skip to primary navigationskip to content

NanoManufacturing

Michael De Volder, Engineering Department - IfM

Studying at Cambridge

Nanoscience News

Optical Nanomaterials and Enabling Technologies for High‐Security‐Level Anticounterfeiting

By Wei Ren, Gungun Lin, Christian Clarke, Jiajia Zhou, Dayong Jin from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

Recent advances in the development of anticounterfeiting technologies are surveyed. It is demonstrated that lanthanide‐doped upconversion nanoparticles hold significant potential for developing next‐generation high‐level anticounterfeiting technologies. This is a result of synthesis scale‐up, their multidimensional optical properties, and design strategies to encrypt information. Engineering compact smartphone‐based decryption devices is a future trend for next‐generation anticounterfeiting technologies. Abstract Optical nanomaterials have been widely used in anticounterfeiting applications. There have been significant developments powered by recent advances in material science, printing technologies, and the availability of smartphone‐based decoding technology. Recent progress in this field is surveyed, including the availability of optical reflection, absorption, scattering, and luminescent nanoparticles. It is demonstrated that advances in the design and synthesis of lanthanide‐doped upconversion nanoparticles will lead to the next generation of anticounterfeiting technologies. Their tunable optical properties and optical responses to a range of external stimuli allow high‐security level information encoding. Challenges in the scale‐up synthesis of nanomaterials, engineering of assessorial devices for smart‐phone‐based decryption, and alignment to the potential markets which will lead to new directions for research, are discussed.

Horizontal Growth of Lithium on Parallelly Aligned MXene Layers towards Dendrite‐Free Metallic Lithium Anodes

By Di Zhang, Shuai Wang, Bin Li, Yongji Gong, Shubin Yang from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

A dendrite‐free lithium anode with good deep striping–plating up to 35 mAh cm−2 is achieved via parallelly aligned MXene (Ti3C2Tx ) layers. This not only allows the efficient guiding of lithium nucleation on the surface of MXene nanosheets, but also facilitates the horizontal growth of lithium on the MXene layers. Abstract Although metallic lithium is an extremely promising anode for lithium‐based batteries due to its high theoretical capacity, the uncontrollable growth of lithium dendrites, in particular under deep stripping and plating, have stagnated its application. It is demonstrated that parallelly aligned MXene (Ti3C2Tx ) layers enable the efficient guiding of lithium nucleation and growth on the surface of 2D MXene nanosheets, giving rise to horizontal‐growth lithium anodes. Moreover, the inherent fluorine terminations in MXene afford a uniform and durable solid electrolyte interface with lithium fluoride at the anode/electrolyte interface, efficiently regulating electromigration of lithium ions. Thus, a dendrite‐free lithium anode with a long cycle life up to 900 h and excellent deep stripping–plating capabilities up to 35 mAh cm−2 is achieved, which can further serve as an anode for a lithium metal battery, exhibiting high cycle stability up to 1000 cycles.

Fabrication of High‐Performance Silver Mesh for Transparent Glass Heaters via Electric‐Field‐Driven Microscale 3D Printing and UV‐Assisted Microtransfer

By Xiaoyang Zhu, Quan Xu, Hongke Li, Mingyang Liu, Zhenghao Li, Kun Yang, Jiawei Zhao, Lei Qian, Zilong Peng, Guangming Zhang, Jianjun Yang, Fei Wang, Dichen Li, Hongbo Lan from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

