Synthesis Gas

By Manuel Gentzen, Dmitry E. Doronkin, Thomas L. Sheppard, Anna Zimina, Haisheng Li, Jelena Jelic, Felix Studt, Jan‐Dierk Grunwaldt, Jörg Sauer, Silke Behrens from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Zinc‐stabilized palladium colloids with a size of about 2 nm are the key building units for bifunctional syngas‐to‐dimethyl ether catalysts with enhanced stability, longevity, and high dimethyl ether selectivity. The catalysts were characterized by combining high‐pressure operando X‐ray absorption spectroscopy and DFT calculations. Abstract The single‐step syngas‐to‐dimethyl ether (STD) process entails economic and technical advantages over the current industrial two‐step process. Pd/ZnO‐based catalysts have recently emerged as interesting alternatives to currently used Cu/ZnO/Al2O3 catalysts, but the nature of the active site(s), the reaction mechanism, and the role of Pd and ZnO in the solid catalyst are not well established. Now, Zn‐stabilized Pd colloids with a size of 2 nm served as the key building blocks for the methanol active component in bifunctional Pd/ZnO‐γ‐Al2O3 catalysts. The catalysts were characterized by combining high‐pressure operando X‐ray absorption spectroscopy and DFT calculations. The enhanced stability, longevity, and high dimethyl ether selectivity observed makes Pd/ZnO‐γ‐Al2O3 an effective alternative system for the STD process compared to Cu/ZnO/γ‐Al2O3.

Enantiospecific Desorption Triggered by Circularly Polarized Light

By Farinaz Mortaheb, Katrin Oberhofer, Johann Riemensberger, Florian Ristow, Reinhard Kienberger, Ulrich Heiz, Hristo Iglev, Aras Kartouzian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Light fantastic: By applying right (RCP) or left (LCP) circularly polarized light to racemic samples of 1,1′‐bi‐2‐naphthol (BINOL) coated onto achiral glass substrates, preferential desorption of enantiomers can be achieved, thereby providing contamination‐free enantioenrichment. There are no known mechanisms for this phenomenon, and a simplified phenomenological model suggests that the contribution of quantum mechanical processes should be revisited. Abstract The interest in enantioseparation and enantiopurification of chiral molecules has been drastically increasing over the past decades, since these are important steps in various disciplines such as pharmaceutical industry, asymmetric catalysis, and chiral sensing. By exposing racemic samples of BINOL (1,1′‐bi‐2‐naphthol) coated onto achiral glass substrates to circularly polarized light, we unambiguously demonstrate that by controlling the handedness of circularly polarized light, preferential desorption of enantiomers can be achieved. There are currently no mechanisms known that would describe this phenomenon. Our observation together with a simplified phenomenological model suggests that the process of laser desorption needs to be further developed and the contribution of quantum mechanical processes should be revisited to account for these data. Asymmetric laser desorption provides us with a contamination‐free technique for the enantioenrichment of chiral compounds.

Tricoordinate Nontrigonal Pnictogen‐Centered Radical Anions: Isolation, Characterization, and Reactivity

By Manas Kumar Mondal, Li Zhang, Zhongtao Feng, Shuxuan Tang, Rui Feng, Yue Zhao, Gengwen Tan, Huapeng Ruan, Xinping Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The selective one‐electron reduction of nontrigonal R3E compounds (E=P, As, Sb) afforded the first stable tricoordinate pnictogen‐centered radical anion salts; the pnictogen atoms retain a planar T‐shaped structure. EPR spectroscopy and calculations reveal that the spin density mainly resides at the p orbital of the pnictogen atom, which is perpendicular to the N3E plane. Abstract The search for main‐group element‐based radicals is one of the main research topics in contemporary chemistry because of their fascinating chemical and physical properties. The Group 15 element‐centered radicals mainly feature a V‐shaped two coordinate structure, with a couple of radical cations featuring trigonal tricoordinated geometry. Now, nontrigonal compounds R3E (E=P, As, Sb) were successfully synthesized by introducing a new rigid tris‐amide ligand. The selective one‐electron reduction of R3E afforded the first stable tricoordinate pnictogen‐centered radical anion salts; the pnictogen atoms retain planar T‐shaped structures. EPR spectroscopy and calculations reveal that the spin density mainly resides at the p orbitals of the pnictogen atoms, which is perpendicular to the N3E planes.

Peptide Brush Polymers for Efficient Delivery of a Gene Editing Protein to Stem Cells

By Angela P. Blum, David A. Nelles, Francisco J. Hidalgo, Mollie A. Touve, Deborah S. Sim, Assael A. Madrigal, Gene W. Yeo, Nathan C. Gianneschi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

(B)rush delivery: The efficient delivery of an active DNA‐modifying enzyme to human stem cells through high‐density cell penetrating peptide brush polymers is reported. Brush polymer formulations utilizing cell penetrating peptides could promote delivery of Cre recombinase, whereas oligopeptides alone or oligopeptides displayed on nanoparticles did not. Abstract The scarcity of effective means to deliver functional proteins to living cells is a central problem in biotechnology and medicine. Herein, we report the efficient delivery of an active DNA‐modifying enzyme to human stem cells through high‐density cell penetrating peptide brush polymers. Cre recombinase is mixed with a fluorophore‐tagged polymer carrier and then applied directly to induced pluripotent stem cells or HEK293T cells. This results in efficient delivery of Cre protein as measured by activation of a genomically integrated Cre‐mediated recombination reporter. We observed that brush polymer formulations utilizing cell penetrating peptides promoted Cre delivery but oligopeptides alone or oligopeptides displayed on nanoparticles did not. Overall, we report the efficient delivery of a genome‐modifying enzyme to stem cells that may be generalizable to other, difficult‐to‐transduce cell types.

Arene‐Free Ruthenium(II/IV)‐Catalyzed Bifurcated Arylation for Oxidative C−H/C−H Functionalizations

By Torben Rogge, Lutz Ackermann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

One way or the other: Experimental and computational studies provide insight into the selectivity‐controlling factors in ruthenium‐catalyzed C−H arylation and oxidative C−H/C−H functionalization. Abstract Experimental and computational studies provide detailed insight into the selectivity‐ and reactivity‐controlling factors in bifurcated ruthenium‐catalyzed direct C−H arylations and dehydrogenative C−H/C−H functionalizations. Thorough investigations revealed the importance of arene‐ligand‐free complexes for the formation of biscyclometalated intermediates within a ruthenium(II/IV/II) mechanistic manifold.

Palladium‐Catalyzed Dearomative syn‐1,4‐Oxyamination

By Conghui Tang, Mikiko Okumura, Hejun Deng, David Sarlah from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Escape from flatland: A dearomative strategy is reported based on combination of arenophile chemistry and Pd catalysis. Non‐activated arenes were readily converted into the corresponding syn‐1,4‐oxyaminated products using oximes or benzyl alcohols as O‐nucleophiles. This process delivers products with an exclusive diastereoselectivity, amenable to myriad of further elaborations. Abstract A palladium‐catalyzed dearomative syn‐1,4‐oxyamination protocol using non‐activated arenes has been developed. This one‐pot procedure utilizes arenophile chemistry, and the corresponding para‐cycloadducts are treated with oxygen nucleophiles via formal allylic substitution, providing direct access to syn‐1,4‐oxyaminated products. The reaction conditions permit a range of arenes, as well as different O‐nucleophiles, such as oximes and benzyl alcohols. Moreover, this process was established in an asymmetric fashion, delivering products with high enantioselectivity. The dearomatized products are amenable to a multitude of further derivatizations ranging from olefin chemistry to C−H activation, giving rise to a diverse set of new functionalities. Overall, this dearomative functionalization offers rapid and controlled formation of molecular complexity, enabling straightforward access to functionalized small molecules from simple and readily available arenes.

Rhodium(I)/Zn(OTf)2‐Catalyzed Asymmetric Ring Opening/Cyclopropanation of Oxabenzonorbornadienes with Phosphorus Ylides

By Tao Chen, Lifei Gan, Ran Wang, Yuhua Deng, Fangzhi Peng, Mark Lautens, Zhihui Shao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

P‐ylides: The use of Rh catalysis in the enantioselective ring‐opening/cyclopropanation reactions of various P‐ylides is demonstrated. This asymmetric reaction occurs through the cleavage of two bridgehead C−O bonds and the formation of two C−C bonds and constitutes the first highly enantioselective direct catalytic asymmetric cyclopropanation of stabilized P‐ylide nucleophiles. Abstract The strong binding ability of P‐ylides with transition metals limits the utilization of stabilized P‐ylide as nucleophiles in asymmetric organometallic catalysis. Herein we describe the first rhodium‐catalyzed asymmetric ring‐opening reaction of P‐ylides utilizing oxabicyclic alkenes as the electrophilic partner. Various P‐ylides including ester‐, ketone‐ and amide‐style P‐ylides are all applicable. This asymmetric reaction occurs through the cleavage of two bridgehead C−O bonds and the formation of two C−C bonds, and oxabenzonorbornadienes are used as 1,4‐biselectrophiles, thus providing access to benzonorcaradienes in good yields with high enantioselectivity and perfect diastereoselectivity. The present protocol also constitutes the first highly enantioselective direct catalytic asymmetric cyclopropanation of stabilized P‐ylide nucleophiles.

Stereoselective Synthesis of Trisubstituted Vinylboronates from Ketone Enolates Triggered by 1,3‐Metalate Rearrangement of Lithium Enolates

By Yue Hu, Wei Sun, Tao Zhang, Nuo Xu, Jianeng Xu, Yu Lan, Chao Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

One to three: An unprecedented stereoselective synthesis of trisubstituted vinylboronates from the transition‐metal‐free borylation of lithium ketone enolates was developed. Carbonyl‐induced 1,3‐metalate rearrangement through a C‐bound boron enolate leads to the stereospecific C−O borylation of lithium enolates. A variety of stereospecific tri‐ and tetrasubstituted vinylboronates were easily obtained. Abstract An unprecedented stereoselective synthesis of trisubstituted vinylboronates is reported to proceed by direct borylation of lithium ketone enolates under transition‐metal‐free conditions. The stereospecific C−O borylation of lithium enolates was triggered by a carbonyl‐induced 1,3‐metalate rearrangement via a C‐bound boron enolate. DFT calculations and control experiments revealed that the stereoselectivity is controlled by sterics. A variety of stereospecific trisubstituted vinylboronates, together with several tetrasubstituted vinylboronates, were conveniently synthesized with the newly developed methodology. Based on the transformation of stereospecific vinylboronate, a single isomer of Dienestrol was efficiently obtained.

Atroposelective Phosphoric Acid Catalyzed Three‐Component Cascade Reaction: Enantioselective Synthesis of Axially Chiral N‐Arylindoles

By Lei Wang, Jialing Zhong, Xufeng Lin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

About the axis: The first organocatalytic atroposelective three‐component cascade heteroannulation of 2,3‐diketoesters, aromatic amines, and 1,3‐cyclohexanediones has been developed. A wide range of axially chiral N‐arylindoles were obtained in high yields and ee values by using a spirocyclic phosphoric acid catalyst. DCM=dichloromethane. Abstract An efficient organocatalytic atroposelective three‐component cascade reaction of 2,3‐diketoesters, aromatic amines, and 1,3‐cyclohexanediones has been developed for the highly enantioselective synthesis of axially chiral N‐arylindoles. The success of this method derives from the use of a newly developed second‐generation chiral spirocyclic phosphoric acid as the catalyst. In addition, this protocol was extended to the synthesis of an axially chiral monophosphorus ligand.

Indeno[1,2‐b]carbazole as Methoxy‐Free Donor Group: Constructing Efficient and Stable Hole‐Transporting Materials for Perovskite Solar Cells

By Jialin Wang, Heng Zhang, Bingxue Wu, Zhihui Wang, Zhe Sun, Song Xue, Yongzhen Wu, Anders Hagfeldt, Mao Liang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Balancing act: The indeno[1,2‐b]carbazole donor not only combines the characteristics of carbazole and fluorene, but also exhibits excellent thermal stability and high hole mobility as a result of the bulky planar structure. Hole‐transporting materials based on this methoxy‐free donor demonstrate a high efficiency and stability simultaneously, providing a promising strategy for developing efficient and stable perovskite‐based solar cells. Abstract With perovskite‐based solar cells (PSCs) now reaching efficiencies of greater than 20 %, the stability of PSC devices has become a critical challenge for commercialization. However, most efficient hole‐transporting materials (HTMs) thus far still rely on the state‐of‐the‐art methoxy triphenylamine (MOTPA) donor unit in which methoxy groups usually reduce the device stability. Herein, a carbazole‐fluorene hybrid has been employed as a methoxy‐free donor to construct organic HTMs. The indeno[1,2‐b]carbazole group not only inherits the characteristics of carbazole and fluorene, but also exhibits additional advantages arising from the bulky planar structure. Consequently, M129, endowed with indeno[1,2‐b]carbazole simultaneously exhibits a promising efficiency of over 20 % and superior long‐term stability. The hybrid strategy toward the methoxy‐free donor opens a new avenue for developing efficient and stable HTMs.

Cobalt‐Catalyzed Asymmetric Hydrogenation of C=N Bonds Enabled by Assisted Coordination and Nonbonding Interactions

By Yanhua Hu, Zhenfeng Zhang, Jian Zhang, Yangang Liu, Ilya D. Gridnev, Wanbin Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Interaction skills: Chiral nitrogen‐containing compounds have been synthesized with excellent enantioselectivity (95–98 % ee) and high productivity (up to 2000 TON) by the Co‐catalyzed asymmetric hydrogenation of C=N bonds. The reaction is facilitated by coordination of an NHBz group in the substrates to the cobalt atom and a nonbonding interaction with the ligand. Abstract An efficient cobalt‐catalyzed asymmetric hydrogenation of C=N bonds has been realized. Chiral hydrazines were obtained in high yields and with excellent enantioselectivities (95–98 % ee). The hydrogenation went smoothly at up to 2000 substrate/catalyst and on a gram scale. The success of this reaction relies on the presence of an NHBz group in the substrates, with the reactivity and enantioselectivity improved by an assisted coordination to the cobalt atom and a nonbonding interaction with the ligand. Furthermore, this reaction has practical applications for the synthesis of several useful chiral nitrogen‐containing compounds.

Pillar[5]arene‐Stabilized Silver Nanoclusters: Extraordinary Stability and Luminescence Enhancement Induced by Host–Guest Interactions

By Madathumpady Abubaker Habeeb Muhammed, Laila Khalil Cruz, Abdul‐Hamid Emwas, Ahmed M. El‐Zohry, Basem Moosa, Omar F. Mohammed, Niveen M. Khashab from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Light pillars: Host–guest interactions of pillar[5]arene (P5)‐capped silver nanoclusters (Ag29(LA‐P5)12(TPP)2 with alkylamines and quaternary ammonium guest molecules resulted in the modulation of optical properties of the NCs, including an extraordinary circa 2000‐fold photoluminescence enhancement. Abstract Herein, we report the synthesis of a new class of functional silver nanoclusters (AgNCs) capped with pillar[5]arene (P5)‐based host ligands. These NCs are readily prepared through direct synthesis or ligand exchange synthesis and are stable at room temperature for over 4 months. The pillar[5]arene‐stabilized NCs (Ag29(LA‐P5)12(TPP)2) endorse reversible host–guest interactions with neutral alkylamines and cationic quaternary ammonium guests. This results in the formation of spherical assemblies with unparalleled changes in their optical properties including an astonishing circa 2000‐fold luminescence enhancement. This is the highest luminescence enhancement ratio reported so far for such atomically precise NCs. Our synthetic protocol paves the way for the preparation of a new generation of metal nanoclusters protected by macrocyclic ligands with molecular recognition and selectivity toward specific guests.

Hooking Together Sigmoidal Monomers into Supramolecular Polymers

By Marco Carini, Mauro Marongiu, Karol Strutyński, Akinori Saeki, Manuel Melle‐Franco, Aurelio Mateo‐Alonso from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Hooked! An approach to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units is presented. It gives rise to micrometer‐sized fibrils that show pseudoconductivities, in line with other conducting materials. Abstract Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties.

Asymmetric Synthesis of Heterocyclic γ‐Amino‐Acid and Diamine Derivatives by Three‐Component Radical Cascade Reactions

By Danqing Zheng, Armido Studer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

One, two, three! A three‐component radical cascade for the enantioselective synthesis of γ‐amino‐acid derivatives is presented. The reactions proceed by redox and phosphoric acid dual catalysis, and work with readily available starting materials. Abstract An enantioselective three‐component radical reaction of quinolines or pyridines with enamides and α‐bromo carbonyl compounds by dual photoredox and chiral Brønsted acid catalysis is presented. A range of valuable chiral γ‐amino‐acid derivatives are accessible in high chemo‐, regio‐, and enantioselectivity from simple, readily available starting materials under mild reaction conditions. Using the same strategy, the asymmetric synthesis of 1,2‐diamine derivatives is also reported.

Exploiting Coordination Isomerism for Controlled Self‐Assembly

By Nils Bäumer, Kalathil K. Kartha, Naveen Kumar Allampally, Shiki Yagai, Rodrigo Q. Albuquerque, Gustavo Fernández from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Size matters: Coordination isomerism was exploited for the first time to control the morphology of a supramolecular polymer. These observations pave the way for novel stimuli‐responsive materials and offer a new approach for size control in self‐assembled systems. Abstract We exploited the inherent geometrical isomerism of a PtII complex as a new tool to control supramolecular assembly processes. UV irradiation and careful selection of solvent, temperature, and concentration leads to tunable coordination isomerism, which in turn allows fully reversible switching between two distinct aggregate species (1D fibers↔2D lamellae) with different photoresponsive behavior. Our findings not only broaden the scope of coordination isomerism, but also open up exciting possibilities for the development of novel stimuli‐responsive nanomaterials.

Metal‐Free Synthesis of Benzothiophenes by Twofold C−H Functionalization: Direct Access to Materials‐Oriented Heteroaromatics

By Jiajie Yan, Alexander P. Pulis, Gregory J. P. Perry, David J. Procter from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Thio‐fusion: Benzothiophenes are accessed from non‐prefunctionalized arenes in a one‐pot sequence involving an interrupted Pummerer reaction, [3,3]‐sigmatropic rearrangement, and cyclization. The process does not require metals, proceeds by twofold C−H functionalization, and can be used to achieve the straightforward π‐extension of polyaromatic hydrocarbons. Abstract Due to their ubiquity in nature and frequent use in organic electronic materials, benzothiophenes are highly sought after. Here we set out an unprecedented procedure for the formation of benzothiophenes by the twofold vicinal C−H functionalization of arenes that does not require metal catalysis. This one‐pot annulation proceeds through an interrupted Pummerer reaction/[3,3]‐sigmatropic rearrangement/cyclization sequence to deliver various benzothiophene products. The procedure is particularly effective for the rapid synthesis of benzothiophenes from non‐prefunctionalized polyaromatic hydrocarbons (PAHs).

Highly Stable Lithium Metal Anode Interface via Molecular Layer Deposition Zircone Coatings for Long Life Next‐Generation Battery Systems

By Keegan R. Adair, Changtai Zhao, Mohammad Norouzi Banis, Yang Zhao, Ruying Li, Mei Cai, Xueliang Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Protection at the nano‐level: Molecular layer deposition is employed to fabricate a nanoscale “zircone” coating that is highly effective at stabilizing the Li metal anode interface. In‐situ XAS is used for the first time to study the lithiation process of the artificial coating and the protected Li metal anode shows significantly enhanced cycling stability and lifetime in Li‐O2 batteries. Abstract Herein, molecular layer deposition is used to form a nanoscale “zircone” protective layer on Li metal to achieve stable and long life Li metal anodes. The zircone‐coated Li metal shows enhanced air stability, electrochemical performance and high rate capability in symmetrical cell testing. Moreover, as a proof of concept, the protected Li anode is used in a next‐generation Li‐O2 battery system and is shown to extend the lifetime by over 10‐fold compared to the batteries with untreated Li metal. Furthermore, in‐situ synchrotron X‐ray absorption spectroscopy is used for the first time to study an artificial SEI on Li metal, revealing the electrochemical stability and lithiation of the zircone film. This work exemplifies significant progress towards the development and understanding of MLD thin films for high performance next‐generation batteries.

Access to Multifunctionalized Benzofurans by Aryl Nickelation of Alkynes: Efficient Synthesis of the Anti‐Arrhythmic Drug Amiodarone

By Naeem Iqbal, Naila Iqbal, Debabrata Maiti, Eun Jin Cho from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

An unconventional nickel‐catalyzed reaction has been developed for the synthesis of multifunctionalized benzofurans through the aryl nickelation of alkynes. A nucleophilic vinyl NiII species, from regioselective syn‐aryl nickelation of an alkyne, undergoes an intramolecular cyclization with phenol ester to yield highly functionalized 1,1‐disubstituted alkenes with 3‐benzofuranyl and (hetero)aryl substituents. Abstract An unconventional nickel‐catalyzed reaction was developed for the synthesis of multifunctionalized benzofurans from alkyne‐tethered phenolic esters. The transformation involves the generation of a nucleophilic vinyl NiII species by the regioselective syn‐aryl nickelation of an alkyne, which then undergoes an intramolecular cyclization with phenol ester to yield highly functionalized 1,1‐disubstituted alkenes with 3‐benzofuranyl and (hetero)aryl substituents. The methodology can be used for the late‐stage benzofuran incorporation of various drug molecules and natural products, such as 2‐propylvaleric acid, gemfibrozil, biotin, and lithocholic acid. Furthermore, this arylative cyclization method was successfully applied for the efficient synthesis of the anti‐arrhythmic drug amiodarone.

Magnesium Cyanide or Isocyanide?

By Gerd Ballmann, Holger Elsen, Sjoerd Harder from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The two faces of CN: Cyanide ligands are generally C‐bound in transition‐metal chemistry, but for Mg, an isocyanide structure was established. Based on experiment and theory, at 298 K, a Mg−NC/Mg−CN ratio of 95:5 is found. In the solid state and in solution, isomerization is facile with a low energy barrier. Abstract Preference for the binding mode of the CN− ligand to Mg (Mg−CN vs. Mg−NC) is investigated. A monomeric Mg complex with a terminal CN ligand was prepared using the dipyrromethene ligand MesDPM which successfully blocks dimerization. While reaction of (MesDPM)MgN(SiMe3)2 with Me3SiCN gave the coordination complex (MesDPM)MgN(SiMe3)2⋅NCSiMe3, reaction with (MesDPM)Mg(nBu) led to (MesDPM)MgNC⋅(THF)2. A Mg−NC/Mg−CN ratio of ≈95:5 was established by crystal‐structure determination and DFT calculations. IR studies show absorbances for CN stretching at 2085 cm−1 (Mg−NC) and 2162 cm−1 (Mg−CN) as confirmed by 13C labeling. In solution and in the solid state, the CN ligand rotates within the pocket. The calculated isomerization barrier is only 12.0 kcal mol−1 and the 13C NMR signal for CN decoalesces at −85 °C (Mg−NC: 175.9 ppm, Mg−CN: 144.3 ppm). Experiment and theory both indicate that Mg complexes with the CN− ligand should not be named cyanides but are more properly defined as isocyanides.

Molybdenum Alkylidyne Complexes with Tripodal Silanolate Ligands: The Next Generation of Alkyne Metathesis Catalysts

By Julius Hillenbrand, Markus Leutzsch, Alois Fürstner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

The canopy: Molybdenum alkylidyne complexes with triarylsilanolate ligands are privileged catalysts for alkyne metathesis, but tethering of the silyl groups seems to make things even better. Crystallographic data and a rare case study based on 95Mo NMR spectroscopy provide insights into why that is so. Abstract A new type of molybdenum alkylidyne catalysts for alkyne metathesis is described, which is distinguished by an unconventional podand topology. These structurally well‐defined complexes are easy to make on scale and proved to be tolerant toward numerous functional groups; even certain protic substituents were found to be compatible. The new catalysts were characterized by X‐ray crystallography and by spectroscopic means, including 95Mo NMR.

Molecular Semiconductor Surfactants with Fullerenol Heads and Colored Tails for Carbon Dioxide Photoconversion

By Marius Kunkel, Sebastian Sutter, Sebastian Polarz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Photosynthesis with soap: Surfactants consisting of dye molecules and a polyhydroxylated fullerene self‐assemble into bilayer vesicles that mimic key functions of photosystems II and I. They can absorb photons of two different visible wavelengths, exchange excited charge carriers, and thus enable the conversion of CO2 into formic acid. Abstract The leaf is a prime example of a material converting waste (CO2) into value with maximum sustainability. As the most important constituent, it contains the coupled photosystems II and I, which are imbedded in the cellular membrane of the chloroplasts. Can key functions of the leaf be packed into soap? We present next‐generation surfactants that self‐assemble into bilayer vesicles (similar to the cellular membrane), are able to absorb photons of two different visible wavelengths, and exchange excited charge carriers (similar to the photosystems), followed by conversion of CO2 (in analogy to the leaf). The amphiphiles contain five dye molecules as the hydrophobic entity attached exclusively to one hemisphere of a polyhydroxylated fullerene (Janus‐type). We herein report on their surfactant, optical, electronic, and catalytic properties. Photons absorbed by the dyes are transferred to the fullerenol head, where they can react with different species such as CO2 to give formic acid.

A Short and Efficient Synthesis of the [3]Triangulene Ring System

By Carter J. Holt, Katelyn J. Wentworth, Richard P. Johnson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Making molecular triangles: The [3]triangulene ring system is easily accessed through a superacid‐catalyzed cascade cyclization of benzyl cations followed by reduction of the planar 4,8,12‐trihydrotriangulenium ion. Preliminary experiments support rapid oligomerization of triangulene in solution. Abstract Triangulenes are of current interest for potential applications in molecular electronics. We describe here a three step synthesis of the 4,8,12‐trihydro[3]triangulenium cation by cascade cyclization of a tetra‐benzyl alcohol precursor in triflic acid solution. This stable carbocation is easily observed by NMR and optical spectroscopy and is highly fluorescent. Quenching of the cation into basic solutions or by hydride transfer from triethylsilane provides access to stable dihydro and tetrahydro[3]triangulenes. These neutral species interconvert with cations in a complex series of proton and hydride transfers. This route provides several important [3]triangulene precursors. Preliminary experiments designed to generate [3]triangulene in the solution phase provide evidence for its formation and rapid oligomerization.

Exposing the Delocalized Cu−S π Bonds on the Au24Cu6(SPhtBu)22 Nanocluster and Its Application in Ring‐Opening Reactions

By Jinsong Chai, Sha Yang, Ying Lv, Hanbao Chong, Haizhu Yu, Manzhou Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Au24Cu6(SPhtBu)22 was synthesized. It is effective in the catalysis of the epoxide ring‐opening reaction. Control experiments and DFT calculations revealed that the π conjugation among the Cu−S bonds played a pivotal role. Abstract Bimetallic nanomaterials are of major importance in catalysis. A Au‐Cu bimetallic nanocluster was synthesized that is effective in catalyzing the epoxide ring‐opening reaction. The catalyst was analyzed by SCXRD and ESI‐MS and found to be Au24Cu6(SPhtBu)22 (Au24Cu6 for short). Six copper atoms exclusively occupy the surface positions in two groups with three atoms for each, and each group was bonded with three thiolate ligands to give a planar motif reminiscent of a benzene ring. In the epoxide‐ring opening reaction, Au24Cu6 exhibited superior catalytic activity compared to other homometallic and Au‐Cu alloy NCs, such as Au25 and Au38−xCux. Control experiments and DFT calculations revealed that the π conjugation among the Cu−S bonds played a pivotal role. This study demonstrates a unique π conjugation established among the Cu−S bonds as a critical structural motif in the nanocluster, which facilitates the catalysis of a ring‐opening reaction.

Global Aromaticity and Antiaromaticity in Porphyrin Nanoring Anions

By Martin D. Peeks, Michael Jirasek, Timothy D. W. Claridge, Harry L. Anderson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Negative isn't always bad: Reduction of a porphyrin nanoring by the addition of 4 or 6 electrons was found to result in global (anti)aromaticity (see picture), as revealed by 1H NMR spectroscopy and DFT calculations. Thus, the Hückel rules apply to huge macrocyclic anions, and the charge in these anions is fully delocalized. Abstract Doping, through oxidation or reduction, is often used to modify the properties of π‐conjugated oligomers. In most cases, the resulting charge distribution is difficult to determine. If the oligomer is cyclic and doping establishes global aromaticity or antiaromaticity, then it is certain that the charge is fully delocalized over the entire perimeter of the ring. Herein we show that reduction of a six‐porphyrin nanoring using decamethylcobaltocene results in global aromaticity (in the 6− state; [90 π]) and antiaromaticity (in the 4− state; [88 π]), consistent with the Hückel rules. Aromaticity is assigned by NMR spectroscopy and density‐functional theory calculations.

6‐Methylenebicyclo[3.2.1]oct‐1‐en‐3‐one: A Twisted Olefin as Diels–Alder Dienophile for Expedited Syntheses of Four Kaurane Diterpenoids

By Junjie Wang, Dawei Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

With a twist: 6‐Methylenebicyclo[3.2.1]oct‐1‐en‐3‐one, a twisted and highly reactive enone, was prepared for the first time by elimination of its bromide precursor. Its reactions as a dienophile with several dienes in Diels–Alder reactions proceeded smoothly to provide tricyclic and tetracyclic adducts, which allowed short syntheses (10–11 steps) of four kurane diterpenoids including 11β‐hydroxy‐16‐kaurene, 11α‐hydroxy‐16‐kaurene, liangshanin G, and gesneroidin B. Abstract 6‐Methylenebicyclo[3.2.1]oct‐1‐en‐3‐one, a twisted and highly reactive enone, was prepared for the first time by elimination of its bromide precursor. Its reactions as a dienophile with several dienes in Diels–Alder reactions proceeded smoothly to provide tricyclic and tetracyclic adducts, which allowed short syntheses (10–11 steps) of four kurane diterpenoids including 11β‐hydroxy‐16‐kaurene, 11α‐hydroxy‐16‐kaurene, liangshanin G, and gesneroidin B.

Electrochemical Arylation of Electron‐Deficient Arenes through Reductive Activation

By Pan Wang, Zhenlin Yang, Ziwei Wang, Chenyang Xu, Lei Huang, Shengchun Wang, Heng Zhang, Aiwen Lei from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

An electrochemical method was developed for arylation of electron‐deficient arenes through reductive activation. Various electron‐deficient arenes and aryldiazonium tetrafluoroborates were examined for the transformation within an undivided cell, furnishing the desired products with up to 92 % yield. Reduction of quinoxaline is a key step in the transformation. Abstract An electrochemical method has been developed to achieve arylation of electron‐deficient arenes through reductive activation. Various electron‐deficient arenes and aryldiazonium tetrafluoroborates are amenable to this transformation within the conditions of an undivided cell, providing the desired products in up to 92 % yield. Instead of preparing diazonium reagents, these reactions can begin from anilines, and they can be carried out in one pot. Electron paramagnetic resonance studies indicate that cathodic reduction of quinoxaline occurs using the transformation. Moreover, cyclic voltammetry indicates that both quinoxaline and aryl diazonium salt have relatively low reduction potentials, which suggests they can be activated through reduction during the reaction.

A Crystallographic Charge Density Study of the Partial Covalent Nature of Strong N⋅⋅⋅Br Halogen Bonds

By Mihael Eraković, Dominik Cinčić, Krešimir Molčanov, Vladimir Stilinović from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Crystallographic charge density analysis of a strong N−Br⋅⋅⋅N halogen bond in a N‐bromosuccinimide and 3,5‐dimethylpyridine co‐crystal (NBS‐lut) reveals a partially covalent character. Comparisons with pure crystalline NBS and the covalent bond in a bis(3‐methylpyridine)bromonium cation suggest that there is a continuum of interactions between the intermolecular “non‐bonding” halogen bond and a three centre–two electron covalent bond. Abstract The covalent nature of strong N−Br⋅⋅⋅N halogen bonds in a cocrystal (2) of N‐bromosuccinimide (NBS) with 3,5‐dimethylpyridine (lut) was determined from X‐ray charge density studies and compared to a weak N−Br⋅⋅⋅O halogen bond in pure crystalline NBS (1) and a covalent bond in bis(3‐methylpyridine)bromonium cation (in its perchlorate salt (3). In 2, the donor N−Br bond is elongated by 0.0954 Å, while the Br⋅⋅⋅acceptor distance of 2.3194(4) is 1.08 Å shorter than the sum of the van der Waals radii. A maximum electron density of 0.38 e Å−3 along the Br⋅⋅⋅N halogen bond indicates a considerable covalent contribution to the total interaction. This value is intermediate to 0.067 e Å−3 for the Br⋅⋅⋅O contact in 1, and approximately 0.7 e Å−3 in both N−Br bonds of the bromonium cation in 3. A calculation of the natural bond order charges of the contact atoms, and the σ*(N1−Br) population of NBS as a function of distance between NBS and lut, have shown that charge transfer becomes significant at a Br⋅⋅⋅N distance below about 3 Å.

A Highly Elastic and Reversibly Stretchable All‐Polymer Supercapacitor

By Yukun Wang, Feng Chen, Zhuoxin Liu, Zijie Tang, Qi Yang, Yan Zhao, Shanyi Du, Qiang Chen, Chunyi Zhi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

Elastic supercaps: An agar/hydrophobically associated polyacrylamide (HPAAm) double network (DN) hydrogel and pure polypyrrole (PPy) film based all‐polymer supercapacitor was fabricated. It is highly elastic and reversibly stretchable. This supercapacitor can be stretched and recovered for 1000 times with no obvious performance degradation and strain residue, exhibiting excellent elasticity at the device level. Abstract Multiple stretchability has never been demonstrated as supercapacitors because the hydrogel used cannot fully recover after being heavily deformed. Now, a highly reversibly stretchable all‐polymer supercapacitor was fabricated using a developed double network hydrogel (DN hydrogel) as electrolyte and pure polypyrrole (PPy) as electrode. The DN hydrogel provides excellent mechanical properties, which can be stretched up to 500 % many times and then restore almost 100 % of the original length. To fabricate the fully recoverable stretchable supercapacitor, we annealed a free‐standing pure conducting polymer film as electrode so that the electrodes induced retardance is minimized. The as‐fabricated DN hydrogel/pure conducting polymer supercapacitors can be perfectly recovered from 100 % strain with almost no residual deformation left and the electrochemical performance can be maintained even after 1000 stretches (but not bending).

Bo Tang

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 21, 2019.

“My favorite saying is: ‘Dedication to public interests, acquisition of all‐round capability, and aspiration for progress with each day'. The most important thing I learned from my parents is to be a man of integrity …” Find out more about Bo Tang in his Author Profile.

[ASAP] MnCaCs-Biomineralized Oncolytic Virus for Bimodal Imaging-Guided and Synergistically Enhanced Anticancer Therapy

By Li-Li Huang†?, Xue Li†?, JinFeng Zhang†, Qian Ru Zhao†, Ming Jing Zhang†, An-An Liu‡, Dai-Wen Pang‡, and Hai-Yan Xie*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03193

[ASAP] Repeated Reuse of Deoxyribozyme-Based Logic Gates

By Bradley I. Harding†, Nina M. Pollak†‡, Darko Stefanovic§?, and Joanne Macdonald*†? from Nano Letters: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02326

[ASAP] Tuning Hot Carrier Cooling Dynamics by Dielectric Confinement in Two-Dimensional Hybrid Perovskite Crystals

By Jun Yin†?, Partha Maity†?, Rounak Naphade†, Bin Cheng‡, Jr-Hau He‡, Osman M. Bakr†, Jean-Luc Bre´das§, and Omar F. Mohammed*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04085

[ASAP] Uniaxial Deformation and Crazing in Glassy Polymer-Grafted Nanoparticle Ultrathin Films

By Jeffrey G. Ethier†, Lawrence F. Drummy‡, Richard A. Vaia‡, and Lisa M. Hall*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05001

[ASAP] Toward Real-Time Monitoring and Control of Single Nanoparticle Properties with a Microbubble Resonator Spectrometer

By Levi T. Hogan†‡, Erik H. Horak†‡, Jonathan M. Ward§, Kassandra A. Knapper†, Si´le Nic Chormaic§, and Randall H. Goldsmith*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04702

[ASAP] In Situ Magnetic Resonance Imaging of a Complete Supercapacitor Giving Additional Insight on the Role of Nanopores

By Ghenima Oukali†‡, Elodie Salager*†‡, Mohamed Ramzi Ammar‡, Charles-Emmanuel Dutoit†‡, Vincent Sarou-Kanian†‡, Patrice Simon†||, Encarnacion Raymundo-Pin~ero*†‡, and Michae¨l Deschamps*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04998

[ASAP] Exploiting the Lymph-Node-Amplifying Effect for Potent Systemic and Gastrointestinal Immune Responses via Polymer/Lipid Nanoparticles

By Yiqun Du†#, Yufei Xia‡§#, Yongjuan Zou‡§, Yuning Hu‡§, Jiaqi Fu‡, Jie Wu*‡?, Xiao-Dong Gao*†, and Guanghui Ma*‡§? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04071

[ASAP] Rapid and Accurate Prediction of pKa Values of C–H Acids Using Graph Convolutional Neural Networks

By Rafal Roszak†§?, Wiktor Beker†§?, Karol Molga†, and Bartosz A. Grzybowski*†‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05895

[ASAP] A Scalable General Synthetic Approach toward Ultrathin Imine-Linked Two-Dimensional Covalent Organic Framework Nanosheets for Photocatalytic CO2 Reduction

By Wenbo Liu†, Xiaokang Li§, Chiming Wang†, Houhe Pan†, Wenping Liu†, Kang Wang*†, Qingdao Zeng*§?, Rongming Wang‡, and Jianzhuang Jiang*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09502

[ASAP] Synthesis of Isomerically Pure (Z)-Alkenes from Terminal Alkynes and Terminal Alkenes: Silver-Catalyzed Hydroalkylation of Alkynes

By Mitchell T. Lee†, Madison B. Goodstein†, and Gojko Lalic* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09336

[ASAP] Unmasking the Ligand Effect in Manganese-Catalyzed Hydrogenation: Mechanistic Insight and Catalytic Application

By Yujie Wang†?, Lei Zhu‡?, Zhihui Shao†, Gang Li§, Yu Lan*‡, and Qiang Liu*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09038

[ASAP] Antiferromagnetic Semiconductor BaFMn0.5Te with Unique Mn Ordering and Red Photoluminescence

By Haijie Chen†§, Rebecca McClain†, Jiangang He‡, Chi Zhang‡, Jack N. Olding†, Roberto dos Reis‡, Jin-Ke Bao§, Ido Hadar†, Ioannis Spanopoulos†, Christos D. Malliakas†, Yihui He†, Duck Young Chung§, Wai-Kwong Kwok§, Emily A. Weiss†, Vinayak P. Dravid‡, Christopher Wolverton‡, and Mercouri G. Kanatzidis*†‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09382

Valley-polarized exciton currents in a van der Waals heterostructure

By Andras Kis from Nature Nanotechnology - Issue - nature.com science feeds. Published on Oct 21, 2019.

Nature Nanotechnology, Published online: 21 October 2019; doi:10.1038/s41565-019-0559-y

Engineering the interlayer coupling in a van der Waals heterostructure enables electrical control over the transport and density of valley-polarized interlayer excitons.

Furin-mediated intracellular self-assembly of olsalazine nanoparticles for enhanced magnetic resonance imaging and tumour therapy

By Jeff W. M. Bulte from Nature Materials - Issue - nature.com science feeds. Published on Oct 21, 2019.

Nature Materials, Published online: 21 October 2019; doi:10.1038/s41563-019-0503-4

An anticancer agent, olsalazine, conjugated to a cell-penetrating peptide has been synthesized and shows the ability to self-assemble intracellularly by the tumour-associated enzyme furin, with the potential for tumour therapy and chemical exchange saturation transfer magnetic resonance imaging in vivo.

Electrocalorics hit the top

By B. Dkhil from Nature Materials - Issue - nature.com science feeds. Published on Oct 21, 2019.

Nature Materials, Published online: 21 October 2019; doi:10.1038/s41563-019-0522-1

A first-order ferroelectric phase transition is driven supercritically in multilayer capacitors of PbSc0.5Ta0.5O3, enabling an electrocaloric response of 5.5 K near room temperature.

Bias-free solar syngas production by integrating a molecular cobalt catalyst with perovskite–BiVO4 tandems

By Erwin Reisner from Nature Materials - Issue - nature.com science feeds. Published on Oct 21, 2019.

Nature Materials, Published online: 21 October 2019; doi:10.1038/s41563-019-0501-6

Photoelectrochemical production of syngas from water and CO2 is technologically attractive but overpotentials, low selectivity and catalyst cost remain challenging. Tunable syngas production integrating cobalt porphyrin catalysts with perovskite and BiVO4 photoabsorbers is now shown.

Crystallization by particle attachment is a colloidal assembly process

By Nico A. J. M. Sommerdijk from Nature Materials - Issue - nature.com science feeds. Published on Oct 21, 2019.

Nature Materials, Published online: 21 October 2019; doi:10.1038/s41563-019-0511-4

The kinetics and thermodynamics of the nucleation of magnetite crystals from primary particles are shown to be described by colloidal assembly theory, allowing for predictions of crystal sizes to be made.

Reciprocal space imaging of ionic correlations in intercalation compounds

By Raymond Osborn from Nature Materials - Issue - nature.com science feeds. Published on Oct 21, 2019.