A high‐performance silver mesh fabrication technique is proposed for transparent glass heaters using electric‐field‐driven microscale 3D printing and a UV‐assisted microtransfer process. The silver mesh exhibits excellent photoelectric properties with Rs = 0.36 Ω sq−1 at T = 92%. Despite the mechanical robustness tests, adhesion fatigue, and operational stability tests, the comprehensive performance of silver mesh has hardly changed. Abstract Great challenges remain concerning the cost‐effective manufacture of high‐performance metal meshes for transparent glass heaters (TGHs). Here, a high‐performance silver mesh fabrication technique is proposed for TGHs using electric‐field‐driven microscale 3D printing and a UV‐assisted microtransfer process. The results show a more optimal trade‐off in sheet resistance (Rs = 0.21 Ω sq−1) and transmittance (T = 93.9%) than for indium tin oxide (ITO) and ITO substitutes. The fabricated representative TGH also exhibits homogeneous and stable heating performance, remarkable environmental adaptability (constant Rs for 90 days), superior mechanical robustness (Rs increase of only 0.04 in harsh conditions–sonication at 100 °C), and strong adhesion force with a negligible increase in Rs (2–12%) after 100 peeling tests. The practical viability of this TGH is successfully demonstrated with a deicing test (ice cube: 21 cm3, melting time: 78 s, voltage and glass thickness: 4 V, 5 mm). All of these advantages of the TGHs are attributed to the successful fabrication of silver meshes with high resolution and high aspect ratio on the glass substrate using the thick film silver paste. The proposed technique is a promising new tool for the inexpensive fabrication of high‐performance TGHs.

Perovskite Bifunctional Device with Improved Electroluminescent and Photovoltaic Performance through Interfacial Energy‐Band Engineering

By Jiangsheng Xie, Pengjie Hang, Han Wang, Shenghe Zhao, Ge Li, Yanjun Fang, Feng Liu, Xinlu Guo, Hepeng Zhu, Xinhui Lu, Xuegong Yu, Christopher C. S. Chan, Kam Sing Wong, Deren Yang, Jianbin Xu, Keyou Yan from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

A type of perovskite bifunctional device (PBD) with high photovoltaic (PV) and electroluminescence (EL) performance is developed. Interfacial energy‐band engineering between the perovskite and hole‐transport layer (HTL) is performed to turn the n‐type surface of perovskite into p‐type and also correct the misalignment to form a well‐defined N–I–P heterojunction. Abstract Currently, photovoltaic/electroluminescent (PV/EL) perovskite bifunctional devices (PBDs) exhibit poor performance due to defects and interfacial misalignment of the energy band. Interfacial energy‐band engineering between the perovskite and hole‐transport layer (HTL) is introduced to reduce energy loss, through adding corrosion‐free 3,3′‐(2,7‐dibromo‐9H‐fluorene‐9,9‐diyl) bis(n,n‐dimethylpropan‐1‐amine) (FN‐Br) into a HTL free of lithium salt. This strategy can turn the n‐type surface of perovskite into p‐type and thus correct the misalignment to form a well‐defined N–I–P heterojunction. The tailored PBD achieves a high PV efficiency of up to 21.54% (certified 20.24%) and 4.3% EL external quantum efficiency. Free of destructive additives, the unencapsulated devices maintain >92% of their initial PV performance for 500 h at maximum power point under standard air mass 1.5G illumination. This strategy can serve as a general guideline to enhance PV and EL performance of perovskite devices while ensuring excellent stability.

Nickel Nitride Particles Supported on 2D Activated Graphene–Black Phosphorus Heterostructure: An Efficient Electrocatalyst for the Oxygen Evolution Reaction

By Xiao Wang, Qiaoxia Li, Penghui Shi, Jinchen Fan, Yulin Min, Qunjie Xu from Wiley: Small: Table of Contents. Published on Jun 24, 2019.

A black phosphorus (BP)–activated graphene (AG) heterostructure is designed for supporting nickel nitride (Ni3N) to enhance the performance of oxygen evolution reaction (OER). The Ni3N/BP‐AG exhibits excellent electrocatalytic performance toward OER with low overpotential and small Tafel slope. It also shows remarkable stability with a retention rate of ≈86.4% OER activity after 10 000 s. Abstract Hydrogen is regarded as the most promising green clean energy in the 21st century. Developing the highly efficient and low‐cost electrocatalysts for oxygen evolution reaction (OER) is of great concern for the hydrogen industry. In the water electrolyzed reaction, the overpotential and the kinetics are the main hurdles for OER. Therefore, an efficient and durable oxygen evolution reaction electrocatalyst is required. In this study, an activated graphene (AG)–black phosphorus (BP) nanosheets hybrid is fabricated for supporting Ni3N particles (Ni3N/BP‐AG) in the application of OER. The Ni3N particles are combined with the BP‐AG heterostructure via facile mechanical ball milling under argon protection. The synthesized Ni3N/BP‐AG shows excellent catalytic performance toward the OER, demanding the overpotential of 233 mV for a current density of 10 mA cm−2 with a Tafel slope of 42 mV dec−1. The Ni3N/BP‐AG catalysts also show remarkable stability with a retention rate of the current density of about 86.4% after measuring for 10 000 s in potentiostatic mode.