Nature Materials, Published online: 21 October 2019; doi:10.1038/s41563-019-0500-7

Conventional diffraction cannot determine short-range order at concentrations that disrupt ionic mobility. Real-space transforms of single-crystal diffuse scattering now allow us to measure ionic correlation length scales in sodium-intercalated V2O5.

Manipulating fluorescence of the exciton-plasmon hybrids in the strong coupling regime with dual resonance enhancements

By Ququan Wang from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR05442A, Paper
Yun-Hang Qiu, Si-Jing Ding, Fan Nan, Qiang Wang, Kai Chen, Zhong-Hua Hao, Li Zhou, Xiaoguang Li, Ququan Wang
Strong couplings between molecular excitons and metal plasmons bring advantages to effectively manipulate the optical properties of the hybrid systems, including both absorption and fluorescence. In contrast to the absorption...
The content of this RSS Feed (c) The Royal Society of Chemistry

A nanofabricated plasmonic core-shell-nanoparticle library

By Christoph Langhammer from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08097J, Paper
Arturo Susarrey-Arce, Krzysztof M. Czajkowski, Iwan Darmadi, Sara Nilsson, Irem Tanyeli, Svetlana Alekseeva, Tomasz J. Antosiewicz, Christoph Langhammer
Three-layer core-shell-nanoparticle nanoarchitectures exhibit properties not achievable by single-element nanostructures alone and have great potential to enable rationally designed functionality. However, nanofabrication strategies for crafting core-shell-nanoparticle structure arrays on surfaces...
The content of this RSS Feed (c) The Royal Society of Chemistry

High performance electroformed Single-crystallite VO2 threshold switch

By Jimmy Xu from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08364B, Paper
Xin Zhou, Deen Gu, Yatao Li, Haoxin Qin, Yadong Jiang, Jimmy Xu
Threshold switches (TSs) is an effective approach for resolving the sneak path problem within a memristor array. VO2 is a promising material for fabricating high-performance TSs. Here we report a...
The content of this RSS Feed (c) The Royal Society of Chemistry

Mapping the Dielectric Constant of a Single Bacterial Cell at the Nanoscale with Scanning Dielectric Force Volume Microscopy

By Gabriel Gomila from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07659J, Paper
Marti Checa, Rubén Millán, Núria Blanco, Eduard Torrents, Rene Fabregas, Gabriel Gomila
Mapping the dielectric constant at the nanoscale of samples showing a complex topography, such as non-planar nanocomposite materials or single cells, poses formidable challenges to existing nanoscale dielectric microscopy techniques....
The content of this RSS Feed (c) The Royal Society of Chemistry

Room-Temperature Photodetectors and VOCs sensors based on Graphene Oxide – ZnO Nano-Heterojunctions

By Antonio Tricoli from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR08901B, Paper
Eleonora Pargoletti, Umme Habiba Hossain, Iolanda Di Bernardo, Hongjun Chen, Thanh Phu Tran, Josh Lipton-Duffin, Giuseppe Cappelletti, Antonio Tricoli
The rapid development of smart wearable electronics is driving the engineering of novel miniaturized sensing materials that can rapidly respond to very small changes in the concentration of biomarkers at...
The content of this RSS Feed (c) The Royal Society of Chemistry

Multifunctional temozolomide-loaded lipid superparamagnetic nanovectors: Dual targeting and disintegration of glioblastoma spheroids by synergic chemotherapy and hyperthermia treatment

By Gianni Ciofani from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07976A, Paper
Attilio Marino, Alice Camponovo, Andrea degl'Innocenti, Martina Bartolucci, Christos Tapeinos, Chiara Martinelli, Daniele de Pasquale, Francesca Santoro, Valentina Mollo, Satoshi Arai, Madoka Suzuki, Yoshie Harada, Andrea Petretto, Gianni Ciofani
Aiming at finding new solutions for fighting glioblastoma multiforme, one of most aggressive and lethal human cancer, here an in vitro validation of multifunctional nanovectors for drug delivery and hyperthermia...
The content of this RSS Feed (c) The Royal Society of Chemistry

Frogspawn Inspired Hollow Fe3C@N-C as an Efficient Sulfur Host for High-rate Lithium-sulfur Batteries

By Meiri Wang from RSC - Nanoscale latest articles. Published on Oct 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07388D, Paper
Huaiyue Zhang, Hongtao Cui, Jing Li, Yuanyuan Liu, Yanzhao Yang, Meiri Wang
Lithium-sulfur (Li-S) batteries with high theoretical energy density of ~2600 Wh kg-1 have been recognized as a promising energy storage device. However, the practical application of Li-S batteries is still...
The content of this RSS Feed (c) The Royal Society of Chemistry

Imaging Cell‐Matrix Adhesions and Collective Migration of Living Cells by Electrochemiluminescence Microscopy

By Hao Ding, Weiliang Guo, Bin Su from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 20, 2019.

Cell‐matrix adhesions not only mediate the binding interactions between cell and extracellular matrix but also play essential roles in a variety of biological processes. Herein we report a label‐free method to map cell‐matrix adhesions of single living cells on the electrode surface by electrochemiluminescence (ECL). The indium tin oxide electrode modified with silica nanochannel membrane was used as the substrate electrode, at which the enhanced ECL generation from freely diffusing luminophores provided a distinct visual contrast between adhesion contacts and noncontacted domains, thus selectively revealing the former in a label‐free manner. With this methodology, we studied the spatial distribution, as well as dynamic variation, of cell‐matrix adhesions and adhesion strength at the subcellular level. Cell‐matrix adhesions of an advancing cell sheet were finally imaged by ECL microscopy to study the moving tendency of cells in the collective migration. A statistical analysis of local orientations of adhesions suggests that cells on the far side of advancing sheet have also the propensity to migrate and do not act as just passive followers.

New Dimension of Coordination Polymers and Metal–Organic Frameworks toward Functional Glasses and Liquids

By Satoshi Horike, Sanjog S. Nagarkar, Tomohiro Ogawa, Susumu Kitagawa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 20, 2019.

The chemistry of coordination polymers (CPs) has progressed significantly in the last century. There are two categories of CPs; one is inorganic CPs (i‐CPs) and the other is organic ligand‐bridged CPs (o‐CPs). o‐CPs rapidly expanded to form a library of crystal structures. The discovery of permanent porosity in o‐CPs is among the most notable breakthroughs, whose appearance was so groundbreaking that they specially named metal–organic frameworks (MOFs) or porous coordination polymers (PCPs). They have played a decisive role in their recognition as porous materials. For the sake of consistency, we will refer to these materials as MOFs. Based on the success of crystal engineering of CPs to the present, we here propose the potentials of non‐crystalline states and functionalities as a new research direction for CPs. As demonstrated for organic polymers, ceramics, and metals, liquid or glassy states in materials are essential to facilitate specific properties and functions. Several recent works have suggested the feasibility of liquid/glassy states in o‐CPs by design principles. The combination of metal ions and organic bridging ligands, together with the phase transformation of liquid/glass o‐CPs, would be related to ionic liquids and other ionic soft matters. Synchrotron facilities and computational approaches contribute to elucidating the structures and dynamics of the liquid/glassy states of o‐CPs. Porosity, conductivity, and transparency would be tunable, and further attractive material properties include high moldability and wide composition ratios. The unique energy landscape of liquid/glass o‐CPs offers opportunities for properties and functions that are complementary to those of the crystalline state.

Naked‐Eye Readout of Analyte‐Induced NIR Fluorescence Responses by an Initiation‐Input‐Transduction Nanoplatform

By Weihong Tan, Dailiang Zhang, Linlin Wang, Xi Yuan, Yijun Gong, Hongwen Liu, Jing Zhang, Xiaobing Zhang, Yanlan Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 19, 2019.

Fluorescence visualization (FV) in the near‐infrared (NIR) window promises to break through the signal‐to‐background ratio (SBR) bottleneck of traditional visible‐light‐driven FV methods, owing to the minimized background and excitation interference, thus offering great opportunities for portable recognition and detection of various analytes with exquisite sensitivity and reliability. However, straightforward NIR‐FV has not been realized, due to the lack of methodologies to readily transduce NIR responses into instrument‐free, naked eye‐recognizable outputs. Here, we report a novel initiation‐input‐transduction platform comprising a well‐designed NIR fluorophore as the signal initiator and lanthanide‐doped nanocrystals as the transduer for facile NIR‐FV. The analyte‐induced “off‐on” NIR signal serves as a sensitizing switch of transducer's visible luminescence for naked‐eye readout. As a proof of concept, the potential of such design is demonstrated for portable, quantitative detection of phosgene with significantly improved SBR and sensitivity. By further exploration of initiators, this strategy holds promise to creat an arsenal of advanced NIR‐FV probes for broad sensing applications.

Finely Controlled Circularly Polarized Luminescence of a Mechano‐Responsive Supramolecular Polymer

By Seonae Lee, Ka Young Kim, Sung Ho Jung, Ji Ha Lee, Mihoko Yamada, Ramarani Sethy, Tsuyoshi Kawai, Jong Hwa Jung from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

We report on finely controlled circularly polarized luminescence (CPL) supramolecular polymerization based on a tetraphenylethene core with four L ‐ or D ‐alanine branch side chains (L ‐ 1 and D ‐ 1 ) in the solution state resulting from the tuning of mechanical stimulus. Weak, green emissions of L ‐ 1 and D ‐ 1 in tetrahydrofuran (THF) were converted to strong blue emissions by tuning the mechanical stimulus. The strong blue emissions were caused by an aggregation‐induced emission (AIE) effect during the formation of a supramolecular polymer. Lag time in the supramolecular polymerization was drastically reduced by the mechanical stimulus, which was indicative of the acceleration of the supramolecular polymerization. Interestingly, a significant enhancement of circular dichronism (CD) and CPL signals of the L ‐ 1 and D ‐ 1 was observed by tuning the rotational speed of the mechanical stimulus, which implies that the chiral supramolecular polymerization was accelerated by the mechanical stimulus. These results imply that the CPL signals were tuned by the strength of the external mechanical stimulus.

An Activatable NIR‐II Nanoprobe for In Vivo Early Real‐Time Diagnosis of Traumatic Brain Injury

By Qiangbin Wang, Chunyan Li, Wanfei Li, Zijing Li, Yejun Zhang, Guangcun Chen, Huanhuan Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Traumatic brain injury (TBI) is one of the most dangerous acute diseases resulting in high morbidity and mortality. Current methods remain limited with respect to early diagnosis and real‐time feedback on the pathological process. Herein, a targeted activatable fluorescent nanoprobe (V&A@Ag 2 S) in the second near‐infrared window (NIR‐II) is presented for  in vivo  optical imaging of TBI. Initially, the fluorescence of V&A@Ag 2 S displays an "off" state owing to energy transfer from Ag 2 S to the A1094 chromophore. Upon intravenous injection, V&A@Ag 2 S quickly accumulates in the inflamed vascular endothelium of TBI based on VCAM1‐mediated endocytosis, after which the nanoprobe achieves rapid recovery of the NIR‐II fluorescence of Ag 2 S quantum dots (QDs) due to the bleaching of A1094 by the prodromal biomarker of TBI, peroxynitrite (ONOO −  ). Taking advantage of the deep tissue penetration and high signal‐to‐noise ratio of NIR‐II fluorescence imaging, this nanoprobe offers high specificity, rapid response, and high sensitivity toward ONOO − , providing a convenient approach for  in vivo  early real‐time assessment of TBI.

Inverting Triiodide Formation Reaction by Synergy between Strong Electrolyte Solvation and Cathode Adsorption

By Xiao-Ping Zhang, Yan-Ni Li, Yi-Yang Sun, Tao Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

An exceptionally strong solvation effect of dimethyl sulfoxide (DMSO) on I 2 is identified by so far the largest observed shift of I 2 Raman peak with respect to I 2 vapor and by elongated I–I bond length in first‐principles molecular‐dynamics simulation. This effect together with strong binding of RuO 2 surface to I 2 is found to invert the direction of the well‐known reaction I − + I 2 à I 3 − to the left‐hand side. Inspired by this finding, we fabricated Li–O 2 battery with the Li/DMSO+LiI/RuO 2 structure. The synergic action of DMSO and RuO 2 on I 2 is found to suppress the shuttle effect of redox mediator (RM) by anchoring I 2 molecules, the oxidation product of the RM. Significantly enhanced stability is demonstrated over 100 cycles at charging voltage below 3.65 V.

Molecular Engineering of 3D Self‐Supported Electrode for Oxygen Electrocatalysis in Neutral Media

By Lisi Xie, Xialiang Li, Bin Wang, Jia Meng, Haitao Lei, Wei Zhang, Rui Cao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Electrodes for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are required in energy conversion and storage technologies. We herein report an assembly strategy by covalently grafting Co corrole 1 onto Fe 3 O 4 nanoarrays grown on Ti mesh. The resulted electrode shows significantly improved activity and durability for OER and ORR in neutral media as compared to Fe 3 O 4 alone and with directly adsorbed 1 . It also displays higher atom efficiency − at least two magnitudes larger turnover frequency − than reported electrodes. Using this electrode in neutral Zn‐air battery, small charge‐discharge voltage gap of 1.19 V, large peak power density of 90.4 mW/cm 2 , and high rechargeable stability for >100 h are achieved, opening a promising avenue of molecular electrocatalysis in metal‐air battery. This work represents molecule‐engineered electrodes for electrocatalysis and demonstrates their potential applications in energy conversion and storage.

Bottom‐Up Assembly of DNA–Silica Nanocomposites into Micrometer‐Sized Hollow Spheres

By Yong Hu, Maximilian Grösche, Sahana Sheshachala, Claude Oelschlaeger, Norbert Willenbacher, Kersten S. Rabe, Christof M. Niemeyer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Hierarchically structured composite materials made from silica nanoparticles and DNA polymers (red) can be self‐assembled by the clamped hybridization chain reaction into thin layers within microfluidically generated water‐in‐oil droplets to produce mechanically stabilized micrometer‐sized hollow spheres that hold potential for applications in the life sciences. Abstract Although DNA nanotechnology has developed into a highly innovative and lively field of research at the interface between chemistry, materials science, and biotechnology, there is still a great need for methodological approaches for bridging the size regime of DNA nanostructures with that of micrometer‐ and millimeter‐sized units for practical applications. We report on novel hierarchically structured composite materials from silica nanoparticles and DNA polymers that can be obtained by self‐assembly through the clamped hybridization chain reaction. The nanocomposite materials can be assembled into thin layers within microfluidically generated water‐in‐oil droplets to produce mechanically stabilized hollow spheres with uniform size distributions at high throughput rates. The fact that cells can be encapsulated in these microcontainers suggests that our concept not only contributes to the further development of supramolecular bottom‐up manufacturing, but can also be exploited for applications in the life sciences.

Low Dose of X‐Ray‐Excited Long‐Lasting Luminescent Concave Nanocubes in Highly Passive Targeting Deep‐Seated Hepatic Tumors

By Zheng‐Zhe Chen, Liu‐Chun Wang, Divinah Manoharan, Chin‐Lai Lee, Lai‐Chin Wu, Wan‐Ting Huang, Eng‐Yen Huang, Chia‐Hao Su, Hwo‐Shuenn Sheu, Chen‐Sheng Yeh from Wiley: Advanced Materials: Table of Contents. Published on Oct 18, 2019.

Dispersed and well‐defined ZnGa2O4:Cr3+ (ZGC) concave nanocubes are reported as providing highly passive targeting of deep‐seated hepatic tumors. They also exhibit much stronger long‐lasting luminescence in UV and X‐ray excitation for the dispersed cubic ZGC compared with the agglomerative form that cannot be charged using X‐rays with a low dose of 0.5 Gy. Abstract Chromium‐doped zinc gallate, ZnGa2O4:Cr3+ (ZGC), is viewed as a long‐lasting luminescence (LLL) phosphor that can avoid tissue autofluorescence interference for in vivo imaging detection. ZGC is a cubic spinel structure, a typical agglomerative or clustered morphology lacking a defined cubic shape, but a sphere‐like feature is commonly obtained for the nanometric ZGC. The substantial challenge remains achieving a well‐defined cubic feature in nanoscale. The process by which dispersed and well‐defined concave cubic ZGC is obtained is described, exhibiting much stronger LLL in UV and X‐ray excitation for the dispersed cubic ZGC compared with the agglomerative form that cannot be excited using X‐rays with a low dose of 0.5 Gy. The cubic ZGC reveals a specific accumulation in liver and 0.5 Gy used at the end of X‐ray excitation is sufficient for imaging of deep‐seated hepatic tumors. The ZGC nanocubes show highly passive targeting of orthotopic hepatic tumors.

Water‐Triggered Hyperbranched Polymer Universal Adhesives: From Strong Underwater Adhesion to Rapid Sealing Hemostasis

By Chunyan Cui, Chuanchuan Fan, Yuanhao Wu, Meng Xiao, Tengling Wu, Dongfei Zhang, Xinyu Chen, Bo Liu, Ziyang Xu, Bo Qu, Wenguang Liu from Wiley: Advanced Materials: Table of Contents. Published on Oct 18, 2019.

A hyperbranched polymer adhesive fabricated using a ternary Michael addition reaction of hydrophobic multi‐vinyl monomers with dopamine demonstrates strong underwater adhesion to diverse materials without any oxidant. This is due to water‐triggered fast coacervation and increased outward exposure of catechols. Introducing long‐chain alkylamine contributes to formation of an injectable hemostatic sealant that can rapidly stop visceral bleeding, especially hemorrhage from deep wound. Abstract Despite recent advance in bioinspired adhesives, achieving strong adhesion and sealing hemostasis in aqueous and blood environments is challenging. A hyperbranched polymer (HBP) with a hydrophobic backbone and hydrophilic adhesive catechol side branches is designed and synthesized based on Michael addition reaction of multi‐vinyl monomers with dopamine. It is demonstrated that upon contacting water, the hydrophobic chains self‐aggregate to form coacervates quickly, displacing water molecules on the adherent surface to trigger increased exposure of catechol groups and thus rapidly strong adhesion to diverse materials from low surface energy to high energy in various environments, such as deionized water, sea water, PBS, and a wide range of pH solutions (pH = 3 to 11) without use of any oxidant. Also, this HBP adhesive (HBPA) exhibits a robust adhesion to fractured bone, precluding the problem of mismatched surface energy and mechanical properties. The HBPA's adhesion is repeatable in a wet condition. Intriguingly, the HBPA is capable of gluing dissimilar materials with distinct properties. Importantly, introducing long alkylamine into this modular hyperbranched architecture contributes to formation of an injectable hemostatic sealant that can rapidly stop visceral bleeding, especially hemorrhage from deep wound.

A Supramolecular Artificial Light‐harvesting System with Two‐step Sequential Energy Transfer for Photochemical Catalysis

By Min Hao, Guangping Sun, Minzan Zuo, Zuqiang Xu, Yuan Chen, Xiao-Yu Hu, Leyong Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

An artificial light‐harvesting system with sequential energy‐transfer process is successfully fabricated in aqueous environment based on the supramolecular strategy. Self‐assembled from the host‐guest complex formed by water‐soluble pillar[5]arene ( WP5 ) and a bola‐type tetraphenylethylene‐functionalized dialkyl ammonium derivative ( TPEDA ), as well as two fluorescent dyes, Eosin Y ( ESY ) and Nile Red ( NiR ), the obtained supramolecular vesicles can achieve efficient energy transfer from the AIE guest TPEDA to ESY at a high energy‐transfer efficiency and donor/acceptor ratio. Moreover, ESY can function as a relay to further transfer the energy to the second acceptor NiR and realize the two‐step sequential energy‐transfer process with good efficiency. By properly tuning the ratio between the donor and acceptors, bright white light emission can be successfully achieved with a CIE coordinate of (0.33, 0.33). More importantly, to better mimic the natural photosynthesis and make full use of the harvested energy, the WP5 ⊃ TPEDA‐ ESY‐NiR system can be utilized as a nanoreactor, where photocatalysed dehalogenation of α‐bromoacetophenone can be realized with 96% yield in aqueous medium.

Boron: Its role in energy related research and applications

By Zhenguo Huang, Suning Wang, Rian D. Dewhurst, Nikolai V. Ignat’ev, Maik Finze, Holger Braunschweig from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Boron’s uniqueposition in the periodic table, i.e. at the apex of the line separating metals and nonmetals, makes it highly versatile in chemical reactions and applications. Contemporary demand for renewable and clean energy and energy‐efficient products has seen boron playing key roles in energy‐related research, from activating and synthesizing energy‐rich small molecules, to storing chemical and electrical energy, to converting electrical energy to light. These applications are fundamentally associated with boron’s unique characteristics, such as its electron‐deficiency and the availability of an unoccupied p orbital, which allow the formation of a myriad of compounds with great tunability in chemical and physical properties. For example, boron's ability to achieve a full octet of electrons with four covalent bonds and a negative charge has led to the synthesis of a wide variety of borate anions of high chemical and electrochemical stability, in particular the useful family of weakly coordinating anions. This review summarizes recent advances in the study of boron compounds for energy‐related research and applications, driven by modern demands and enabled by breakthroughs in the synthesis and understanding of boron chemistry.

Enantioselective Synthesis of Chiral Synthons for Artificial Dipeptide Sweeteners Catalyzed by an Engineered C‐N Lyase

By Jielin Zhang, Eleonora Grandi, Haigen Fu, Thangavelu Saravanan, Laura Bothof, Pieter G. Tepper, Andy-Mark W. H. Thunnissen, Gerrit Jan Poelarends from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Aspartic acid derivatives with branched N ‐alkyl or N ‐arylalkyl substituents are valuable precursors to artificial dipeptide sweeteners such as neotame and advantame, which have wide‐ranging applications in the food industry. Despite the potential applications of these amino acid precursors to aspartame‐based sweeteners, the development of a biocatalyst to synthesize these compounds in a single asymmetric step is an as yet unmet challenge. Herein we report an enantioselective biocatalytic synthesis of various difficult N ‐substituted aspartic acids including N ‐(3,3‐dimethylbutyl)‐L‐aspartic acid and N ‐[3‐(3‐hydroxy‐4‐methoxyphenyl)propyl]‐L‐aspartic acid, precursors to neotame and advantame respectively, using an engineered variant of ethylenediamine‐ N , N '‐disuccinic acid (EDDS) lyase from Chelativorans sp. BNC1. This engineered C‐N lyase (mutant D290M/Y320M) displayed a remarkable 1140‐fold increase in activity for the selective hydroamination of fumarate compared to that of the wild‐type enzyme, which could be rationalized from the analysis of crystal structures. These results open up new opportunities to develop practical multienzymatic processes for the more sustainable and step‐economic synthesis of an important class of food additives.

Cu‐Mediated Amination of (Hetero)aryl C–H bonds with NH Azaheterocycles

By Jin-Feng Yu, Jian-Jun Li, Peng Wang, Jin-Quan Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

The direct synthesis of N ‐(hetero)arylated heteroarenes has been realized via Cu‐mediated C–N coupling of NH azaheterocycles with aryl C–H bonds under aerobic conditions. This protocol features a broad scope of both heterocyclic arenes (pyridine, quinoline, pyrazole, imidazole, furan, thiophene, benzofuran, and indole) and NH azaheterocycles (imidazole, pyrazole, indole, azindole, purine, indazole, benzimidazole, pyridone, carbazole), providing a versatile method for the synthesis of pharmaceutically important N ‐(hetero)arylated heteroarenes. The versatility of this reaction was further demonstrated by late‐stage modification of marketed drugs, and by synthesis of a key intermediate for accessing a class of Angiotensin II receptor 1 antagonists.

The core fucose on an IgG antibody is an endogenous ligand of Dectin‐1

By Yoshiyuki Manabe, Roberta Marchetti, Yohei Takakura, Masahiro Nagasaki, Wataru Nihei, Tomoyuki Takebe, Katsunori Tanaka, Kazuya Kabayama, Fabrizio Chiodo, Shinya Hanashima, Yoshihiro Kamada, Eiji Miyoshi, Hari Prasad Dulal, Yoshiki Yamaguchi, Yoshiyuki Adachi, Naohito Ohno, Hiroshi Tanaka, Alba Silipo, Koichi Fukase, Antonio Molinaro from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

The core fucose, a major modification of  N ‐glycans, is implicated in immune regulation, such as the attenuation of the antibody‐dependent cell‐mediated cytotoxicity of antibody drugs and the inhibition of anti‐tumor responses via promotion of PD‐1 expression on T cells. Although the core fucose regulates many biological processes, no core fucose recognition molecule has been identified in mammals. In the present study, we discovered that Dectin‐1, a known anti‐ b ‐glucan lectin, recognizes the core fucose on IgGs. A combination of biophysical experiments further suggested that Dectin‐1 recognizes aromatic amino acids adjacent to the  N ‐terminal asparagine residue at the glycosylation site as well as core fucose residue. Thus, Dectin‐1 appears to be the first lectin‐like molecule involved in the hetero‐valent and specific recognition of characteristic  N ‐glycans on antibodies.

Dynamic Open Coordination Cage from Non‐symmetrical Imidazole‐Pyridine Ditopic Ligands for Turn‐On/Off Anion Binding

By Daiji Ogata, Junpei Yuasa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

This work demonstrates a new non‐conventional ligand design, imidazole/pyridine‐based non‐symmetrical ditopic ligands ( 1 and 1 S ), to construct a dynamic open coordination cage from non‐symmetrical building constituents. Upon complex formation with Pd 2+ at a 1:4 molar ratio, 1 and 1 S initially form mononuclear PdL 4 complexes (Pd 2+ ( 1 ) 4 and Pd 2+ ( 1 S ) 4 ) without formation of a cage. The PdL 4 complexes undergo a stoichiometrically controlled structural transition to Pd 2 L 4 open cages ((Pd 2+ ) 2 ( 1 ) 4 and (Pd 2+ ) 2 ( 1 S ) 4 ) capable of anion binding, leading to turn‐on anion binding. The structural transitions between the Pd 2 L 4 open cage and the  PdL 4 complex are reversible. Thus, stoichiometric addition (2 eq) of free 1 S to the (Pd 2+ ) 2 ( 1 S ) 4 open cage holding a guest anion ((Pd 2+ ) 2 ( 1 S ) 4 ·G – ) enables the structural transition to the Pd 2+ ( 1 S ) 4 complex without the cage, which causes the release of the guest anion (Pd 2+ ( 1 S ) 4 + G – ).

Palladium‐Borane Cooperation: Evidence for an Anionic Pathway and its Application to Catalytic Hydro‐ / Deutero‐dechlorination

By Hajime Kameo, Jun Yamamoto, Ayaka Asada, Hiroshi Nakazawa, Hiroyuki Matsuzaka, Didier Bourissou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Metal‐Lewis acid cooperation provides new opportunities in catalysis. In this work, we report a new type of palladium‐borane cooperation involving anionic Pd(0) species. The air‐stable DPB palladium complex 1 (DPB = diphosphine‐borane) was prepared and reacted with KH to give the Pd(0) borohydride 2, the first monomeric anionic Pd(0) species to be structurally characterized. The boron moiety acts as an acceptor towards Pd in 1 via Pd→B interaction, but as a donor in 2 thanks to B–H–Pd bridging. This enables the activation of C–Cl bonds and the system is amenable to catalysis, as demonstrated by the hydro‐ / deutero‐dehalogenation of a variety of (hetero)aryl chlorides (20 examples, average yield 85%).

An Organic Crystal with High Elasticity at an Ultra‐Low Temperature (77 K) and Shapeability at High Temperatures

By Hongyu Zhang, Huapeng Liu, Kaiqi Ye, Zuolun Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Organic single crystals with the elastic bending capability have been known recently, and potential applications of this type of unusual crystals in flexible devices and sensors have been elucidated. Exploring the temperature compatibility of elasticity is essential for defining application boundaries of elastic materials. However, related studies have rarely been reported for elastic organic crystals. Here, we show an organic crystal which displays elasticity even in liquid nitrogen (77 K). The elasticity can be maintained below ca. 150 °C. At higher temperatures, the heat setting property enabling us to make various shapes of crystals based on this single kind of crystal can be achieved. Through detailed crystallographic analyses and contrast experiments, the mechanisms behind the unusual low‐temperature elasticity and high‐temperature heat setting are disclosed.

Phosphorylation Reduces the Mechanical Stability of α‐Catenin/β‐Catenin Complex

By Jie Yan, Shimin Le, Miao Yu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

The α‐catenin/β‐catenin complex serves as a critical molecular interface involved in the cadherin‐catenin based mechanosensing at cell‐cell adherence junction (AJ) that plays a critical role in tissue integrity, repair and embryonic development. The α‐catenin/β‐catenin complex is subject to tensile forces due to internal actomyosin contractility and external mechanical micro‐environmental perturbation. However, the mechanical stability of this critical inter‐molecular complex has yet to be quantified. In this work, by direct quantification of the mechanical stability of the α‐catenin/β‐catenin complex, we found that the complex has sufficient mechanical stability to survive for tens to hundreds of seconds within physiological level of forces up to 10 pN. Importantly, tyrosine‐phosphorylation or tyrosine‐phosphorylation‐mimic mutation (Y142E) on β‐catenin shorten the mechanical lifetime of the complex by 10‐to‐100 folds over the same force range. Furthermore, phosphorylation‐mimic mutations of both tyrosine (Y142E) and threonine (T120E) on β‐catenin cause a further decrease in the mechanical stability of the complex. Together, these results provide the quantification of the α‐catenin/β‐catenin complex’s mechanical stability and important insights into its regulation by phosphorylation.

Disclosing Interfaces of ZnO Nanocrystals Using Dynamic Nuclear Polarization: Sol‐Gel versus Organometallic Approach

By Daniel Lee, Małgorzata Wolska‐Pietkiewicz, Saumya Badoni, Agnieszka Grala, Janusz Lewiński, Gaël De Paëpe from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Strong and stable. ZnO nanocrystals derived from a one‐pot self‐supporting organometallic (OSSOM) approach have a stable and organized surface‐ligand union. Conversely, a sol‐gel approach provides limited stable cold spots with the majority of native ligands having their surface‐supporting roles taken by foreign solvent molecules. This highlights the superiority of the OSSOM approach for the preparation of quantum‐sized ZnO crystals. Abstract The unambiguous characterization of the coordination chemistry of nanocrystal surfaces produced by wet‐chemical synthesis presently remains highly challenging. Here, zinc oxide nanocrystals (ZnO NCs) coated by monoanionic diphenyl phosphate (DPP) ligands were derived by a sol‐gel process and a one‐pot self‐supporting organometallic (OSSOM) procedure. Atomic‐scale characterization through dynamic nuclear polarization (DNP‐)enhanced solid‐state NMR (ssNMR) spectroscopy has notably enabled resolving their vastly different surface‐ligand interfaces. For the OSSOM‐derived NCs, DPP moieties form stable and strongly‐anchored μ2‐ and μ3‐bridging‐ligand pairs that are resistant to competitive ligand exchange. The sol‐gel‐derived NCs contain a wide variety of coordination modes of DPP ligands and a ligand exchange process takes place between DPP and glycerol molecules. This highlights the power of DNP‐enhanced ssNMR for detailed NC surface analysis and of the OSSOM approach for the preparation of ZnO NCs.

Surface Plasmon Resonance Microscopy: From Single‐Molecule Sensing to Single‐Cell Imaging

By Xiao‐Li Zhou, Yunze Yang, Shaopeng Wang, Xian‐Wei Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Surface plasmon resonance microscopy has emerged as a versatile platform for single‐molecule sensing and single‐cell imaging with high spatiotemporal resolution. This Minireview highlights the recent advances in the SPRM‐based analysis of single entities. Future challenges and their limitations as well as potential research directions are discussed. Abstract Surface plasmon resonance microscopy (SPRM) is a versatile platform for chemical and biological sensing and imaging. Great progress in exploring its applications, ranging from single‐molecule sensing to single‐cell imaging, has been made. In this Minireview, we introduce the principles and instrumentation of SPRM. We also summarize the broad and exciting applications of SPRM to the analysis of single entities. Finally, we discuss the challenges and limitations associated with SPRM and potential solutions.

Novel DNA Helical Wire Containing HgII‐Mediated T:T and T:G Pairs

By Akira Ono, Hiroki Kanazawa, Hikari Ito, Misato Goto, Koudai Nakamura, Hisao Saneyoshi, Jiro Kondo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 18, 2019.

Live wire: A Hg‐DNA helical wire containing HgII‐mediated T:T and T:G base pairs and water‐mediated C:C pairs was obtained by mixing the short oligonucleotide 5′‐d(TTTGC)‐3′ and HgII ions. This novel DNA nanowire, which contains no Watson–Crick base pairs, was structurally characterized by X‐ray crystallography. Abstract Numerous applications of metal‐mediated base pairs (metallo‐base‐pairs) to nucleic acid based nanodevices and genetic code expansion have been extensively studied. Many of these metallo‐base‐pairs are formed in DNA and RNA duplexes containing Watson–Crick base pairs. Recently, a crystal structure of a metal–DNA nanowire with an uninterrupted one‐dimensional silver array was reported. We now report the crystal structure of a novel DNA helical wire containing HgII‐mediated T:T and T:G base pairs and water‐mediated C:C base pairs. The Hg‐DNA wire does not contain any Watson–Crick base pairs. Crystals of the Hg‐DNA wire, which is the first DNA wire structure driven by HgII ions, were obtained by mixing the short oligonucleotide d(TTTGC) and HgII ions. This study demonstrates the potential of metallo‐DNA to form various structural components that can be used for functional nanodevices.

[ASAP] Anisotropic Hollow Microgels That Can Adapt Their Size, Shape, and Softness

By Anne C. Nickel†, Andrea Scotti*†, Judith E. Houston‡§, Thiago Ito?, Je´ro^me Crassous†, Jan Skov Pedersen?, and Walter Richtering*†# from Nano Letters: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03507

[ASAP] Label-Free Detection of Post-translational Modifications with a Nanopore

By Laura Restrepo-Pe´rez†, Chun Heung Wong†, Giovanni Maglia‡, Cees Dekker*†, and Chirlmin Joo*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03134

[ASAP] Electronic Skin for Closed-Loop Systems

By Chunfeng Wang†‡§, Caofeng Pan*†‡?, and Zhonglin Wang*†‡?? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06576

[ASAP] Surface Wettability-Directed Propulsion of Glucose-Powered Nanoflask Motors

By Changyong Gao†, Chang Zhou†, Zhihua Lin†, Mingcheng Yang*‡, and Qiang He*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04708

[ASAP] Extravasating Neutrophils Open Vascular Barrier and Improve Liposomes Delivery to Tumors

By Victor A. Naumenko*†, Kseniya Yu. Vlasova‡, Anastasiia S. Garanina†, Pavel A. Melnikov§, Daria M. Potashnikova?, Daniil A. Vishnevskiy§, Stepan S. Vodopyanov†, Vladimir P. Chekhonin§, Maxim A. Abakumov†§, and Alexander G. Majouga†? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03848

[ASAP] Graphene Sandwich Stable Perovskite Quantum-Dot Light-Emissive Ultrasensitive and Ultrafast Broadband Vertical Phototransistors

By Krishna Prasad Bera†‡, Golam Haider§, Yu-Ting Huang†, Pradip Kumar Roy†, Christy Roshini Paul Inbaraj‡?, Yu-Ming Liao†‡, Hung-I Lin†, Cheng-Hsin Lu?, Chun Shen?, Wan Y Shih#, Wei-Heng Shih?, and Yang-Fang Chen*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03165

[ASAP] Isotopic-Perturbation NMR Study of Hydrogen-Bond Symmetry in Solution: Temperature Dependence and Comparison of OHO and ODO Hydrogen Bonds

By Charles L. Perrin*, Annadka Shrinidhi, and Kathryn D. Burke† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08492

[ASAP] Macrocyclization of a Class of Camptothecin Analogues into Tubular Supramolecular Polymers

By Hao Su†, Feihu Wang†, Yuzhu Wang†, Andrew G. Cheetham†, and Honggang Cui*†‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09848

[ASAP] Diastereo- and Atroposelective Synthesis of Bridged Biaryls Bearing an Eight-Membered Lactone through an Organocatalytic Cascade

By Shenci Lu†‡, Jun-Yang Ong†§, Hui Yang†, Si Bei Poh†, Xi Liew†, Chwee San Deborah Seow†, Ming Wah Wong*†, and Yu Zhao*†¶ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08510

[ASAP] Re(tBu-bpy)(CO)3Cl Supported on Multi-Walled Carbon Nanotubes Selectively Reduces CO2 in Water

By Almagul Zhanaidarova†, Simon C. Jones‡, Emmanuelle Despagnet-Ayoub‡§, Brian R. Pimentel?, and Clifford P. Kubiak*†? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08445

[ASAP] Tuning the Molecular and Cationic Affinity in a Series of Multifunctional Metal–Organic Frameworks Based on Dodecanuclear Zn(II) Carboxylate Wheels

By Anna A. Lysova†‡, Denis G. Samsonenko†‡, Pavel V. Dorovatovskii§, Vladimir A. Lazarenko§, Victor N. Khrustalev?, Konstantin A. Kovalenko†‡, Danil N. Dybtsev*†‡, and Vladimir P. Fedin†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08322

[ASAP] Transition from Ferromagnetic Semiconductor to Ferromagnetic Metal with Enhanced Curie Temperature in Cr2Ge2Te6 via Organic Ion Intercalation

By Naizhou Wang†?, Huaibao Tang‡?, Mengzhu Shi†, Hui Zhang‡, Weizhuang Zhuo†, Dayong Liu§, Fanbao Meng†, Likuan Ma†, Jianjun Ying†, Liangjian Zou*§, Zhe Sun?, and Xianhui Chen*†?#¶ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06929

[ASAP] Separation of Monochlorotoluene Isomers by Nonporous Adaptive Crystals of Perethylated Pillar[5]arene and Pillar[6]arene

By Mengbin Wang, Jiong Zhou, Errui Li, Yujuan Zhou, Qing Li, and Feihe Huang* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09988

Light Activated Synthesis of the Atomically Precise Fluorescent Silver Cluster Ag18(Capt)14

By Kevin Stamplecoskie from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07626C, Communication
Hannah Ramsay, Max Silverman, David J Simon, Richard Oleschuk, Kevin Stamplecoskie
Metal clusters of gold and silver with highly tunable optical and electronic properties are attractive candidates for next generation medical imaging and therapy. Of these two most commonly studied metals,...
The content of this RSS Feed (c) The Royal Society of Chemistry

Repurposing of Cetuximab in antibody-directed chemotherapy-loaded nanoparticles in EGFR therapy-resistant pancreatic tumours

By Christopher J. Scott from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR07257H, Paper
William J. McDaid, Michelle K. Greene, Michael C. Johnston, Ellen Pollheimer, Peter Smyth, Kirsty McLaughlin, Sandra Van Schaeybroeck, Robert M. Straubinger, Daniel B. Longley, Christopher J. Scott
The use of CTX as a targeting agent for camptothecin-loaded polymeric nanoparticles directed against KRAS mutant CTX-resistant cancer cells was investigated. CTX increased CPT internalisation into cancer cells resulting in elevated cancer cell death.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Photocatalytic activity of exfoliated graphite–TiO2 nanoparticle composites

By Marco Montalti from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR06760D, Communication
Gloria Guidetti, Eva A. A. Pogna, Lucia Lombardi, Flavia Tomarchio, Iryna Polishchuk, Rick R. M. Joosten, Alessandro Ianiro, Giancarlo Soavi, Nico A. J. M. Sommerdijk, Heiner Friedrich, Boaz Pokroy, Anna K. Ott, Marco Goisis, Francesco Zerbetto, Giuseppe Falini, Matteo Calvaresi, Andrea C. Ferrari, Giulio Cerullo, Marco Montalti
We report the photocatalytic performance of composites prepared in a one-step process by liquid phase exfoliation of graphite and TiO2 at atmospheric pressure and in water, without heat or surfactants, starting from low-cost commercial reagents.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Large-area, lithography-free, narrow-band and highly directional thermal emitter

By Xuechu Shen from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR06181A, Communication
Open Access Open Access
Xingxing Liu, Zhiwei Li, Zhengji Wen, Mingfei Wu, Jialiang Lu, Xu Chen, Xinchao Zhao, Tao Wang, Ruonan Ji, Yafeng Zhang, Liaoxin Sun, Bo Zhang, Hao Xu, Jing Zhou, Jiaming Hao, Shaowei Wang, Xiaoshuang Chen, Ning Dai, Wei Lu, Xuechu Shen
In this work, the authors propose and experimentally demonstrate a large-area long-wavelength infrared thermal emitter, which is spectrally selective, highly directional, and easily fabricated.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Chiroptical Study of Bimetal-cysteine Hybrid Composite: Interaction between Cysteine and Au/Ag Alloyed Nanotubes

By Yu Wang from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07421J, Paper
Huali Liu, Zhen Li, Yan Yan, Jiaqi Zhao, Yu Wang
The coupling between noble metal nanostructures and chiral molecules gives rise to strong chiroptical response in the range from Ultraviolet (UV) to visible spectrum. In this work, the cysteine-modified Au/Ag...
The content of this RSS Feed (c) The Royal Society of Chemistry

Synthesis of sub-micrometer biphasic Au-AuGa2 / Liquid Metal frameworks

By Norihisa Miki from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR05551G, Paper
Romain David, Norihisa Miki
A novel biphasic sub-micrometer Au-AuGa2/liquid metal framework, consisting of solid nanoparticles encapsulating liquid metal (LM) droplets, is introduced. By utilizing oxide-free galvanic replacement of Ga-alloy LM with alkaline KAuBr4, the...
The content of this RSS Feed (c) The Royal Society of Chemistry

Molecular Mechanism of Robust Macrophage Immune Responses Induced by PEGylated Molybdenum Disulfide

By Ruhong Zhou from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04358F, Paper
Zonglin Gu, Serena H. Chen, Zhaowen Ding, Wei Song, Wei Wei, Shengtang Liu, Guanghui Ma, Ruhong Zhou
Molybdenum disulfide (MoS2), a representative hexagonal transition metal dichalcogenide (TMD), has been extensively exploited in biomedical applications due to its unique physicochemical properties and biocompatibility. However, the lack of adequate...
The content of this RSS Feed (c) The Royal Society of Chemistry

Investigation of surface confinement effect of copper nanoclusters: construction of ultrasensitive fluorescence turn-on bio-enzyme sensing platform

By Qiong Jia from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06036G, Paper
Jinlan Yang, Naizhong Song, Qiong Jia
Copper nanoclusters (CuNCs) have attracted considerable research interest due to their good physicochemical properties, easy preparation, and low price. However, the low quantum yield and poor stability in aqueous solutions...
The content of this RSS Feed (c) The Royal Society of Chemistry

3D Halos Assembled from Fe3O4/Au NPs with Enhanced Catalytic and Optical Properties

By Weihong Tan from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR05874E, Paper
Ren Cai, Dan Yang, Keng-Te Lin, Thai Son Cao, Yifan Lv, Kangfu Chen, Lu Yang, Jia Ge, Lian Xia, George Christou, yuliang zhao, Zhuo Chen, Weihong Tan
3D structures assembled from multiple components have attracted increasing research interest based on their enriched functionalities and broadened applications. Here, we report a bottom-up strategy to fabricate 3D halos through...
The content of this RSS Feed (c) The Royal Society of Chemistry

High-Performance NO2 Sensors Based on Spontaneously Functionalized Hexagonal Boron Nitride Nanosheets via Chemical Exfoliation

By Yanfeng Sun from RSC - Nanoscale latest articles. Published on Oct 18, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07153A, Paper
Yue He, Dongdong Li, Wei Gao, Hong Yin, Fang Chen, Yanfeng Sun
Atomically thin hexagonal boron nitride nanosheets (BNNSs) have been widely explored for various applications due to their unique properties; however, sensing gas molecules with high sensitivity and selectivity remains challenging...
The content of this RSS Feed (c) The Royal Society of Chemistry

Heteroatom‐Mediated Interactions between Ruthenium Single Atoms and an MXene Support for Efficient Hydrogen Evolution

By Vinoth Ramalingam, Purushothaman Varadhan, Hui‐Chun Fu, Hyunho Kim, Daliang Zhang, Shuangming Chen, Li Song, Ding Ma, Yun Wang, Husam N. Alshareef, Jr‐Hau He from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

Ti3C2Tx MXene is demonstrated as a 2D solid support to host a ruthenium single atom (RuSA) catalyst for water splitting. The resultant RuSA‐N‐S‐Ti3C2Tx catalyst coupled with n+np+‐Si photocathode enables photoelectrochemical H2 production with exceptionally high photocurrent density of 37.6 mA cm−2 under AM 1.5G illumination. Abstract A titanium carbide (Ti3C2Tx) MXene is employed as an efficient solid support to host a nitrogen (N) and sulfur (S) coordinated ruthenium single atom (RuSA) catalyst, which displays superior activity toward the hydrogen evolution reaction (HER). X‐ray absorption fine structure spectroscopy and aberration corrected scanning transmission electron microscopy reveal the atomic dispersion of Ru on the Ti3C2Tx MXene support and the successful coordination of RuSA with the N and S species on the Ti3C2Tx MXene. The resultant RuSA‐N‐S‐Ti3C2Tx catalyst exhibits a low overpotential of 76 mV to achieve the current density of 10 mA cm−2. Furthermore, it is shown that integrating the RuSA‐N‐S‐Ti3C2Tx catalyst on n+np+‐Si photocathode enables photoelectrochemical hydrogen production with exceptionally high photocurrent density of 37.6 mA cm−2 that is higher than the reported precious Pt and other noble metals catalysts coupled to Si photocathodes. Density functional theory calculations suggest that RuSA coordinated with N and S sites on the Ti3C2Tx MXene support is the origin of this enhanced HER activity. This work would extend the possibility of using the MXene family as a solid support for the rational design of various single atom catalysts.

Room‐Temperature Active Modulation of Valley Dynamics in a Monolayer Semiconductor through Chiral Purcell Effects

By Zilong Wu, Jingang Li, Xiaotian Zhang, Joan M. Redwing, Yuebing Zheng from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

Monolayer semiconductors with spin‐dependent contrasting phenomena at K and K′ valleys feature addressable valley degree of freedom for valleytronic applications. Chiral Purcell effects in plasmonic chiral metamaterials are demonstrated to be able to control the relaxation of targeted valley excitons at a monolayer WSe2 in a versatile way, allowing the actively tunable modulation of valley dynamics at room temperature. Abstract Spin‐dependent contrasting phenomena at K and K′ valleys in monolayer semiconductors have led to addressable valley degree of freedom, which is the cornerstone for emerging valleytronic applications in information storage and processing. Tunable and active modulation of valley dynamics in a monolayer WSe2 is demonstrated at room temperature through controllable chiral Purcell effects in plasmonic chiral metamaterials. The strong spin‐dependent modulation on the spontaneous decay of valley excitons leads to tunable handedness and spectral shift of valley‐polarized emission, which is analyzed and predicted by an advanced theoretical model and further confirmed by experimental measurements. Moreover, large active spectral tuning (≈24 nm) and reversible ON/OFF switching of circular polarization of emission are achieved by the solvent‐controllable thickness of the dielectric spacer in the metamaterials. With the on‐demand and active tunability in valley‐polarized emission, chiral Purcell effects can provide new strategies to harness valley excitons for applications in ultrathin valleytronic devices.

A novel long‐range n to π* interaction secures the smallest known α‐helix in water

By Huy N. Hoang, Chongyang Wu, Timothy A. Hill, Aline D. de Araujo, Paul V. Bernhardt, Ligong Liu, David P Fairlie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

An amide bond linking side chains of the first and fifth amino acids forms a cyclic pentapeptide that optimally stabilizes the smallest known alpha helix in water. The origin of stabilization is unclear. Dependence of alpha helicity on solvent and cyclization linker led us to discover a novel long‐range n to p* interaction between a mainchain amide oxygen and a uniquely positioned carbonyl group in the linker of cyclic pentapeptides. CD and NMR spectra, NMR and X‐ray structures, modelling and MD simulations reveal this first example of a synthetically incorporated long‐range n to p* CO…C=O interaction that uniquely enforces an almost perfect and remarkably stable peptide alpha helix in water, but not in DMSO. This unusual interaction with a covalent amide bond outside the helical backbone suggests new approaches to synthetically stabilize peptide structures in water.

Polymorphism of L‐Tryptophan

By Okba Al Rahal, Colan Hughes, Andrew Williams, Andrew J Logsdail, Yael Diskin-Posner, Kenneth David Maclean Harris from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

A new polymorph of L‐tryptophan has been prepared by crystallization from the gas phase, with structure determination carried out directly from powder XRD data augmented by periodic DFT‐D calculations. The new polymorph (denoted β) and the previously reported polymorph (denoted α) are both based on alternating hydrophilic and hydrophobic layers, but with substantially different hydrogen‐bonding arrangements. The β polymorph exhibits the energetically favourable L2‐L2 hydrogen‐bonding arrangement, which is unprecedented for amino acids with aromatic side‐chains; the specific molecular conformations adopted in the β polymorph facilitate this hydrogen‐bonding scheme while avoiding steric conflict of the side‐chains.

The electron spin as a chiral reagent

By Ron Naaman, Tzuriel S. Metzger, Suryakant Mishra, Brian P. Bloom, Naama Goren, Avner Neubauer, Guy Shmul, Jimeng Wei, Shira Yochelis, Francesco Tassinari, Claudio Fontanesi, David H. Waldeck, Yossi Paltiel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

In contrast to the notion that enantiospecific chemical reactions require a chiral reagent molecule or catalyst, this work shows that enantioselective chemical transformations can be induced by the electron spin itself. As electrons are injected from a magnetized electrode into an adsorbed molecule, they have a distinct spin orientation relative to their velocity; i.e., they have a well‐defined helicity. Thus, it is possible to replace a conventional enantiopure chemical reagent by spin‐polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry, resulting from electron spin polarization, are presented. The first example demonstrates enantioselective association of a chiral molecule with an achiral self‐assembled monolayer film that is spin‐polarized. The other two studies show that the chiral bias provided by the electron helicity can drive both reduction and oxidation enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interaction of the molecule with the ferromagnetic electrode, but rather it arises from the polarized spin that crosses the interface between the substrate and the molecule. In all three cases, the direction of the electron spin polarization defines the sense (left‐handed versus right‐handed) of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry.

Chemoenzymatic posttranslational modification reactions for the synthesis of Ψ[CH2NH]‐containing peptides

By Yasuharu Kato, Tomohiro Kuroda, Yichao Huang, Risa Ohta, Yuki Goto, Hiroaki Suga from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

The Ψ[CH2NH] reduced amide bond is a peptide isostere widely used in the development of bioactive pseudopeptides. Here we report a method of chemoenzymatic posttranslational modification for the synthesis of Ψ[CH2NH]‐containing peptides converted from ribosomally expressed peptides. The posttranslational conversion composed of an enzymatic cyclodehydration and facile 2‐step chemical reduction achieves deoxygenation of a specific amide bond present on non‐protected peptide in water. This method generating the Ψ[CH2NH] bond in peptide is applicable to various peptide sequences, potentially enabling for the library preparation of Ψ[CH2NH]‐containing peptides.

Compartmentalized Jet Polymerization as a High‐Resolution Process to Continuously Produce Anisometric Microgel Rods with Adjustable Size and Stiffness

By Andreas J. D. Krüger, Onur Bakirman, Luis. P. B. Guerzoni, Alexander Jans, David B. Gehlen, Dirk Rommel, Tamás Haraszti, Alexander J. C. Kuehne, Laura De Laporte from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

Compartmentalized microfluidic jet gelation allows for the continuous high‐throughput fabrication of anisometric microgel rods with adjustable aspect ratio and stiffness. High‐frequency laser pulses initiate local ultra‐fast photopolymerization in jet leading to microgels with rod diameter significantly smaller than the channel diameter to overcome the size limits of established microfluidic plug flow gelation. Abstract In the past decade, anisometric rod‐shaped microgels have attracted growing interest in the materials‐design and tissue‐engineering communities. Rod‐shaped microgels exhibit outstanding potential as versatile building blocks for 3D hydrogels, where they introduce macroscopic anisometry, porosity, or functionality for structural guidance in biomaterials. Various fabrication methods have been established to produce such shape‐controlled elements. However, continuous high‐throughput production of rod‐shaped microgels with simultaneous control over stiffness, size, and aspect ratio still presents a major challenge. A novel microfluidic setup is presented for the continuous production of rod‐shaped microgels from microfluidic plug flow and jets. This system overcomes the current limitations of established production methods for rod‐shaped microgels. Here, an on‐chip gelation setup enables fabrication of soft microgel rods with high aspect ratios, tunable stiffness, and diameters significantly smaller than the channel diameter. This is realized by exposing jets of a microgel precursor to a high intensity light source, operated at specific pulse sequences and frequencies to induce ultra‐fast photopolymerization, while a change in flow rates or pulse duration enables variation of the aspect ratio. The microgels can assemble into 3D structures and function as support for cell culture and tissue engineering.

LiMII(IO3)3 (MII=Zn and Cd): Two Promising Nonlinear Optical Crystals Derived from a Tunable Structure Model of α‐LiIO3

By Ying‐Jie Jia, Yi‐Gang Chen, Yao Guo, Xiao‐Fang Guan, Chengbo Li, Bingxuan Li, Min‐Min Liu, Xian‐Ming Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

3D structure: Two promising nonlinear optical (NLO) crystals LiMII(IO3)3 (MII=Zn and Cd) are rationally designed by the aliovalent substitution strategy. They achieve a suitable balance of excellent properties of larger second‐harmonic generation (SHG) response, wider energy band‐gap and optical transparency window, high large optical‐damage thresholds (LDT) and good stability. Abstract Excellent nonlinear optical materials simultaneously meet the requirements of large SHG response, phase‐matching capability, wide transparency windows, considerable energy band‐gap, good thermal stability and structure stability. Herein, two new promising nonlinear optical (NLO) crystals LiMII(IO3)3 (MII=Zn and Cd) are rationally designed by the aliovalent substitution strategy from the commercialized α‐LiIO3 with the perfect parallel alignment of IO3 groups. Compared with parent α‐LiIO3 and related AI2MIV(IO3)6, the title compounds exhibit more stable covalent 3D structure, and overcome the racemic twinning problem of AI2MIV(IO3)6. More importantly, both compounds inherit NLO‐favorable structure merits of α‐LiIO3 and show larger SHG response (≈14× and ≈12×KDP), shorter absorption edge (294 and 297 nm) with wider energy band‐gap (4.21 and 4.18 eV), good thermal stability (460 and 430 °C), phase‐matching behaviors, wider optical transparency window and good structure stability, achieving an excellent balance of NLO properties.

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

By Jamie Hicks, Andreas Heilmann, Petra Vasko, Jose M. Goicoechea, Simon Aldridge from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Polar opposites: A molecular aluminium oxide anion bearing a highly polarised Al−O bond is found to heterolytically cleave H2 at room temperature and ambient pressure. Abstract Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al bridges, the synthesis of well‐defined, soluble, molecular models for these materials is challenging. Here we show that reactions of the potassium aluminyl complex K2[(NON)Al]2 (NON=4,5‐bis(2,6‐diiso‐propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) with CO2, PhNCO and N2O all proceed via a common aluminium oxide intermediate. This highly reactive species can be trapped by coordination of a THF molecule as the anionic oxide complex [(NON)AlO(THF)]−, which features discrete Al−O bonds and dimerizes in the solid state via weak O⋅⋅⋅K interactions. This species reacts with a range of small molecules including N2O (to give a hyponitrite ([N2O2]2−) complex) and H2, the latter offering an unequivocal example of heterolytic E−H bond cleavage across a main group M−O bond.

The Origin of Superhydrophobicity for Intrinsically Hydrophilic Metal Oxides: A Preferential O2 Adsorption Dominated by Oxygen Vacancies

By Gaocan Qi, Xijun Liu, Chao Li, Cheng Wang, Zhihao Yuan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

The wettability of intrinsically hydrophilic rough‐textured metal oxides is related to oxygen‐vacancy‐dominated gas adsorption. Rough‐textured metal oxides show superhydrophobicity in oxygen but superhydrophilicity in nitrogen. Superhydrophobicity and superhydrophilicity can be achieved on the same metal oxide by tuning the proportion of planes defective in oxygen vacancies. Abstract The superhydrophobicity of intrinsically hydrophilic materials is still not well understood. Now, intrinsically hydrophilic metal oxides with different topographic structures are taken as model materials to reveal the origin of their superhydrophobicity. These metal oxides show enhanced hydrophobicity or superhydrophobicity in O2 relative to that in air, but exhibit superhydrophilic behavior in N2. The presence of rich oxygen vacancies greatly enhanced the adsorption of O2 with an adsorption energy larger than N2 and H2O, resulting in a stable O2 adsorption rather than air‐trapping within grooves of rough‐textured surfaces, which endows these intrinsically hydrophilic oxides with superhydrophobicity. Our results highlight a further understanding of the origin of superhydrophobicity for intrinsically hydrophilic materials, and is of great significance for designing novel devices with desired wettability.

Metal‐Chelated Polymer Nanodiscs for NMR Studies

By Nathaniel Z. Hardin, Vojč Kocman, Giacomo M. Di Mauro, Thirupathi Ravula, Ayyalusamy Ramamoorthy from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Speeding up data acquisition: Design of a polymer nanodisc containing a DOTA chelator enables the utilization of the PRE effect in studies using lipid nanodiscs. This new technique can be applied to water‐soluble biomolecules such as G‐quadruplexes. Abstract Paramagnetic relaxation enhancement (PRE) is commonly used to speed up spin lattice relaxation time (T1) for rapid data acquisition in NMR structural studies. Consequently, there is significant interest in novel paramagnetic labels for enhanced NMR studies on biomolecules. Herein, we report the synthesis and characterization of a modified poly(styrene‐co‐maleic acid) polymer which forms nanodiscs while showing the ability to chelate metal ions. Cu2+‐chelated nanodiscs are demonstrated to reduce the T1 of protons for both polymer and lipid‐nanodisc components. The chelated nanodiscs also decrease the proton T1 values for a water‐soluble DNA G‐quadruplex. These results suggest that polymer nanodiscs functionalized with paramagnetic tags can be used to speed‐up data acquisition from lipid bilayer samples and also to provide structural information from water‐soluble biomolecules.

Hierarchical Micro‐Mesoporous Carbon‐Framework‐Based Hybrid Nanofibres for High‐Density Capacitive Energy Storage

By Hengyang Cheng, Jinku Meng, Guan Wu, Su Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Flexible storage: A microdroplet assembly and microfluidic‐blow‐spinning method gives micro‐mesoporous carbon‐framework fibres for high‐density capacitive energy storage. The supercapacitors display high volumetric energy density, specific capacitance, are deformable and can be self‐powered to light up displays. Abstract Advanced methods, allowing the controllable synthesis of ordered structural nanomaterials with favourable charges transfer and storage, are highly important to achieve ideal supercapacitors with high energy density. Herein, we report a microliter droplet‐based method to synthesize hierarchical‐structured metal–organic framework/graphene/carbon nanotubes hybrids. The confined ultra‐small‐volume reaction, give well‐defined hybrids with a large specific‐surface‐area (1206 m2 g−1), abundant ionic‐channels (narrow pore of 0.86 nm), and nitrogen active‐sites (10.63 %), resulting in high pore‐size utilization (97.9 %) and redox‐activity (32.3 %). We also propose a scalable microfluidic‐blow‐spinning method to consecutively generate nanofibre‐based flexible supercapacitor electrodes with striking flexibility and mechanical strength. The supercapacitors display large volumetric energy density (147.5 mWh cm−3), high specific capacitance (472 F cm−3) and stably deformable energy‐supply.

Engineering of Ruthenium–Iron Oxide Colloidal Heterostructures: Improved Yields in CO2 Hydrogenation to Hydrocarbons

By Aisulu Aitbekova, Emmett D. Goodman, Liheng Wu, Alexey Boubnov, Adam S. Hoffman, Arda Genc, Huikai Cheng, Lee Casalena, Simon R. Bare, Matteo Cargnello from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Ruthenium promotes reduction of iron oxide in ruthenium–iron oxide heterodimers by a proximal hydrogen spillover effect, leading to the formation of ruthenium–iron core–shell structures active for CO2 hydrogenation to hydrocarbons. Tuning the shell thickness leads to a fourfold increase in hydrocarbon yield. Abstract Catalytic CO2 reduction to fuels and chemicals is a major pursuit in reducing greenhouse gas emissions. One approach utilizes the reverse water‐gas shift reaction, followed by Fischer–Tropsch synthesis, and iron is a well‐known candidate for this process. Some attempts have been made to modify and improve its reactivity, but resulted in limited success. Now, using ruthenium–iron oxide colloidal heterodimers, close contact between the two phases promotes the reduction of iron oxide via a proximal hydrogen spillover effect, leading to the formation of ruthenium–iron core–shell structures active for the reaction at significantly lower temperatures than in bare iron catalysts. Furthermore, by engineering the iron oxide shell thickness, a fourfold increase in hydrocarbon yield is achieved compared to the heterodimers. This work shows how rational design of colloidal heterostructures can result in materials with significantly improved catalytic performance in CO2 conversion processes.

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr, Ba)

By Qian Wang, Sudip Pan, Yan‐Bo Wu, Guohai Deng, Jian‐Hong Bian, Guanjun Wang, Lili Zhao, Mingfei Zhou, Gernot Frenking from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Bonding scenarios: The synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)3 (M=Sr, Ba) in low‐temperature Ne matrix is reported. The complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals. Abstract We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)3 (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D3 symmetric structure involving three equivalent η6‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n−1)d AOs of M and strong backdonation from the occupied (n−1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.

Exploring the Trans‐Cleavage Activity of CRISPR‐Cas12a (cpf1) for the Development of a Universal Electrochemical Biosensor

By Yifan Dai, Rodrigo A Somoza, Liu Wang, Jean F. Welter, Yan Li, Arnold I Caplan, Chung Chiun Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

An electrochemical biosensor based on CRISPR‐Cas12a (cpf1), termed E‐CRISPR, is reported. Utilizing the trans‐cleavage activity of Cas12a, E‐CRISPR delivers a cost‐effective and portable biosensing platform for the detection of nucleic acids and proteins. Abstract An accurate, rapid, and cost‐effective biosensor for the quantification of disease biomarkers is vital for the development of early‐diagnostic point‐of‐care systems. The recent discovery of the trans‐cleavage property of CRISPR type V effectors makes CRISPR a potential high‐accuracy bio‐recognition tool. Herein, a CRISPR‐Cas12a (cpf1) based electrochemical biosensor (E‐CRISPR) is reported, which is more cost‐effective and portable than optical‐transduction‐based biosensors. Through optimizing the in vitro trans‐cleavage activity of Cas12a, E‐CRIPSR was used to detect viral nucleic acids, including human papillomavirus 16 (HPV‐16) and parvovirus B19 (PB‐19), with a picomolar sensitivity. An aptamer‐based E‐CRISPR cascade was further designed for the detection of transforming growth factor β1 (TGF‐β1) protein in clinical samples. As demonstrated, E‐CRISPR could enable the development of portable, accurate, and cost‐effective point‐of‐care diagnostic systems.

Suk Bong Hong

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

“If I could be any age I would be 20, the most unstable, but the most dynamic moment in my life. My favorite saying is: you can try …” Find out more about Suk Bong Hong in his Author Profile.

The Ultrafast and Continuous Fabrication of a Polydimethylsiloxane Membrane by Ultraviolet‐Induced Polymerization

By Zhihao Si, Jingfang Li, Liang Ma, Di Cai, Shufeng Li, Jan Baeyens, Jan Degrève, Jun Nie, Tianwei Tan, Peiyong Qin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

The ultrafast and continuous fabrication of a polydimethylsiloxane membrane was realized by an ultraviolet‐induced polymerization strategy. It takes less than 30 s, which is three orders of magnitude faster than conventional methods. The freezing effect towards fillers in the polymer results in an extremely high loading of silicalite‐1/MA‐PDMS MMM with uniform particle distribution. Abstract The polydimethylsiloxane (PDMS) membrane commonly used for separation of biobutanol from fermentation broth fails to meet demand owing to its discontinuous and polluting thermal fabrication. Now, an UV‐induced polymerization strategy is proposed to realize the ultrafast and continuous fabrication of the PDMS membrane. UV‐crosslinking of synthesized methacrylate‐functionalized PDMS (MA‐PDMS) is complete within 30 s. The crosslinking rate is three orders of magnitude larger than the conventional thermal crosslinking. The MA‐PDMS membrane shows a versatile potential for liquid and gas separations, especially featuring an excellent pervaporation performance for n‐butanol. Filler aggregation, the major bottleneck for the development of high‐performance mixed matrix membranes (MMMs), is overcome, because the UV polymerization strategy demonstrates a freezing effect towards fillers in polymer, resulting in an extremely high‐loading silicalite‐1/MA‐PDMS MMM with uniform particle distribution.

Constrained Peptides with Fine‐Tuned Flexibility Inhibit NF‐Y Transcription Factor Assembly

By Sadasivam Jeganathan, Mathias Wendt, Sebastian Kiehstaller, Diego Brancaccio, Arne Kuepper, Nicole Pospiech, Alfonso Carotenuto, Ettore Novellino, Sven Hennig, Tom N. Grossmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Set Me Free: A peptide‐derived inhibitor of the NF‐Y transcription factor was developed by constraining the conformation of an epitope through hydrocarbon stapling and then fine‐tuning its flexibility. In the initial set of constrained peptides, a non‐interacting α‐methyl group was observed to have a detrimental effect on complex stability. Adaption of the methylation pattern gave a peptide that inhibits transcription factor assembly and subsequent DNA binding. Abstract Protein complex formation depends on the interplay between preorganization and flexibility of the binding epitopes involved. The design of epitope mimetics typically focuses on stabilizing a particular bioactive conformation, often without considering conformational dynamics, which limits the potential of peptidomimetics against challenging targets such as transcription factors. We developed a peptide‐derived inhibitor of the NF‐Y transcription factor by first constraining the conformation of an epitope through hydrocarbon stapling and then fine‐tuning its flexibility. In the initial set of constrained peptides, a single non‐interacting α‐methyl group was observed to have a detrimental effect on complex stability. Biophysical characterization revealed how this methyl group affects the conformation of the peptide in its bound state. Adaption of the methylation pattern resulted in a peptide that inhibits transcription factor assembly and subsequent recruitment to the target DNA.

Efficient Non‐dissociative Activation of Dinitrogen to Ammonia over Lithium‐Promoted Ruthenium Nanoparticles at Low Pressure

By Jianwei Zheng, Fenglin Liao, Simson Wu, Glenn Jones, Tian‐Yi Chen, Joshua Fellowes, Tim Sudmeier, Ian J. McPherson, Ian Wilkinson, Shik Chi Edman Tsang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Lithium treatment: Introduction of Li+ on Ru based catalysts can polarize and stabilize adsorbed dinitrogen on the metal surface, which facilitates the non‐dissociative pathway to produce ammonia under mild conditions. The Li–Ru catalysts are suitable for new green ammonia synthesis at lower pressure, and many times better than the commercial Fe counterparts. Abstract There is an exciting possibility to decentralize ammonia synthesis for fertilizer production or energy storage without carbon emission from H2 obtained from renewables at small units operated at lower pressure. However, no suitable catalyst has yet been developed. Ru catalysts are known to be promoted by heavier alkali dopants. Instead of using heavy alkali metals, Li is herein shown to give the highest rate through surface polarisation despite its poorest electron donating ability. This exceptional promotion rate makes Ru–Li catalysts suitable for ammonia synthesis, which outclasses industrial Fe counterparts by at least 195 fold. Akin to enzyme catalysis, it is for the first time shown that Ru–Li catalysts hydrogenate end‐on adsorbed N2 stabilized by Li+ on Ru terrace sites to ammonia in a stepwise manner, in contrast to typical N2 dissociation on stepped sites adopted by Ru–Cs counterparts, giving new insights in activating N2 by metallic catalysts.

Trans‐selective Insertional Dihydroboration of a cis‐Diborene: Synthesis of Linear sp3‐sp2‐sp3‐Triboranes and Subsequent Cationization

By Uwe Schmidt, Luis Werner, Merle Arrowsmith, Andrea Deissenberger, Alexander Hermann, Alexander Hofmann, Stefan Ullrich, James Mattock, Alfredo Vargas, Holger Braunschweig from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

The reaction of aryl‐ and amino(dihydro)boranes with dibora[2]ferrocenophane 1 leads to the formation 1,3‐ trans ‐dihydrotriboranes by formal hydrogenation and insertion of a borylene unit into the B=B bond. The aryltriborane derivatives undergo reversible photoisomerization to the cis ‐1,2‐ μ ‐H‐3‐hydrotriboranes, while hydride abstraction affords cationic triboranes, which represent the first doubly base‐stabilized B 3 H 4 + analogues.

Flexible Honeycombed Nanoporous/Glassy Hybrid for Efficient Electrocatalytic Hydrogen Generation

By Rui Li, Xiongjun Liu, Ruoyu Wu, Jing Wang, Zhibin Li, K. C. Chan, Hui Wang, Yuan Wu, Zhaoping Lu from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

A free‐standing honeycombed nanoporous/glassy sandwich hybrid is developed through dealloying metallic glass (MG) precursor. The honeycombed Pt‐rich nanoporous structure providing fertile active sites and large contact areas combined with the introduced compressive lattice‐strain on surface gives rise to better hydrogen evolution activity. Furthermore, the ductility of the intermediate MG matrix contributes to the excellent flexibility of the hybrid. Abstract Hydrogen evolution reaction (HER) in alkaline media urgently requires electrocatalysts concurrently possessing excellent activity, flexible free‐standing capability, and low cost. A honeycombed nanoporous/glassy sandwich structure fabricated through dealloying metallic glass (MG) is reported. This free‐standing hybrid shows outstanding HER performance with a very small overpotential of 37 mV at 10 mA cm−2 and a low Tafel slope of 30 mV dec−1 in alkaline media, outperforming commercial Pt/C. By alloying 3 at% Pt into the MG precursor, a honeycombed Pt75Ni25 solid solution nanoporous structure, with fertile active sites and large contact areas for efficient HER, is created on the dealloyed MG surface. Meanwhile, the surface compressive lattice‐strain effect is also introduced by substituting the Pt lattice sites with the smaller Ni atoms, which can effectively reduce the hydrogen adsorption energy and thus improve the hydrogen evolution. Moreover, the outstanding stability and flexibility stemming from the ductile MG matrix also make the hybrid suitable for practical electrode application. This work not only offers a reliable strategy to develop cost‐effective and flexible multicomponent catalysts with low Pt usage for efficient HER, but also sheds light on understanding the alloying effects of the catalytic process.

Reactions of Bromine Fluoride Dioxide, BrO2F,

By Konrad Seppelt from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

A reliable synthesis for unstable and highly reactive BrO 2 F is reported. This is converted into BrO 2 + SbF 6 ‐ , BrO 2 + AsF 6 ‐ , and BrO 2 + AsF 6 ‐ * BrO 2 F. The latter decomposes into the mixed valent Br 3 O 4 *Br 2 + AsF 6 ‐ with five, three, one, and zero valent bromine. BrO 2 + H(SO 3 CF 3 ) 2 ‐ is formed with HSO 3 CF 3 . Excess BrO 2 F yields mixed valent Br 3 O 6 + OSO 3 CF 3 ‐ with five and three valent bromine. Reactions of BrO 2 F and MoF 5 or in SO 2 ClF or CH 2 ClF result in Cl 2 BrO 6 + Mo 3 O 3 F 13 ‐ . NO 2 and BrO 2 F combine to NO 2 + Br(ONO 2 ) 2 ‐ . All these compounds are also thermodynamically unstable.

A novel meta‐stable pentavalent plutonium solid phase on the pathway from aqueous Pu(VI) to PuO2 nanoparticles

By Kristina Kvashnina, Anna Romanchuk, Ivan Pidchenko, Lucia Amidani, Evgeny Gerber, Alexander Trigub, Andre Rossberg, Stephan Weiss, Karin Popa, Olaf Walter, Roberto Caciuffo, Andreas Scheinost, Sergei Butorin, Stepan Kalmykov from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

We report here experimental evidence that the formation of PuO 2 nanoparticles from oxidized Pu(VI) under alkaline conditions proceeds through the formation of an intermediate Pu(V) solid phase, similar to NH 4 PuO 2 CO 3 , which is stable over a period of several months. For the first time, state‐of‐the‐art experiments at Pu M 4 and at L 3 absorption edges combined with theoretical calculations unambiguously allowed to determine the oxidation state and the local structure of this intermediate phase.

Boosting the Performance of Environmentally Friendly Quantum Dot‐Sensitized Solar Cells over 13% Efficiency by Dual Sensitizers with Cascade Energy Structure

By Zhenxiao Pan, Liang Yue, Huashang Rao, Jie Zhang, Xinhua Zhong, Zonglong Zhu, Alex K.‐Y. Jen from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

A cosensitization strategy with use of dual heavy‐metal‐free NIR absorption Zn–Cu–In–Se and Zn–Cu–In–S quantum dots (QDs) as cosensitizers is applied to control the light‐absorption, electron‐injection, and charge‐recombination processes simultaneously in QD‐sensitized solar cells (QDSCs). An average power conversion efficiency of 13.18% and a new certified efficiency record of 12.98% are obtained for environmentally friendly QDSCs under AM 1.5G 1 sun irradiation. Abstract Generally, high light‐harvesting efficiency, electron‐injection efficiency, and charge‐collection efficiency are the prerequisites for high‐efficiency quantum‐dot‐sensitized solar cells (QDSCs). However, it is fairly difficult for a single QD sensitizer to meet these three requirements simultaneously. It is demonstrated that these parameters can be felicitously balanced by a cosensitization strategy through the adoption of environmental‐friendly Zn–Cu–In–Se and Zn–Cu–In–S dual QD sensitizers with cascade energy structure. Experimental results indicate that: i) the combination of the dual QDs can improve the light‐harvesting capability of the cells, especially in the visible light window; ii) the cosensitization approach can facilitate electron injection, benefitting from the cascade energy structure of the two QD sensitizers employed; iii) the charge‐collection efficiency can be remarkably enhanced by the suppressed charge‐recombination process due to the improved QD coverage on TiO2. Consequently, this cosensitization strategy delivers a new certified efficiency record of 12.98% for liquid‐junction QDSCs under AM 1.5G 1 sun irradiation. Moreover, the constructed cells exhibit good stability in a high‐humidity environment.

High‐Performance Thermally Conductive Phase Change Composites by Large‐Size Oriented Graphite Sheets for Scalable Thermal Energy Harvesting

By Si Wu, Tingxian Li, Zhen Tong, Jingwei Chao, Tianyao Zhai, Jiaxing Xu, Taisen Yan, Minqiang Wu, Zhenyuan Xu, Hua Bao, Tao Deng, Ruzhu Wang from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

A method for synthesizing high‐performance thermally conductive phase‐ change composites is demonstrated. Large aligned graphite sheets inside the composite are generated from worm‐like expanded graphite. The aligned and interconnected graphite framework enhances KPCM up to 4.4–35.0 W m−1 K−1 at graphite loadings below 40.0 wt%, which could accelerate the high‐power‐density, low‐cost, and large‐scale applications of phase‐change materials. Abstract Efficient thermal energy harvesting using phase‐change materials (PCMs) has great potential for cost‐effective thermal management and energy storage applications. However, the low thermal conductivity of PCMs (KPCM) is a long‐standing bottleneck for high‐power‐density energy harvesting. Although PCM‐based nanocomposites with an enhanced thermal conductivity can address this issue, achieving a higher K (>10 W m−1 K−1) at filler loadings below 50 wt% remains challenging. A strategy for synthesizing highly thermally conductive phase‐change composites (PCCs) by compression‐induced construction of large aligned graphite sheets inside PCCs is demonstrated. The millimeter‐sized graphite sheet consists of lateral van‐der‐Waals‐bonded and oriented graphite nanoplatelets at the micro/nanoscale, which together with a thin PCM layer between the sheets synergistically enhance KPCM in the range of 4.4–35.0 W m−1 K−1 at graphite loadings below 40.0 wt%. The resulting PCCs also demonstrate homogeneity, no leakage, and superior phase change behavior, which can be easily engineered into devices for efficient thermal energy harvesting by coordinating the sheet orientation with the thermal transport direction. This method offers a promising route to high‐power‐density and low‐cost applications of PCMs in large‐scale thermal energy storage, thermal management of electronics, etc.

Skin‐Friendly Electronics for Acquiring Human Physiological Signatures

By Yujia Zhang, Tiger H. Tao from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

A set of degradable epidermal electronics consisting of both physical and biochemical sensors is presented as skin‐friendly electronics. Featuring stable operation and on‐demand decomposition, strong adhesion and easy detachment are achieved concurrently through a genetically engineered plasticized copolymer. Human experiments show that multidimensional physiological signals can be measured using these devices and analyzed for important states using a machine learning algorithm. Abstract Epidermal sensing devices offer great potential for real‐time health and fitness monitoring via continuous characterization of the skin for vital morphological, physiological, and metabolic parameters. However, peeling them off can be difficult and sometimes painful especially when these skin‐mounted devices are applied on sensitive or wounded regions of skin due to their strong adhesion. A set of biocompatible and water‐decomposable “skin‐friendly” epidermal electronic devices fabricated on flexible, stretchable, and degradable protein‐based substrates are reported. Strong adhesion and easy detachment are achieved concurrently through an environmentally benign, plasticized protein platform offering engineered mechanical properties and water‐triggered, on‐demand decomposition lifetime (transiency). Human experiments show that multidimensional physiological signals can be measured using these innovative epidermal devices consisting of electro‐ and biochemical sensing modules and analyzed for important physiological signatures using an artificial neural network. The advances provide unique, versatile capabilities and broader applications for user‐ and environmentally friendly epidermal devices.

Liberating N‐CNTs Confined Highly Dispersed CoNx Sites for Selective Hydrogenation of Quinolines

By Wanbing Gong, Qinglin Yuan, Chun Chen, Yang Lv, Yue Lin, Changhao Liang, Guozhong Wang, Haimin Zhang, Huijun Zhao from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

A “laser irradiation in liquid” technique is innovatively utilized to liberate the abundant highly dispersed single‐atom CoNx sites confined inside carbon nanotubes. They can be used as a high‐performance selective hydrogenation catalyst to convert quinoline and its derivatives into value‐added fine chemicals. Abstract Selective hydrogenation of quinoline and its derivatives is an important means to produce corresponding 1,2,3,4‐tetrahydroquinolines for a wide spectrum of applications. A facile and efficient “laser irradiation in liquid” technique to liberate the inaccessible highly dispersed CoNx active sites confined inside N‐doped carbon nanotubes is demonstrated. The liberated CoNx sites possess generic catalytic activities toward selective hydrogenation of quinoline and its hydroxyl, methyl, and halogen substituted derivatives into corresponding 1,2,3,4‐tetrahydroquinolines with almost 100% conversion efficiency and selectivity. This laser irradiation treatment approach should be widely applicable to unlock the catalytic powers of inaccessible catalytic active sites confined by other materials.

In‐situ Observation of Dynamic Galvanic Replacement Reactions in Twined Metallic Nanowires via Liquid Cell Transmission Electron Microscopy

By CHUNQIANG ZHUANG, Heyang Qi, Xing Cheng, Ge Chen, Chunlang Gao, Lihua Wang, Shaorui Sun, Jin Zou, Xiaodong Han from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Galvanic replacement is a versatile approach to prepare hollow nanostructures with controllable morphology and elemental composition for wide applications on catalysts and biomedicines. Towards a full understanding of galvanic replacement, the primary issue is to identify its fundamental mechanism. In this study, in‐situ liquid cell transmission electron microscopy was employed to monitor the dynamic reaction process and to explore the mechanism of galvanic replacement. From which, detailed reaction process was revealed based on in‐situ experiments, in which small Au particles firstly appeared around Ag nanowires; they coalesced, grew and adhered to Ag nanowires. After that, small pits grew from the edge of Ag nanowires till to form tubular structures, and then extended along the Ag nanowires to obtain hollowed structures. All our experimental observations from the viewpoint of electron microscopy, combined with DFT calculations, contribute towards an in‐depth understanding of the galvanic replacement reaction process and the design of new materials with hollowed structures.

Engineering III–V Semiconductor Nanowires for Device Applications

By Jennifer Wong‐Leung, Inseok Yang, Ziyuan Li, Siva Krishna Karuturi, Lan Fu, Hark Hoe Tan, Chennupati Jagadish from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

With regards to III–V nanowires, the epitaxial growth of axial and radial heterostructures using catalyst and catalyst‐free methods, which are then used for optoelectronic devices such as lasers, light‐emitting diodes, and solar cells, is reviewed. In addition, the top‐down approach to fabricate nanowires for applications in photo‐electrochemical water splitting is also addressed. Abstract III–V semiconductor nanowires offer potential new device applications because of the unique properties associated with their 1D geometry and the ability to create quantum wells and other heterostructures with a radial and an axial geometry. Here, an overview of challenges in the bottom‐up approaches for nanowire synthesis using catalyst and catalyst‐free methods and the growth of axial and radial heterostructures is given. The work on nanowire devices such as lasers, light emitting nanowires, and solar cells and an overview of the top‐down approaches for water splitting technologies is reviewed. The authors conclude with an analysis of the research field and the future research directions.

Biomimetic Nanosilica–Collagen Scaffolds for In Situ Bone Regeneration: Toward a Cell‐Free, One‐Step Surgery

By Shao‐Jie Wang, Dong Jiang, Zheng‐Zheng Zhang, You‐Rong Chen, Zheng‐Dong Yang, Ji‐Ying Zhang, Jinjun Shi, Xing Wang, Jia‐Kuo Yu from Wiley: Advanced Materials: Table of Contents. Published on Oct 17, 2019.

A biosilicification strategy is developed to provide a uniform and robust osteoinductive surface on porous natural collagen scaffolds. The resultant nanosilica–collagen (nSC) scaffolds possess topographical and chemical cues for superior in situ bone defect repair, without the use of exogenous cells or growth factors. This novel preparation of biomimetic bone scaffolds shows promising clinical applications in the treatment of bone defects. Abstract Current approaches to fabrication of nSC composites for bone tissue engineering (BTE) have limited capacity to achieve uniform surface functionalization while replicating the complex architecture and bioactivity of native bone, compromising application of these nanocomposites for in situ bone regeneration. A robust biosilicification strategy is reported to impart a uniform and stable osteoinductive surface to porous collagen scaffolds. The resultant nSC composites possess a native‐bone‐like porous structure and a nanosilica coating. The osteoinductivity of the nSC scaffolds is strongly dependent on the surface roughness and silicon content in the silica coating. Notably, without the use of exogenous cells and growth factors (GFs), the nSC scaffolds induce successful repair of a critical‐sized calvarium defect in a rabbit model. It is revealed that topographic and chemical cues presented by nSC scaffolds could synergistically activate multiple signaling pathways related to mesenchymal stem cell recruitment and bone regeneration. Thus, this facile surface biosilicification approach could be valuable by enabling production of BTE scaffolds with large sizes, complex porous structures, and varied osteoinductivity. The nanosilica‐functionalized scaffolds can be implanted via a cell/GF‐free, one‐step surgery for in situ bone regeneration, thus demonstrating high potential for clinical translation in treatment of massive bone defects.