Rectification of Mobile Leidenfrost Droplets by Planar Ratchets

By Jing Li, Xiaofeng Zhou, Yujie Zhang, Chonglei Hao, Fuwang Zhao, Minfei Li, Hui Tang, Wenjing Ye, Zuankai Wang from Wiley: Small: Table of Contents. Published on Jun 24, 2019.

2D planar ratchets are developed to enable the rectification of Leidenfrost droplets. Distinct from classic millimetric ratchets where the Leidenfrost droplet moves along the asymmetric ratchet, droplets on planar ratchets rely on both the individual features and their collective arrangements. This results in the varying droplet mobility ranging from 10 cm s−1 along the descending slope to −7 cm s−1 against the descending slope. Abstract The self‐transportation of mobile Leidenfrost droplets with well‐defined direction and velocity on millimetric ratchets is one of the most representative and spectacular phenomena in droplet dynamics. Despite extensive progress in the ability to control the spatiotemporal propagation of droplets, it remains elusive how the individual ratchet units, as well as the interactions within their arrays, are translated into the collective droplet dynamics. Here, simple planar ratchets characterized by uniform height normal to the surface are designed. It is revealed that on planar ratchets, the transport dynamics of Leidenfrost droplets is dependent not only on individual units, but also on the elegant coordination within their arrays dictated by their topography. The design of planar ratchets enriches the fundamental understanding of how the surface topography is translated into dynamic and collective droplet transport behaviors, and also imparts higher applicability in microelectromechanical system based fluidic devices.

Anisotropic Thermal Boundary Resistance across 2D Black Phosphorus: Experiment and Atomistic Modeling of Interfacial Energy Transport

By Man Li, Joon Sang Kang, Huu Duy Nguyen, Huan Wu, Toshihiro Aoki, Yongjie Hu from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

Energy transport across metal–2D material interfaces is systematically investigated and shows a highly anisotropic thermal boundary resistance (TBR). Experimental measurements and atomistic calculations of the interface thermal transport reveal detailed fundamental understanding of TBR–structure relationships. This study may open up new opportunities in the rational design and control of novel interface materials for advanced thermal management technologies. Abstract Interfacial thermal boundary resistance (TBR) plays a critical role in near‐junction thermal management of modern electronics. In particular, TBR can dominate heat dissipation and has become increasingly important due to the continuous emergence of novel nanomaterials with promising electronic and thermal applications. A highly anisotropic TBR across a prototype 2D material, i.e., black phosphorus, is reported through a crystal‐orientation‐dependent interfacial transport study. The measurements show that the metal–semiconductor TBR of the cross‐plane interfaces is 241% and 327% as high as that of the armchair and zigzag direction‐oriented interfaces, respectively. Atomistic ab initio calculations are conducted to analyze the anisotropic and temperature‐dependent TBR using density functional theory (DFT)‐derived full phonon dispersion relation and molecular dynamics simulation. The measurement and modeling work reveals that such a highly anisotropic TBR can be attributed to the intrinsic band structure and phonon spectral transmission. Furthermore, it is shown that phonon hopping between different branches is important to modulate the interfacial transport process but with directional preferences. A critical fundamental understanding of interfacial thermal transport and TBR–structure relationships is provided, which may open up new opportunities in developing advanced thermal management technology through the rational control over nanostructures and interfaces.