Lattice Distortion in Hollow Multi‐shelled Structures for Efficient Visible Light CO2 Reduction with SnS2/SnO2 Junction

By Dan Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Precisely control the micro‐/nanostructures of nanomaterials, such as hollow multi‐shelled structure (HoMS), has shown its great advantages in various applications. In this paper, we moved forward our research direction to control the crystal structure of building blocks of HoMS, i.e., introducing the lattice distortion in HoMS, for the first time. The lattice distortion located at the nanoscale interface of SnS 2 /SnO 2 can provide additional active sites, which not only provide the catalytic activity under visible light but also improve the separation of photoexcited electron‐hole pairs. Combine with the efficient light utilization, the natural advantage of HoMS, a record catalytic activity was achieved in solid‐gas system for CO 2 reduction, with an excellent stability and 100% CO selectivity without using any sensitizers or noble metals.

Tackling the World’s Phosphate Problem: Synthetic Humic Acids solubilize otherwise insoluble Phosphates for Fertilization

By Markus Antonietti, Fan Yang, Shuaishuai Zhang, Jingpeng Song, Qing Du, Guixiang Li, Nadezda V. Tarakina from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

Artificial humic acids (A‐HA) made from biomass in a hydrothermal process turn otherwise highly insoluble phosphates (e.g. iron phosphate as a model) into highly available phosphorus, which contributes to the fertility of soils and the coupled plant growth. A detailed electron microscopy study revealed etching of the primary iron phosphate crystals by the ‐COOH and phenolic groups of humic acids, but also illustrated the importance of the redox properties of humic matter on the nanoscale. The combined effects result in the formation of then bioavailable phosphate nanoparticles stabilized by humic matter. Typical agricultural chemical tests indicate that the content of total P and directly plant‐available P improved largely. Comparative pot planting experiments before and after treatment of phosphates with A‐HA demonstrate significantly enhanced plant growth, as quantified in higher aboveground and belowground plant biomass.

In‐depth TEM Investigation on Structural Inhomogeneity within a Primary LixNi0.835Co0.15Al0.015O2 Particle: Origin of Capacity Decay during High‐rate Discharge

By Hyesu Lee, Eunmi Jo, Kyung Yoon Chung, Dongjin Byun, Seung Min Kim, Wonyoung Chang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

The structural stability of cathode materials during electrochemical reactions, in particular, under high‐rate discharge, is pertinent to the design and development of new electrode materials that can satisfy the stringent requirements of high energy and power density for electric vehicles. This study investigates the structural inhomogeneity that develops within a single LiNi 0.835 Co 0.15 Al 0.015 O 2 (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8 V) developed surface areas in which layered structure was recovered, although the interiors retained the degraded spinel structure. These micro‐ and nano‐scale structural inversions during high‐rate discharge from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni‐rich cathode materials.

Acyl Migration versus Epoxidation in Gold Catalysis: Facile, Switchable and Atom‐Economic Synthesis of Acylindoles and Quinoline Derivatives

By Xianhai Tian, Lina Song, Kaveh Farshadfar, Matthias Rudolph, Frank Rominger, Thomas Oeser, Alireza Ariafard, A. Stephen K. Hashmi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 17, 2019.

We report a switchable synthesis of acylindoles and quinoline derivatives via gold‐catalyzed annulations of anthranils and ynamides. With an N,O‐ligand on a gold(III) catalyst α‐imino gold carbenes, in situ generated from anthranils, could undergo electrophilic attack to the aryl π‐bond followed by unexpected and highly selective 1,4‐ or 1,3‐acyl migrations to form 6‐acylindoles or 5‐acylindoles. With the JohnPhos ligand gold(I) carbenes experienced carbene/carbonyl additions to deliver quinoline oxides. Some of these epoxides represent valuable substrates for the preparation of 3‐hydroxylquinolines, quinolin‐3(4H)‐ones and polycyclic compounds via facile in situ rearrangements. The reaction can be efficiently conducted on gram scale and the obtained products are valuable substrates for preparing other potential useful compounds. A computational study explained the unexpected selectivities and the dependency of the reaction pathway on the oxidation state and ligand of gold. With gold(III) the barrier for the formation of the strained oxirane ring is too high, with gold(I) this transition state becomes accessible. Also, the barriers for the migrations of the substituents on the intermediate sigma‐complexes perfectly explain the observed substitution pattern in the final product.

[ASAP] Aggregable Nanoparticles-Enabled Chemotherapy and Autophagy Inhibition Combined with Anti-PD-L1 Antibody for Improved Glioma Treatment

By Shaobo Ruan†, Rou Xie†, Lin Qin†, Meinan Yu†, Wei Xiao†, Chuan Hu†, Wenqi Yu†, Zhiyong Qian‡, Liang Ouyang‡, Qin He†, and Huile Gao*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03968

[ASAP] In Situ Atomic-Scale Study on the Ultralarge Bending Behaviors of TiO2–B/Anatase Dual-Phase Nanowires

By Qiong Liu†, Haifei Zhan†, Huaiyong Zhu†, Hongwei Liu‡, Ziqi Sun†, John Bell†, Arixin Bo†*, and Yuantong Gu†* from Nano Letters: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02685

[ASAP] High-Temperature Polaritons in Ceramic Nanotube Antennas

By Ryan Starko-Bowes†, Xueji Wang‡, Zhujing Xu‡, Sandipan Pramanik†, Na Lu‡, Tongcang Li‡, and Zubin Jacob*‡† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03059

[ASAP] Bone Biomineral Properties Vary across Human Osteonal Bone

By Nina K. Wittig†, Jonas Palle†, Maja Østergaard†, Simon Frølich†, Mie E. Birkbak†, Kathryn M. Spiers‡, Jan Garrevoet‡, and Henrik Birkedal*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05535

[ASAP] Adaptation of Patterns of Motile Filaments under Dynamic Boundary Conditions

By Daisuke Inoue†, Greg Gutmann‡, Takahiro Nitta§, Arif Md. Rashedul Kabir†, Akihiko Konagaya‡, Kiyotaka Tokuraku?, Kazuki Sada†?, Henry Hess#, and Akira Kakugo*†? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01450

[ASAP] Photo-organometallic, Nanoparticle Nucleation on Graphene for Cascaded Doping

By Songwei Che, Sanjay K. Behura, and Vikas Berry* from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05484

[ASAP] Strong Thermopower Enhancement and Tunable Power Factor via Semimetal to Semiconductor Transition in a Transition-Metal Dichalcogenide

By Hongjae Moon†, Joonho Bang‡, Seokkyoon Hong†, Gwansik Kim†, Jong Wook Roh§, Jeongmin Kim*†, and Wooyoung Lee*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06523

[ASAP] On the Maximal Output Energy Density of Nanogenerators

By Jingjing Fu†‡, Xin Xia†, Guoqiang Xu†, Xiaoyi Li†, and Yunlong Zi*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06272

[ASAP] Binary Phosphorene Redox Behavior in Oxidoreductase Enzymatic Systems

By Carmen C. Mayorga-Martinez†, Zdene?k Sofer†, and Martin Pumera*†‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06230

[ASAP] Quasi-Two-Dimensional Se-Terminated Bismuth Oxychalcogenide (Bi2O2Se)

By Qilin Wei†?, Ruiping Li†?, Changqing Lin†, Ali Han‡, Anmin Nie§, Yiran Li†, Lain-Jong Li‡?, Yingchun Cheng*†, and Wei Huang? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b07000

[ASAP] Hyperthermia and Controllable Free Radical Coenhanced Synergistic Therapy in Hypoxia Enabled by Near-Infrared-II Light Irradiation

By Jun Yang†#, Rui Xie‡§#, Lili Feng*‡?, Bin Liu?, Ruichan Lv?, Chunxia Li‡, Shili Gai?, Fei He?, Piaoping Yang*?, and Jun Lin*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05985

[ASAP] Total Synthesis and Stereochemical Assignment of Streptide

By Nicholas A. Isley†, Yusuke Endo†, Zhi-Chen Wu†, Brett C. Covington‡, Leah B. Bushin‡, Mohammad R. Seyedsayamdost‡, and Dale L. Boger*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09067

[ASAP] Solar-Driven Photoelectrochemical Water Oxidation over an n-Type Lead–Titanium Oxyfluoride Anode

By Naoki Hirayama†, Hiroko Nakata†, Haruki Wakayama†, Shunta Nishioka†‡, Tomoki Kanazawa†‡, Ryutaro Kamata†, Yosuke Ebato†, Kosaku Kato§, Hiromu Kumagai†?, Akira Yamakata§, Kengo Oka?#, and Kazuhiko Maeda*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06570

[ASAP] Dehydroalkylative Activation of CNN- and PNN-Pincer Ruthenium Catalysts for Ester Hydrogenation

By Tianyi He, John C. Buttner, Eamon F. Reynolds, John Pham, Jack C. Malek, Jason M. Keith*, and Anthony R. Chianese* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09326

[ASAP] Synthesis of Organic Super-Electron-Donors by Reaction of Nitrous Oxide with N-Heterocyclic Olefins

By Le´onard Y. M. Eymann†, Paul Varava†, Andrei M. Shved†, Basile F. E. Curchod‡, Yizhu Liu†, Ophe´lie M. Planes†, Andrzej Sienkiewicz§, Rosario Scopelliti†, Farzaneh Fadaei Tirani†, and Kay Severin*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b10660

[ASAP] Elucidating Proton-Coupled Electron Transfer Mechanisms of Metal Hydrides with Free Energy- and Pressure-Dependent Kinetics

By Tianfei Liu§, Robin Tyburski§, Shihuai Wang, Ricardo Ferna´ndez-Tera´n, Sascha Ott, and Leif Hammarstro¨m* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08189

[ASAP] Establishing a Thermodynamic Landscape for the Active Site of Mo-Dependent Nitrogenase

By David P. Hickey†?, Rong Cai†?, Zhi-Yong Yang‡, Katharina Grunau§, Oliver Einsle*§, Lance C. Seefeldt*‡, and Shelley D. Minteer*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06546

[ASAP] Ru-Catalyzed Migratory Geminal Semihydrogenation of Internal Alkynes to Terminal Olefins

By Lijuan Song†#?, Qiang Feng‡?, Yong Wang‡, Shengtao Ding‡, Yun-Dong Wu†¶?, Xinhao Zhang†?, Lung Wa Chung*§, and Jianwei Sun*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09658

[ASAP] Molecular Magnetic Resonance Imaging with Gd(III)-Based Contrast Agents: Challenges and Key Advances

By Hao Li† and Thomas J. Meade*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09149

[ASAP] A Series of Iron Nitrosyl Complexes {Fe–NO}6–9 and a Fleeting {Fe–NO}10 Intermediate en Route to a Metalacyclic Iron Nitrosoalkane

By Martin Keilwerth†, Johannes Hohenberger†, Frank W. Heinemann†, Jo¨rg Sutter†, Andreas Scheurer†, Huayi Fang‡?, Eckhard Bill‡, Frank Neese§, Shengfa Ye*§, and Karsten Meyer*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08053

[ASAP] High-Spin Diradical Dication of Chiral p-Conjugated Double Helical Molecule

By Chan Shu, Hui Zhang, Arnon Olankitwanit, Suchada Rajca, and Andrzej Rajca* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08711

[ASAP] Enzyme-Instructed Activation of Pro-protein Therapeutics In Vivo

By Jin Chang†‡, Weiqi Cai†‡, Chunjing Liang†‡, Qiao Tang†‡, Xianghan Chen†‡, Ying Jiang§, Lanqun Mao†‡, and Ming Wang*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08669

[ASAP] Oxidative Approach Enables Efficient Access to Cyclic Azobenzenes

By Martin S. Maier†‡, Katharina Hu¨ll†‡#, Martin Reynders†‡#, Bryan S. Matsuura†‡#, Philipp Leippe†?, Tongil Ko‡, Lukas Scha¨ffer†, and Dirk Trauner*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08794

[ASAP] Efficient Z-Selective Semihydrogenation of Internal Alkynes Catalyzed by Cationic Iron(II) Hydride Complexes

By Nikolaus Gorgas†, Julian Bru¨nig†, Berthold Sto¨ger‡, Stefan Vanicek§, Mats Tilset§, Luis F. Veiros#, and Karl Kirchner*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09907

[ASAP] Tracking the Metal-Centered Triplet in Photoinduced Spin Crossover of Fe(phen)32+ with Tabletop Femtosecond M-Edge X-ray Absorption Near-Edge Structure Spectroscopy

By Kaili Zhang†, Ryan Ash†, Gregory S. Girolami, and Josh Vura-Weis* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07332

[ASAP] Unraveling the Dynamic Network in the Reactions of an Alkyl Aryl Ether Catalyzed by Ni/?-Al2O3 in 2-Propanol

By Long Qi†‡§, Ali Chamas†, Zachary R. Jones†, Eric D. Walter?, David W. Hoyt?, Nancy M. Washton?, and Susannah L. Scott*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09071

Hybrid nanovaccine for co-delivery of mRNA antigen and adjuvant

By Quan Li from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR05475H, Paper
Jingnan Yang, Smriti Arya, Pingsai Lung, Qiubin Lin, Jiandong Huang, Quan Li
For efficient cancer vaccines, antitumor function largely relies on cytotoxic T cells, whose activation can be effectively induced via antigen-encoding mRNA, making mRNA-based cancer vaccines an attractive approach for personalized...
The content of this RSS Feed (c) The Royal Society of Chemistry

Self-Assembled Injectable Biomolecular Hydrogels towards Phototherapy

By Qianli Zou from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06266A, Review Article
Xuehai Yan, Ruirui Xing, Yamei Liu, Qianli Zou
Biomolecular hydrogels assembled from biomolecules, such as proteins, peptides, and polysaccharides, are promising candidates for facilitating biomedical applications due to their advantages of high biocompatibility, adjustable mechanical properties, functional diversity,...
The content of this RSS Feed (c) The Royal Society of Chemistry

Sandwich-like Electron Transport Layer to Assist Highly Efficient Planar Perovskite Solar Cells

By Cheng Mu from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07876B, Paper
zhichao lin, Jingjing Yan, Qingbin Cai, Xiaoning Wen, Hongye Dong , Cheng Mu
Co-modification of electron transport layer (ETL) with metal oxides and organic can optimize molecules the structure of the ETL and improve the performance of perovskite solar cells (PSCs). Here, a...
The content of this RSS Feed (c) The Royal Society of Chemistry

Effective immobilization of nanoscale Pd on carbon hybrid for enhanced electrocatalytic performances: stabilization mechanism investigations

By Juan Wang from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR05966K, Paper
Liang Yang, Daoping Liu, Guoming Cui, Binlin Dou, Juan Wang
The grand challenge leading to use of electrocatalysts is the degradation of active species which results in poor durability and long-term performances. Studying the origin of active metal particle stabilization...
The content of this RSS Feed (c) The Royal Society of Chemistry

A facile synthetic approach to nanostructured Li2S cathodes for rechargeable solid-state Li–S batteries

By Serena A. Corr from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR06239D, Communication
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Hany El-Shinawi, Edmund J. Cussen, Serena A. Corr
We report a facile and scalable microwave approach to directly synthesize nanostructured Li2S which presents an ideal architecture for the construction of free-standing cathodes for all-solid-state Li–S batteries.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Bioinspired Surfaces with Wettability for Antifouling Application

By Zhiguang Guo from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR05870B, Review Article
Zhihao Li, Zhiguang Guo
Wettability is a special character found in nature, including the superhydrophobicity of lotus leaves, the underwater superoleophobicity of fish scales and the slipperiness of pitcher plants. These surfaces exhibit unique...
The content of this RSS Feed (c) The Royal Society of Chemistry

Iron Phosphorus Trichalcogenide Ultrathin Nanosheets: Enhance Photoelectrochemical Activity under Visible-light Irradiation

By Ying Zhang from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR07300K, Paper
Hao Huang, Mengxiang Shang, Yongjin Zou, Wenbo Song, Ying Zhang
Exploiting novel visible-light sensitive materials for photoelectrochemical (PEC) technique is deeply meaningful for energy conversion and analytic detection. Owing to the tunable bandgap structure and strong absorption of visible-light, the...
The content of this RSS Feed (c) The Royal Society of Chemistry

Tuning the nanostructure of nitrogen-doped graphene laminates for forward osmosis desalination

By In S. Kim from RSC - Nanoscale latest articles. Published on Oct 17, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR06845G, Paper
Jun-Ho Song, Ho Kyong Shon, Peng Wang, Am Jang, In S. Kim
Studies of graphene-based membranes have concentrated on physicochemical properties that can replace polymeric membrane for use of forward osmosis (FO) systems. However, recent researches have focused on mixtures of two...
The content of this RSS Feed (c) The Royal Society of Chemistry

Direct Visualization of Local Spin Transition Behaviors in Thin Molecular Films by Bimodal AFM

By Victoria Shalabaeva, Alin‐Ciprian Bas, Mario Piedrahita‐Bello, Karl Ridier, Lionel Salmon, Christophe Thibault, William Nicolazzi, Gábor Molnár, Azzedine Bousseksou from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

A spatially resolved investigation of the spin transition in thin films by atomic force microscopy enables detection of an ≈30% variation of the elastic modulus between the two spin states. Film defects are shown to stabilize the high spin state locally due to strain relaxation. This visualization of local spin‐crossover properties has particular relevance for applications in nanoscale devices. Abstract Thin films of the molecular spin‐crossover complex [Fe(HB(1,2,4‐triazol‐1‐yl)3)2] undergo spin transition above room temperature, which can be exploited in sensors, actuators, and information processing devices. Variable temperature viscoelastic mapping of the films by atomic force microscopy reveals a pronounced decrease of the elastic modulus when going from the low spin (5.2 ± 0.4 GPa) to the high spin (3.6 ± 0.2 GPa) state, which is also accompanied by increasing energy dissipation. This technique allows imaging, with high spatial resolution, of the formation of high spin puddles around film defects, which is ascribed to local strain relaxation. On the other hand, no clustering process due to cooperative phenomena was observed. This experimental approach sets the stage for the investigation of spin transition at the nanoscale, including phase nucleation and evolution as well as local strain effects.

Constructing Ionic Gradient and Lithiophilic Interphase for High‐Rate Li‐Metal Anode

By Yimei Lai, Yun Zhao, Weiping Cai, Jun Song, Yongtang Jia, Bin Ding, Jianhua Yan from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

An ionic gradient and lithiophilic interphase film is developed to protect Li‐metal anodes from dendrite growth. The top Li0.33La0.56TiO3 nanofiber layer forms a spatially homogenous ionic field distribution over the anode, while the bottom Al2O3 nanofiber layer reduces the driving force of dendrite formation by decreasing the nucleation barrier, promising to produce a durable and high‐rate Li anode. Abstract Li metal is the optimal choice as an anode due to its high theoretical capacity, but it suffers from severe dendrite growth, especially at high current rates. Here, an ionic gradient and lithiophilic inter‐phase film is developed, which promises to produce a durable and high‐rate Li‐metal anode. The film, containing an ionic‐conductive Li0.33La0.56TiO3 nanofiber (NF) layer on the top and a thin lithiophilic Al2O3 NF layer on the bottom, is fabricated with a sol–gel electrospinning method followed by sintering. During cycling, the top layer forms a spatially homogenous ionic field distribution over the anode, while the bottom layer reduces the driving force of Li‐dendrite formation by decreasing the nucleation barrier, enabling dendrite‐free plating‐stripping behavior over 1000 h at a high current density of 5 mA cm−2. Remarkably, full cells of Li//LiNi0.8Co0.15Al0.05O2 exhibit a high capacity of 133.3 mA h g−1 at 5 C over 150 cycles, contributing a step forward for high‐rate Li‐metal anodes.

Advanced Wearable Microfluidic Sensors for Healthcare Monitoring

By Sheng Li, Zhong Ma, Zhonglin Cao, Lijia Pan, Yi Shi from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

Wearable microfluidic sensors enable sweat analysis for healthcare monitoring. Due to their utilization of soft material, unique structure, and precise fluid flow control, microfluidic sensors possess intrinsic flexibility and stretchability and are capable of capturing health information from skin surfaces. Herein, the materials, fabrication, working principles, and strategies of microfluidic sensors are reviewed, and perspectives on future development are discussed. Abstract Wearable flexible sensors based on integrated microfluidic networks with multiplex analysis capability are emerging as a new paradigm to assess human health status and show great potential in application fields such as clinical medicine and athletic monitoring. Well‐designed microfluidic sensors can be attached to the skin surface to acquire various pieces of physiological information with high precision, such as sweat loss, information regarding metabolites, and electrolyte balance. Herein, the recent progress of wearable microfluidic sensors for applications in healthcare monitoring is summarized, including analysis principles and microfabrication methods. Finally, the challenges and opportunities for wearable microfluidic sensors in practical applications are discussed.

Perforated Pd Nanosheets with Crystalline/Amorphous Heterostructures as a Highly Active Robust Catalyst toward Formic Acid Oxidation

By Lian Ying Zhang, Yirui Ouyang, Shuo Wang, Diben Wu, Mengchao Jiang, Fengqian Wang, Weiyong Yuan, Chang Ming Li from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

Perforated Pd nanosheets with crystalline/amorphous heterostructures are successfully synthesized by using a facile confined growth method, offering a large electrochemically active surface area up to 172.6 m2 g−1. Toward formic acid oxidation, the Pd nanosheets show the highest peak current density (2653.3 mA mg−1Pd) among reported Pd‐based electrocatalysts. Abstract Perforated ultrathin Pd nanosheets with crystalline/amorphous heterostructures are rationally synthesized to offer a large electrochemically active surface area of 172.6 m2 g−1 and deliver a 5.6 times higher apparent reaction rate in comparison to commercial Pd/C, thus offering a facile confined growth method to generate superior catalysts.

Sensing Infrared Photons at Room Temperature: From Bulk Materials to Atomic Layers

By Peng Wang, Hui Xia, Qing Li, Fang Wang, Lili Zhang, Tianxin Li, Piotr Martyniuk, Antoni Rogalski, Weida Hu from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

Room‐temperature operating means a profound reduction of volume, power consumption, and cost for infrared photodetectors. Infrared photon detectors show broad development prospects with theoretically superior performance limits at room temperature, and progress from bulk to atomic layers, which promise a wide range of applications in many aspects. Abstract Room‐temperature operating means a profound reduction of volume, power consumption, and cost for infrared (IR) photodetectors, which promise a wide range of applications in both military and civilian areas, including individual soldier equipment, automatic driving, etc. Inspired by this fact, since the beginning of 1990s, great efforts have been made in the development of uncooled thermal detectors. During the last two decades, similar efforts have been devoted using IR photon detectors, especially based on photovoltaic effects. Herein, the proven technologies, which have been commercialized with a large format, like InGaAs/InP pin diodes, InAsSb barrier detectors, and high‐operating‐temperature HgCdTe devices, are reviewed. The newly developed technology is emphasized, which has shown unique superiority in detecting mid‐wavelength and long‐wavelength IR signals, such as quantum cascade photodetectors. Finally, brand‐new concept devices based on 2D materials are introduced, which are demonstrated to provide additional degrees of freedom in designing and fabricating room‐temperature IR devices, for example, the construction of multi‐heterojunctions without introducing lattice strain, the convenient integration of optical waveguides and electronic gratings. All information provided here aims to supply a full view of the progress and challenges of room‐temperature IR detectors.

Flexible Piezoelectric Acoustic Sensors and Machine Learning for Speech Processing

By Young Hoon Jung, Seong Kwang Hong, Hee Seung Wang, Jae Hyun Han, Trung Xuan Pham, Hyunsin Park, Junyeong Kim, Sunghun Kang, Chang D. Yoo, Keon Jae Lee from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

Flexible piezoelectric acoustic sensors and machine learning for speech processing can change the paradigm of voice technologies for the hyperconnected society, offering personalized intelligent services such as biometric authentication, AI secretaries, and IoT appliances. The recent advances in the fields of self‐powered flexible acoustic sensors and machine learning algorithms for speech recognition are comprehensively summarized. Abstract Flexible piezoelectric acoustic sensors have been developed to generate multiple sound signals with high sensitivity, shifting the paradigm of future voice technologies. Speech recognition based on advanced acoustic sensors and optimized machine learning software will play an innovative interface for artificial intelligence (AI) services. Collaboration and novel approaches between both smart sensors and speech algorithms should be attempted to realize a hyperconnected society, which can offer personalized services such as biometric authentication, AI secretaries, and home appliances. Here, representative developments in speech recognition are reviewed in terms of flexible piezoelectric materials, self‐powered sensors, machine learning algorithms, and speaker recognition.

Multilayer PZT 95/5 Antiferroelectric Film Energy Storage Devices with Giant Power Density

By Sergey I. Shkuratov, Jason Baird, Vladimir G. Antipov, Shujun Zhang, Jay B. Chase from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

The great advantages of energy‐storage devices utilizing multilayer Pb(Zr0.95Ti0.05)0.98Nb0.02O3 films studied are their extra‐long storage life, ability to generate multi‐kiloampere currents and a wide range of voltages, high energy density, and giant power density being four orders of magnitude higher than that for energy storage devices of any other type. Abstract A new type of energy storage devices utilizing multilayer Pb(Zr0.95Ti0.05)0.98Nb0.02O3 films is studied experimentally and numerically. To release the stored energy, the multilayer ferroelectric structures are subjected to adiabatic compression perpendicular to the polarization direction. Obtained results indicate that electrical interference between layers (10–120 layers) during stress wave transit through the structures has an effect on the generated current waveforms, but no impact on the released electric charge. The multilayer films undergo a pressure‐induced phase transition to antiferroelectric phase at 1.7 GPa adiabatic compression and become completely depolarized, releasing surface screening charge with density equal to their remnant polarization. An energy density of 3 J cm−3 is successfully achieved with giant power density on the order of 2 MW cm−3, which is four orders of magnitude higher than that of any other type of energy storage device. The outputs of multilayer structures can be precisely controlled by the parameters of the ferroelectric layer and the number of layers. Multilayer film modules with a volume of 0.7 cm3 are capable of producing 2.4 kA current, not achievable in electrochemical capacitors or batteries, which will greatly enhance the miniaturization and integration requirements for emerging high‐power applications.

SnSe/MoS2 van der Waals Heterostructure Junction Field‐Effect Transistors with Nearly Ideal Subthreshold Slope

By Jian Guo, Laiyuan Wang, Yiwei Yu, Peiqi Wang, Yu Huang, Xiangfeng Duan from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

A 2D SnSe/MoS2 van der Waals heterostructure‐based junction field effect transistor (JFET) is constructed and systematically studied. It exhibits well‐behavioured n‐channel JFET characteristics with a nearly ideal subthreshold swing SS of 60.3 mV dec−1, a small pinch‐off voltage VP of −0.25 V and high ON/OFF ratio over 106, demonstrating excellent electronic performance especially in the subthreshold regime. Abstract The minimization of the subthreshold swing (SS) in transistors is essential for low‐voltage operation and lower power consumption, both critical for mobile devices and internet of things (IoT) devices. The conventional metal‐oxide‐semiconductor field‐effect transistor requires sophisticated dielectric engineering to achieve nearly ideal SS (60 mV dec−1 at room temperature). However, another type of transistor, the junction field‐effect transistor (JFET) is free of dielectric layer and can reach the theoretical SS limit without complicated dielectric engineering. The construction of a 2D SnSe/MoS2 van der Waals (vdW) heterostructure‐based JFET with nearly ideal SS is reported. It is shown that the SnSe/MoS2 vdW heterostructure exhibits excellent p–n diode rectifying characteristics with low saturate current. Using the SnSe as the gate and MoS2 as the channel, the SnSe/MoS2 vdW heterostructure exhibit well‐behavioured n‐channel JFET characteristics with a small pinch‐off voltage VP of −0.25 V, nearly ideal subthreshold swing SS of 60.3 mV dec−1 and high ON/OFF ratio over 106, demonstrating excellent electronic performance especially in the subthreshold regime.

Glycogen as a Building Block for Advanced Biological Materials

By Quinn A. Besford, Francesca Cavalieri, Frank Caruso from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

Glycogen is one of nature's unique biological polysaccharide nanoparticles, which holds promise as a material for biomedical, including therapeutic, applications. The recent literature on advancing glycogen as a building block for advanced biofunctional materials is reviewed. Abstract Biological nanoparticles found in living systems possess distinct molecular architectures and diverse functions. Glycogen is a unique biological polysaccharide nanoparticle fabricated by nature through a bottom‐up approach. The biocatalytic synthesis of glycogen has evolved over time to form a nanometer‐sized dendrimer‐like structure (20–150 nm) with a highly branched surface and a dense core. This makes glycogen markedly different from other natural linear or branched polysaccharides and particularly attractive as a platform for biomedical applications. Glycogen is inherently biodegradable, nontoxic, and can be functionalized with diverse surface and internal motifs for enhanced biofunctional properties. Recently, there has been growing interest in glycogen as a natural alternative to synthetic polymers and nanoparticles in a range of applications. Herein, the recent literature on glycogen in the material‐based sciences, including its use as a constituent in biodegradable hydrogels and fibers, drug delivery vectors, tumor targeting and penetrating nanoparticles, immunomodulators, vaccine adjuvants, and contrast agents, is reviewed. The various methods of chemical functionalization and physical assembly of glycogen nanoparticles into multicomponent nanodevices, which advance glycogen toward a functional therapeutic nanoparticle from nature and back again, are discussed in detail.

Recent Progress on Layered Cathode Materials for Nonaqueous Rechargeable Magnesium Batteries

By Lin Li, Yong Lu, Qiu Zhang, Shuo Zhao, Zhe Hu, Shu‐Lei Chou from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

Layered cathode materials for rechargeable magnesium batteries have attracted extensive attention in recent years. In this review, the recent progress and the strategies to further improve the electrochemical performance of layered cathode materials for rechargeable magnesium batteries are systematically summarized. Abstract Rechargeable magnesium batteries (RMBs) are promising candidates for next‐generation energy storage systems owing to their high safety and the low cost of magnesium resources. One of the main challenges for RMBs is to develop suitable high‐performance cathode materials. Layered materials are one of the most promising cathode materials for RMBs due to their relatively high specific capacity and facile synthesis process. This review focuses on recent progress on layered cathode materials for RMBs, including layered oxides, sulfides, selenides, and other layered materials. In addition, effective strategies to improve the electrochemical performance of layered cathode materials are summarized. Moreover, future perspectives about the application of layered materials in RMBs are also discussed. This review provides some significant guidance for the further development of layered materials for RMBs.

Biosynthesis of Norsesquiterpene Aculenes Requires Three Cytochrome P450s to Catalyze a Stepwise Demethylation Process

By Chi-Fang Lee, Li-Xun Chen, Chen-Yu Chiang, Chen-Yu Lai, Hsiao-Ching Lin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Aculenes are a unique class of norsequiterpenes (C 14 ) produced from Aspergillus aculeatus. The nordaucane skeleton in aculenes A−D may be derived from an ent‐daucane precursor through a demethylation process. Despite their unprecedented structures, the genetic basis and enzymatic mechanisms involved in the biosynthesis of aculenes remained unexplored. Here, we identified the biosynthetic gene cluster of aculenes and characterized the biosynthetic pathway based on gene inactivation, feeding experiments and heterologous reconstitution in both Saccharomyces cerevisiae and Aspergillus oryzae. Notably, we discovered three cytochrome P450 monoxygenases that are required to catalyze the stepwise demethylation process. AneF converts the 12‐methyl group to a carboxylic acid and AneD installs the 10‐hydroxyl group for later tautomerization and stabilization. Finally, AneG installs a necessary electron withdrawing carbonyl group at the C‐2 position, which subsequently triggers C‐12 decarboxylation to yield the nordaucane skeleton. A terpene cyclase (AneC) is also characterized to form a new product named dauca‐4,7‐diene.

High‐entropy chemistry stabilizing layered O3‐type structure in Na‐ion cathode

By Chenglong Zhao, Feixiang Ding, Yaxiang Lu, Liquan Chen, Yong-Sheng Hu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Material innovation on high‐performance Na‐ion cathodes and the corresponding understanding of structural chemistry still remain elusive. Herein, we report a new concept of high‐entropy chemistry for Na‐ion cathodes. An example of layered O3‐type NaNi 0.12 Cu 0.12 Mg 0.12 Fe 0.15 Co 0.15 Mn 0.1 Ti 0.1 Sn 0.1 Sb 0.04 O 2 has been designed and prepared successfully, which exhibits the l onger cycling stability ( ~ 83% of capacity retention after 500 cycles) and the outstanding rate capability ( ~ 80% of capacity retention at the rate of 5.0C). A highly reversible phase‐transition behavior is presented between O3 and P3 structures during the charge‐discharge process, and importantly, this behavior is delayed effectively with more than 60% of the total capacity being stored in O3‐type region . Possible mechanism can be attributed to the multi‐component transition metals in this high‐entropy material which can accommodate the changes of local interactions during Na + (de)intercalation . This strategy on high‐entropy chemistry opens new insights into the development of advanced cathode materials.

Drawing with Iron on a Gel Containing a Supramolecular Siderophore

By Jeffery Thayer Davis, Songjun Xiao, Paul Paukstelis, Peter Zavalij, Richard Ash from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Guanosine‐5ʹ‐hydroxamic acid (3) forms hydrogels when mixed with guanosine (1) and KCl. The 5ʹ‐hydroxamic acid (HA) unit is pH‐responsive and also chelates Fe3+. When gels are prepared under basic conditions the 5ʹ‐HA groups are deprotonated and the anionic hydrogel binds cationic thiazole orange (TO), signaled by enhanced fluorescence. The HA nucleoside 3, when immobilized in the G‐quartet gel, acts as a supramolecular siderophore to form red complexes with Fe3+. We patterned the hydrogel’s surface with FeCl3, by hand and by using a 3D printer. Patterns form instantly, are visible by eye, and can be erased using vitamin C. This hydrogel, combining self‐assembled G4‐quartet and siderophore‐Fe3+ motifs, is strong, can be molded into different shapes and is stable on the bench or under salt water.

Excitation‐Dependent Long‐Life Luminescent Polymeric Systems under Ambient Conditions

By Yanli Zhao, Yan Su, Yongfeng Zhang, Zhonghao Wang, Weichen Gao, Peng Jia, Dan Zhang, Chaolong Yang, Youbing Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Organic room temperature luminescent materials present unique phosphorescence emission with long lifetime. However, a lot of these materials only emit single blue or green color in spite of external stimulation, whereas their color tunability is strictly limited. Herein, we report a rational design to extend the emission color range from blue to red by controlling the doping simple pyrene derivatives into robust polymer matrix. The integration of these pyrene molecules in the polymer films enhances the intersystem crossing pathway, decreases the first triplet level of the system, and ensures the films with sensitive response to excitation energy, finally yielding the excitation‐dependent long‐life luminescent polymeric systems under ambient conditions. By virtue of the exceptional behavior, these materials were utilized as a versatile platform for constructing anti‐counterfeiting patterns with multicolor interconversion, presenting a promising application potential in the field of information security.

New Wine in Old Bottle: Prolonging Room‐Temperature Phosphorescence of Crown Ethers by Supramolecular Interactions

By Peifa Wei, Junkai Liu, Guo-Gang Shan, Xuepeng Zhang, Haoke Zhang, Ji Qi, Weijun Zhao, Herman H.-Y. Sung, Ian D. Williams, Jacky W. Y. Lam, Ben Zhong Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Supramolecular macrocyclic hosts have been of great interest in smart materials for years, whereas their triplet emission and regulation at crystal level is still rarely excavated. Herein, ultralong and universal room temperature phosphorescence (RTP) phenomenon is evacuated for traditional crown ethers. Supramolecular strategy involving chain length adjustment and morphological locking through complexation with K+ was explored as general methods to tune phosphorescence lifetime in solid state. Significantly, B15C5 exhibits 10‐folds increasing of lifetime after forming complex accompany with invisible to visible phosphorescence. A deep encryption based on this activated RTP strategy was facile fabricated. This work open a new world for supramolecular macrocycles and their intrinsic guest responsiveness offers new avenue for versatile smart luminescent materials.

Inverting External Asymmetric Induction via Selective Energy Transfer Catalysis: A Strategy to β‐Chiral Phosphonate Antipodes

By Carina Onneken, Kathrin Bussmann, Ryan Gilmour from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Enantiodivergent, catalytic reduction of activated alkenes relays stereochemical information encoded in the antipodal chiral catalysts to the pro‐chiral substrate. Although powerful, the strategy remains vulnerable to costs and availability of sourcing both catalyst enantiomers. Herein, a stereodivergent hydrogenation of α,β‐unsaturated phosphonates is disclosed using a single enantiomer of the catalyst. This enables generation of the R ‐ or S ‐configured β‐chiral phosphonate with equal and opposite selectivity. Enantiodivergence is regulated at the substrate level through the development of a facile E → Z isomerisation. This has been enabled for the first time by selective energy transfer catalysis using anthracene as an inexpensive organic photosensitiser. Synthetically valuable in its own right, this process enables subsequent Rh(I)‐mediated stereospecific hydrogenation to generate both enantiomers of the product using only the S ‐catalyst (up to 99:1 and 1:99 e.r. ). This strategy out‐competes the selectivities observed with the E ‐substrate and the R ‐catalyst.

Freeing the polarons to facilitate charge transport in BiVO4 from oxygen vacancies with an oxidative 2D precursor

By Weitao Qiu, Shuang Xiao, Jingwen Ke, Zheng Wang, Songtao Tang, Kai Zhang, Wei Qian, Yongchao Huang, Duan Huang, Yexiang Tong, Shihe Yang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

The BiVO 4 photoelectrochemical (PEC) electrode in tandem with a photovoltaic (PV) cell has shown great potential to become a compact and cost‐efficient device for solar hydrogen generation. However, the PEC part is still facing problems such as the poor charge transport efficiency due to the drag of oxygen vacancy bound polarons. In the present work, to effectively suppress oxygen vacancy formation, we have developed a new route to synthesize BiVO 4 photoanodes, by using a highly oxidative two‐dimensional (2D) precursor, bismuth oxy‐iodate (BiOIO 3 ), as an internal oxidant. With the reduced defects, namely the oxygen vacancies, the bound polarons were released, enabling a fast charge transport inside BiVO4 and doubling the performance in tandem devices based on the oxygen vacancy eliminated BiVO4 . Our work presents a new avenue for elaborately designing the precursor and breaking the limitation of charge transport for highly efficient PEC‐PV solar fuel devices.

Atomically Dispersed Binary Co‐Ni Sites in Nitrogen‐Doped Hollow Carbon Nanocubes for Reversible Oxygen Reduction and Evolution

By Xiaopeng Han, Xiaofei Ling, Deshuang Yu, Dengyu Xie, Linlin Li, Shengjie Peng, Cheng Zhong, Naiqin Zhao, Yida Deng, Wenbin Hu from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

Atomically dispersed Co‐Ni sites embedded in N‐doped hollow carbon nanocubes are synthesized, promoting oxygen reduction/evolution and zinc–air batteries with reduced overpotentials, increased energy efficiency, and enhanced reversibility. The single atomic sites and synergistic effect of dual metal centers can decrease the energetic barrier and accelerate reaction kinetics, contributing to superior electrochemical properties of resultant hybrid catalysts. Abstract With the inspiration of developing bifunctional electrode materials for reversible oxygen electrocatalysis, one strategy of heteroatom doping is proposed to fabricate dual metal single‐atom catalysts. However, the identification and mechanism functions of polynary single‐atom structures remain elusive. Atomically dispersed binary Co‐Ni sites embedded in N‐doped hollow carbon nanocubes (denoted as CoNi‐SAs/NC) are synthesized via proposed pyrolysis of dopamine‐coated metal‐organic frameworks. The atomically isolated bimetallic configuration in CoNi‐SAs/NC is identified by combining microscopic and spectroscopic techniques. When employing as oxygen electrocatalysts in alkaline medium, the resultant CoNi‐SAs/NC hybrid manifests outstanding catalytic performance for bifunctional oxygen reduction/evolution reactions, boosting the realistic rechargeable zinc–air batteries with high efficiency, low overpotential, and robust reversibility, superior to other counterparts and state‐of‐the‐art precious‐metal catalysts. Theoretical computations based on density functional theory demonstrate that the homogenously dispersed single atoms and the synergistic effect of neighboring Co‐Ni dual metal center can optimize the adsorption/desorption features and decrease the overall reaction barriers, eventually promoting the reversible oxygen electrocatalysis. This work not only sheds light on the controlled synthesis of atomically isolated advanced materials, but also provides deeper understanding on the structure–performance relationships of nanocatalysts with multiple active sites for various catalytic applications.

Are Cu2Te‐Based Compounds Excellent Thermoelectric Materials?