Extrinsic Green Photoluminescence from the Edges of 2D Cesium Lead Halides

By Chong Wang, Yanan Wang, Xinghua Su, Viktor G. Hadjiev, Shenyu Dai, Zhaojun Qin, Hector A. Calderon Benavides, Yizhou Ni, Qiang Li, Jie Jian, Md. Kamrul Alam, Haiyan Wang, Francisco C. Robles Hernandez, Yan Yao, Shuo Chen, Qingkai Yu, Guoying Feng, Zhiming Wang, Jiming Bao from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

Same‐spot Raman photoluminescence with two lasers in a diamond anvil cell under hydrostatic pressure reveals that CsPbBr3 nanocrystals, mostly located on the edges of CsPb2Br5 2D platelets, are responsible for CsPb2Br5's green emission. This sensitive noninvasive technique combining static and dynamic probes establishes a one‐to‐one property–structure relationship and distinguishes light emission from point defects versus nanoinclusions. Abstract Since the first report of the green emission of 2D all‐inorganic CsPb2Br5, its bandgap and photoluminescence (PL) origin have generated intense debate and remained controversial. After the discovery that PL centers occupy only specific morphological structures in CsPb2Br5, a two‐step highly sensitive and noninvasive optical technique is employed to resolve the controversy. Same‐spot Raman‐PL as a static property–structure probe reveals that CsPbBr3 nanocrystals are contributing to the green emission of CsPb2Br5; pressure‐dependent Raman‐PL with a diamond anvil cell as a dynamic probe further rules out point defects such as Br vacancies as an alternative mechanism. Optical absorption under hydrostatic pressure shows that the bandgap of CsPb2Br5 is 0.3–0.4 eV higher than previously reported values and remains nearly constant with pressure up to 2 GPa in good agreement with full‐fledged density functional theory (DFT) calculations. Using ion exchange of Br with Cl and I, it is further proved that CsPbBr3−x Xx (X = Cl or I) is responsible for the strong visible PL in CsPb2Br5−x Xx . This experimental approach is applicable to all PL‐active materials to distinguish intrinsic defects from extrinsic nanocrystals, and the findings pave the way for new design and development of highly efficient optoelectronic devices based on all‐inorganic lead halides.

Additive Manufacturing of 3D‐Architected Multifunctional Metal Oxides

By Daryl W. Yee, Max L. Lifson, Bryce W. Edwards, Julia R. Greer from Wiley: Advanced Materials: Table of Contents. Published on Jun 24, 2019.

Fabrication of 3D nanoarchitected multifunctional metal oxides is performed through a facile method using a metal‐ion‐containing aqueous photoresin, which is polymerized using two‐photon lithography and calcined to give the metal oxide structure. Zinc oxide microstructures, with submicrometer features, fabricated using this technique exhibit an electromechanical response that could enable the production of previously impossible 3D smart devices. Abstract Additive manufacturing (AM) of complex three‐dimensional (3D) metal oxides at the micro‐ and nanoscales has attracted considerable attention in recent years. State‐of‐the‐art techniques that use slurry‐based or organic–inorganic photoresins are often hampered by challenges in resin preparation and synthesis, and/or by the limited resolution of patterned features. A facile process for fabricating 3D‐architected metal oxides via the use of an aqueous metal‐ion‐containing photoresin is presented. The efficacy of this process, which is termed photopolymer complex synthesis, is demonstrated by creating nanoarchitected zinc oxide (ZnO) architectures with feature sizes of 250 nm, by first patterning a zinc‐ion‐containing aqueous photoresin using two‐photon lithography and subsequently calcining them at 500 ºC. Transmission electron microscopy (TEM) analysis reveals their microstructure to be nanocrystalline ZnO with grain sizes of 5.1 ± 1.6 nm. In situ compression experiments conducted in a scanning electron microscope show an emergent electromechanical response: a 200 nm mechanical compression of an architected ZnO structure results in a voltage drop of 0.52 mV. This photopolymer complex synthesis provides a pathway to easily create arbitrarily shaped 3D metal oxides that could enable previously impossible devices and smart materials.

Tue 25 Jun 13:30: PRECOG: PREdiction Conditioned On Goals in Visual Multi-Agent Settings Please note, this event may be recorded. Microsoft will own the copyright of any recording and reserves the right to distribute it as required.

From All Talks (aka the CURE list). Published on Jun 24, 2019.