By Kunpeng Zhao, Ke Liu, Zhongmou Yue, Yancheng Wang, Qingfeng Song, Jian Li, Mengjia Guan, Qing Xu, Pengfei Qiu, Hong Zhu, Lidong Chen, Xun Shi from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

By introducing Ag2Te into Cu2Te, the phase transition features are well tuned and the high carrier concentration is substantially reduced, leading to a record‐high zT of 1.8. It is demonstrated that Cu2Te, Cu2S, and Cu2Se are all excellent thermoelectric (TE) materials that are beyond all other state‐of‐the‐art TE materials. Abstract Most of the state‐of‐the‐art thermoelectric (TE) materials exhibit high crystal symmetry, multiple valleys near the Fermi level, heavy constituent elements with small electronegativity differences, or complex crystal structure. Typically, such general features have been well observed in those well‐known TE materials such as Bi2X3‐, SnX‐, and PbX‐based compounds (X = S, Se, and Te). The performance is usually high in the materials with heavy constituent elements such as Te and Se, but it is low for light constituent elements such as S. However, there is a great abnormality in Cu2X‐based compounds in which Cu2Te has much lower TE figure of merit (zT) than Cu2S and Cu2Se. It is demonstrated that the Cu2Te‐based compounds are also excellent TE materials if Cu deficiency is sufficiently suppressed. By introducing Ag2Te into Cu2Te, the carrier concentration is substantially reduced to significantly improve the zT with a record‐high value of 1.8, 323% improvement over Cu2Te and outperforms any other Cu2Te‐based materials. The single parabolic band model is used to further prove that all Cu2X‐based compounds are excellent TE materials. Such finding makes Cu2X‐based compounds the only type of material composed of three sequent main group elements that all possess very high zT  s above 1.5.

Interfacial Residual Stress Relaxation in Perovskite Solar Cells with Improved Stability

By Hao Wang, Cheng Zhu, Lang Liu, Sai Ma, Pengfei Liu, Jiafeng Wu, Congbo Shi, Qin Du, Yanmin Hao, Sisi Xiang, Haining Chen, Pengwan Chen, Yang Bai, Huanping Zhou, Yujing Li, Qi Chen from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

The elastic modulus of 3D perovskite is very close to that of human bones and the elastic modulus of 2D perovskite with long chains is close to that of cartilage. By reconstructing a crystal lattice with different A cations at the surface of perovskite films, a nature “bone‐joint” configuration is built in perovskite, which provides a cushioning effect to external stresses. Abstract To improve the photovoltaic performance (both efficiency and stability) in hybrid organic–inorganic halide perovskite solar cells, perovskite lattice distortion is investigated with regards to residual stress (and strain) in the polycrystalline thin films. It is revealed that residual stress is concentrated at the surface of the as‐prepared film, and an efficient method is further developed to release this interfacial stress by A site cation alloying. This results in lattice reconstruction at the surface of polycrystalline thin films, which in turn results in low elastic modulus. Thus, a “bone‐joint” configuration is constructed within the interface between the absorber and the carrier transport layer, which improves device performance substantially. The resultant photovoltaic devices exhibit an efficiency of 21.48% with good humidity stability and improved resistance against thermal cycling.

Metasurface‐Empowered Optical Multiplexing and Multifunction

By Shuqi Chen, Wenwei Liu, Zhancheng Li, Hua Cheng, Jianguo Tian from Wiley: Advanced Materials: Table of Contents. Published on Oct 16, 2019.

Metasurfaces enabling concurrent tasks through a dramatic compact design have drawn great interest from the scientific community due to their profound potential in integrated photonic systems. A classification of multiplexing and multifunctional metasurfaces is provided, the evolving trends are discussed, and the development of integrated and on‐chip multifunctional metasurfaces is summarized. Abstract Metasurfaces are planar photonic elements composed of subwavelength nanostructures, which can deeply interact with light and exploit new degrees of freedom (DOF) to manipulate optical fields. In the past decade, metasurfaces have drawn great interest from the scientific community due to their profound potential to arbitrarily control light. Here, recent developments of multiplexing and multifunctional metasurfaces, which enable concurrent tasks through a dramatic compact design, are reviewed. The fundamental properties, design strategies, and applications of multiplexing and multifunctional metasurfaces are then discussed. First, recent progress on angular momentum multiplexing, including its behavior under different incident conditions, is considered. Second, a detailed overview of polarization‐controlled, wavelength‐selective, angle‐selective, and reconfigurable multiplexing/multifunctional metasurfaces is provided. Then, the integrated and on‐chip design of multifunctional metasurfaces is addressed. Finally, future directions and potential applications are presented.

Nucleation and Growth of Amino‐acid and Peptide Supramolecular Polymers through Liquid‐liquid Phase Separation

By Xuehai Yan, Chengqian Yuan, Aviad Levin, Wei Chen, Ruirui Xing, Qianli Zou, Therese W. Herling, Pavan Kumar Challa, Tuomas P.J. Knowles from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

The transition of peptides and proteins from solution into fibrillar structures is a general phenomenon encountered in functional and aberrant biology and is increasingly exploited in soft materials science. However, the fundamental molecular events underpinning the early stages of their assembly and subsequent growth have remained challenging to elucidate. Here, we show that liquid‐liquid phase separation into solute‐rich and solute‐poor phases is a fundamental step leading to the nucleation of supramolecular nanofibrils from molecular building blocks, including peptides and even amphiphilic amino acids. The solute‐rich liquid droplets act as nucleation sites, allowing the formation of thermodynamically favorable nanofibrils following Ostwald’s step rule. The solution to liquid droplets transition is entropy driven while the liquid droplets to nanofibrils transition is mediated by enthalpic interactions and characterized by structural reorganization. These findings shed light on how the nucleation barrier toward the formation of solid phases can be lowered through a kinetic mechanism which proceeds through a metastable liquid phase.

Efficient BiVO4 photoanodes by postsynthetic treatment: remarkable improvements in photoelectrochemical performance from facile borate modification

By Qijun Meng, Biaobiao Zhang, Lizhou Fan, Haidong Liu, Mario Valvo, Kristina Edström, Maria Cuartero, Roland De Marco, Gaston A. Crespo, Licheng Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 16, 2019.

Water‐splitting photoanodes based on semiconductor materials typically require a dopant in the structure and co‐catalysts on the surface to overcome the problems of charge recombination and high catalytic barrier. Unlike these conventional strategies, we herein report a simple treatment by soaking a sample of pristine BiVO4 in a borate buffer solution. This modifies the catalytic local environment of BiVO4 by the introduction of a borate moiety at the molecular level. The self‐anchored borate plays the role of a passivator in reducing the surface charge recombination as well as that of a ligand in modifying the catalytic site to facilitate faster water oxidation. The modified BiVO4 photoanode, without typical doping or catalyst modification, achieved a photocurrent density of 3.5 mA cm‐2 at 1.23 V and a cathodically shifted onset potential of 250 mV. This work provides an extremely simple method to improve the intrinsic photoelectrochemical performance of BiVO4 photoanodes.

A Paclitaxel‐Based Mucoadhesive Nanogel with Multivalent Interactions for Cervical Cancer Therapy

By Qiuhui Qian, Leilei Shi, Xihui Gao, Yuan Ma, Jiapei Yang, Zhihao Zhang, Jiwen Qian, Xinyuan Zhu from Wiley: Small: Table of Contents. Published on Oct 16, 2019.

A mucoadhesive nanogel is introduced to prolong the residence time and dramatically improve the drug efficiency in local cervical cancer therapy. This nanogel not only displays mucoadhesive properties that adhere strongly to mucins but also contributes to the penetration of drugs in epithelial cell monolayers. The new design with multivalent interactions exerts excellent anticancer activity in cervical cancer. Abstract Cervical cancer treatment is subject to limited drug access to locally diseased targets and generally resistant to chemotherapy, thus it is essential to develop a local drug delivery system to overcome these problems, premised on guaranteeing drug efficacy. With this goal in mind, a multivalent interactions‐based mucoadhesive nanogel for vaginal delivery is proposed. Briefly, the nanogel is constructed with mucoadhesive poly(acrylic acid) as the backbone and multiple inclusions between β‐cyclodextrin and paclitaxel as the crosslinking points. The in vitro experiments demonstrate that nanogel exerts high cytotoxicity to cancer cells, reverses multidrug resistance effectively, and successfully promotes the permeation of drugs. More to the point, as proved in the in vivo experiments, the retention time in the vagina is prolonged and the tumor growth is effectively suppressed by the nanogel without any side effects in the orthotopic cervical cancer model. As mentioned above, this novel mucoadhesive nanogel is believed to be a useful tool toward designing drug delivery systems for cervical cancer treatment.

[ASAP] Optical Processing of DNA-Programmed Nanoparticle Superlattices

By Leonardo Z. Zornberg, Paul A. Gabrys, and Robert J. Macfarlane* from Nano Letters: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03258

[ASAP] In Situ Droplet Microgoniometry Using Optical Microscopy

By Hyeongyun Cha†?, Jingcheng Ma†, Young Seong Kim†, Longnan Li†, Luwen Sun†, Jiashuo Tong†, and Nenad Miljkovic*†‡§? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06687

[ASAP] Interstitial Hydrogen Atom Modulation to Boost Hydrogen Evolution in Pd-Based Alloy Nanoparticles

By Jinchang Fan†, Xiaoqiang Cui*†, Shansheng Yu†, Lin Gu‡, Qinghua Zhang‡, Fanqi Meng‡, Zhangquan Peng§, Lipo Ma§, Jing-Yuan Ma?, Kun Qi?, Qiaoliang Bao?, and Weitao Zheng† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05615

[ASAP] Conformal 3D Nanopatterning by Block Copolymer Lithography with Vapor-Phase Deposited Neutral Adlayer

By Geon Gug Yang†?, Junhwan Choi‡?, Seung Keun Cha†, Gil Yong Lee†, Hyeong Min Jin§, Ho Seong Hwang†, Taeyeong Yun†, Juyeon Kang‡, Kyu Hyo Han†, Jang Hwan Kim†, Hee Jae Choi†, Sung Gap Im*‡, and Sang Ouk Kim*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05859

[ASAP] Pyonitrins A–D: Chimeric Natural Products Produced by Pseudomonas protegens

By Emily Mevers†?, Josep Sauri´‡?, Eric J. N. Helfrich†?, Matthew Henke†, Kenneth J. Barns§, Tim S. Bugni§, David Andes?, Cameron R. Currie?, and Jon Clardy*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09739

[ASAP] The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation

By Nicholas E. Smith†, Wesley H. Bernskoetter‡, and Nilay Hazari*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09062

[ASAP] Engineering the hCRBPII Domain-Swapped Dimer into a New Class of Protein Switches

By Alireza Ghanbarpour‡, Cody Pinger, Rahele Esmatpour Salmani, Zahra Assar§, Elizabeth M. Santos†, Meisam Nosrati, Kathryn Pawlowski, Dana Spence, Chrysoula Vasileiou, Xiangshu Jin, Babak Borhan*, and James. H. Geiger* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04664

[ASAP] Mechanisms for Hydrogen-Atom Abstraction by Mononuclear Copper(III) Cores: Hydrogen-Atom Transfer or Concerted Proton-Coupled Electron Transfer?

By Mukunda Mandal†, Courtney E. Elwell†, Caitlin J. Bouchey†‡, Timothy J. Zerk‡, William B. Tolman*‡, and Christopher J. Cramer*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08109

[ASAP] Site-Specific Sequential Protein Labeling Catalyzed by a Single Recombinant Ligase

By Fabian B. H. Rehm†‡, Thibault J. Harmand†, Kuok Yap‡, Thomas Durek‡, David J. Craik‡, and Hidde L. Ploegh*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09166

[ASAP] Strong p-Backbonding Enables Record Magnetic Exchange Coupling Through Cyanide

By Juan A. Valdez-Moreira†, Agnes E. Thorarinsdottir‡, Jordan A. DeGayner‡, Sean A. Lutz†, Chun-Hsing Chen†, Yaroslav Losovyj†, Maren Pink†, T. David Harris*‡, and Jeremy M. Smith*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b09445

[ASAP] Fe-Catalyzed Reductive Couplings of Terminal (Hetero)Aryl Alkenes and Alkyl Halides under Aqueous Micellar Conditions

By Haobo Pang†, Ye Wang†, Fabrice Gallou‡, and Bruce H. Lipshutz*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04510

[ASAP] Architecture-Controlled Ring-Opening Polymerization for Dynamic Covalent Poly(disulfide)s

By Yun Liu*†§||‡, Yuan Jia†§||‡, Qiong Wu§||, and Jeffrey S. Moore*†§|| from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08957

[ASAP] Mechanism and Scope of Nickel-Catalyzed Decarbonylative Borylation of Carboxylic Acid Fluorides

By Christian A. Malapit, James R. Bour, Simon R. Laursen, and Melanie S. Sanford* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b08961

[ASAP] Aptamer Displacement Reaction from Live-Cell Surfaces and Its Applications

By Long Li†, Xigao Chen†, Cheng Cui†‡§, Xiaoshu Pan†, Xiaowei Li†, Hoda Safari Yazd†, Qiong Wu†, Liping Qiu‡, Juan Li*§?, and Weihong Tan*‡§? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Oct 16, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b07191

Conformational Entropy as a Means to Control the Behavior of Poly(diketoenamine) Vitrimers In and Out of Equilibrium

By Changfei He, Peter R. Christensen, Trevor J. Seguin, Eric A. Dailing, Brandon M. Wood, Rebecca K. Walde, Kristin A. Persson, Thomas P. Russell, Brett A. Helms from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Poly(diketoenamine) (PDK) vitrimers are an emerging platform for sustainable plastics, providing additive‐tolerant chemical circularity after depolymerization.  Here we show how to control the equilibrium and non‐equilibrium thermomechanical behavior of PDKs by incorporating into the dynamic covalent network linear polymer segments varying in both molecular weight ( MW = 0–12 kg mol –1 ) and conformational degrees of freedom. While increasing  MW of linear segments predictably yields a lower storage modulus ( E ’) at the rubbery plateau after softening above the glass transition ( T g ), due to the lower network density, we further find that both  T g and the characteristic time ( t *) of stress‐relaxation when deformed are independently governed by the conformational entropy of the embodied linear segments. We also find that activation energies ( E a ) for bond exchange in the solid‐state are lower, by as much as 19  kJ mol − 1 , for networks incorporating flexible chains, and that the network’s topology freezing temperature ( T v ) decreases with increasing  MW of flexible linear segments, but increases with increasing  MW of stiff linear segments . Therefore, the dynamics of vitrimer reconfigurability are influenced not only by the energetics of associative bond exchange for a given network density, but also foundationally by the entropy of polymer chains within the network.

Fabrication of Large Single Crystals for Pt‐Based Linear Polymers with Controlled‐Release and Photoactuator Performance

By Qi Yu, Mingmin Li, Jia Gao, Peixin Xu, Qizhe Chen, Dong Xing, Jie Yan, Michael J. Zaworotko, Jun Xu, Yao Chen, Peng Cheng, Zhenjie Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Preparation of large single crystals for linear polymers that are amenable to X‐ray analysis is very challenging in polymer science. Herein, we employed a coordination driven self‐assembly strategy to secure appropriate head‐to‐tail alignment of anthracene moieties, and for the first time obtained large‐sized Pt‐based linear polymer crystals through a [4+4] cycloaddition of anthracene in a single‐crystal to single‐crystal fashion. Using X‐ray diffraction analysis to precisely determine polymer crystal structure, we revealed that both the polymerisation and depolymerisation steps proceed via a stable intermediate. Taking advantage of the temperature‐dependent slow depolymerization, the afforded Pt‐based linear polymer showed potential as a sustained release anticancer drug platform. Furthermore, utilizing the reversible contraction effect of unit‐cell volume upon irradiation or heating, the stimuli‐responsive crystals were hybridized with polyvinylidene fluoride to obtain a‘smart material’ with outstanding photoactuator performance. This work not only provides a new approach to prepare metal‐containing linear polymer crystals, but also broadens their potential applications towards drug controlled‐release and actuator functions.

Functionalized DNA Enables Programming Exosomes/Vesicles for Tumor Imaging and Therapy

By Zhijin Fan, Keng Xiao, Jingyan Lin, Yuhui Liao, Xi Huang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Functionalized DNA and engineered artificial vesicles of M1 macrophage (M1mv) realize moderate labeling and functionalization of exosomes/vesicles. The constructed artificial drug‐delivery vesicles realize target‐triggered drug delivery systems, that simultaneously possess biological treatment and chemotherapy functions, and thus have the potential to serve as a new paradigm for tumor labeling and therapy. Abstract Exosomes serve as significant information carriers that regulate important physiological and pathological processes. Herein, functionalized DNA is engineered to be a hinge that anchors quantum dots (QDs) onto the surface of exosomes, realizing a moderate and biocompatible labeling strategy. The QDs‐labeled exosomes (exosome–DNA–QDs complex) can be swiftly engulfed by tumor cells, indicating that exosome–DNA–QDs can be applied as a specific agent for tumor labeling. Furthermore, the engineered artificial vesicles of M1 macrophages (M1mv) are constructed via a pneumatic liposome extruder. The results reveal that the individual M1mv can kill tumor cells and realize desirable biological treatment. To reinforce the antitumor efficacy of M1mv and the specificity of drug release, a target‐triggered drug delivery system is constructed to realize a specific microRNA‐responded delivery system for visual therapy of tumors. These strategies facilitate moderate labeling and functionalization of exosomes/vesicles and construct artificial drug‐delivery vesicles that simultaneously possess biological treatment and chemotherapy functions, and thus have the potential to serve as a new paradigm for tumor labeling and therapy.

Photoactivated Trifunctional Platinum Nanobiotics for Precise Synergism of Multiple Antibacterial Modes

By Tian Deng, Hao Zhao, Miusi Shi, Yun Qiu, Shuting Jiang, Xiangliang Yang, Yanbing Zhao, Yufeng Zhang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

When dual‐valent platinum nanoparticles (dvPtNPs) are activated by near‐infrared irradiation, precise cooperation of multiple antibacterial modes occurs. The photothermal effect leads to the bacterial membrane perforation and RNA leakage, and owing to the photodynamic effect, the ROS level rises up while ATP level declines. Moreover, Pt2+ ions release as “chemotherapy” resulting in DNA damage and bacterial growth inhibition. Abstract Integrating multiple strategies of antibacterial mechanisms into one has been proven to have tremendous promise for improving antimicrobial efficiency. Hence, dual‐valent platinum nanoparticles (dvPtNPs) with a zero‐valent platinum core (Pt0) and bi‐valent platinum shell (Pt2+ ions), combining photothermal and photodynamic therapy, together with “chemotherapy,” emerge as spatiotemporally light‐activatable platinum nano‐antibiotics. Under near‐infrared (NIR) exposure, the multiple antibacterial modes of dvPtNPs are triggered. The Pt0 core reveals significant hyperthermia via effective photothermal conversion while an immediate release of chemotherapeutic Pt2+ ions occurs through hyperthermia‐initiated destabilization of metallic interactions, together with reactive oxygen species (ROS) level increase, thereby resulting in synergistic antibacterial effects. The precise cooperative effects between photothermal, photodynamic, and Pt2+ antibacterial effects are achieved on both Gram‐negative Escherichia coli and Gram‐positive methicillin‐resistant Staphylococcus aureus, where bacterial viability and colony‐forming units are significantly reduced. Moreover, similar results are observed in mice subcutaneous abscess models. Significantly, after NIR treatment, dvPtNP exhibits a more robust bacteria‐killing efficiency than other PtNP groups, owing to its integration of dramatic damage to the bacterial membrane and DNA, and alteration to ATP and ROS metabolism. This study broadens the avenues for designing and synthesizing antibacterial materials with higher efficiency.

A Chiral Polycyclic Aromatic Hydrocarbon Monkey Saddle

By Michael Mastalerz, Tobias Kirschbaum, Frank Rominger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

A contorted polycyclic aromatic hydrocarbon (PAH) in the shape of a monkey saddle has been synthesized in three steps from a readily available truxene precursor. The monkey saddle PAH is consisting of three five‐, seven six‐, and three eight‐membered rings and has been unambiguously characterized by single‐crystal X‐ray diffraction. Due to the three biaryl axes the monkey saddle PAH is inherently chiral. The inversion of the two enantiomeric structures into each other preferably occurs via a twisting of peripheral rings rather than by a fully planar intermediate, as has been calculated by DFT methods. Enantiomers were separated by chiral HPLC and inversion barriers determined by variable temperature circular dichroism spectroscopy, supporting the twisting mechanism.

Quantum Topological Boundary States in Quasi‐Crystals

By Yao Wang, Yong‐Heng Lu, Jun Gao, Ke Sun, Zhi‐Qiang Jiao, Hao Tang, Xian‐Min Jin from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The quantum features of single photons can be well preserved in quasi‐crystals via topological boundary states, particularly, in the appearance of the diffusion‐induced decoherence and the environmental noise decoherence. The confirmed compatibility between topological states and single photons leads to a new an avenue to “quantum topological photonics” and provides more possibilities for quantum materials and quantum technologies. Abstract Topological phases play a novel and fundamental role in matter and display extraordinary robustness to smooth changes in material parameters or disorder. A crossover between topological material and quantum information may lead to inherent fault‐tolerant quantum simulations and quantum computing. Quantum features may be preserved by being encoded among topological structures of physical evolution systems. This requires stimulation, manipulation, and observation of topological phenomena at the single quantum particle level, which has not, however, yet been realized. It is asked whether the quantum features of single photons can be preserved in topological structures. The boundary states are experimentally observed at the genuine single‐photon level and the performance of the topological phase is demonstrated to protect the quantum features against diffusion‐induced decoherence in coupled waveguides and noise decoherence from the ambient environment. Compatibility between macroscopic topological states and microscopic single photons in the ambient environment is thus confirmed, leading to a new avenue to “quantum topological photonics” and providing more new possibilities for quantum materials and quantum technologies.

Cascade One‐Pot Synthesis of Orange‐Red Fluorescent Polycyclic Cinnolino[2,3‐f]phenanthridin‐9‐ium Salts by Palladium(II)‐Catalyzed C‐H Bond Activation of 2‐Azobiaryls and Alkenes

By Jayachandran Jayakumar, Guganchandar Vedarethinam, Huan-Chang Hsiao, Shang-You Sun, Shih-Ching Chuang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

The first palladium‐catalyzed synthesis of quaternary ammonium salts through double oxidative C‐H bond activation on azobenzenes in moderate to good yields is reported. In this study, we disclose a highly regioselective synthesis of orange‐red fluorescent cinnolino[2,3‐ f ]phenanthridin‐9‐ium salts and 15 H ‐cinnolino[2,3‐ f ]phenanthridin‐9‐ium‐10‐ide from 2‐azobiaryls and alkenes catalyzed by palladium(II). The reaction mechanism is proposed involving an ortho C‐H olefination of 2‐azobiaryls with alkenes, intramolecular aza‐Michael addition, concerted metalation deprotonation (CMD), reductive elimination and oxidation.

CyClick Chemistry for Synthesis of Cyclic Peptides

By Monika Raj, Ryan D. Cohen, Victor Adebomi, Rachel Wills, Gary Martin, Holland Chavers from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Cyclic peptides are emerging as important class of therapeutics and small‐to‐medium sized rings have been of particular interest. The laboratory synthesis of cyclic peptides can prove to be a difficult and long‐standing problem. One of the major challenges with conventional macrocyclization techniques is the formation of undesirable dimers and cyclooligomers at high concentrations due to intermolecular reactions between linear peptides. Here, we report a novel “CyClick” strategy for the macrocyclization of peptides that works in an exclusively intramolecular fashion that precludes the formation of dimers/oligomers via intermolecular reactions. The cyc‐click chemistry is highly chemoselective for the N‐terminus of the peptide and aldehyde group. In this protocol, the conformation of the peptide during the cyclization acts as an internal directing group for the activation of the backbone amide bond that facilitates the formation of the stable 4‐imidazolidinone‐cyclic peptide with high stereoselectivity (>99%). This method is tolerant to variety of peptide aldehydes and has been applied for the synthesis of 12‐,15‐,18‐, 21‐ and 24‐membered rings with varying amino acid compositions in one‐pot, under mild reaction conditions. The reaction generated peptide macrocycles featuring a 4‐imidazolidinone in their scaffolds, which acts as an endocyclic control element that promotes intramolecular hydrogen‐bonding pattern and leads to macrocycles with conformationally rigid turn structures.

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single Molecule Conductance

By Feng Jiang, Douglas Trupp, Norah Algethami, Haining Zheng, Wenxiang He, Afaf Alqorashi, Chenxu Zhu, Chun Tang, Ruihao Li, Junyang Liu, Hatef Sadeghi, Jia Shi, Ross Davidson, Marcus Korb, Masnun Naher, Alexandre N. Sobolev, Sara Sangtarash, Paul J. Low, Wenjing Hong, Colin Lambert from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple, flexible molecular design strategies to understand, control and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of pendant methoxy (OMe) substituents around the central phenylene ring. These substituents play the role of molecular‐scale ‘taps’, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic ratio and orbital product rules, and highlight a novel chemical design strategy for tuning and gating DQI features, to create single‐molecule devices with desirable electronic functions.

Electrostatic Complementarity drives Amyloid/Nucleic Acid Co‐assembly

By Allisandra Rha, Dibyendu Das, Olga Taran, Yonggang Ke, Anil Mehta, David G Lynn from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Proteinaceous plaques associated with neurodegenerative diseases contain many biopolymers including the polyanions glycosaminoglycans and nucleic acids. Polyanion‐induced amyloid fibrillation has been implicated in disease etiology, but structural models for amyloid/nucleic acid co‐assemblies remain limited. Here we constrain nucleic acid/peptide interactions with model peptides that exploit electrostatic complementarity and define a novel amyloid/nucleic acid co‐assembly. The structure provides a model for nucleic acid/amyloid co‐assembly as well as insight into the energetic determinants involved in templating amyloid assembly.

Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols

By Wen Zhang, Keith Carpenter, Song Lin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Riboflavin‐derived photocatalysts have been extensively studied in the context of alcohol oxidation. However, to date, the scope of this catalytic methodology has been limited to benzyl alcohols. In this work, we gained further mechanistic understanding of flavin‐catalyzed oxidation reactions in the absence or presence of thiourea as a cocatalyst. The mechanistic insights enabled us to develop an electrochemically driven photochemical oxidation of primary and secondary aliphatic alcohols using a pair of flavin and dialkylthiourea catalysts. Electrochemistry makes it possible to avoid using O2 oxidant and generating H2O2 byproduct, both of which oxidatively degrade thiourea under the reaction conditions. This modification unlocks a new mechanistic pathway in which the oxidation of unactivated alcohols is achieved via thiyl radical‐mediated hydrogen‐atom abstraction.

Elucidating the Ultrafast Molecular Permeation through Well‐defined 2D Nanochannels of Lamellar Membranes

By Xiaoli Wu, Xulin Cui, Wenjia Wu, Jingtao Wang, Yifan Li, Zhongyi Jiang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

Lamellar membranes with well‐defined 2D nanochannels exhibit fast, selective permeation. However, the underlying molecular transport mechanism remains unexplored. Here in , regular and robust MXene Ti 3 C 2 T x lamellar membranes are prepared, and the size and wettability of nanochannels are manipulated by chemically grafted hydrophilic (‒NH 2 ) or hydrophobic (‒C 6 H 5 , ‒C 12 H 25 ) groups. These nanochannels have sharp difference in mass transfer behaviors. Hydrophilic nanochannels , in which polar molecules form orderly aligned aggregate s along channel walls , impart ultrahigh permeance of over 3000 L m ‐2 h ‐1 bar ‐1 , which is over 3 times higher than that in hydrophobic nanochannels with disordered molecular configuration . In contrast, nonpolar molecules with disordered configuration in both hydrophilic and hydrophobic nanochannels have comparable permeance. Finally , two phenomenological transport model s to correlate t he permeance with the mass transport mechanism of molecules that display ordered and disordered configuration are established, which is conductive to designing high performance 2D channel materials .

Strong N−X···O−N Halogen Bonds: Comprehensive Study on N‐Halosaccharin Pyridine N‐oxide Complexes

By Kari Rissanen, Rakesh Puttreddy, Mikko Rautiainen, Toni Mäkelä from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

A detailed study of the strong N−X⋯−O−N+ (X = I, Br) halogen bonding interactions in solution and in the solid‐state reports 2×27 donor×acceptor complexes of N‐halosaccharins and pyridine N‐oxides (PyNO). Density Functional Theory (DFT) calculations were used to investigate the X···O halogen bond (XB) interaction energies in 54 complexes. The XB interaction energies were found to vary from –47.5 to –120.3 kJ mol–1, with the strongest N−I⋯−O−N+ XBs approaching those of 3‐center‐4‐electron [N–I–N]+ halogen‐bonded systems (∼160 kJ mol–1). Using a subset of 32 complexes, stabilized only through N−X···−O−N+ XB interactions, a simplified, computationally fast, electrostatic model to predict the X···O bond energies, was developed. Energies predicted by this simple model and much higher‐level theory DFT calculations agree excellently, illustrating the usefulness of the simplified electrostatic model. In solution, the 1H NMR association constants (KXB) determined in CDCl3 and acetone‐d6 vary from 2.0 x100 to >108 M‐1 following accurately the calculated σ‐hole nature on the donor halogen. The donor×acceptor complexation enthalpies calculated in CHCl3 using polarized continuum model very between –38.4 and –77.5 kJ mol–1 and correlate well with the pKXB values determined by 1H NMR in CDCl3 indicating the formation of strong and robust 1:1 XB complexes in solution. In X‐ray crystal structures, the N‐iodosaccharin‐PyNO complexes manifest short normalized interaction ratios (RXB) between 0.65 – 0.67 for the N−I⋯−O−N+ halogen bond.

Oxide Catalysts with Ultrastrong Resistance to SO2 Deactivation for Removing Nitric Oxide at Low Temperature

By Zhaoxia Ma, Liping Sheng, Xinwei Wang, Wentao Yuan, Shiyuan Chen, Wei Xue, Gaorong Han, Ze Zhang, Hangsheng Yang, Yunhao Lu, Yong Wang from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

A low‐temperature selective catalytic reduction (SCR) catalyst (MnOX/CeO2) with outstanding SO2 resistance is designed and fabricated. This unprecedented performance is achieved by establishing a dynamic equilibrium between sulfate formation and decomposition over the CeO2 surface during the reactions and preventing the MnOx cluster from the steric hindrance induced by SO2, which minimizes the deactivation of the active sites of MnOx/CeO2. Abstract Nitrogen oxides are one of the major sources of air pollution. To remove these pollutants originating from combustion of fossil fuels remains challenging in steel, cement, and glass industries as the catalysts are severely deactivated by SO2 during the low‐temperature selective catalytic reduction (SCR) process. Here, a MnOX/CeO2 nanorod catalyst with outstanding resistance to SO2 deactivation is reported, which is designed based on critical information obtained from in situ transmission electron microscopy (TEM) experiments under reaction conditions and theoretical calculations. The catalysts show almost no activity loss (apparent NOX reaction rate kept unchanged at 1800 µmol g−1 h−1) for 1000 h test at 523 K in the presence of 200 ppm SO2. This unprecedented performance is achieved by establishing a dynamic equilibrium between sulfates formation and decomposition over the CeO2 surface during the reactions and preventing the MnOX cluster from the steric hindrance induced by SO2, which minimized the deactivation of the active sites of MnOX/CeO2. This work presents the ultralong lifetime of catalysts in the presence of SO2, along with decent activity, marking a milestone in practical applications in low‐temperature selective catalytic reduction (SCR) of NOX.

Tuning Oxygen Redox Chemistry in Li‐Rich Mn‐Based Layered Oxide Cathodes by Modulating Cation Arrangement

By Jicheng Zhang, Fangyi Cheng, Shulei Chou, Jianli Wang, Lin Gu, Heng Wang, Hirofumi Yoshikawa, Yong Lu, Jun Chen from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The oxygen redox chemistry in Li‐rich Mn‐based layered oxides can be tuned by modulating the cation arrangement. When cation disorder and Li vacancies in the bulk lattice exist, the formation of peroxide species is restrained. The material without forming peroxide shows improved performance in suppressing oxygen overoxidation, mitigating cation dissolution and voltage decay. Abstract Li‐rich Mn‐based oxides (LRMO) are promising cathode materials to build next‐generation lithium‐ion batteries with high energy density exceeding 400 W h kg−1. However, due to a lack of in‐depth understanding of oxygen redox chemistry in LRMO, voltage decay is not resolved thoroughly. Here, it is demonstrated that the oxygen redox chemistry could be tuned by modulating cation arrangement. It declares that the materials with Li/Ni disorder and Li vacancies can inhibit the formation of OO dimers. Because of the high chemical activity, OO dimers could accelerate lattice oxygen release and NiO/spinel formation. The samples without forming OO dimers show improved performance in suppressing oxygen overoxidation and mitigating cation dissolution. As a result, the optimized cathode exhibits a high capacity over 280 mA h g−1 at 0.1 C and a high plateau voltage of 3.58 V with a very low voltage decay of 1.6% after 150 cycles at 1 C. This study opens an attractive path in designing Li‐rich electrodes with stabilized redox chemistry.

Narrowband Organic Light‐Emitting Diodes for Fluorescence Microscopy and Calcium Imaging

By Caroline Murawski, Andreas Mischok, Jonathan Booth, Jothi Dinesh Kumar, Emily Archer, Laura Tropf, Chang‐Min Keum, Ya‐Li Deng, Kou Yoshida, Ifor D. W. Samuel, Marcel Schubert, Stefan R. Pulver, Malte C. Gather from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Organic light‐emitting diodes (OLEDs) are used as light source for fluorescence microscopy. Spectral multiplexing enables high contrast and results in fluorescence images of live cells with similar image quality to conventional illumination. Furthermore, the device is applied to recording neuronal activity in small‐animal models at video rates. Abstract Fluorescence imaging is an indispensable tool in biology, with applications ranging from single‐cell to whole‐animal studies and with live mapping of neuronal activity currently receiving particular attention. To enable fluorescence imaging at cellular scale in freely moving animals, miniaturized microscopes and lensless imagers are developed that can be implanted in a minimally invasive fashion; but the rigidity, size, and potential toxicity of the involved light sources remain a challenge. Here, narrowband organic light‐emitting diodes (OLEDs) are developed and used for fluorescence imaging of live cells and for mapping of neuronal activity in Drosophila melanogaster via genetically encoded Ca2+ indicators. In order to avoid spectral overlap with fluorescence from the sample, distributed Bragg reflectors are integrated onto the OLEDs to block their long‐wavelength emission tail, which enables an image contrast comparable to conventional, much bulkier mercury light sources. As OLEDs can be fabricated on mechanically flexible substrates and structured into arrays of cell‐sized pixels, this work opens a new pathway for the development of implantable light sources that enable functional imaging and sensing in freely moving animals.

Chemically Tuned p‐ and n‐Type WSe2 Monolayers with High Carrier Mobility for Advanced Electronics

By Hyun Goo Ji, Pablo Solís‐Fernández, Daisuke Yoshimura, Mina Maruyama, Takahiko Endo, Yasumitsu Miyata, Susumu Okada, Hiroki Ago from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Selective tuning of ambipolar WSe2 monolayer to p‐ and n‐type semiconductors by chemical doping is demonstrated. The chemical doping not only allows to control over the main charge carriers, but also increases the carrier mobility of the WSe2 significantly. Furthermore, a complementary metal‐oxide‐semiconductor inverter and an in‐plane p–n junction with superior performance are successfully fabricated by integrating the chemically doped WSe2. Abstract Monolayers of transition metal dichalcogenides (TMDCs) have attracted a great interest for post‐silicon electronics and photonics due to their high carrier mobility, tunable bandgap, and atom‐thick 2D structure. With the analogy to conventional silicon electronics, establishing a method to convert TMDC to p‐ and n‐type semiconductors is essential for various device applications, such as complementary metal‐oxide‐semiconductor (CMOS) circuits and photovoltaics. Here, a successful control of the electrical polarity of monolayer WSe2 is demonstrated by chemical doping. Two different molecules, 4‐nitrobenzenediazonium tetrafluoroborate and diethylenetriamine, are utilized to convert ambipolar WSe2 field‐effect transistors (FETs) to p‐ and n‐type, respectively. Moreover, the chemically doped WSe2 show increased effective carrier mobilities of 82 and 25 cm2 V−1s−1 for holes and electrons, respectively, which are much higher than those of the pristine WSe2. The doping effects are studied by photoluminescence, Raman, X‐ray photoelectron spectroscopy, and density functional theory. Chemically tuned WSe2 FETs are integrated into CMOS inverters, exhibiting extremely low power consumption (≈0.17 nW). Furthermore, a p‐n junction within single WSe2 grain is realized via spatially controlled chemical doping. The chemical doping method for controlling the transport properties of WSe2 will contribute to the development of TMDC‐based advanced electronics.

High‐Efficiency Red Organic Light‐Emitting Diodes with External Quantum Efficiency Close to 30% Based on a Novel Thermally Activated Delayed Fluorescence Emitter

By Yuan‐Lan Zhang, Quan Ran, Qiang Wang, Yuan Liu, Christian Hänisch, Sebastian Reineke, Jian Fan, Liang‐Sheng Liao from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

A novel red thermally activated delayed fluorescence (TADF) emitter, TPA–PZCN, is designed and synthesized. It simultaneously possesses a high ΦPL of 97% and a small ΔEST of 0.13 eV. Red, deep‐red, and near‐infrared organic light‐emitting diodes (LEDs) based on it achieve record external quantum efficiencies of 27.4%, 28.1%, and 5.3%, respectively, which are the best performances in comparison with LEDs having a similar device structure. Abstract Researchers have spared no effort to design new thermally activated delayed fluorescence (TADF) emitters for high‐efficiency organic light‐emitting diodes (OLEDs). However, efficient long‐wavelength TADF emitters are rarely reported. Herein, a red TADF emitter, TPA–PZCN, is reported, which possesses a high photoluminescence quantum yield (ΦPL) of 97% and a small singlet–triplet splitting (ΔEST) of 0.13 eV. Based on the superior properties of TPA–PZCN, red, deep‐red, and near‐infrared (NIR) OLEDs are fabricated by utilizing different device structure strategies. The red devices obtain a remarkable maximum external quantum efficiency (EQE) of 27.4% and an electroluminescence (EL) peak at 628 nm with Commission Internationale de L'Eclairage (CIE) coordinates of (0.65, 0.35), which represents the best result with a peak wavelength longer than 600 nm among those of the reported red TADF devices. Furthermore, an exciplex‐forming cohost strategy is adopted. The devices achieve a record EQE of 28.1% and a deep‐red EL peak at 648 nm with the CIE coordinates of (0.66, 0.34). Last, nondoped devices exhibit 5.3% EQE and an NIR EL peak at 680 nm with the CIE coordinates of (0.69, 0.30).

In Situ Grown Monolayer N‐Doped Graphene on CdS Hollow Spheres with Seamless Contact for Photocatalytic CO2 Reduction

By Chuanbiao Bie, Bicheng Zhu, Feiyan Xu, Liuyang Zhang, Jiaguo Yu from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Monolayer N‐doped graphene is in situ grown on CdS hollow spheres for photocatalytic CO2 reduction. The constructed photocatalyst achieves a seamless and large‐area contact of the heterojunction, which facilitates the charge separation and transfer. It provides a hollow structure for promoting light utilization, a thin shell for shortening the transfer distance of photogenerated electrons, and N atoms for adsorbing and activating CO2 molecules. Abstract Photocatalytic CO2 reduction is an effective way to simultaneously mitigate the greenhouse effect and the energy crisis. Herein, CdS hollow spheres, on which monolayer nitrogen‐doped graphene is in situ grown by chemical vapor deposition, are applied for realizing effective photocatalytic CO2 reduction. The constructed photocatalyst possesses a hollow interior for strengthening light absorption, a thin shell for shortening the electron migration distance, tight adhesion for facilitating separation and transfer of carriers, and a monolayer nitrogen‐doped graphene surface for adsorbing and activating CO2 molecules. Achieving seamless contact between a photocatalyst and a cocatalyst, which provides a pollution‐free and large‐area transport interface for carriers, is an effective strategy for improving the photocatalytic CO2 reduction performance. Therefore, the yield of CO and CH4, as dominating products, can be increased by four and five times than that of pristine CdS hollow spheres, respectively. This work emphasizes the importance of contact interface regulation between the photocatalyst and the cocatalyst and provides new ideas for the seamless and large‐area contact of heterojunctions.

A Single‐Electron Transistor Made of a 3D Topological Insulator Nanoplate

By Yumei Jing, Shaoyun Huang, Jinxiong Wu, Mengmeng Meng, Xiaobo Li, Yu Zhou, Hailin Peng, Hongqi Xu from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

A topological insulator single‐electron transistor device is fabricated using state‐of‐the‐art nanofabrication techniques, and the device shows well‐defined Coulomb current oscillations and Coulomb‐diamond‐shaped charge stability diagrams. Abstract Quantum confined devices of 3D topological insulators are proposed to be promising and of great importance for studies of confined topological states and for applications in low‐energy‐dissipative spintronics and quantum information processing. The absence of energy gap on the topological insulator surface limits the experimental realization of a quantum confined system in 3D topological insulators. Here, the successful realization of single‐electron transistor devices in Bi2Te3 nanoplates using state‐of‐the‐art nanofabrication techniques is reported. Each device consists of a confined central island, two narrow constrictions that connect the central island to the source and drain, and surrounding gates. Low‐temperature transport measurements demonstrate that the two narrow constrictions function as tunneling junctions and the device shows well‐defined Coulomb current oscillations and Coulomb‐diamond‐shaped charge‐stability diagrams. This work provides a controllable and reproducible way to form quantum confined systems in 3D topological insulators, which should greatly stimulate research toward confined topological states, low‐energy‐dissipative devices, and quantum information processing.