PRECOG: PREdiction Conditioned On Goals in Visual Multi-Agent Settings

For autonomous vehicles (AVs) to behave appropriately on roads populated by human-driven vehicles, they must be able to reason about the uncertain intentions and decisions of other drivers from rich perceptual information. Towards these capabilities, we present a probabilistic forecasting model of future interactions of multiple agents. We perform both standard forecasting and conditional forecasting with respect to the AV’s goals. Conditional forecasting reasons about how all agents will likely respond to specific decisions of a controlled agent. We train our model on real and simulated data to forecast vehicle trajectories given past positions and LIDAR . Our evaluation shows that our model is substantially more accurate in multi-agent driving scenarios compared to existing state-of-the-art. Beyond its general ability to perform conditional forecasting queries, we show that our model’s predictions of all agents improve when conditioned on knowledge of the AV’s intentions, further illustrating its capability to model agent interactions.

Please note, this event may be recorded. Microsoft will own the copyright of any recording and reserves the right to distribute it as required.

Add to your calendar or Include in your list

Tue 08 Oct 14:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 24, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

[ASAP] Low Resistivity and High Breakdown Current Density of 10 nm Diameter van der Waals TaSe3 Nanowires by Chemical Vapor Deposition

By Thomas A. Empante†, Aimee Martinez†, Michelle Wurch†, Yanbing Zhu‡, Adane K. Geremew§, Koichi Yamaguchi†, Miguel Isarraraz†, Sergey Rumyantsev§?, Evan J. Reed‡, Alexander A. Balandin§, and Ludwig Bartels*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00958

[ASAP] Tunable Synthesis of Hollow Metal–Nitrogen–Carbon Capsules for Efficient Oxygen Reduction Catalysis in Proton Exchange Membrane Fuel Cells

By Hui Yang†‡, Xing Chen§, Wan-Ting Chen?, Qing Wang?, Nelly Cantillo Cuello?, Ayman Nafady#, Abdullah M. Al-Enizi#, Geoffrey I. N. Waterhouse*?, Gabriel A. Goenaga?, Thomas A. Zawodzinski?, Paul E. Kruger¶, John E. Clements?, Jian Zhang*†, He Tian*§, Shane G. Telfer*?, and Shengqian Ma*‡# from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02930

[ASAP] High Aspect Ratio ß-Ga2O3 Fin Arrays with Low-Interface Charge Density by Inverse Metal-Assisted Chemical Etching

By Hsien-Chih Huang†#, Munho Kim†#?, Xun Zhan‡, Kelson Chabak§, Jeong Dong Kim†, Alexander Kvit?, Dong Liu?, Zhenqiang Ma??, Jian-Min Zuo‡, and Xiuling Li*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01709

[ASAP] Application of Displacement-Current-Governed Triboelectric Nanogenerator in an Electrostatic Discharge Protection System for the Next-Generation Green Tire

By Wenjie Wu†‡, Tianxiao Yang†‡, Yuxin Zhang†‡, Feng Wang§, Qiuhai Nie§, Yong Ma§, Xia Cao*??, Zhong Lin Wang*?#, Ning Wang*?, and Liqun Zhang*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03427

[ASAP] Sensor-Instrumented Scaffold Integrated with Microporous Spongelike Ultrabuoy for Long-Term 3D Mapping of Cellular Behaviors and Functions

By Hyungjun Kim†?, Min Ku Kim†?, Hanmin Jang‡?, Bongjoong Kim§, Dong Rip Kim*‡, and Chi Hwan Lee*†§¥ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02291

[ASAP] Probing the in-Plane Near-Field Enhancement Limit in a Plasmonic Particle-on-Film Nanocavity with Surface-Enhanced Raman Spectroscopy of Graphene

By Danjun Liu†?, Tingting Wu‡?, Qiang Zhang§?, Ximiao Wang??, Xuyun Guo†, Yunkun Su?, Ye Zhu†, Minhua Shao?, Huanjun Chen?, Yu Luo‡, and Dangyuan Lei*†#¶ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00776

[ASAP] Ultrahigh-Performance Optoelectronics Demonstrated in Ultrathin Perovskite-Based Vertical Semiconductor Heterostructures

By Tiefeng Yang†‡#, Xiao Wang‡#, Biyuan Zheng†#, Zhaoyang Qi†#, Chao Ma†, Yuhao Fu§, Yongping Fu?, Matthew P. Hautzinger?, Ying Jiang‡, Ziwei Li†, Peng Fan‡, Fang Li‡, Weihao Zheng‡, Ziyu Luo†, Jie Liu?, Bin Yang†, Shula Chen†, Dong Li†, Lijun Zhang§, Song Jin?, and Anlian Pan*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02676

[ASAP] Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive Metal–Organic Frameworks

By Luming Yang†, Xin He†, and Mircea Dinca?* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04822

[ASAP] Correction to “Intrinsic Activity of Oxygen Evolution Catalysts Probed at Single CoFe2O4 Nanoparticles”

By Abdelilah El Arrassi, Zhibin Liu, Mathies V. Evers, Niclas Blanc, Georg Bendt, Sascha Saddeler, David Tetzlaff, Darius Pohl, Christine Damm, Stephan Schulz, and Kristina Tschulik* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06330

[ASAP] Correction to “Tuning the Reactivity of Difluoromethyl Sulfoximines from Electrophilic to Nucleophilic: Stereoselective Nucleophilic Difluoromethylation of Aryl Ketones”

By Xiao Shen, Wei Zhang, Chuanfa Ni, Yucheng Gu, and Jinbo Hu* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06390

[ASAP] Optimization of the Turnover in Artificial Enzymes via Directed Evolution Results in the Coupling of Protein Dynamics to Chemistry

By Joseph W. Schafer†, Ioanna Zoi†, Dimitri Antoniou, and Steven D. Schwartz* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04515

[ASAP] Elucidating the Growth of Metal–Organic Nanotubes Combining Isoreticular Synthesis with Liquid-Cell Transmisson Electron Microscopy

By Kristina M. Vailonis†‡, Karthikeyan Gnanasekaran§‡, Xian B. Powers†, Nathan C. Gianneschi*§, and David M. Jenkins*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04586

[ASAP] Correction to “Selective Formation of Yttrium Manganese Oxides through Kinetically Competent Assisted Metathesis Reactions”

By Paul K. Todd and James R. Neilson* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06496

[ASAP] Divergent Synthesis of Densely Substituted Arenes and Pyridines via Cyclotrimerization Reactions of Alkynyl Triazenes

By Jin-Fay Tan†, Carl T. Bormann‡, Florian G. Perrin‡, F. Mark Chadwick‡, Kay Severin*‡, and Nicolai Cramer*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 24, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04111

Long-term pulmonary exposure to multi-walled carbon nanotubes promotes breast cancer metastatic cascades

By Tao Zhu from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 24, 2019.

Nature Nanotechnology, Published online: 24 June 2019; doi:10.1038/s41565-019-0472-4

In a breast cancer animal model, long-term exposure to carbon nanotubes promotes tumour invasiveness and metastasis through activation of local and systemic inflammation.

Far-reaching effects from carbon nanotubes

By Iseult Lynch from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 24, 2019.

Nature Nanotechnology, Published online: 24 June 2019; doi:10.1038/s41565-019-0477-z

A single dose of carbon nanotubes enhances breast cancer metastasis in mouse models.

Shape-encoded dynamic assembly of mobile micromachines

By Metin Sitti from Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2019.

Nature Materials, Published online: 24 June 2019; doi:10.1038/s41563-019-0407-3

Mobile micromachines with advanced configurations and functions self-assembled through designed dielectrophoretic interactions between structural and motor units.

Long-term implant fibrosis prevention in rodents and non-human primates using crystallized drug formulations

By Daniel G. Anderson from Nature Materials - Issue - nature.com science feeds. Published on Jun 24, 2019.

Nature Materials, Published online: 24 June 2019; doi:10.1038/s41563-019-0377-5

Foreign body response can result in failure of biomaterials in vivo. Solvent-free crystals containing anti-fibrotic drugs now show the potential for long-term inhibition of fibrosis on a number of implantable devices in rodents and non-human primates.