Highly Stable and Efficient FASnI3‐Based Perovskite Solar Cells by Introducing Hydrogen Bonding

By Xiangyue Meng, Jianbo Lin, Xiao Liu, Xin He, Yong Wang, Takeshi Noda, Tianhao Wu, Xudong Yang, Liyuan Han from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The OH…I− hydrogen bonding interactions between poly(vinyl alcohol) (PVA) and FASnI3 have the effects of introducing nucleation sites, slowing down crystal growth, directing the crystal orientation, reducing the trap states, and suppressing the migration of the ions. By adding PVA, the FASnI3–PVA perovskite solar cells attain improved power conversion efficiency and stability. Abstract Tin‐based perovskites with narrow bandgaps and high charge‐carrier mobilities are promising candidates for the preparation of efficient lead‐free perovskite solar cells (PSCs). However, the crystalline rate of tin‐based perovskites is much faster, leading to abundant trap states and much lower open‐circuit voltage (Voc). Here, hydrogen bonding is introduced to retard the crystalline rate of the FASnI3 perovskite. By adding poly(vinyl alcohol) (PVA), the OH…I− hydrogen bonding interactions between PVA and FASnI3 have the effects of introducing nucleation sites, slowing down the crystal growth, directing the crystal orientation, reducing the trap states, and suppressing the migration of the iodide ions. In the presence of the PVA additive, the FASnI3–PVA PSCs attain higher power conversion efficiency of 8.9% under a reverse scan with significantly improved Voc from 0.55 to 0.63 V, which is one of the highest Voc values for FASnI3‐based PSCs. More importantly, the FASnI3–PVA PSCs exhibit striking long‐term stability, with no decay in efficiency after 400 h of operation at the maximum power point. This approach, which makes use of the OH…I− hydrogen bonding interactions between PVA and FASnI3, is generally applicable for improving the efficiency and stability of the FASnI3‐based PSCs.

Conjugated Carbon Cyclic Nanorings as Additives for Intrinsically Stretchable Semiconducting Polymers

By Jaewan Mun, Jiheong Kang, Yu Zheng, Shaochuan Luo, Hung‐Chin Wu, Naoji Matsuhisa, Jie Xu, Ging‐Ji Nathan Wang, Youngjun Yun, Gi Xue, Jeffrey B.‐H. Tok, Zhenan Bao from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Conjugated carbon cyclic nanoring compounds are used as molecular additives to enhance the stretchability of semiconducting polymers without compromising mobility. The additives are shown to significantly decrease long‐range crystalline order, while short‐range ordered aggregates are well‐maintained. Fully stretchable transistors fabricated with the newly established polymer semiconductor/molecular additive blend films exhibit improved mobility retention under strain and after repeated applied strain. Abstract Molecular additives are often used to enhance dynamic motion of polymeric chains, which subsequently alter the functional and physical properties of polymers. However, controlling the chain dynamics of semiconducting polymer thin films and understanding the fundamental mechanisms of such changes is a new area of research. Here, cycloparaphenylenes (CPPs) are used as conjugated molecular additives to tune the dynamic behaviors of diketopyrrolopyrrole‐based (DPP‐based) semiconducting polymers. It is observed that the addition of CPPs results in significant improvement in the stretchability of the DPP‐based polymers without adversely affecting their mobility, which arises from the enhanced polymer dynamic motion and reduced long‐range crystalline order. The polymer films retain their fiber‐like morphology and short‐range ordered aggregates, which leads to high mobility. Fully stretchable transistors are subsequently fabricated using CPP/semiconductor composites as active layers. These composites are observed to maintain high mobilities when strained and after repeated applied strains. Interestingly, CPPs are also observed to improve the contact resistance and charge transport of the fully stretchable transistors. ln summary, these results collectively indicate that controlling the dynamic motion of polymer semiconductors is proved to be an effective way to improve their stretchability.

Transient Light‐Emitting Diodes Constructed from Semiconductors and Transparent Conductors that Biodegrade Under Physiological Conditions

By Di Lu, Tzu‐Li Liu, Jan‐Kai Chang, Dongsheng Peng, Yi Zhang, Jiho Shin, Tao Hang, Wubin Bai, Quansan Yang, John A. Rogers from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Light‐emitting diodes constructed from biodegradable materials—ZnO as a direct bandgap semiconductor and Mo as semitransparent ultrathin electrodes—convert electrical power into light, in a platform that dissolves completely in aqueous solutions to biologically and environmentally benign end products. Such systems pave the way toward applications that cannot be addressed with conventional optoelectronic technologies, such as temporary medical implants and environmentally friendly displays. Abstract Transient forms of electronics, systems that disintegrate, dissolve, resorb, or sublime in a controlled manner after a well‐defined operating lifetime, are of interest for applications in hardware secure technologies, temporary biomedical implants, “green” consumer devices and other areas that cannot be addressed with conventional approaches. Broad sets of materials now exist for a range of transient electronic components, including transistors, diodes, antennas, sensors, and even batteries. This work reports the first examples of transient light‐emitting diodes (LEDs) that can completely dissolve in aqueous solutions to biologically and environmentally benign end products. Thin films of highly textured ZnO and polycrystalline Mo serve as semiconductors for light generation and conductors for transparent electrodes, respectively. The emitted light spans a range of visible wavelengths, where nanomembranes of monocrystalline silicon can serve as transient filters to yield red, green, and blue LEDs. Detailed characterization of the material chemistries and morphologies of the constituent layers, assessments of their performance properties, and studies of their dissolution processes define the underlying aspects. These results establish an electroluminescent light source technology for unique classes of optoelectronic systems that vanish into benign forms when exposed to aqueous conditions in the environment or in living organisms.

A Designer Scaffold with Immune Nanoconverters for Reverting Immunosuppression and Enhancing Immune Checkpoint Blockade Therapy

By Hathaichanok Phuengkham, Chanyoung Song, Yong Taik Lim from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

A designer scaffold loaded with immune nanoconverters encapsulated with resiquimod (iNCVs(R848)) and doxorubicin can polarize immunosuppressive cells into tumoricidal antigen presenting cells (APCs) and generate an in situ vaccine to favor antigen‐specific T cell responses. Reshaping the tumor microenvironment (TME) using the scaffold‐induced synergistic antitumor immunity with immune checkpoint blockade (ICB) effects results in the prevention of postsurgical tumor recurrence and metastasis. Abstract Current cancer immunotherapy based on immune checkpoint blockade (ICB) still suffers from low response rate and systemic toxicity. To overcome the limitation, a novel therapeutic platform that can revert nonimmunogenic tumors into immunogenic phenotype is highly required. Herein, a designer scaffold loaded with both immune nanoconverters encapsulated with resiquimod (iNCVs (R848)) and doxorubicin, which provides the polarization of immunosuppressive tumor‐associated macrophages (TAMs) and myeloid‐derived suppressor cells (MDSCs) into tumoricidal antigen‐presenting cells (APCs), rather than depleting them, as well as in situ vaccination that can be generated in vivo without the need to previously analyze and sequence tumor antigens to favor neoantigen‐specific T cell responses is suggested. Local and sustained release of iNCVs (R848) and doxorubicin from the designer scaffold not only reduces the frequency of immunosuppressive cells in tumors but also increases systemic antitumor immune response, while minimizing systemic toxicity. Reshaping the tumor microenivronment (TME) using the designer‐scaffold‐induced synergistic antitumor immunity with ICB effects and long‐term central and effector memory T cell responses, results in the prevention of postsurgical tumor recurrence and metastasis. The spatiotemporal modulation of TMEs through designer scaffolds is expected to be a strategy to overcome the limitations and improve the therapeutic efficacy of current immunotherapies with minimized systemic toxicity.

A Highly Emissive Surface Layer in Mixed‐Halide Multication Perovskites

By Zahra Andaji‐Garmaroudi, Mojtaba Abdi‐Jalebi, Dengyang Guo, Stuart Macpherson, Aditya Sadhanala, Elizabeth M. Tennyson, Edoardo Ruggeri, Miguel Anaya, Krzysztof Galkowski, Ravichandran Shivanna, Kilian Lohmann, Kyle Frohna, Sebastian Mackowski, Tom J. Savenije, Richard H. Friend, Samuel D. Stranks from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The changes in photophysical properties of mixed‐halide perovskite films under solar‐equivalent illumination are studied. The illumination generates localized low‐bandgap surface domains, onto which photoexcited charge carriers transfer and recombine with high radiative efficiency. The fraction of radiative and nonradiative (Auger) recombination bandgap can be balanced to achieve extremely high photoluminescence quantum yields at low excitation densities. Abstract Mixed‐halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution‐processed triple‐cation mixed‐halide (Cs0.06MA0.15FA0.79)Pb(Br0.4I0.6)3 perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar‐equivalent illumination. It is found that the illumination leads to localized surface sites of iodide‐rich perovskite intermixed with passivating PbI2 material. Time‐ and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide‐rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed‐halide mixed‐cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.

1 cm2 Organic Photovoltaic Cells for Indoor Application with over 20% Efficiency

By Yong Cui, Huifeng Yao, Tao Zhang, Ling Hong, Bowei Gao, Kaihu Xian, Jinzhao Qin, Jianhui Hou from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Organic photovoltaic (OPV) cells promise to have a good photovoltaic performance under the indoor light environment. Via optimizing the active layers, 1 cm2 OPV cells are fabricated and a top power conversion efficiency of 22% under 1000 lux illumination is demonstrated. Abstract Organic photovoltaic (OPV) technologies have the advantages of fabricating larger‐area and light‐weight solar panels on flexible substrates by low‐cost roll‐to‐toll production. Recently, OPV cells have achieved many significant advances with power conversion efficiency (PCE) increasing rapidly. However, large‐scale solar farms using OPV modules still face great challenges, such as device stability. Herein, the applications of OPV cells in indoor light environments are studied. Via optimizing the active layers to have a good match with the indoor light source, 1 cm2 OPV cells are fabricated and a top PCE of 22% under 1000 lux light‐emitting diode (2700 K) illumination is demonstrated. In this work, the light intensities are measured carefully. Incorporated with the external quantum efficiency and photon flux spectrum, the integral current densities of the cells are calculated to confirm the reliability of the photovoltaic measurement. In addition, the devices show much better stability under continuous indoor light illumination. The results suggest that designing wide‐bandgap active materials to meet the requirements for the indoor OPV cells has a great potential in achieving higher photovoltaic performance.

Volumetric Bioprinting of Complex Living‐Tissue Constructs within Seconds

By Paulina Nuñez Bernal, Paul Delrot, Damien Loterie, Yang Li, Jos Malda, Christophe Moser, Riccardo Levato from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Spatially coordinated patterns of visible light tomographic projections onto cell‐laden photoresponsive hydrogels enable the rapid bioprinting of 3D tissue constructs with clinically relevant size and complex geometries. Centimeter‐scale structures are built within seconds, outperforming conventional layer‐by‐layer bioprinting approaches and demonstrating high cell viability. Stem cells retain functionality postprinting, demonstrating potential for the biofabrication of vascularized and mature tissue grafts. Abstract Biofabrication technologies, including stereolithography and extrusion‐based printing, are revolutionizing the creation of complex engineered tissues. The current paradigm in bioprinting relies on the additive layer‐by‐layer deposition and assembly of repetitive building blocks, typically cell‐laden hydrogel fibers or voxels, single cells, or cellular aggregates. The scalability of these additive manufacturing technologies is limited by their printing velocity, as lengthy biofabrication processes impair cell functionality. Overcoming such limitations, the volumetric bioprinting of clinically relevant sized, anatomically shaped constructs, in a time frame ranging from seconds to tens of seconds is described. An optical‐tomography‐inspired printing approach, based on visible light projection, is developed to generate cell‐laden tissue constructs with high viability (>85%) from gelatin‐based photoresponsive hydrogels. Free‐form architectures, difficult to reproduce with conventional printing, are obtained, including anatomically correct trabecular bone models with embedded angiogenic sprouts and meniscal grafts. The latter undergoes maturation in vitro as the bioprinted chondroprogenitor cells synthesize neo‐fibrocartilage matrix. Moreover, free‐floating structures are generated, as demonstrated by printing functional hydrogel‐based ball‐and‐cage fluidic valves. Volumetric bioprinting permits the creation of geometrically complex, centimeter‐scale constructs at an unprecedented printing velocity, opening new avenues for upscaling the production of hydrogel‐based constructs and for their application in tissue engineering, regenerative medicine, and soft robotics.

Fine Multi‐Phase Alignments in 2D Perovskite Solar Cells with Efficiency over 17% via Slow Post‐Annealing

By Guangbao Wu, Xing Li, Jiyu Zhou, Jianqi Zhang, Xuning Zhang, Xuanye Leng, Peijun Wang, Ming Chen, Dongyang Zhang, Kui Zhao, Shengzhong (Frank) Liu, Huiqiong Zhou, Yuan Zhang from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Application of the proposed slow post‐annealing for layered 2D perovskite solar cells based on BA2MA3Pb4I13 photo‐absorber leads to a favorable alignment on the multi‐perovskite phases and resultant champion power conversion efficiency to 17.26%, showing simultaneously enhanced open‐circuit voltage and short‐circuit current. Abstract Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA2MA3Pb4I13 (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with

Halogenated‐Methylammonium Based 3D Halide Perovskites

By Sheng Huang, Peng Huang, Lei Wang, Junbo Han, Yu Chen, Haizheng Zhong from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The variation of A‐site cations is promising to achieve enhanced properties; however, it is limited to a few available choices of methylamine, formamidine, and cesium. Halogenated methylammoniums are reported as novel A cations to broaden the family of hybrid perovskites, which breaks through the limitation of A cations. Abstract 3D perovskites with typical structure of ABX3 are emerging as key materials to achieve high‐performance optoelectronic devices. The variation of A‐site cation is promising to achieve enhanced properties; however, is limited to a few available choices of methylamine, formamidine, and cesium. In this work, halogenated‐methylammoniums are developed as A cation to broaden the family of hybrid perovskites. Single crystals and colloidal nanocrystals of halogenated‐methylammoniums based perovskites are successfully synthesized, showing bright future as alternatives for device exploration. In particular, the improved thermal stability and low exciton binding energy from single crystals measurements are demonstrated and bright tunable emission from blue to green for colloidal nanocrystals is achieved.

Biocorrosion Zoomed In: Evidence for Dealloying of Nanometric Intermetallic Particles in Magnesium Alloys

By Martina Cihova, Patrik Schmutz, Robin Schäublin, Jörg F. Löffler from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Dealloying of intermetallic nanoprecipitates governs the electrochemical reactivity of multicomponent Mg alloys. TEM‐based analyses allow the direct observation of intermetallic‐particle (IMP) dealloying at the nanoscale. Electrochemically active Ca preferentially dissolves, while electrochemically more noble Zn is cathodically protected. Zn enrichment leads to a gradual ennoblement of the IMP concomitant with its enhancing cathodic reactivity. Abstract Biodegradable magnesium alloys generally contain intermetallic phases on the micro‐ or nanoscale, which can initiate and control local corrosion processes via microgalvanic coupling. However, the experimental difficulties in characterizing active degradation on the nanoscale have so far limited the understanding of how these materials degrade in complex physiological environments. Here a quasi‐in situ experiment based on transmission electron microscopy (TEM) is designed, which enables the initial corrosion attack at nanometric particles to be accessed within the first seconds of immersion. Combined with high‐resolution ex situ cross‐sectional TEM analysis of a well‐developed corrosion‐product layer, mechanistic insights into Mg‐alloys' degradation on the nanoscale are provided over a large range of immersion times. Applying this methodology to lean Mg–Zn‒Ca alloys and following in detail the dissolution of their nanometric Zn‐ and Ca‐rich particles the in statu nascendi observation of intermetallic‐particle dealloying is documented for magnesium alloys, where electrochemically active Ca and Mg preferentially dissolve and electropositive Zn enriches, inducing the particles' gradual ennoblement. Based on electrochemical theory, here, the concept of cathodic‐polarization‐induced dealloying, which controls the dynamic microstructural changes, is presented. The general prerequisites for this new dealloying mechanism to occur in multicomponent alloys and its distinction to other dealloying modes are also discussed.

Graphdiyne: The Fundamentals and Application of an Emerging Carbon Material

By Changshui Huang, Yuliang Zhao, Yuliang Li from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Masthead: (Adv. Mater. 42/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Contents: (Adv. Mater. 42/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Membrane‐Based Separation: Graphynes for Water Desalination and Gas Separation (Adv. Mater. 42/2019)

By Hu Qiu, Minmin Xue, Chun Shen, Zhuhua Zhang, Wanlin Guo from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Membrane‐based separation is involved in a variety of important industrial processes, such as water desalination and gas purification. Graphynes, allotropes of graphene yet containing intrinsic uniform pores, are attractive as next‐generation membrane materials. In article number 1803772, Hu Qiu, Wanlin Guo, and co‐workers present a comprehensive overview of the potential for various graphynes in membrane‐based separation applications, focusing on their outstanding performance, as well as remaining challenges, in order to assist future design.

Graphdiynes: The Accelerating World of Graphdiynes (Adv. Mater. 42/2019)

By Ryota Sakamoto, Naoya Fukui, Hiroaki Maeda, Ryota Matsuoka, Ryojun Toyoda, Hiroshi Nishihara from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

In article number 1804211, Ryota Sakamoto, Hiroshi Nishihara, and co‐workers discuss the accelerating world of graphdiynes from the points of view of history, variations, syntheses, theoretical and experimental approaches for physical properties, and the wide variety of applications. Research on the GDY family has begun in earnest, and further work given the accelerating progress in the current period, should ensure it fulfils its potential.

Electrochemical Energy Storage: Graphdiyne‐Based Materials: Preparation and Application for Electrochemical Energy Storage (Adv. Mater. 42/2019)

By Ning Wang, Jianjiang He, Kun Wang, Yingjie Zhao, Tonggang Jiu, Changshui Huang, Yuliang Li from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

In article number 1803202, Changshui Huang and co‐workers summarize the up‐to‐date research progress in electrochemical energy storage materials and devices based on graphdiyne. The relevance between the structure modification of graphdiyne and the corresponding promotion for the device performance is comprehensively discussed.

Chemical Doping: Chemically Tuned p‐ and n‐Type WSe2 Monolayers with High Carrier Mobility for Advanced Electronics (Adv. Mater. 42/2019)

By Hyun Goo Ji, Pablo Solís‐Fernández, Daisuke Yoshimura, Mina Maruyama, Takahiko Endo, Yasumitsu Miyata, Susumu Okada, Hiroki Ago from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

In article number 1903613, Hiroki Ago and co‐workers demonstrate the chemical‐doping‐induced conversion of ambipolar WSe2 monolayers to p‐ and n‐type semiconductors. The chemical doping not only allows control over the main carriers, but also significantly increases the carrier mobility. By integrating the chemically doped WSe2, a CMOS inverter and an in‐plane p–n junction with superior performance are successfully fabricated.

Biofabrication: Volumetric Bioprinting of Complex Living‐Tissue Constructs within Seconds (Adv. Mater. 42/2019)

By Paulina Nuñez Bernal, Paul Delrot, Damien Loterie, Yang Li, Jos Malda, Christophe Moser, Riccardo Levato from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Volumetric bioprinting enables the biofabrication of centimeter‐scale 3D tissue constructs. In article number 1904209, Christophe Moser, Riccardo Levato, and co‐workers load a cell‐laden photoresponsive hydrogel reservoir on a rotating platform and expose it to visible‐light tomographic projections. A printed model appears at once after a few tens of seconds, and the bioprinted stem cells retain high viability and functionality, showing potential for the engineering of complex vascularized tissue grafts. Image credit: Daimon J. Hall of www.carbonandneon.com.

On‐Surface Synthesis of Graphyne‐Based Nanostructures

By Xuechao Li, Haiming Zhang, Lifeng Chi from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

On‐surface construction of acetylenic or diacetylenic linkages is a promising strategy to prepare low‐dimensional graphyne‐based nanostructures. The methodologies to fabricate 1D graphyne (graphdiyne) nanowires and their functionalized derivatives are presented to illustrate how on‐surface synthesis may contribute to 2D graphyne‐related structures. Abstract The successful synthesis of stacking graphdiynes has stimulated numerous fascinating applications. However, it still remains challenging to prepare atomically precise 2D graphdiyne and other graphyne‐based structures. The development of on‐surface synthesis has contributed to many secondary graphyne‐based structures that are directive in fabricating extended graphyne networks. Herein, the recent progress concerning on‐surface synthesis of graphyne‐based nanostructures, especially atomically precise graphdiyne nanowires, is summarized.

Multiscale Design of Graphyne‐Based Materials for High‐Performance Separation Membranes

By Jingjie Yeo, Gang Seob Jung, Francisco J. Martín‐Martínez, Jennifer Beem, Zhao Qin, Markus J. Buehler from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The mechanical, thermal, and chemical properties of different types of graphynes are reviewed. The studies include the analysis of crack propagation, stress concentrations, atomic stress distributions under tensile loads, and Fukui function, among others. Graphyne's superior performance for separation and desalination membranes is also reviewed. Abstract By varying the number of acetylenic linkages connecting aromatic rings, a new family of atomically thin graph‐n‐yne materials can be designed and synthesized. Generating immense scientific interest due to its structural diversity and excellent physical properties, graph‐n‐yne has opened new avenues toward numerous promising engineering applications, especially for separation membranes with precise pore sizes. Having these tunable pore sizes in combination with their excellent mechanical strength to withstand high pressures, free‐standing graph‐n‐yne is theoretically posited to be an outstanding membrane material for separating or purifying mixtures of either gases or liquids, rivaling or even dramatically exceeding the capabilities of current, state‐of‐art separation membranes. Computational modeling and simulations play an integral role in the bottom‐up design and characterization of these graph‐n‐yne materials. Thus, here, the state of the art in modeling α‐, β‐, γ‐, δ‐, and 6,6,12‐graphyne nanosheets for synthesizing graph‐2‐yne materials and 3D architectures thereof is discussed. Different synthesis methods are described and a broad overview of computational characterizations of graph‐n‐yne's electrical, chemical, and thermal properties is provided. Furthermore, a series of in‐depth computational studies that delve into the specifics of graph‐n‐yne's mechanical strength and porosity, which confer superior performance for separation and desalination membranes, are reviewed.

Graphdiyne‐Based Materials: Preparation and Application for Electrochemical Energy Storage

By Ning Wang, Jianjiang He, Kun Wang, Yingjie Zhao, Tonggang Jiu, Changshui Huang, Yuliang Li from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Graphdiyne (GDY)‐based materials, which have 2D chemical structures and exhibit good physical and electrochemical properties, are widely used as electrode materials in rechargeable energy‐storage devices. Related research progress, the structure–performance relationship, and further perspectives are summarized. Abstract Graphdiyne (GDY) has drawn much attention for its 2D chemical structure, extraordinary intrinsic properties, and wide application potential in a variety of research fields. In particular, some structural features and basic physical properties including expanded in‐plane pores, regular nanostructuring, and good transporting properties make GDY a promising candidate for an electrode material in energy‐storage devices, including batteries and supercapacitors. The chemical structure, synthetic strategy, basic chemical–physical properties of GDY, and related theoretical analysis on its energy‐storage mechanism are summarized here. Moreover, through a view of the mutual promotion between the structure modification of GDY and the corresponding electrochemical performance improvement, research progress on the application of GDY for electrochemical energy storage is systematically explored and discussed. Furthermore, the development trends of GDY in energy‐storage devices are also comprehensively assessed. GDY‐based materials represent a bright future in the field of electrochemical energy storage.

The Accelerating World of Graphdiynes

By Ryota Sakamoto, Naoya Fukui, Hiroaki Maeda, Ryota Matsuoka, Ryojun Toyoda, Hiroshi Nishihara from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Graphdiynes are 2D carbon materials that may be synthesized from organic monomers, such as hexaethynylbenzene, and significant interest of researchers has recently been drawn to the new 2D nanomaterial series. This work assembles comprehensive knowledge on graphdiynes: history, variations, syntheses, theoretical and experimental approaches for physical properties, and the wide varieties of application. Abstract Graphdiyne (GDY), a 2D allotrope of graphene, is first synthesized in 2010 and has attracted attention as a new low‐dimensional carbon material. This work surveys the literature on GDYs. The history of GDYs is summarized, including their relationship with 2D graphyne carbons and yearly publication trends. GDY is a molecule‐based nanosheet woven from a molecular monomer, hexaethynylbenzene; thus, it is synthesized by bottom‐up approaches, which allow rich variation via monomer design. The GDY family and the synthetic procedures are also described. Highly developed π‐conjugated electronic structures are common important features in GDY and graphene; however, the coexistence of sp and sp2 carbons differentiates GDY from graphene. This difference gives rise to unique physical properties, such as high conductivity and large carrier mobility. Next, the theoretical and experimental studies of these properties are described in detail. A wide variety of applications are proposed for GDYs, including electrocatalysts and energy devices, which exploit the carbon‐rich nature, porous framework, and expanded π‐electron system of these compounds. Finally, potential uses are discussed.

Graphynes for Water Desalination and Gas Separation

By Hu Qiu, Minmin Xue, Chun Shen, Zhuhua Zhang, Wanlin Guo from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Graphynes, allotropes of graphene yet containing intrinsic uniform pores, are attractive for membrane‐based separation applications including water desalination and gas separation. A comprehensive overview of various graphynes for these separation applications is presented, focusing on their predicted outstanding performance as well as remaining challenges in order to assist the future design of these membranes. Abstract Selective transport of mass through membranes, so‐called separation, is fundamental to many industrial applications, e.g., water desalination and gas separation. Graphynes, graphene analogs yet containing intrinsic uniformly distributed pores, are excellent candidates for highly permeable and selective membranes owing to their extreme thinness and high porosity. Graphynes exhibit computationally determined separation performance far beyond experimentally measured values of commercial state‐of‐the‐art polyamide membranes; they also offer advantages over other atomically thin membranes like porous graphene in terms of controllability in pore geometry. Here, recent progress in proof‐of‐concept computational research into various graphynes for water desalination and gas separation is discussed, and their theoretically predicted outstanding permeability and selectivity are highlighted. Challenges associated with the future development of graphyne‐based membranes are further analyzed, concentrating on controlled synthesis of graphyne, maintenance of high structural stability to withstand loading pressures, as well asthe demand for accurate computational characterization of separation performance. Finally, possible directions are discussed to align future efforts in order to push graphynes and other 2D material membranes toward practical separation applications.

Exploring Approaches for the Synthesis of Few‐Layered Graphdiyne

By Jingyuan Zhou, Jiaqiang Li, Zhongfan Liu, Jin Zhang from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

The state‐of‐art research of graphdiyne (GDY) with a focus on exploring approaches for few‐layered GDY synthesis is critically summarized. The obstacles and challenges of GDY synthesis are also analyzed in detail. The advantages and limitations of different methods are analyzed comprehensively. These synthetic methods provide considerable inspiration to approaching the synthesis of single/few‐layered GDY film. Abstract Graphdiyne (GDY) is an emerging carbon allotrope in the graphyne (GY) family, demonstrating extensive potential applications in the fields of electronic devices, catalysis, electrochemical energy storage, and nonlinear optics. Synthesis of few‐layered GDY is especially important for both electronic applications and structural characterization. This work critically summarizes the state‐of‐art of GDY and focuses on exploring approaches for few‐layered GDY synthesis. The obstacles and challenges of GDY synthesis are also analyzed in detail. Recently developed synthetic methods are discussed such as i) the copper substrate‐based method, ii) the chemical vapor deposition (CVD) method, iii) the interfacial construction method, and iv) the graphene‐templated method. Throughout the discussion, the superiorities and limitations of different methods are analyzed comprehensively. These synthetic methods have provided considerable inspiration approaching synthesis of few‐layered or single‐layered GDY film. The work concludes with a perspective on promising research directions and remaining barriers for layer‐controlled and morphology‐controlled synthesis of GDY with higher crystalline quality.

Progress and Prospects of Graphdiyne‐Based Materials in Biomedical Applications

By Jiaming Liu, Chunying Chen, Yuliang Zhao from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Current research progress indicates that graphdiyne‐based materials are useful in the biomedical field, including biosensing, radiation protection, and cancer therapy. In these applications, graphdiyne (GDY) is proven to be better than other carbon‐based materials. Though the biomedical applications of GDY are still rare and some difficulties need to be solved, graphdiyne has great potential in its future applications. Abstract Graphdiyne is a new member of the family of carbon‐based nanomaterials that possess two types of carbon atoms, sp‐ and sp2‐hybridized carbon atoms. As a novel 2D carbon‐based nanomaterial with unique planar structure, such as uniformly distributed nanopores and large conjugated structure, graphdiyne has shown many fascinating properties in mechanics, electronics, and optics since it was first experimentally synthesized in 2010. Up to now, graphdiyne and its derivatives have been reported to be successfully applied in many areas, such as catalysis, energy, environment, and biomedicine, due to these excellent properties. Herein, the current research progress of graphdiyne‐based materials in biomedical fields is summarized, including biosensing, biological protection, cancer therapy, tissue engineering, etc. The advantages of graphdiyne and its derivatives are presented and compared with other carbon‐based materials. Considering the potential biomedical and clinical applications of graphdiyne‐based materials, the toxicity and biocompatibility are also discussed based on current studies. Finally, future perspectives and possible biomedical applications of graphdiyne‐based materials are also discussed.

Graphdiyne and its Assembly Architectures: Synthesis, Functionalization, and Applications

By Huidi Yu, Yurui Xue, Yuliang Li from Wiley: Advanced Materials: Table of Contents. Published on Oct 15, 2019.

Recent progress on graphdiyne, with its fascinating structure and physical and chemical properties, is summarized. Research efforts toward controllable electronic structure, chemical modification, and applications of graphdiyne in different research fields and corresponding mechanisms are discussed, and critical research insights into the future development of graphdiyne materials are proposed and presented. Abstract Graphdiyne (GDY), a novel one‐atom‐thick carbon allotrope that features assembled layers of sp‐ and sp2‐hybridized carbon atoms, has attracted great interest from both science and industry due to its unique and fascinating structural, physical, and chemical properties. GDY‐based materials with different morphologies, such as nanowires, nanotube arrays, nanosheets, and ordered stripe arrays, have been applied in various areas such as catalysis, solar cells, energy storage, and optoelectronic devices. After an introduction to the fundamental properties of GDY, recent advances in the fabrication of GDY‐based nanostructures and their applications, and corresponding mechanisms, are covered, and future critical perspectives are also discussed.

Asymmetric Synthesis of Oxa‐Bridged Oxazocines by Rh(II)/Zn(II) Relay Catalytic [4+3] Cycloaddition Reaction

By Chaoran Xu, Kaixuan Wang, Dawei Li, Lili Lin, Xiaoming Feng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

The oxa‐bridged oxazocines bearing three chiral carbon centers were synthesized efficiently through a dual‐metallic catalytic asymmetric tandem reaction of β,γ‐unsaturated α‐ketoesters with diazoimides. The process contained a rhodium‐promoted in situ generation of isomünchnone from diazoimide decomposition, and a chiral N,N’ ‐dioxide‐Zn(II) complex‐catalyzed intermolecular [4+3]‐cycloaddition of β,γ‐unsaturated α‐ketoester. Ligand‐acceleration catalysis was found, and a possible transition state model was proposed to explain the origin of stereoselectivity.

Highly Active Core–Shell Carbon/NiCo2O4 Double Microtubes for Efficient Oxygen Evolution Reaction: Ultralow Overpotential and Superior Cycling Stability

By Xiaofeng Zhang, Xiaocui Li, Ruchun Li, Yang Lu, Shuqin Song, Yi Wang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Wet tissues are innovatively identified as the template and the carbon resource to synthesize double microtubes composed of carbon and ultrathin NiCo2O4 nanosheet arrays as the inner and outer microtubes, respectively, for the first time. The synergistic effects of defects in NiCo2O4 nanosheet arrays, the robust carbon skeleton, and the double microtubular structure provide the NCO‐400‐N2 electrode with excellent OER performance. Abstract Developing highly efficient electrocatalysts with earth abundant elements for oxygen evolution reaction (OER) is a promising way to store light or electrical energy in the form of chemical energy. Here, a new type of electrocatalyst with core–shell carbon/NiCo2O4 double microtubes architecture is successfully synthesized through a hydrothermal method combined with the calcination process with wet tissues as the template and carbon resource. The outer NiCo2O4 nanosheet arrays contain abundant defects, which come from reduction of the carbon in wet tissues. This indicates that carbon is a very excellent defect inducer. The inner carbon microtubes can act as the robust structure skeleton and these core–shell double microtubes provide abundant diffusion channels for oxygen and electrolyte, both of which contribute to improving the stability by avoiding damage to the electrode from produced O2 bubbles and the collapse of the outer NiCo2O4 microtubes. Electrochemical results show that the electrode, core–shell carbon/NiCo2O4 double microtubes loaded on carbon cloth, exhibits prominent electrocatalytic activity with an overpotential of only 168 mV at 10 mA cm−2 and a Tafel slope as low as 57.6 mV dec−1 in 1.0 mol L−1 KOH. This new type of electrocatalyst possesses great potential in water electrolyzers and rechargeable metal–air batteries.

CO Gas Induced Phase Separation in PtPb@Pt Catalyst and Formation of Ultrathin Pb Nanosheets Probed by In Situ Transmission Electron Microscopy

By Qi Wang, Zhi Liang Zhao, Meng Gu from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

The phase stability of PtPb@Pt catalyst is probed in both CO gas and vacuum conditions at elevated temperatures using aberration‐corrected in situ transmission electron microscopy. A phase separation process, in which Pb atoms are stripped off the original PtPb@Pt nanoparticles, is unambiguously identified. The results shine light on the “toxic” effect of CO. Abstract PtPb@Pt catalysts are very useful and widely applied in various industrial reactions. Here, the phase stability of such catalysts is compared in both CO gas and vacuum conditions at elevated temperatures using aberration‐corrected in situ transmission electron microscopy (TEM). A Pt aggregation process takes place affected by CO gas, which results in direct exposure of the PtPb core to CO. A phase separation process, in which Pb atoms are stripped off the original PtPb@Pt nanoparticles, is unambiguously identified in CO gas. At initial stages, the as nucleated Pb islands are amorphous. Once the ultrathin Pb islands reach ≈3.5 nm or higher, they suddenly became crystalline. The interaction between Pb and CO gas stabilizes the ultrathin Pb nanosheets, resulting in the formation of a large quantity of Pb nanosheets and Pb‐depleted PtPb0.08 nanoparticles. In sharp contrast, when heated up in a vacuum, the PtPb@Pt catalyst remains intact. The results of this study shine light on the “toxic” effect of CO that results in failures of many Pt‐based catalysts and discloses formation mechanism of ultrathin Pb nanosheets.

Lithium Titanate Cuboid Arrays Grown on Carbon Fiber Cloth for High‐Rate Flexible Lithium‐Ion Batteries

By Chao Wang, Xianfen Wang, Chunfu Lin, Xiu Song Zhao from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A composite electrode with lithium titanate cuboid arrays grown on carbon fiber cloth exhibits a remarkable high‐rate performance and ultralong cycling stability as a binder‐free electrode for flexible lithium‐ion batteries. The electrode also displays excellent flexibility and electrochemical performance. The unique cuboid array architecture of the composite electrode facilitates lithium ion transport and enhances electron conductivity. Abstract High‐rate performance flexible lithium‐ion batteries are desirable for the realization of wearable electronics. The flexibility of the electrode in the battery is a key requirement for this technology. In the present work, spinel lithium titanate (Li4Ti5O12, LTO) cuboid arrays are grown on flexible carbon fiber cloth (CFC) to fabricate a binder‐free composite electrode (LTO@CFC) for flexible lithium‐ion batteries. Experimental results show that the LTO@CFC electrode exhibits a remarkably high‐rate performance with a capacity of 105.8 mAh g−1 at 50C and an excellent electrochemical stability against cycling (only 2.2% capacity loss after 1000 cycles at 10C). A flexible full cell fabricated with the LTO@CFC as the anode and LiNi0.5Mn1.5O4 coated on Al foil as the cathode displays a reversible capacity of 109.1 mAh g−1 at 10C, an excellent stability against cycling and a great mechanical stability against bending. The observed high‐rate performance of the LTO@CFC electrode is due to its unique corn‐like architecture with LTO cuboid arrays (corn kernels) grown on CFC (corn cob). This work presents a new approach to preparing LTO‐based composite electrodes with an architecture favorable for ion and electron transport for flexible energy storage devices.

Unraveling In Vivo Brain Transport of Protein‐Coated Fluorescent Nanodiamonds

By Pierpaolo Moscariello, Marco Raabe, Weina Liu, Sandra Bernhardt, Haoyuan Qi, Ute Kaiser, Yuzhou Wu, Tanja Weil, Heiko J. Luhmann, Jana Hedrich from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

The blood–brain barrier is the biggest hurdle to overcome for the treatment of neurological disorders. Here, protein‐coated nanodiamonds are delivered to the brain and taken up by neurovascular unit cells after intravenous injection. Thus, for the first time, nanodiamonds with their unique properties and a flexible protein coating for the attachment of therapeutics emerge as a potential platform for nanotheranostics of neurological disorders. Abstract Nanotheranostics, combining diagnostics and therapy, has the potential to revolutionize treatment of neurological disorders. But one of the major obstacles for treating central nervous system diseases is the blood–brain barrier (BBB) preventing systemic delivery of drugs and optical probes into the brain. To overcome these limitations, nanodiamonds (NDs) are investigated in this study as they are a powerful sensing and imaging platform for various biological applications and possess outstanding stable far‐red fluorescence, do not photobleach, and are highly biocompatible. Herein, fluorescent NDs encapsulated by a customized human serum albumin–based biopolymer (polyethylene glycol) coating (dcHSA‐PEG) are taken up by target brain cells. In vitro BBB models reveal transcytosis and an additional direct cell–cell transport via tunneling nanotubes. Systemic application of dcHSA‐NDs confirms their ability to cross the BBB in a mouse model. Tracking of dcHSA‐NDs is possible at the single cell level and reveals their uptake into neurons and astrocytes in vivo. This study shows for the first time systemic NDs brain delivery and suggests transport mechanisms across the BBB and direct cell–cell transport. Fluorescent NDs are envisioned as traceable transporters for in vivo brain imaging, sensing, and drug delivery.

Artificial Engineered Natural Killer Cells Combined with Antiheat Endurance as a Powerful Strategy for Enhancing Photothermal‐Immunotherapy Efficiency of Solid Tumors

By Da Zhang, Youshi Zheng, Ziguo Lin, Shanyou Lan, Xiaolong Zhang, Aixian Zheng, Juan Li, Gang Liu, Huanghao Yang, Xiaolong Liu, Jingfeng Liu from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Herein, a programmable antitumor strategy that combines artificial engineered natural killer cells with the antiheat endurance of DNAzyme as a powerful strategy for immuno‐improving the therapeutic efficiency of photothermal therapy is reported. Abstract Although photothermal therapy (PTT) is preclinically applied in solid tumor treatment, incomplete tumor removal of PTT and heat endurance of tumor cells induces significant tumor relapse after treatment, therefore lowering the therapeutic efficiency of PTT. Herein, a programmable therapeutic strategy that integrates photothermal therapeutic agents (PTAs), DNAzymes, and artificial engineered natural killer (A‐NK) cells for immunotherapy of hepatocellular carcinoma (HCC) is designed. The novel PTAs, termed as Mn‐CONASHs, with 2D structure are synthesized by the coordination of tetrahydroxyanthraquinone and Mn2+ ions. By further adsorbing polyetherimide/DNAzymes on the surface, the DNAzymes@Mn‐CONASHs exhibit excellent light‐to‐heat conversion ability, tumor microenvironment enhanced T1‐MRI guiding ability, and antiheat endurance ability. Furthermore, the artificial engineered NK cells with HCC specific targeting TLS11a‐aptamer decoration are constructed for specifically eliminating any possible residual tumor cells after PTT, to systematically enhance the therapeutic efficacy of PTT and avoid tumor relapse. Taken together, the potential of A‐NK cells combined with antiheat endurance as a powerful strategy for immuno‐enhancing photothermal therapy efficiency of solid tumors is highlighted, and the current strategy might provide promising prospects for cancer therapy.

Unconventional Atomic Structure of Graphene Sheets on Solid Substrates

By Jinjin Zhang, Yizhou Yang, Shuo Yang, Jie Song, Ying Wang, Xiaoguo Liu, Qingqing Yang, Yue Shen, Shuo Wang, Haijun Yang, Junhong Lü, Bin Li, Haiping Fang, Ratnesh Lal, Daniel M. Czajkowsky, Jun Hu, Guosheng Shi, Yi Zhang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A novel orthorhombic crystal of graphene with 5 Å period formed on various substrates is revealed and applied to control the epitaxial self‐assembly of amyloids. First‐principles computations show that this atomic structure can be attributed to dipoles between the graphene surface and substrates. A locally generated interfacial electric field is used for the controllable formation of the atomic structure. Abstract The atomic structure of free‐standing graphene comprises flat hexagonal rings with a 2.5 Å period, which is conventionally considered the only atomic period and determines the unique properties of graphene. Here, an unexpected highly ordered orthorhombic structure of graphene is directly observed with a lattice constant of ≈5 Å, spontaneously formed on various substrates. First‐principles computations show that this unconventional structure can be attributed to the dipole between the graphene surface and substrates, which produces an interfacial electric field and induces atomic rearrangement on the graphene surface. Further, the formation of the orthorhombic structure can be controlled by an artificially generated interfacial electric field. Importantly, the 5 Å crystal can be manipulated and transformed in a continuous and reversible manner. Notably, the orthorhombic lattice can control the epitaxial self‐assembly of amyloids. The findings reveal new insights about the atomic structure of graphene, and open up new avenues to manipulate graphene lattices.

Model‐Free Rheo‐AFM Probes the Viscoelasticity of Tunable DNA Soft Colloids

By José A. Moreno‐Guerra, Ivany C. Romero‐Sánchez, Alejandro Martinez‐Borquez, Manlio Tassieri, Emmanuel Stiakakis, Marco Laurati from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A model‐free atomic force microscopy rheological measurement (Rheo‐AFM) method allows the measurement of the viscoelastic properties of DNA star‐like colloids in aqueous solution, revealing a pronounced softening of the particle with increasing salt concentration. This is related to a critical reduction of the corona size due to topological changes of the DNA chains. The method can be applied to determine the viscoelasticity of soft colloids and nanoparticles. Abstract Atomic force microscopy rheological measurements (Rheo‐AFM) of the linear viscoelastic properties of single, charged colloids having a star‐like architecture with a hard core and an extended, deformable double‐stranded DNA (dsDNA) corona dispersed in aqueous saline solutions are reported. This is achieved by analyzing indentation and relaxation experiments performed on individual colloidal particles by means of a novel model‐free Fourier transform method that allows a direct evaluation of the frequency‐dependent linear viscoelastic moduli of the system under investigation. The method provides results that are consistent with those obtained via a conventional fitting procedure of the force‐relaxation curves based on a modified Maxwell model. The outcomes show a pronounced softening of the dsDNA colloids, which is described by an exponential decay of both the Young's and the storage modulus as a function of the salt concentration within the dispersing medium. The strong softening is related to a critical reduction of the size of the dsDNA corona, down to ≈70% of its size in a salt‐free solution. This can be correlated to significant topological changes of the dense star‐like polyelectrolyte forming the corona, which are induced by variations in the density profile of the counterions. Similarly, a significant reduction of the stiffness is obtained by increasing the length of the dsDNA chains, which we attribute to a reduction of the DNA density in the outer region of the corona.

The Crystallinity and Aspect Ratio of Cellulose Nanomaterials Determine Their Pro‐Inflammatory and Immune Adjuvant Effects In Vitro and In Vivo

By Xiang Wang, Chong Hyun Chang, Jinhong Jiang, Qi Liu, Yu‐Pei Liao, Jianqin Lu, Linjiang Li, Xiangsheng Liu, Joshua Kim, Ayman Ahmed, André E. Nel, Tian Xia from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Immune responses of cellulose nanofibrils (CNF) and nanocrystals (CNC) at different lengths are compared. They are not cytotoxic; however, 200–300 nm CNCs induce higher lysosomal damage and IL‐1β production than shorter or longer CNCs and CNFs. They also induce higher dendritic cell maturation and adjuvant effects in mice in vivo. These effects correlate with their higher crystallinity and hydroxyl density. Abstract Nanocellulose is increasingly considered for applications; however, the fibrillar nature, crystalline phase, and surface reactivity of these high aspect ratio nanomaterials need to be considered for safe biomedical use. Here a comprehensive analysis of the impact of cellulose nanofibrils (CNF) and nanocrystals (CNC) is performed using materials provided by the Nanomaterial Health Implications Research Consortium of the National Institute of Environmental Health Sciences. An intermediary length of nanocrystals is also derived by acid hydrolysis. While all CNFs and CNCs are devoid of cytotoxicity, 210 and 280 nm fluorescein isothiocyanate (FITC)‐labeled CNCs show higher cellular uptake than longer and shorter CNCs or CNFs. Moreover, CNCs in the 200–300 nm length scale are more likely to induce lysosomal damage, NLRP3 inflammasome activation, and IL‐1β production than CNFs. The pro‐inflammatory effects of CNCs are correlated with higher crystallinity index, surface hydroxyl density, and reactive oxygen species generation. In addition, CNFs and CNCs can induce maturation of bone marrow–derived dendritic cells and CNCs (and to a lesser extent CNFs) are found to exert adjuvant effects in ovalbumin (OVA)‐injected mice, particularly for 210 and 280 nm CNCs. All considered, the data demonstrate the importance of length scale, crystallinity, and surface reactivity in shaping the innate immune response to nanocellulose.

A Novel Approach to High‐Performance Aliovalent‐Substituted Catalysts—2D Bimetallic MOF‐Derived CeCuOx Microsheets

By Qingyue Wang, Zhimin Li, Miguel A. Bañares, Lu‐Tao Weng, Qinfen Gu, Jason Price, Wei Han, King Lun Yeung from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A mixed transition metal oxide catalyst is prepared via the thermal transformation of a bimetallic metal–organic framework precursor. The as‐synthesized CeCuOx catalyst exhibits unique properties with high aliovalent substitution, abundant oxygen vacancies, and exposed active crystal planes, leading to high reactivity and moisture tolerance for the complete oxidation of various volatile organic compounds (i.e., toluene, o‐xylene, acetone, and methanol). Abstract Mixed transition metal oxides (MTMOs) have enormous potential applications in energy and environment. Their use as catalysts for the treatment of environmental pollution requires further enhancement in activity and stability. This work presents a new synthesis approach that is both convenient and effective in preparing binary metal oxide catalysts (CeCuOx) with excellent activity by achieving molecular‐level mixing to promote aliovalent substitution. It also allows a single, pure MTMO to be prepared for enhanced stability under reaction by using a bimetallic metal–organic framework (MOF) as the catalyst precursor. This approach also enables the direct manipulation of the shape and form of the MTMO catalyst by controlling the crystallization and growth of the MOF precursor. A 2D CeCuOx catalyst is investigated for the oxidation reactions of methanol, acetone, toluene, and o‐xylene. The catalyst can catalyze the complete reactions of these molecules into CO2 at temperatures below 200 °C, representing a significant improvement in performance. Furthermore, the catalyst can tolerate high moisture content without deactivation.

Porous Copper Microspheres for Selective Production of Multicarbon Fuels via CO2 Electroreduction

By Chengqin Zou, Cong Xi, Deyao Wu, Jing Mao, Min Liu, Hui Liu, Cunku Dong, Xi‐Wen Du from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Porous copper microspheres with an average coordination number of 7.7 are synthesized via electrical reduction of Cu2O microspheres in an aqueous solution of KI. As the catalyst for electroreduction of carbon dioxides, porous copper microspheres deliver a high multicarbon Faradaic efficiency at rather low applied voltages as well as long‐term durability. Abstract The electroreduction of carbon dioxide (CO2) toward high‐value fuels can reduce the carbon footprint and store intermittent renewable energy. The iodide‐ion‐assisted synthesis of porous copper (P‐Cu) microspheres with a moderate coordination number of 7.7, which is beneficial for the selective electroreduction of CO2 into multicarbon (C2+) chemicals is reported. P‐Cu delivers a C2+ Faradaic efficiency of 78 ± 1% at a potential of −1.1 V versus a reversible hydrogen electrode, which is 32% higher than that of the compact Cu counterpart and approaches the record (79%) reported in the same cell configuration. In addition, P‐Cu shows good stability without performance loss throughout a continuous operation of 10 h.

Microscopic Determination of Carrier Density and Mobility in Working Organic Electrochemical Transistors

By Federica Mariani, Felipe Conzuelo, Tobias Cramer, Isacco Gualandi, Luca Possanzini, Marta Tessarolo, Beatrice Fraboni, Wolfgang Schuhmann, Erika Scavetta from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

The operation mechanisms of organic electrochemical transistors are explored by in operando probing of the local electrochemical potential of the organic semiconductor. Experimental data give direct access to fundamental device parameters, such as local charge carrier concentration and mobility, and unprecedented insight into the organic semiconductor/electrolyte interface. Abstract A comprehensive understanding of electrochemical and physical phenomena originating the response of electrolyte‐gated transistors is crucial for improved handling and design of these devices. However, the lack of suitable tools for direct investigation of microscale effects has hindered the possibility to bridge the gap between experiments and theoretical models. In this contribution, a scanning probe setup is used to explore the operation mechanisms of organic electrochemical transistors by probing the local electrochemical potential of the organic film composing the device channel. Moreover, an interpretative model is developed in order to highlight the meaning of electrochemical doping and to show how the experimental data can give direct access to fundamental device parameters, such as local charge carrier concentration and mobility. This approach is versatile and provides insight into the organic semiconductor/electrolyte interface and useful information for materials characterization, device scaling, and sensing optimization.

Phosphorus and Yttrium Codoped Co(OH)F Nanoarray as Highly Efficient and Bifunctional Electrocatalysts for Overall Water Splitting

By Gengwei Zhang, Bin Wang, Lu Li, Shengchun Yang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Yttrium and phosphorus co‐doped Co(OH)F are prepared and employed as a bifunctional electrocatalyst for overall water splitting. The introduction of Y and P leads to a much improved water splitting activity. The solar‐driven two‐electrode device constructed by a YP‐Co(OH)F catalyst as both anode and cathode could generate hydrogen bubbles robustly in the sun, demonstrating the potential application in large‐scale hydrogen production. Abstract Rational design and synthesis of bifunctional electrocatalysts with high efficiency and low‐cost for overall water splitting is still a challenge. A simple approach is reported to prepare a phosphorus and yttrium codoped cobalt hydroxyfluoride (YP‐Co(OH)F) nanoarray on nickel foam, which displays high‐performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction in alkaline solution. The codoping of yttrium and phosphorus into Co(OH)F leads to a tuned electronic environment and favorable electron transfer, thus resulting in superior water splitting activity. The YP‐Co(OH)F electrode only requires an overpotential of 238 mV to reach a current density of 10 mA cm−2 (η10), much smaller than RuO2 (302 mV). Moreover, it displays an overpotential of 55 mV at η10 for HER, similar to that of Pt/C. When YP‐Co(OH)F is used as both anode and cathode in a two‐electrode configuration, it only demands a cell potential of 1.54 V at η10, lower than the IrO2||Pt/C couple (1.6 V) as well as other recently reported electrocatalysts. It even maintains stable water splitting for 300 h. Such a two‐electrode device can be easily driven by a 1.5 V silicon solar cell in sunlight, proving the potential of the promising catalyst for large‐scale electrolytic water splitting.

Compound‐Droplet‐Pairs‐Filled Hydrogel Microfiber for Electric‐Field‐Induced Selective Release

By Xiaokang Deng, Yukun Ren, Likai Hou, Weiyu Liu, Tianyi Jiang, Hongyuan Jiang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Compound‐droplet‐pairs‐filled hydrogel microfibers are fabricated for selective controlled release under an AC electric field. The release sequence can be precisely controlled by the shell thickness or ion concentration of the embedded compound droplet pairs. These reported compound‐droplet‐pairs‐filled microfibers provide novel multidelivery system for a wide range of applications that require controlled release of multiple ingredients in a prescribed sequence. Abstract The separate co‐encapsulation and selective controlled release of multiple encapsulants in a predetermined sequence has potentially important applications for drug delivery and tissue engineering. However, the selective controlled release of distinct contents upon one triggering event for most existing microcarriers still remains challenging. Here, novel microfluidic fabrication of compound‐droplet‐pairs‐filled hydrogel microfibers (C‐Fibers) is presented for two‐step selective controlled release under AC electric field. The parallel arranged compound droplets enable the separate co‐encapsulation of distinct contents in a single microfiber, and the release sequence is guaranteed by the discrepancy of the shell thickness or core conductivity of the encapsulated droplets. This is demonstrated by using a high‐frequency electric field to trigger the first burst release of droplets with higher conductivity or thinner shell, followed by the second release of the other droplets under low‐frequency electric field. The reported C‐Fibers provide novel multidelivery system for a wide range of applications that require controlled release of multiple ingredients in a prescribed sequence.

Zwitterionic PMCP‐Modified Polycaprolactone Surface for Tissue Engineering: Antifouling, Cell Adhesion Promotion, and Osteogenic Differentiation Properties

By Xingyu Chen, Zaifu Lin, Ying Feng, Hong Tan, Xinyuan Xu, Jun Luo, Jianshu Li from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A multifunctional PCL‐PMCP film is prepared with the properties of antiprotein adsorption and promoting cell adhesion. Bone marrow mesenchymal stem cells proliferation on this film is remarkably improved, and osteogenic differentiation is detected, even without adding any osteogenesis‐inducing supplements. Moreover, the PCL‐PMCP films are more stable at the early stage of degradation. Abstract Biodegradable polycaprolactone (PCL) has been widely applied as a scaffold material in tissue engineering. However, the PCL surface is hydrophobic and adsorbs nonspecific proteins. Some traditional antifouling modifications using hydrophilic moieties have been successful but inhibit cell adhesion, which is not ideal for tissue engineering. The PCL surface is modified with bioinspired zwitterionic poly[2‐(methacryloyloxy)ethyl choline phosphate] (PMCP) via surface‐initiated atom transfer radical polymerization to improve cell adhesion through the unique interaction between choline phosphate (CP, on PMCP) and phosphate choline (PC, on cell membranes). The hydrophilicity of the PCL surface is significantly enhanced after surface modification. The PCL‐PMCP surface reduces nonspecific protein adsorption (e.g., up to 91.7% for bovine serum albumin) due to the zwitterionic property of PMCP. The adhesion and proliferation of bone marrow mesenchymal stem cells on the modified surface is remarkably improved, and osteogenic differentiation signs are detected, even without adding any osteogenesis‐inducing supplements. Moreover, the PCL‐PMCP films are more stable at the early stage of degradation. Therefore, the PMCP‐functionalized PCL surface promotes cell adhesion and osteogenic differentiation, with an antifouling background, and exhibits great potential in tissue engineering.

Unraveling Structural Information of Turkevich Synthesized Plasmonic Gold–Silver Bimetallic Nanoparticles

By Natan Blommaerts, Hans Vanrompay, Silvia Nuti, Silvia Lenaerts, Sara Bals, Sammy W. Verbruggen from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Turkevich synthesis of Au–Ag bimetallic nanoparticles results in core–shell‐like nanostructures with a gradually varying alloy composition in the radial direction. A complete analysis including wet‐chemical experiments, advanced electron microscopy, and extensive finite element method modeling is performed to reveal that the core is enriched in gold (80% Au) and the shell is enriched in silver (65% Ag). Abstract For the synthesis of gold–silver bimetallic nanoparticles, the Turkevich method has been the state‐of‐the‐art method for several decades. It is presumed that this procedure results in a homogeneous alloy, although this has been debatable for many years. In this work, it is shown that neither a full alloy, nor a perfect core–shell particle is formed but rather a core–shell‐like particle with altering metal composition along the radial direction. In‐depth wet‐chemical experiments are performed in combination with advanced transmission electron microscopy, including energy‐dispersive X‐ray tomography, and finite element method modeling to support the observations. From the electron tomography results, the core–shell structure can be clearly visualized and the spatial distribution of gold and silver atoms can be quantified. Theoretical simulations are performed to demonstrate that even though UV–vis spectra show only one plasmon band, this still originates from core–shell type structures. The simulations also indicate that the core–shell morphology does not so much affect the location of the plasmon band, but mainly results in significant band broadening. Wet‐chemistry experiments provide the evidence that the synthesis pathway starts with gold enriched alloy cores, and later on in the synthesis mainly silver is incorporated to end up with a silver enriched alloy shell.

Anionic Se‐Substitution toward High‐Performance CuS1−xSex Nanosheet Cathode for Rechargeable Magnesium Batteries

By Zhitao Wang, Youqi Zhu, Chen Qiao, Shuo Yang, Jian Jia, Souleymen Rafai, Xilan Ma, Shide Wu, Fengqiu Ji, Chuanbao Cao from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

An anionic Se‐substitution strategy is proposed to enhance the rate capability and the cycling stability of a 2D CuS1−xSex nanosheet cathode through an efficient microwave‐induced heating method. With the structural and compositional merits, the CuS1−xSex nanosheet shows attractive electrochemical properties as the cathode material for rechargeable magnesium batteries. Abstract Rechargeable magnesium batteries (rMBs) are promising as the most ideal further energy storage systems but lack competent cathode materials due to sluggish redox reaction kinetics. Herein, developed is an anionic Se‐substitution strategy to improve the rate capability and the cycling stability of 2D CuS1−xSex nanosheet cathodes through an efficient microwave‐induced heating method. The optimized CuS1−xSex (X = 0.2) nanosheet cathode can exhibit high reversible capacity of 268.5 mAh g−1 at 20 mA g−1 and good cycling stability (140.4 mAh g−1 at 300 mA g−1 upon 100 cycles). Moreover, the CuS1−xSex (X = 0.2) nanosheet cathode can deliver remarkable rate capability with a reversible capacity of 119.2 mAh g−1 at 500 mA g−1, much higher than the 21.7 mAh g−1 of pristine CuS nanosheets. The superior electrochemical performance can be ascribed to the enhanced reaction kinetics, enriched cation storage active sites, and shortened ion diffusion pathway of the CuS1−xSex nanosheet. Therefore, tuning anionic chemical composition demonstrates an effective strategy to develop novel cathode materials for rMBs.

A Sequential Target‐Responsive Nanocarrier with Enhanced Tumor Penetration and Neighboring Effect In Vivo

By Tingting Cui, Zhengqing Yan, Hongshuang Qin, Yuhuan Sun, Jinsong Ren, Xiaogang Qu from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

An intelligent nanocarrier, which combines acidic tumor microenvironment‐responsive hyaluronidase (HAase) release and remarkable neighboring effect with size reduction, is envisaged. The released HAase can efficiently decompose excessive hyaluronic acid (HA) in the extracellular matrix, improving the diffusion of nanodrugs. Additionally, the integration of HAase and neighboring effect with size reduction can overcome the problem of HA regeneration, and enhance tumor penetration and the antitumor effect. Abstract Nanodrug‐based cancer therapy is impeded by poor penetration into deep tumor tissues mainly due to the overexpression of hyaluronic acid (HA) in the tumor extracellular matrix (ECM). Although modification of nanoparticles (NPs) with hyaluronidase (HAase) is a potent strategy, it remains challenging to get a uniform distribution of drug at the tumor site because of the internalization of NPs by the cells in the tumor and HA regeneration. Herein, an intelligent nanocarrier, which can release HAase in response to the acidic tumor microenvironment (pH 6.5) and perform a strong neighboring effect with size reduction to overcome the above two problems and accomplish drug deep tumor penetration in vivo, is reported. In this design, HAase is encapsulated on the surfaces of doxorubicin (DOX) preloaded ZnO‐DOX NPs using a charge convertible polymer PEG‐PAH‐DMMA (ZDHD). The polymer can release HAase to degrade HA in the tumor ECM (pH 6.5). ZnO‐DOX NPs can release DOX in lysosomes (pH 4.5) to induce cell apoptosis, and exert a neighboring effect with size reduction to infect neighboring cells. The hierarchical targeted release of HAase and drugs is demonstrated to enhance tumor penetration and decrease side effects in vivo. This work shows promise for further application of ZDHD NPs in cancer therapy.

Designed Formation of Hybrid Nanobox Composed of Carbon Sheathed CoSe2 Anchored on Nitrogen‐Doped Carbon Skeleton as Ultrastable Anode for Sodium‐Ion Batteries

By Baoqiang Li, Yi Liu, Xu Jin, Shuhong Jiao, Gongrui Wang, Bo Peng, Suyuan Zeng, Liang Shi, Jianming Li, Genqiang Zhang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

The designed formation of hybrid nanoboxes composed of carbon‐protected CoSe2 nanoparticles strongly coupled with nitrogen‐doped carbon skeletons (denoted as CoSe2@C∩NC) is achieved via a template‐assisted refluxing process followed by conventional selenization treatment, which enables the excellent electrochemical performance for sodium‐ion storage. Abstract Research on sodium‐ion batteries (SIBs) has recently been revitalized due to the unique features of much lower costs and comparable energy/power density to lithium‐ion batteries (LIBs), which holds great potential for grid‐level energy storage systems. Transition metal dichalcogenides (TMDCs) are considered as promising anode candidates for SIBs with high theoretical capacity, while their intrinsic low electrical conductivity and large volume expansion upon Na+ intercalation raise the challenging issues of poor cycle stability and inferior rate performance. Herein, the designed formation of hybrid nanoboxes composed of carbon‐protected CoSe2 nanoparticles anchored on nitrogen‐doped carbon hollow skeletons (denoted as CoSe2@C∩NC) via a template‐assisted refluxing process followed by conventional selenization treatment is reported, which exhibits tremendously enhanced electrochemical performance when applied as the anode for SIBs. Specifically, it can deliver a high reversible specific capacity of 324 mAh g−1 at current density of 0.1 A g−1 after 200 cycles and exhibit outstanding high rate cycling stability at the rate of 5 A g−1 over 2000 cycles. This work provides a rational strategy for the design of advanced hybrid nanostructures as anode candidates for SIBs, which could push forward the development of high energy and low cost energy storage devices.

Rolling up MoSe2 Nanomembranes as a Sensitive Tubular Photodetector

By Xuefei Zhou, Ziao Tian, Hyuk Jin Kim, Yang Wang, Borui Xu, Ruobing Pan, Young Jun Chang, Zengfeng Di, Peng Zhou, Yongfeng Mei from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A 3D tubular photodetector based on a rolled‐up molybdenum diselenide microtubes is demonstrated. Due to its circular geometry, multiple reflections inside the microtube contribute to enhanced optical absorption. Thus, the tubular photodetector exhibits a much higher photocurrent than its planar counterparts. This tubular device offers a new idea for high‐performance transition metal dichalcogenide photodetectors. Abstract Transition metal dichalcogenides, as a kind of 2D material, are suitable for near‐infrared to visible photodetection owing to the bandgaps ranging from 1.0 to 2.0 eV. However, limited light absorption restricts photoresponsivity due to the ultrathin thickness of 2D materials. 3D tubular structures offer a solution to solve the problem because of the light trapping effect which can enhance optical absorption. In this work, thanks to mechanical flexibility of 2D materials, self‐rolled‐up technology is applied to build up a 3D tubular structure and a tubular photodetector is realized based on the rolled‐up molybdenum diselenide microtube. The tubular device is shown to present one order higher photosensitivity compared with planar counterparts. Enhanced optical absorption arising from the multiple reflections inside the tube is the main reason for the increased photocurrent. This tubular device offers a new design for increasing the efficiency of transition metal dichalcogenide–based photodetection and could hold great potential in the field of 3D optoelectronics.

Controllable Fabrication of Inhomogeneous Microcapsules for Triggered Release by Osmotic Pressure

By Weixia Zhang, Liangliang Qu, Hao Pei, Zhao Qin, Jonathan Didier, Zhengwei Wu, Frank Bobe, Donald E. Ingber, David A. Weitz from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Inhomogeneous microcapsules are designed and controllably fabricated to encapsulate biomolecules through a single‐step microfluidic process. The inhomogeneous microcapsules are demonstrated to be preferable for controlled release triggered by osmotic shock. These inhomogeneous microcapsules can be used to encapsulate biomolecules for long‐term incubation and can be triggered by osmotic shock to release the encapsulated biomolecules without impairing their biological activity. Abstract Inhomogeneous microcapsules that can encapsulate various cargo for controlled release triggered by osmotic shock are designed and reported. The microcapsules are fabricated using a microfluidic approach and the inhomogeneity of shell thickness in the microcapsules can be controlled by tuning the flow rate ratio of the middle phase to the inner phase. This study demonstrates the swelling of these inhomogeneous microcapsules begins at the thinnest part of shell and eventually leads to rupture at the weak spot with a low osmotic pressure. Systematic studies indicate the rupture fraction of these microcapsules increases with increasing inhomogeneity, while the rupture osmotic pressure decreases linearly with increasing inhomogeneity. The inhomogeneous microcapsules are demonstrated to be impermeable to small probe molecules, which enables long‐term storage. Thus, these microcapsules can be used for long‐term storage of enzymes, which can be controllably released through osmotic shock without impairing their biological activity. The study provides a new approach to design effective carriers to encapsulate biomolecules and release them on‐demand upon applying osmotic shock.

Atomically Sharp Dual Grain Boundaries in 2D WS2 Bilayers

By Jun Chen, Gang Seob Jung, Gyeong Hee Ryu, Ren‐Jie Chang, Si Zhou, Yi Wen, Markus J. Buehler, Jamie H. Warner from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Long‐range atomically sharp dual tilt grain boundaries are found within bilayer WS2 2D layered crystals grown by chemical vapor deposition. In situ heating experiments within the electron microscope show they are stable to at least 800 °C. The dislocation cores needed for these bilayer interfaces are more complex than monolayer grain boundaries due to competing van der Waals interlayer forces. Abstract It is shown that tilt grain boundaries (GBs) in bilayer 2D crystals of the transition metal dichalcogenide WS2 can be atomically sharp, where top and bottom layer GBs are located within sub‐nanometer distances of each other. This expands the current knowledge of GBs in 2D bilayer crystals, beyond the established large overlapping GB types typically formed in chemical vapor deposition growth, to now include atomically sharp dual bilayer GBs. By using atomic‐resolution annular dark‐field scanning transmission electron microscopy (ADF‐STEM) imaging, different atomic structures in the dual GBs are distinguished considering bilayers with a 3R (AB stacking)/2H (AA′ stacking) interface as well as bilayers with 2H/2H boundaries. An in situ heating holder is used in ADF‐STEM and the GBs are stable to at least 800 °C, with negligible thermally induced reconstructions observed. Normal dislocation cores are seen in one WS2 layer, but the second WS2 layer has different dislocation structures not seen in freestanding monolayers, which have metal‐rich clusters to accommodate the stacking mismatch of the 2H:3R interface. These results reveal the competition between maintaining van der Waals bilayer stacking uniformity and dislocation cores required to stitch tilted bilayer GBs together.

Size‐, Water‐, and Defect‐Regulated Potassium Manganese Hexacyanoferrate with Superior Cycling Stability and Rate Capability for Low‐Cost Sodium‐Ion Batteries

By Aijun Zhou, Zemin Xu, Hongcai Gao, Leigang Xue, Jingze Li, John B. Goodenough from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A K2MnFe(CN)6 Prussian blue analogue with low amount of crystal water and defects, and uniform size distribution can be obtained by precipitation in a citrate medium. This material shows high stability and rate capability as a hybrid sodium‐ion battery cathode, with both Na+ and K+ being reversible cations in the monoclinic framework. Abstract Potassium manganese hexacyanoferrate (KMHCF) is a low‐cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high‐performance cathode in sodium‐ion batteries (NIBs) is reported. High‐quality KMHCF with low amounts of crystal water and defects and with homogeneous microstructure is obtained by controlling the nucleation and grain growth by using a high‐concentration citrate solution as a precipitation medium. The obtained KMHCF exhibits superior cycling and rate performance as a NIB cathode, showing 80% capacity retention after 1000 cycles at 1 C and a high capacity of 95 mA h g−1 at 20 C. Unlike conventional single‐cation batteries, the hybrid NIB with KMHCF as cathode and Na as anode in Na‐ion electrolyte displays three reversible plateaus that involve stepwise insertion/extraction of both K+ and Na+ in the PBA framework. In later cycling, the K+–Na+ cointercalated phase is partially converted into a cubic sodium manganese hexacyanoferrate (NaMHCF) phase due to the increasing replacement of Na+ for K+.

Charge‐Accumulation Effect in Transition Metal Dichalcogenide Heterobilayers

By Tong Ye, Junze Li, Dehui Li from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Charge accumulation can play important roles in 2D‐heterostructure devices; however, it has been rarely studied so far. This work provides an in‐depth view of the charge‐accumulation effect in a WSe2/WS2 heterobilayer. The interlayer‐exciton emission increases more rapidly than intralayer excitons with increasing excitation power, which can be attributed to the charge‐accumulation effect. Abstract Charge transfer in transition‐metal‐dichalcogenides (TMDs) heterostructures is a prerequisite for the formation of interlayer excitons, which hold great promise for optoelectronics and valleytronics. Charge accumulation accompanied by a charge‐transfer process can introduce considerable effect on interlayer exciton‐based applications; nevertheless, this aspect has been rarely studied up to date. This work demonstrates how the charge accumulation affects the light emission of interlayer excitons in van der Waals heterobilayers (HBs) consisting of monolayer WSe2 and WS2. As excitation power increases, the photoluminescence intensity of interlayer excitons increases more rapidly than that of intralayer excitons. The phenomenon can be explained by charge‐accumulation effect, which not only increases the recombination probability of interlayer excitons but also saturates the charge‐transfer process. This scenario is further confirmed by a careful examination of trion binding energy of WS2, which nonlinearly increases with the increase of the excitation power before reaching a maximum of about 75 meV. These investigations provide a better understanding of interlayer excitons and trions in HBs, which may provoke further explorations of excitonic physics as well as TMDs‐based devices.

Tumor pH‐Responsive Albumin/Polyaniline Assemblies for Amplified Photoacoustic Imaging and Augmented Photothermal Therapy

By Qiwei Tian, Yaping Li, Shanshan Jiang, Lu An, Jiaomin Lin, Huixia Wu, Peng Huang, Shiping Yang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

A facile strategy is developed for the preparation of a bovine serum albumin (BSA)–polyaniline (PANI) assemblies with tumor pH‐responsivity for amplified photoacoustic imaging and augmented photothermal therapy, through intermolecular acid–base reactions between carboxyl groups of BSA and imine moieties of PANI. Abstract Tumor‐microenvironment‐responsive theranostics have great potential for precision diagnosis and effective treatment of cancer. Polyaniline (PANI) is the first reported pH‐responsive organic photothermal agent and is widely used as a theranostic agent. However, tumor pH‐responsive PANI‐based theranostic agents are not explored, mainly because the conversion from the emeraldine base (EB) to emeraldine salt (ES) state of PANI requires pH

Masthead: (Small 42/2019)

By from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Graphene Structure: Unconventional Atomic Structure of Graphene Sheets on Solid Substrates (Small 42/2019)

By Jinjin Zhang, Yizhou Yang, Shuo Yang, Jie Song, Ying Wang, Xiaoguo Liu, Qingqing Yang, Yue Shen, Shuo Wang, Haijun Yang, Junhong Lü, Bin Li, Haiping Fang, Ratnesh Lal, Daniel M. Czajkowsky, Jun Hu, Guosheng Shi, Yi Zhang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

In article number 1902637, Guosheng Shi, Yi Zhang, and co‐workers discover an orthorhombic crystal of graphene with an ≈5 Å period formed on various substrates, which can be applied to control the epitaxial self‐assembly of amyloid peptides. First‐principle computations show that this atomic structure can be attributed to dipoles between the graphene surface and substrates.

Bimetallic Catalysts: A Novel Approach to High‐Performance Aliovalent‐Substituted Catalysts—2D Bimetallic MOF‐Derived CeCuOx Microsheets (Small 42/2019)

By Qingyue Wang, Zhimin Li, Miguel A. Bañares, Lu‐Tao Weng, Qinfen Gu, Jason Price, Wei Han, King Lun Yeung from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

In article number 1903525, Wei Han, King Lun Yeung, and co‐workers develop a synthesis approach to binary metal oxides by controlled thermal transformation of bimetallic metal–organic framework precursors. The approach is capable of manipulating the morphology and structure of binary metal oxides as high‐performance environmental catalysts for complete oxidation of volatile organic compounds under the conditions of low temperature and high humidity.

Sodium‐Ion Batteries: Designed Formation of Hybrid Nanobox Composed of Carbon Sheathed CoSe2 Anchored on Nitrogen‐Doped Carbon Skeleton as Ultrastable Anode for Sodium‐Ion Batteries (Small 42/2019)

By Baoqiang Li, Yi Liu, Xu Jin, Shuhong Jiao, Gongrui Wang, Bo Peng, Suyuan Zeng, Liang Shi, Jianming Li, Genqiang Zhang from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

In article number 1902881, Liang Shi, Jianming Li, Genqiang Zhang, and co‐workers achieve the designed formation of hybrid nanoboxes composed of carbon protected CoSe2 nanoparticles strongly coupled with nitrogen‐doped carbon skeleton (denoted as CoSe2@C∩NC) via a template assisted refluxing process followed by conventional selenization treatment, which enables excellent electrochemical performance for sodium‐ion storage with both high specific capacity and cycling stability.

Immunotherapy: Artificial Engineered Natural Killer Cells Combined with Antiheat Endurance as a Powerful Strategy for Enhancing Photothermal‐Immunotherapy Efficiency of Solid Tumors (Small 42/2019)

By Da Zhang, Youshi Zheng, Ziguo Lin, Shanyou Lan, Xiaolong Zhang, Aixian Zheng, Juan Li, Gang Liu, Huanghao Yang, Xiaolong Liu, Jingfeng Liu from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Photothermal therapy (PTT) has been pre‐clinically used in cancer treatment, but incomplete tumor removal and heat endurance of tumor cells could induce significant tumor relapse. In article number 1902636, Xiaolong Liu, Jingfeng Liu, and co‐workers report a programmable antitumor strategy that combines artificially engineered natural killer cells with anti‐heat endurance of DNAzyme as a powerful adjuvant for immuno‐enhancing the therapeutic efficiency of PTT.

Tubular Photodetectors: Rolling up MoSe2 Nanomembranes as a Sensitive Tubular Photodetector (Small 42/2019)

By Xuefei Zhou, Ziao Tian, Hyuk Jin Kim, Yang Wang, Borui Xu, Ruobing Pan, Young Jun Chang, Zengfeng Di, Peng Zhou, Yongfeng Mei from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

In article number 1902528, Yongfeng Mei and co‐workers demonstrate a 3D tubular photodetector based on a rolled‐up molybdenum diselenide microtube to enhance the photoresponsibility of 2D materials. Such a tubular design could boost the efficiency of 2D materials–based photodetectors and hold great potential in the field of 3D optoelectronics.

Applications of Catalytic Hairpin Assembly Reaction in Biosensing

By Jumei Liu, Ye Zhang, Huabin Xie, Li Zhao, Lei Zheng, Huiming Ye from Wiley: Small: Table of Contents. Published on Oct 15, 2019.

Catalytic hairpin assembly (CHA), a robust, versatile, and enzyme‐free nucleic acid isothermal amplification method, has attracted broad attention. Herein, the mechanisms of several extended CHA systems, hairpin designs, and reaction conditions are introduced in detail. Various analytical platforms are applied for signal output of CHA. Biosensors based on CHA are presented. Finally, challenges and the outlook of CHA developments are considered. Abstract Nucleic acids are considered as perfect programmable materials for cascade signal amplification and not merely as genetic information carriers. Among them, catalytic hairpin assembly (CHA), an enzyme‐free, high‐efficiency, and isothermal amplification method, is a typical example. A typical CHA reaction is initiated by single‐stranded analytes, and substrate hairpins are successively opened, resulting in thermodynamically stable duplexes. CHA circuits, which were first proposed in 2008, present dozens of systems today. Through in‐depth research on mechanisms, the CHA circuits have been continuously enriched with diverse reaction systems and improved analytical performance. After a short time, the CHA reaction can realize exponential amplification under isothermal conditions. Under certain conditions, the CHA reaction can even achieve 600 000‐fold signal amplification. Owing to its promising versatility, CHA is able to be applied for analysis of various markers in vitro and in living cells. Also, CHA is integrated with nanomaterials and other molecular biotechnologies to produce diverse readouts. Herein, the varied CHA mechanisms, hairpin designs, and reaction conditions are introduced in detail. Additionally, biosensors based on CHA are presented. Finally, challenges and the outlook of CHA development are considered.

Unusual Through‐Space Interactions between Oxygen Atoms Mediate Inverse Morphochromism of an AIE Luminogen

By Lucia Viglianti, Ni Xie, Herman H. Y. Sung, Alexander A. Voityuk, Nelson L. C. Leung, Yujie Tu, Clara Baldoli, Ian D. Williams, Ryan T. K. Kwok, Jacky W. Y. Lam, Emanuela Licandro, Lluis Blancafort, Ben Zhong Tang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Oct 15, 2019.

We have studied the photophysics of tetrafurylethene, an aggregation‐induced emission luminogen that has exceptionally short intramolecular O‐O distances of 2.80 Å and shows a significant redshifted morphochromism (27 nm) when going from the aggregate to the crystal. The short O‐O distances, which are substantially smaller than the sum of the van der Waals radii (3.04 Å), are due to the fact that the oxygen atoms act as an electronic bridge connecting the furan rings on opposite ends of the central double bond, giving rise to a circular delocalization of the π electron density across the rings. In the excited state the O‐O distance is further reduced to 2.70 Å, and the increased O‐O interaction causes a narrowing of the HOMO‐LUMO gap that results in the red morphochromism of the emission. Our results establish that the structural origin of the red‐shifted emission lies in the close O‐O contacts, and pave the way for understanding the clusteroluminescence of oxygen‐rich, non‐conjugated systems that emit visible light. Introduction

[ASAP] Correction to Nanoscale Coordination Polymers for Synergistic NO and Chemodynamic Therapy of Liver Cancer

By Yihui Hu, Tian Lv†, Yu Ma, Junjie Xu, Yihua Zhang, Yanglong Hou, Zhangjian Huang*, and Ya Ding* from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b04125

[ASAP] Design of Patchy Rhombi: From Close-Packed Tilings to Open Lattices

By Carina Karner*†, Christoph Dellago†, and Emanuela Bianchi*‡§ from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02829

[ASAP] Ultrasound-Responsive Conversion of Microbubbles to Nanoparticles to Enable Background-Free in Vivo Photoacoustic Imaging

By Zhouqi Meng, Xuanfang Zhou, Jialin She, Yaojia Zhang, Liangzhu Feng, and Zhuang Liu* from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03331

[ASAP] Proline Isomerization-Regulated Tumor Microenvironment-Adaptable Self-Assembly of Peptides for Enhanced Therapeutic Efficacy

By Mingming Li†, Yashan Ning†, Jialiang Chen‡, Xingchen Duan§, Na Song†, Dan Ding*§, Xuncheng Su*‡, and Zhilin Yu*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03136

[ASAP] Electron Optics in Phosphorene pn Junctions: Negative Reflection and Anti-Super-Klein Tunneling

By Yonatan Betancur-Ocampo*†, Franc¸ois Leyvraz†‡, and Thomas Stegmann*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02720

[ASAP] Kinked Silicon Nanowires: Superstructures by Metal-Assisted Chemical Etching

By Georgiana Sandu†¶, Jonathan Avila Osses†¶, Marine Luciano‡¶, Darwin Caina†§, Antoine Stopin?, Davide Bonifazi?, Jean-Franc¸ois Gohy?, Alejandro Silhanek#, Ileana Florea?, Mounib Bahri?, Ovidiu Ersen?, Philippe Lecle`re?, Sylvain Gabriele‡, Alexandru Vlad?, and Sorin Melinte*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02568

[ASAP] Engineering Magnetic Phases in Two-Dimensional Non-van der Waals Transition-Metal Oxides

By Arkamita Bandyopadhyay†, Nathan C. Frey†, Deep Jariwala†‡, and Vivek B. Shenoy*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02801

[ASAP] Intrathecal Administration of Nanoclusters for Protecting Neurons against Oxidative Stress in Cerebral Ischemia/Reperfusion Injury

By Shiyong Li†‡, Dawei Jiang‡, Emily B. Ehlerding‡, Zachary T. Rosenkrans‡, Jonathan W. Engle‡, Ye Wang§, Huisheng Liu?, Dalong Ni*‡, and Weibo Cai*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06780

[ASAP] Evolutionary Refinement of DNA Nanostructures Using Coarse-Grained Molecular Dynamics Simulations

By Erik Benson, Marco Lolaico, Yevgen Tarasov, Andreas Ga°din, and Bjo¨rn Ho¨gberg* from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03473

[ASAP] Dual-Responsive DNA Nanodevice for the Available Imaging of an Apoptotic Signaling Pathway in Situ

By Hai Shi†, Yanxia Wang†, Ji Zheng†, Limin Ning‡, Yue Huang§, Anzhi Sheng?, Tianshu Chen?, Yang Xiang†, Xiaoli Zhu*?, and Genxi Li*†? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05082

[ASAP] Dynamic Transport Control of Colloidal Particles by Repeatable Active Switching of Solute Gradients

By Dogyeong Ha, Sangjin Seo, Kyunghun Lee, and Taesung Kim* from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05507

[ASAP] Massively Parallel Nanoparticle Synthesis in Anisotropic Nanoreactors

By Liban Jibril†‡, Peng-Cheng Chen†‡, Jingtian Hu†‡, Teri W. Odom†‡§, and Chad A. Mirkin*†‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05781

[ASAP] Engineering an Enzyme for Direct Electrical Monitoring of Activity

By Bintian Zhang†?, Hanqing Deng‡?, Sohini Mukherjee‡, Weisi Song†, Xu Wang‡, and Stuart Lindsay*†‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06875

[ASAP] Stacking as a Key Property for Creating Nanoparticles with Tunable Shape: The Case of Squalenoyl-Doxorubicin

By Julie Mougin†, Semen O. Yesylevskyy‡?, Claudie Bourgaux†, David Chapron†, Jean-Philippe Michel†, Franco Dosio§, Barbara Stella§, Christophe Ramseyer?, and Patrick Couvreur*† from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05303

[ASAP] A Universal Length-Dependent Vibrational Mode in Graphene Nanoribbons

By Jan Overbeck*†‡¶@, Gabriela Borin Barin†@, Colin Daniels§@, Mickael L. Perrin†, Oliver Braun†‡, Qiang Sun†, Rimah Darawish†?, Marta De Luca‡, Xiao-Ye Wang??, Tim Dumslaff?, Akimitsu Narita?, Klaus Mu¨llen?#, Pascal Ruffieux†, Vincent Meunier*§, Roman Fasel*†?, and Michel Calame*†‡¶ from ACS Nano: Latest Articles (ACS Publications). Published on Oct 15, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05817

Synthesis, applications and potential photoluminescence mechanism of spectrally tunable carbon dots

By Christy L. Haynes from RSC - Nanoscale latest articles. Published on Oct 15, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR05028K, Minireview
Bo Zhi, XiaoXiao Yao, Yi Cui, Galya Orr, Christy L. Haynes
Due to the prominent characteristics of carbon dots, such as inexpensive precursors, low toxicity, and intrinsic fluorescence, they are regarded as potential candidates to replace traditional quantum dots.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Black Phosphorous Quantum Dots Sandwiched Organic Solar Cells

By Yifan Wang, Jie Li, Tengfei Li, Jiayu Wang, Kuan Liu, Qianqian Jiang, Jianguo Tang, Xiaowei Zhan from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

Black phosphorous quantum dots are used as interlayers to modify both electron and hole transport layers in organic solar cells. The power conversion efficiencies of the nonfullerene and fullerene‐based devices are enhanced. Abstract Black phosphorous quantum dots (BPQDs) possess ambipolar charge transport, high mobility, and a tunable direct bandgap. Here, liquid‐exfoliated BPQDs are used as interlayers to modify both the electron transport layer and hole transport layer in organic solar cells (OSCs). The incorporation of BPQDs is beneficial to the formation of a cascade band structure and electron/hole transfer and extraction. The power conversion efficiency of the BPQDs‐incorporated OSC based on PTB7‐Th:FOIC blend is enhanced from 11.8% to 13.1%. In addition, power conversion efficiency enhancement is also achieved for other nonfullerene and fullerene‐based devices, demonstrating the universality of this interlayer methodology.