Gold Nanoparticle Superlattice Monolayer with Tunable Interparticle Gap for Surface-Enhanced Raman Spectroscopy

By Jintao Zhu from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03590G, Paper
Huayang Wang, Ling Yao, Xi Mao, Ke Wang, Lihua Zhu, Jintao Zhu
Taking into account of near-field coupling interaction, non-close-packed two-dimensional nanoparticle (NP) assemblies with centimeter-scale and tunable interparticle gap (d) have attracted considerable attention due to their remarkably physicochemical properties, which...
The content of this RSS Feed (c) The Royal Society of Chemistry

Formation of silicate nanoscrolls through solvothermal treatment of layered octosilicate intercalated with organoammonium ions

By Kazuyuki Kuroda from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01651A, Paper
Yusuke Asakura, Megumi Sugihara, Takeru Hirohashi, Aya Torimoto, Takuya Matsumoto, Masakazu Koike, Yoshiyuki Kuroda, Hiroaki Wada, Atsushi Shimojima, Kazuyuki Kuroda
We report silicate nanoscrolls composed of only SiO4 tetrahedra with crystalline walls for the first time in this study. The procedure consists of the intercalation of layered octosilicate with dioctadecyldimethylammonium...
The content of this RSS Feed (c) The Royal Society of Chemistry

High-performance asymmetric supercapacitor electrode based on three-dimensional ZnMoO4/CoO nanohybrid on nickel foam High-performance asymmetric supercapacitor electrode based on three-dimensional ZnMoO4/CoO nanohybrid on nickel foam

By Yibing Xie from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03784E, Paper
Pengxi Li, Chaohui Ruan, Jing Xu, Yibing Xie
A two-step hydrothermal route was employed to fabricate ZnMoO4/CoO nanohybrid supported on Ni foam. The ZnMoO4/CoO nanohybrid shows a three-dimensional criss-crossed structure. The specific surface area is enhanced from 45...
The content of this RSS Feed (c) The Royal Society of Chemistry

Nanobiomaterials: from 0D to 3D for tumor therapy and tissue regeneration

By Chengtie Wu from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02955A, Review Article
Yaqin Liu, Qingqing Yu, Jiang Chang, Chengtie Wu
Nanobiomaterials have attracted tremendous attention in the biomedical field. Especially in the past few years, a large number of low dimensional nanobiomaterials, including 0D nanostructures, 1D nanotubes and 2D nanosheets,...
The content of this RSS Feed (c) The Royal Society of Chemistry

Electrochemical Exfoliation of Ultrathin Ternary Molybdenum Sulfoselenide Nanosheets to Boost Energy-efficient Hydrogen Evolution Reaction

By Yang Hou from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04587B, Communication
Jincheng Si, Hanlin Chen, Chaojun Lei, Yange Suo, Bin Yang, Zhiguo Zhang, Zhongjian Li, Lecheng Lei, Junhong Chen, Yang Hou
Developing low-cost and highly efficient transition metal dichalcogenides as alternative electrocatalysts has become an urgent need for hydrogen evolution reaction (HER). However, the inert basal planes of transition metal dichalcogenides...
The content of this RSS Feed (c) The Royal Society of Chemistry

Bio-inspired transparent structural color film and its application in biomimetic camouflage

By Shufen Zhang from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04360H, Paper
Zhipeng Meng, baoting Huang, Suli Wu, Lu Li, Shufen Zhang
The transparent wings of insets with intelligent structural colors or good invisibility at different surroundings provide them with a unique camouflage capability for protecting themselves and exchanging information. Inspired by...
The content of this RSS Feed (c) The Royal Society of Chemistry

An ultra-thin carbon-fabric/graphene/poly(vinylidene fluoride) film for enhanced electromagnetic interference shielding

By Kwok Siong Teh from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03603B, Paper
Xiaokang Mei, Longsheng Lu, Yingxi Xie, Wentao Wang, Yong Tang, Kwok Siong Teh
Highly conductive carbon-based fibrous composites have become one of the most sought-after components in electromagnetic interference (EMI) shielding field due to their excellent comprehensive performance. In this work, a flexible...
The content of this RSS Feed (c) The Royal Society of Chemistry

High Active (102) Surface Induced Rapid Degradation of CuS Nanotheranostic Platform for in Situ T1-weighted Magnetic Resonance Imaging Guided Synergistic Therapy