Discontinuity‐Enhanced Thin Film Electrocatalytic Oxygen Evolution

By Ming‐Chi Shih, Ren‐Huai Jhang, Ya‐Ting Tsai, Chia‐Wei Huang, Yung‐Jr Hung, Mei‐Yi Liao, Jiaxing Huang, Chun‐Hu Chen from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

A discontinuous cobalt manganese oxyhydroxide (CMOH) film, which is deposited on gold‐coated pyramidal substrates, shows much higher atom efficiency and performance in the oxygen evolution reaction (OER) than completely continuous ones. The heterojunction edges facilitate charge transport and kinetics. This concept is highly valuable to reduce the quantity of catalysts, while gaining even better, durable OER activity. Abstract Thin film electrocatalysts allow strong binding and intimate electrical contact with electrodes, rapid mass transfer during reaction, and are generally more durable than powder electrocatalysts, which is particularly beneficial for gas evolution reactions. In this work, using cobalt manganese oxyhydroxide, an oxygen evolution reaction (OER) electrocatalyst that can be grown directly on various electrodes as a model system, it is demonstrated that breaking a continuous film into discontinuous patches can significantly enhance the overall OER performance without sacrificing long‐term stability even under elevated electrocatalytic stress. Discontinuous films with higher edge‐to‐area ratios exhibits reduced overpotentials, increased turnover frequency, and more pronounced current increase after electrochemical conditioning. Operando Raman spectroscopy studies during electrocatalysis reveal that the film edges require lower potential barrier for activation. Introducing discontinuity into thin film electrocatalysis can thus lead to the realization of high performance yet highly robust systems for harsh gas evolution reactions.

MOF‐Derived CuS@Cu‐BTC Composites as High‐Performance Anodes for Lithium‐Ion Batteries

By Ping Wang, Mengqi Shen, Hu Zhou, Chunfeng Meng, Aihua Yuan from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

CuS@Cu‐BTC composites are used as anode materials for lithium‐ion batteries for the first time, which exhibit improved Li‐ion storage abilities originating from the synergistic effect between the Cu‐BTC and nano‐CuS components. Abstract The CuS(x wt%)@Cu‐BTC (BTC = 1,3,5‐benzenetricarboxylate; x = 3, 10, 33, 58, 70, 99.9) materials are synthesized by a facile sulfidation reaction. The composites are composed of octahedral Cu3(BTC)2·(H2O)3 (Cu‐BTC) with a large specific surface area and CuS with a high conductivity. The as‐prepared CuS@Cu‐BTC products are first applied as the anodes of lithium‐ion batteries (LIBs). The synergistic effect between Cu‐BTC and CuS components can not only accommodate the volume change and stress relaxation of electrodes but also facilitate the fast transport of Li ions. Thus, it can greatly suppress the transformation process from Li2S to polysulfides by improving the reversibility of the conversion reaction. Benefiting from the unique structural features, the optimal CuS(70 wt%)@Cu‐BTC sample exhibits a remarkably improved electrochemical performance, showing an over‐theoretical capacity up to 1609 mAh g−1 after 200 cycles (100 mA g−1) with an excellent rate‐capability of ≈490 mAh g−1 at 1000 mA g−1. The outstanding LIB properties indicate that the CuS(70 wt%)@Cu‐BTC sample is a highly desirable electrode material candidate for high‐performance LIBs.

Van der Waals Heterostructures for High‐Performance Device Applications: Challenges and Opportunities

By Shi‐Jun Liang, Bin Cheng, Xinyi Cui, Feng Miao from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

The diverse properties of van der Waals heterostructures open unprecedented opportunities for various types of device applications inaccessible in conventional heterostructure materials. Research progress of vertical heterostructure device applications in vertical transistors, infrared photodetectors, and spintronic devices is reviewed, together with a discussion on the challenges and opportunities in the future development of multifunctional devices. Abstract The discovery of two‐dimensional (2D) materials with unique electronic, superior optoelectronic, or intrinsic magnetic order has triggered worldwide interest in the fields of material science, condensed matter physics, and device physics. Vertically stacking 2D materials with distinct electronic and optical as well as magnetic properties enables the creation of a large variety of van der Waals heterostructures. The diverse properties of the vertical heterostructures open unprecedented opportunities for various kinds of device applications, e.g., vertical field‐effect transistors, ultrasensitive infrared photodetectors, spin‐filtering devices, and so on, which are inaccessible in conventional material heterostructures. Here, the current status of vertical heterostructure device applications in vertical transistors, infrared photodetectors, and spintronic memory/transistors is reviewed. The relevant challenges for achieving high‐performance devices are presented. An outlook into the future development of vertical heterostructure devices with integrated electronic and optoelectronic as well as spintronic functionalities is also provided.

Tough, Self‐Healing Hydrogels Capable of Ultrafast Shape Changing

By Zhen Jiang, Broden Diggle, India C. G. Shackleford, Luke A. Connal from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

A multifunctional shape‐changing hydrogel is fabricated through rational design of dynamic networks. By harnessing acid–ether hydrogen bonding and imine bonds, high strength/toughness, fast self‐healing, rapid and programmable actuation, and memory effect are simultaneously achieved. This material design strategy offers an avenue for synergistically engineering the properties of hydrogel actuators that are promising in diverse applications. Abstract Achieving multifunctional shape‐changing hydrogels with synergistic and engineered material properties is highly desirable for their expanding applications, yet remains an ongoing challenge. The synergistic design of multiple dynamic chemistries enables new directions for the development of such materials. Herein, a molecular design strategy is proposed based on a hydrogel combining acid–ether hydrogen bonding and imine bonds. This approach utilizes simple and scalable chemistries to produce a doubly dynamic hydrogel network, which features high water uptake, high strength and toughness, excellent fatigue resistance, fast and efficient self‐healing, and superfast, programmable shape changing. Furthermore, deformed shapes can be memorized due to the large thermal hysteresis. This new type of shape‐changing hydrogel is expected to be a key component in future biomedical, tissue, and soft robotic device applications.

A 0D/3D Heterostructured All‐Inorganic Halide Perovskite Solar Cell with High Performance and Enhanced Phase Stability

By Fujin Bai, Jie Zhang, Yufei Yuan, Hongbin Liu, Xiaosong Li, Chu‐Chen Chueh, He Yan, Zonglong Zhu, Alex K.‐Y. Jen from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

A 0D Cs4PbI6/3D CsPbI3 heterostructure is achieved by tuning the stoichiometry of the precursors. The coexistent Cs4PbI6 not only reduces the grain size of the CsPbI3 and serves as a molecular lock to stabilize the black‐phase CsPbI3, but also passivates the defects in the grain boundaries and improves the surface coverage to improve the device performance to 16.39%. Abstract Although organic–inorganic hybrid perovskite solar cells (PVSCs) have achieved dramatic improvement in device efficiency, their long‐term stability remains a major concern prior to commercialization. To address this issue, extensive research efforts are dedicated to exploiting all‐inorganic PVSCs by using cesium (Cs)‐based perovskite materials, such as α‐CsPbI3. However, the black‐phase CsPbI3 (cubic α‐CsPbI3 and orthorhombic γ‐CsPbI3 phases) is not stable at room temperature, and it tends to convert to the nonperovskite δ‐CsPbI3 phase. Here, a simple yet effective approach is described to prepare stable black‐phase CsPbI3 by forming a heterostructure comprising 0D Cs4PbI6 and γ‐CsPbI3 through tuning the stoichiometry of the precursors between CsI and PbI. Such heterostructure is manifested to enable the realization of a stable all‐inorganic PVSC with a high power conversion efficiency of 16.39%. This work provides a new perspective for developing high‐performance and stable all‐inorganic PVSCs.

Nanostructured Carbon Nitrides for CO2 Capture and Conversion

By Siddulu Naidu Talapaneni, Gurwinder Singh, In Young Kim, Khalid AlBahily, Ala'a H. Al‐Muhtaseb, Ajay S. Karakoti, Ehsan Tavakkoli, Ajayan Vinu from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

Nanostructured carbon nitride (CN) is studied as an advantageous platform for simultaneous CO2 capture and conversion to valuable feedstock using photocatalysis and electrocatalysis, with remarkable catalytic activity, long durability, and high selectivity. The progressively discovered various novel CN materials and their hybrid nanostructures for the catalytic reduction of CO2 are highlighted, along with research challenges, opportunities, and future perspectives on this topic. Abstract Carbon nitride (CN), a 2D material composed of only carbon (C) and nitrogen (N), which are linked by strong covalent bonds, has been used as a metal‐devoid and visible‐light‐active photocatalyst owing to its magnificent optoelectronic and physicochemical properties including suitable bandgap, adjustable energy‐band positions, tailor‐made surface functionalities, low cost, metal‐free nature, and high thermal, chemical, and mechanical stabilities. CN‐based materials possess a lot of advantages over conventional metal‐based inorganic photocatalysts including ease of synthesis and processing, versatile functionalization or doping, flexibility for surface engineering, low cost, sustainability, and recyclability without any leaching of toxic metals from photocorrosion. Carbon nitrides and their hybrid materials have emerged as attractive candidates for CO2 capture and its reduction into clean and green low‐carbon fuels and valuable chemical feedstock by using sustainable and intermittent renewable energy sources of sunlight and electricity through the heterogeneous photo(electro)catalysis. Here, the latest research results in this field are summarized, including implementation of novel functionalized nanostructured CNs and their hybrid heterostructures in meeting the stringent requirements to raise the efficiency of the CO2 reduction process by using state‐of‐the‐art photocatalysis, electrocatalysis, photoelectrocatalysis, and feedstock reactions. The research in this field is primarily focused on advancement in the synthesis of nanostructured and functionalized CN‐based hybrid heterostructured materials. More importantly, the recent past has seen a surge in studies focusing significantly on exploring the mechanism of their application perspectives, which include the behavior of the materials for the absorption of light, charge separation, and pathways for the transport of CO2 during the reduction process.

Flexible Zinc‐Ion Hybrid Fiber Capacitors with Ultrahigh Energy Density and Long Cycling Life for Wearable Electronics

By Xinshi Zhang, Zengxia Pei, Chaojun Wang, Ziwen Yuan, Li Wei, Yuqi Pan, Asif Mahmood, Qian Shao, Yuan Chen from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

The first quasisolid‐state zinc‐ion hybrid fiber capacitor delivers a high energy density of 48.5 mWh cm−3. The capacitor contains three rationally designed components: a positive electrode hydrothermally assembled from reduced graphene oxide/carbon nanotubes, a negative electrode made of graphite fibers coated with a uniform Zn layer, and a neutral ZnSO4‐filled stretchable polyacrylic acid hydrogel. Abstract Emerging wearable electronics require flexible energy storage devices with high volumetric energy and power densities. Fiber‐shaped capacitors (FCs) offer high power densities and excellent flexibility but low energy densities. Zn‐ion capacitors have high energy density and other advantages, such as low cost, nontoxicity, reversible Faradaic reaction, and broad operating voltage windows. However, Zn‐ion capacitors have not been applied in wearable electronics due to the use of liquid electrolytes. Here, the first quasisolid‐state Zn‐ion hybrid FC (ZnFC) based on three rationally designed components is demonstrated. First, hydrothermally assembled high surface area and conductive reduced graphene oxide/carbon nanotube composite fibers serve as capacitor‐type positive electrodes. Second, graphite fibers coated with a uniform Zn layer work as battery‐type negative electrodes. Third, a new neutral ZnSO4‐filled polyacrylic acid hydrogel act as the quasisolid‐state electrolyte, which offers high ionic conductivity and excellent stretchability. The assembled ZnFC delivers a high energy density of 48.5 mWh cm−3 at a power density of 179.9 mW cm−3. Further, Zn dendrite formation that commonly happens under high current density is efficiently suppressed on the fiber electrode, leading to superior cycling stability. Multiple ZnFCs are integrated as flexible energy storage units to power wearable devices under different deformation conditions.

Metal‐Based Electrocatalysts for Methanol Electro‐Oxidation: Progress, Opportunities, and Challenges

By Yueyu Tong, Xiao Yan, Ji Liang, Shi Xue Dou from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

Efficient catalysts are critical for the electrocatalytic oxidation reaction of methanol. Metal‐based anode catalysts with well‐defined nanoarchitectures and optimal chemical compositions can provide superior performance with lower costs. The possible effects, challenges, and future development are elaborately discussed to shed light on the further design of metal‐based anode catalysts for the methanol electro‐oxidation reaction, leading to a renewable energy supply future. Abstract Direct methanol fuel cells (DMFCs) are among the most promising portable power supplies because of their unique advantages, including high energy density/mobility of liquid fuels, low working temperature, and low emission of pollutants. Various metal‐based anode catalysts have been extensively studied and utilized for the essential methanol oxidation reaction (MOR) due to their superior electrocatalytic performance. At present, especially with the rapid advance of nanotechnology, enormous efforts have been exerted to further enhance the catalytic performance and minimize the use of precious metals. Constructing multicomponent metal‐based nanocatalysts with precisely designed structures can achieve this goal by providing highly tunable compositional and structural characteristics, which is promising for the modification and optimization of their related electrochemical properties. The recent advances of metal‐based electrocatalytic materials with rationally designed nanostructures and chemistries for MOR in DMFCs are highlighted and summarized herein. The effects of the well‐defined nanoarchitectures on the improved electrochemical properties of the catalysts are illustrated. Finally, conclusive perspectives are provided on the opportunities and challenges for further refining the nanostructure of metal‐based catalysts and improving electrocatalytic performance, as well as the commercial viability.

Van der Waals Integration of Bismuth Quantum Dots–Decorated Tellurium Nanotubes (Te@Bi) Heterojunctions and Plasma‐Enhanced Optoelectronic Applications

By Ye Zhang, Feng Zhang, Leiming Wu, Yupeng Zhang, Weichun Huang, Yanfeng Tang, Lanping Hu, Pu Huang, Xiuwen Zhang, Han Zhang from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

Bismuth quantum dots–decorated tellurium nanotubes van der Waals heterojunctions (Te@Bi vdWHs) are synthesized through hydrothermal bottom‐up assembly. Both the experiments and density functional theory calculations demonstrate enhanced optoelectronics due to the plasma and built‐in electronic field effects at the interface, which can significantly improve the photoresponse behavior of Te@Bi vdWHs‐based photodetectors. Abstract Van der Waals (vdW)‐integrated heterojunctions have been widely investigated in optoelectronics due to their superior photoelectric conversion capability. In this work, 0D bismuth quantum dots (Bi QDs)‐decorated 1D tellurium nanotubes (Te NTs) vdW heterojunctions (Te@Bi vdWHs) are constructed by a facile bottom‐up assembly process. Transient absorption spectroscopy suggests that Te@Bi vdWH is a promising candidate for new‐generation optoelectronic devices with fast response properties. The subsequent experiments and density functional theory calculations demonstrate the vdW interaction between Te NTs and Bi QDs, as well as the enhanced optoelectronic characteristics owing to the plasma effects at the interface between Te NTs and Bi QDs. Moreover, Te@Bi vdWHs‐based photodetectors show significantly improved photoresponse behavior in the ultraviolet region compared to pristine Te NTs or Bi QDs‐based photodetectors. The proposed integration of vdWHs is expected to pave the way for constructing new nanoscale heterodevices.

Freeform, Reconfigurable Embedded Printing of All‐Aqueous 3D Architectures

By Guanyi Luo, Yafeng Yu, Yuxue Yuan, Xue Chen, Zhou Liu, Tiantian Kong from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

Freeform, reconfigurable all‐aqueous three‐dimensional (3D) architectures are fabricated by embedded‐bioprinting using aqueous two‐phase systems (ATPSs). The reconfigurable aqueous‐in‐aqueous 3D microstructures can be stabilized for weeks by interfacial membranes via hydrogen bonds. By incorporating living cells in compartmentalized ink, this approach can be used in engineering tissue‐like constructs for applications in drug screening, in vitro tissue models and regenerative medicine. Abstract Aqueous microstructures are challenging to create, handle, and preserve since their surfaces tend to shrink into spherical shapes with minimum surface areas. The creation of freeform aqueous architectures will significantly advance the bioprinting of complex tissue‐like constructs, such as arteries, urinary catheters, and tracheae. The generation of complex, freeform, three‐dimensional (3D) all‐liquid architectures using formulated aqueous two‐phase systems (ATPSs) is demonstrated. These all‐liquid microconstructs are formed by printing aqueous bioinks in an immiscible aqueous environment, which functions as a biocompatible support and pregel solution. By exploiting the hydrogen bonding interaction between polymers in ATPS, the printed aqueous‐in‐aqueous reconfigurable 3D architectures can be stabilized for weeks by the noncovalent membrane at the interface. Different cells can be separately combined with compartmentalized bioinks and matrices to obtain tailor‐designed microconstructs with perfusable vascular networks. The freeform, reconfigurable embedded printing of all‐liquid architectures by ATPSs offers unique opportunities and powerful tools since limitless formulations can be designed from among a breadth of natural and synthetic hydrophilic polymers to mimic tissues. This printing approach may be useful to engineer biomimetic, dynamic tissue‐like constructs for potential applications in drug screening, in vitro tissue models, and regenerative medicine.

Goethite Quantum Dots as Multifunctional Additives for Highly Efficient and Stable Perovskite Solar Cells

By Hui Chen, Qiang Luo, Tao Liu, Jing Ren, Shuang Li, Meiqian Tai, Hong Lin, Hongcai He, Jinshu Wang, Ning Wang from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

Low‐cost n‐type goethite (FeOOH) quantum dots (QDs) are introduced into the perovskite light‐absorber layer to fabricate efficient and stable perovskite solar cells (PSCs). As a result, the PSCs with FeOOH QDs obtain a significant efficiency enhancement from 16.6% to 19.7%. Most strikingly, the long‐term stability of PSCs with FeOOH QDs is significantly enhanced. Abstract Minimization of defects and ion migration in organic–inorganic lead halide perovskite films is desirable for obtaining photovoltaic devices with high power conversion efficiency (PCE) and long‐term stability. However, achieving this target is still a challenge due to the lack of efficient multifunctional passivators. Herein, to address this issue, n‐type goethite (FeOOH) quantum dots (QDs) are introduced into the perovskite light‐absorption layer for achieving efficient and stable perovskite solar cells (PSCs). It is found that the iron, oxygen, and hydroxyl of FeOOH QDs can interact with iodine, lead, and methylamine, respectively. As a result, the crystallization kinetics process can be retarded, thereby resulting in high quality perovskite films with large grain size. Meanwhile, the trap states of perovskite can be effectively passivated via interaction with the under‐coordinated metal (Pb) cations, halide (I) anions on the perovskite crystal surface. Consequently, the PSCs with FeOOH QDs achieve a high efficiency close to 20% with negligible hysteresis. Most strikingly, the long‐term stability of PSCs is significantly enhanced. Furthermore, compared with the CH3NH3PbI3‐based device, a higher PCE of 21.0% is achieved for the device assembled with a Cs0.05FA0.81MA0.14PbBr0.45I2.55 perovskite layer.

Covalent‐Organic‐Framework‐Based Li–CO2 Batteries

By Xing Li, Hui Wang, Zhongxin Chen, Hai‐Sen Xu, Wei Yu, Cuibo Liu, Xiaowei Wang, Kun Zhang, Keyu Xie, Kian Ping Loh from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

A covalent organic framework (COF) is deployed in a Li–CO2 battery to function as diffusion channels to improve gas/ion migration. Owing to its ability for CO2 capture/release, the COF greatly increases battery's specific discharge capacity. Importantly, the COF also enhances the battery's rate performance and cycling life at high current density due to the presence of the 1D channels that enable fast gas/ion diffusion. Abstract Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials constructed from designer molecular building blocks that are linked and extended periodically via covalent bonds. Their high stability, open channels, and ease of functionalization suggest that they can function as a useful cathode material in reversible lithium batteries. Here, a COF constructed from hydrazone/hydrazide‐containing molecular units, which shows good CO2 sequestration properties, is reported. The COF is hybridized to Ru‐nanoparticle‐coated carbon nanotubes, and the composite is found to function as highly efficient cathode in a Li–CO2 battery. The robust 1D channels in the COF serve as CO2– and lithium‐ion‐diffusion channels and improve the kinetics of electrochemical reactions. The COF‐based Li–CO2 battery exhibits an ultrahigh capacity of 27 348 mAh g−1 at a current density of 200 mA g−1, and a low cut‐off overpotential of 1.24 V within a limiting capacity of 1000 mAh g−1. The rate performance of the battery is improved considerably with the use of the COF at the cathode, where the battery shows a slow decay of discharge voltage from a current density of 0.1 to 4 A g−1. The COF‐based battery runs for 200 cycles when discharged/charged at a high current density of 1 A g−1.

Conformable Hybrid Systems for Implantable Bioelectronic Interfaces

By Florian Fallegger, Giuseppe Schiavone, Stéphanie P. Lacour from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

Conformable hybrid systems for implantable bioelectronic interfaces enable safe diagnosis and therapy inside the body. Combining soft materials and high‐performance electronics within thin‐films or engineered form factors enables complex devices that can read/write into organs and tissues with unmet precision. Recent advances in materials science, micro/nanofabrication, packaging, and biomedical engineering are analyzed. Current challenges are highlighted with possible future solutions. Abstract Conformable bioelectronic systems are promising tools that may aid the understanding of diseases, alleviate pathological symptoms such as chronic pain, heart arrhythmia, and dysfunctions, and assist in reversing conditions such as deafness, blindness, and paralysis. Combining reduced invasiveness with advanced electronic functions, hybrid bioelectronic systems have evolved tremendously in the last decade, pushed by progress in materials science, micro‐ and nanofabrication, system assembly and packaging, and biomedical engineering. Hybrid integration refers here to a technological approach to embed within mechanically compliant carrier substrates electronic components and circuits prepared with traditional electronic materials. This combination leverages mechanical and electronic performance of polymer substrates and device materials, respectively, and offers many opportunities for man‐made systems to communicate with the body with unmet precision. However, trade‐offs between materials selection, manufacturing processes, resolution, electrical function, mechanical integrity, biointegration, and reliability should be considered. Herein, prominent trends in manufacturing conformable hybrid systems are analyzed and key design, function, and validation principles are outlined together with the remaining challenges to produce reliable conformable, hybrid bioelectronic systems.

Defect Promoted Capacity and Durability of N‐MnO2–x Branch Arrays via Low‐Temperature NH3 Treatment for Advanced Aqueous Zinc Ion Batteries

By Yan Zhang, Shengjue Deng, Mi Luo, Guoxiang Pan, Yinxiang Zeng, Xihong Lu, Changzhi Ai, Qi Liu, Qinqin Xiong, Xiuli Wang, Xinhui Xia, Jiangping Tu from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

With a facile hydrothermal process and subsequent low‐temperature (200 °C) NH3 treatment, N‐doped MnO2–x (N‐MnO2–x) branch arrays with concomitant oxygen vacancies are fabricated on conductive TiC/C backbones to form N‐MnO2–x@TiC/C core/branch arrays. By virtue of an integrated conductive framework, enhanced electron density, and increased surface capacitive contribution, the designed N‐MnO2–x@TiC/C arrays cathode exhibits excellent electrochemical performance in zinc ion batteries. Abstract Defect engineering (doping and vacancy) has emerged as a positive strategy to boost the intrinsic electrochemical reactivity and structural stability of MnO2‐based cathodes of rechargeable aqueous zinc ion batteries (RAZIBs). Currently, there is no report on the nonmetal element doped MnO2 cathode with concomitant oxygen vacancies, because of its low thermal stability with easy phase transformation from MnO2 to Mn3O4 (≥300 °C). Herein, for the first time, novel N‐doped MnO2–x (N‐MnO2–x) branch arrays with abundant oxygen vacancies fabricated by a facile low‐temperature (200 °C) NH3 treatment technology are reported. Meanwhile, to further enhance the high‐rate capability, highly conductive TiC/C nanorods are used as the core support for a N‐MnO2–x branch, forming high‐quality N‐MnO2–x@TiC/C core/branch arrays. The introduced N dopants and oxygen vacancies in MnO2 are demonstrated by synchrotron radiation technology. By virtue of an integrated conductive framework, enhanced electron density, and increased surface capacitive contribution, the designed N‐MnO2–x@TiC/C arrays are endowed with faster reaction kinetics, higher capacity (285 mAh g−1 at 0.2 A g−1) and better long‐term cycles (85.7% retention after 1000 cycles at 1 A g−1) than other MnO2‐based counterparts (55.6%). The low‐temperature defect engineering sheds light on construction of advanced cathodes for aqueous RAZIBs.

2D In2S3 Nanoflake Coupled with Graphene toward High‐Sensitivity and Fast‐Response Bulk‐Silicon Schottky Photodetector

By Jianting Lu, Zhaoqiang Zheng, Jiandong Yao, Wei Gao, Yu Zhao, Ye Xiao, Jingbo Li from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

A novel strategy for coupling 2D In2S3 with graphene/Si photodetectors is demonstrated. The introduction of a double‐heterojunction design not only strengthens the light absorption of graphene/Si but also combines the advantages of the photogating effect and photovoltaic effect, which suppresses the dark current, accelerates the separation of photogenerated carriers, and brings photoconductive gain. Abstract Silicon‐based electronic devices, especially graphene/Si photodetectors (Gr/Si PDs), have triggered tremendous attention due to their simple structure and flexible integration of the Schottky junction. However, due to the relatively poor light–matter interaction and mobility of silicon, these Gr/Si PDs typically suffer an inevitable compromise between photoresponsivity and response speed. Herein, a novel strategy for coupling 2D In2S3 with Gr/Si PDs is demonstrated. The introduction of the double‐heterojunction design not only strengthens the light absorption of graphene/Si but also combines the advantages of the photogating effect and photovoltaic effect, which suppresses the dark current, accelerates the separation of photogenerated carriers, and brings photoconductive gain. As a result, In2S3/graphene/Si devices present an ultrahigh photoresponsivity of 4.53 × 104 A W−1 and fast response speed less than 40 µs, simultaneously. These parameters are an order of magnitude higher than pristine Gr/Si PDs and among the best values compared with reported 2D materials/Si heterojunction PDs. Furthermore, the In2S3/graphene/Si PD expresses outstanding long‐term stability, with negligible performance degradation even after 1 month in air or 1000 cycles of operation. These findings highlight a simple and novel strategy for constructing high‐sensitivity and ultrafast Gr/Si PDs for further optoelectronic applications.

Rapid, High‐Temperature, In Situ Microwave Synthesis of Bulk Nanocatalysts

By Geng Zhong, Shaomao Xu, Mingjin Cui, Qi Dong, Xizheng Wang, Qinqin Xia, Jinlong Gao, Yong Pei, Yun Qiao, Glenn Pastel, Takeshi Sunaoshi, Bao Yang, Liangbing Hu from Wiley: Small: Table of Contents. Published on Oct 14, 2019.

A rapid, in situ high‐temperature microwave heating strategy is reported for the synthesis of carbon‐supported nanocatalysts. The temperature of this method reaches up to 1270 K in 6 s. The optimized loading amount of the carbon black is crucial to achieve the rapid high‐temperature heating. Abstract Carbon‐black‐supported nanoparticles (CNPs) have attracted considerable attention for their intriguing catalytic properties and promising applications. The traditional liquid synthesis of CNPs commonly involves demanding operation conditions and complex pre‐ or post‐treatments, which are time consuming and energy inefficient. Herein, a rapid, scalable, and universal strategy is reported to synthesize highly dispersed metal nanoparticles embedded in a carbon matrix via microwave irradiation of carbon black with preloaded precursors. By optimizing the amount of carbon black, the microwave absorption is dramatically improved while the thermal dissipation is effectively controlled, leading to a rapid temperature increase in carbon black, ramping to 1270 K in just 6 s. The whole synthesis process requires no capping agents or surfactants, nor tedious pre‐ or post‐treatments of carbon black, showing tremendous potential for mass production. As a proof of concept, the synthesis of ultrafine Ru nanoparticles (≈2.57 nm) uniformly embedded in carbon black using this microwave heating technique is demonstrated, which displays remarkable electrocatalytic performance when used as the cathode in a Li–O2 battery. This microwave heating method can be extended to the synthesis of other nanoparticles, thereby providing a general methodology for the mass production of carbon‐supported catalytic nanoparticles.

Bayesian Machine Learning in Metamaterial Design: Fragile Becomes Supercompressible

By Miguel A. Bessa, Piotr Glowacki, Michael Houlder from Wiley: Advanced Materials: Table of Contents. Published on Oct 14, 2019.

Bayesian machine learning can predict material behavior and quantify the uncertainty of those predictions, even in the presence of manufacturing imperfections. This means that computational data‐driven design of imperfection‐sensitive materials and structures becomes possible, replacing the typical experimental trial‐and‐error process. This paradigm shift is illustrated by transforming brittle materials into supercompressible metamaterials. Abstract Designing future‐proof materials goes beyond a quest for the best. The next generation of materials needs to be adaptive, multipurpose, and tunable. This is not possible by following the traditional experimentally guided trial‐and‐error process, as this limits the search for untapped regions of the solution space. Here, a computational data‐driven approach is followed for exploring a new metamaterial concept and adapting it to different target properties, choice of base materials, length scales, and manufacturing processes. Guided by Bayesian machine learning, two designs are fabricated at different length scales that transform brittle polymers into lightweight, recoverable, and supercompressible metamaterials. The macroscale design is tuned for maximum compressibility, achieving strains beyond 94% and recoverable strengths around 0.1 kPa, while the microscale design reaches recoverable strengths beyond 100 kPa and strains around 80%. The data‐driven code is available to facilitate future design and analysis of metamaterials and structures (https://github.com/mabessa/F3DAS).

[ASAP] Ferroelectric Domain Walls in PbTiO3 Are Effective Regulators of Heat Flow at Room Temperature

By Eric Langenberg*†‡, Dipanjan Saha§, Megan E. Holtz†?, Jian-Jun Wang?, David Bugallo‡, Elias Ferreiro-Vila‡, Hanjong Paik†, Isabelle Hanke#, Steffen Ganschow#, David A. Muller?, Long-Qing Chen?, Gustau Catalan?, Neus Domingo?, Jonathan Malen§, Darrell G. Schlom*†?, and Francisco Rivadulla*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Oct 14, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02991

[ASAP] Plasmonic Nanopores for Single-Molecule Detection and Manipulation: Toward Sequencing Applications

By Denis Garoli*†, Hirohito Yamazaki‡, Nicolo` Maccaferri§, and Meni Wanunu*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Oct 14, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02759

[ASAP] Photoinduced Surface Charging in Iron-Carbonyl-Functionalized Colloidal Semiconductor Nanocrystals

By Keith A. Schival, Robert R. Gipson, Keaton V. Prather, and Emily Y. Tsui* from Nano Letters: Latest Articles (ACS Publications). Published on Oct 14, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02726

[ASAP] Linearly Polarized Luminescence of Atomically Thin MoS2 Semiconductor Nanocrystals

By Andre´s Granados del A´guila†, Sheng Liu†, T. Thu Ha Do†, Zhuangchai Lai‡, Thu Ha Tran‡, Sean Ryan Krupp†, Zhi-Rui Gong¶, Hua Zhang‡§, Wang Yao?, and Qihua Xiong*†?# from ACS Nano: Latest Articles (ACS Publications). Published on Oct 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b05656

[ASAP] Colloidal Gelation in Liquid Metals Enables Functional Nanocomposites of 2D Metal Carbides (MXenes) and Lightweight Metals

By Vladislav Kamysbayev†, Nicole M. James†, Alexander S. Filatov†, Vishwas Srivastava†, Babak Anasori‡#, Heinrich M. Jaeger§, Yury Gogotsi‡, and Dmitri V. Talapin*†? from ACS Nano: Latest Articles (ACS Publications). Published on Oct 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b06207

[ASAP] Machine-Learning Analysis to Predict the Exciton Valley Polarization Landscape of 2D Semiconductors

By Kenya Tanaka, Kengo Hachiya, Wenjin Zhang, Kazunari Matsuda, and Yuhei Miyauchi* from ACS Nano: Latest Articles (ACS Publications). Published on Oct 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04220

A non-precious metal hydrogen catalyst in a commercial polymer electrolyte membrane electrolyser

By Thomas F. Jaramillo from Nature Nanotechnology - Issue - nature.com science feeds. Published on Oct 14, 2019.

Nature Nanotechnology, Published online: 14 October 2019; doi:10.1038/s41565-019-0550-7

A non-precious metal cobalt phosphide hydrogen evolution catalyst is found to be active and durable in a commercial-scale polymer electrolyte membrane electrolyser.

Origin of lithium whisker formation and growth under stress

By Chongmin Wang from Nature Nanotechnology - Issue - nature.com science feeds. Published on Oct 14, 2019.

Nature Nanotechnology, Published online: 14 October 2019; doi:10.1038/s41565-019-0558-z

Lithium whisker growth can be suppressed under mechanical constraints, as revealed by an experimental set-up combining an environmental transmission electron microscope and an atomic force microscope.

Soft dendritic microparticles with unusual adhesion and structuring properties

By Orlin D. Velev from Nature Materials - Issue - nature.com science feeds. Published on Oct 14, 2019.

Nature Materials, Published online: 14 October 2019; doi:10.1038/s41563-019-0508-z

Polymer precipitation under turbulent flows generates soft microparticles with branched dendritic coronas and high adhesive properties.

Shrewd detectives find a dissipation channel

By Bernd Gotsmann from Nature Materials - Issue - nature.com science feeds. Published on Oct 14, 2019.

Nature Materials, Published online: 14 October 2019; doi:10.1038/s41563-019-0509-y

The non-contact friction between a metal tip and a Bi2Se3 surface is controlled by a single charge in an image potential state.

Author Correction: Titanium-carbide MXenes for work function and interface engineering in perovskite solar cells

By A. Di Carlo from Nature Materials - Issue - nature.com science feeds. Published on Oct 14, 2019.

Nature Materials, Published online: 14 October 2019; doi:10.1038/s41563-019-0527-9

Author Correction: Titanium-carbide MXenes for work function and interface engineering in perovskite solar cells

Tetrahedral framework nucleic acids prevent retina ischemia-reperfusion injury from oxidative stress via activating the Akt/Nrf2 pathway

By XiaoXiao Cai from RSC - Nanoscale latest articles. Published on Oct 12, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR07171G, Paper
Xin Qin, Ni Li, Mei Zhang, Shiyu Lin, Junyao Zhu, Dexuan Xiao, Weitong Cui, Tianyi Zhang, Yunfeng Lin, XiaoXiao Cai
Retinal ischemia-reperfusion (I/R) injuries are involved in the universal pathological processes of many ophthalmic diseases, including glaucoma, diabetic retinopathy, and retinal arterial occlusion.
To cite this article before page numbers are assigned, use the DOI form of citation above.
The content of this RSS Feed (c) The Royal Society of Chemistry

Designed Patterning of Mesoporous Metal Films Based on Electrochemical Micelle Assembly Combined with Lithographical Techniques

By Hyunsoo Lim, Jeonghun Kim, Kenya Kani, Mostafa Kamal Masud, Hyeongyu Park, Minjun Kim, Saad M. Alsheri, Tansir Ahamad, Norah Alhokbany, Jongbeom Na, Victor Malgras, Yoshio Bando, Yusuke Yamauchi from Wiley: Small: Table of Contents. Published on Oct 11, 2019.

Patterned mesoporous metal films can be fabricated with photolithographic techniques. Not only can they be produced on various patterned substrates, but palladium and palladium–copper alloy pattern mesoporous films can also be fabricated. These patterned mesoporous metal films show high electrochemically‐active surface area and high sensitivity toward glucose oxidation applications. Abstract Mesoporous noble metals and their patterning techniques for obtaining unique patterned structures are highly attractive for electrocatalysis, photocatalysis, and optoelectronics device applications owing to their expedient properties such as high level of exposed active locations, cascade electrocatalytic sites, and large surface area. However, patterning techniques for mesoporous substrates are still limited to metal oxide and silica films, although there is growing demand for developing techniques related to patterning mesoporous metals. In this study, the first demonstration of mesoporous metal films on patterned gold (Au) substrates, prefabricated using photolithographic techniques, is reported. First, different growth rates of mesoporous Au metal films on patterned Au substrates are demonstrated by varying deposition times and voltages. In addition, mesoporous Au films are also fabricated on various patterns of Au substrates including stripe and mesh lines. An alternative fabrication method using a photoresist insulating mask also yields growth of mesoporous Au within the patterning. Moreover, patterned mesoporous films of palladium (Pd) and palladium–copper alloy (PdCu) are demonstrated on the same types of substrates to show versatility of this method. Patterned mesoporous Au films (PMGF) shows higher electrochemically‐active surface area (ECSA) and higher sensitivity toward glucose oxidation than nonpatterned mesoporous Au films (NMGF).

Microfluidics for Biosynthesizing: from Droplets and Vesicles to Artificial Cells

By Yongjian Ai, Ruoxiao Xie, Jialiang Xiong, Qionglin Liang from Wiley: Small: Table of Contents. Published on Oct 11, 2019.

The synthesis of artificial cells as a substitute for natural cells is of high significance for multidisciplinary applications and is currently being intensively pursued. High‐throughput, easy‐to‐operate, and controllable manufacturing of robust “alive” artificial cells has been achieved utilizing microfluidic techniques. Herein, the state‐of‐the art microfluidic‐based methods for the fabrication of droplets, vesicles, and artificial cells are summarized. Abstract Fabrication of artificial biomimetic materials has attracted abundant attention. As one of the subcategories of biomimetic materials, artificial cells are highly significant for multiple disciplines and their synthesis has been intensively pursued. In order to manufacture robust “alive” artificial cells with high throughput, easy operation, and precise control, flexible microfluidic techniques are widely utilized. Herein, recent advances in microfluidic‐based methods for the synthesis of droplets, vesicles, and artificial cells are summarized. First, the advances of droplet fabrication and manipulation on the T‐junction, flow‐focusing, and coflowing microfluidic devices are discussed. Then, the formation of unicompartmental and multicompartmental vesicles based on microfluidics are summarized. Furthermore, the engineering of droplet‐based and vesicle‐based artificial cells by microfluidics is also reviewed. Moreover, the artificial cells applied for imitating cell behavior and acting as bioreactors for synthetic biology are highlighted. Finally, the current challenges and future trends in microfluidic‐based artificial cells are discussed. This review should be helpful for researchers in the fields of microfluidics, biomaterial fabrication, and synthetic biology.

[ASAP] Spectroscopic Comparison of Thermal Transport at Organic–Inorganic and Organic-Hybrid Interfaces Using CsPbBr3 and FAPbBr3 (FA = Formamidinium) Perovskite Nanocrystals

By Benjamin T. Diroll†, Arun Mannodi-Kanakkithodi†, Maria K. Y. Chan†, and Richard D. Schaller*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Oct 11, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b03502

[ASAP] NanoRNP Overcomes Tumor Heterogeneity in Cancer Treatment

By Qi Liu†, Jinquan Cai§, Yadan Zheng†, Yanli Tan?, Yunfei Wang‡, Zhanzhan Zhang†, Chunxiong Zheng†, Yu Zhao†, Chaoyong Liu‡, Yingli An†, Chuanlu Jiang*§, Linqi Shi*†, Chunsheng Kang*‡, and Yang Liu*† from Nano Letters: Latest Articles (ACS Publications). Published on Oct 11, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02501

[ASAP] Microfluidic Sonication To Assemble Exosome Membrane-Coated Nanoparticles for Immune Evasion-Mediated Targeting

By Chao Liu†‡, Wei Zhang†‡, Yike Li†‡, Jianqiao Chang†, Fei Tian†‡, Fanghao Zhao†, Yao Ma†‡, and Jiashu Sun*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Oct 11, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02841

[ASAP] Anodic Imprint Lithography: Direct Imprinting of Single Crystalline GaAs with Anodic Stamp

By Kyunghwan Kim, Bugeun Ki, Keorock Choi, and Jungwoo Oh* from ACS Nano: Latest Articles (ACS Publications). Published on