By Hongjie Zhang from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03830B, Paper
lile Dong, Kai Li, Ding Wen, Yu Lu, Kaimin Du, Manli Zhang, Xuan Gao, Jing Feng, Hongjie Zhang
Polyvinylpyrrolidone modified CuS nanocrystals (CuS NCs) with high photothermal conversion efficiency (46%), pH and near infrared (NIR) light-triggered degradation properties are promising nanotheranostic platform for in situ magnetic resonance imaging...
The content of this RSS Feed (c) The Royal Society of Chemistry

Understanding the role of aluminium on determining the surface structure and electrochemical performance of layered cathode

By Renchao Che from RSC - Nanoscale latest articles. Published on Jun 24, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02799H, Paper
Qi Liu, Yunhao Zhao, weiwei Liu, Meiyu Wang, Jingjun Ding, Yuzhang Feng, Wenbin You, Peng Wang, Pengfei Guan, Renchao Che
The electrochemical properties of layered cathodes could be enhanced by doping aluminium. However, the underlying mechanism of Al-ions behaviour is deficient, which obstructs further application. Herein, by adjusting the aluminium...
The content of this RSS Feed (c) The Royal Society of Chemistry

Thu 16 Jan 14:15: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 23, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Ultraefficient Conversion of CO2 into Morphology‐Controlled Nanocarbons: A Sustainable Strategy toward Greenhouse Gas Utilization

By Chu Liang, Liangbin Pan, Sheng Liang, Yang Xia, Zhiqiang Liang, Yongping Gan, Hui Huang, Jun Zhang, Wenkui Zhang from Wiley: Small: Table of Contents. Published on Jun 23, 2019.

A variety of nanocarbons with different morphology and porosity are successfully synthesized by water introduction, ball milling, or heating LiH‐CO2 at the low temperatures. The reactant of LiH can be regenerated through a two closed‐loop reaction process including five‐stage reactions. This new strategy opens up a new avenue in tackling the long‐term challenges of greenhouse effect and environmental problems. Abstract The ability to efficiently convert CO2 into nanocarbons at low temperatures is highly desirable, as it would enable the environmentally benign utilization of greenhouse gases, yet this remains a considerable challenge. Herein, a one‐step, ultrafast, and scalable strategy is demonstrated to efficiently convert CO2 into morphology‐controlled nanocarbons at low temperatures. The conversion reactions between CO2 and LiH are achieved in less than 30 s at moderate conditions by introducing a very small amount of water, ball milling, or heating. Nanocarbons featuring wildly tunable morphology with characteristic dimensions ranging from nanoscale to macroscale are successfully synthesized by controlling the CO2 pressure and the synthesis routes. The gas blowing velocity and its distribution are revealed as the main reasons for the CO2 pressure and synthesis route dependent morphology and porosity of nanocarbons. Moreover, a two closed‐loop reaction process including five‐stage reactions is proposed for nanocarbons synthesis and LiH regeneration. The strategy provides a new opportunity for efficient and environmentally benign nanocarbons synthesis.

Development of a Chemo‐ and Enantioselective Pd‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation of α‐Nitroesters

By Barry M. Trost, Johnathan E. Schultz, Yu Bai from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 23, 2019.

We describe the development of a Pd‐catalyzed decarboxylative asymmetric allylic alkylation of α‐nitro allyl esters to afford acyclic tetrasubstituted nitroalkanes. Optimization of the reaction parameters revealed unique ligand and solvent combinations crucial for achieving chemo‐ and enantioselective C‐alkylation of electronically challenging benzylic nitronates and sterically encumbered 2‐allyl esters. Substrates were efficiently accessed in a combinatorial fashion by a cross‐Claisen / α‐arylation sequence. The method provides functional group orthogonality that complements nucleophilic imine allylation strategies for α‐tertiary amine synthesis.

Biomimetic Omnidirectional Antireflective Glass via Direct Ultrafast Laser Nanostructuring

By Antonis Papadopoulos, Evangelos Skoulas, Alexandros Mimidis, George Perrakis, George Kenanakis, George D. Tsibidis, Emmanuel Stratakis from Wiley: Advanced Materials: Table of Contents. Published on Jun 23, 2019.

A novel single‐step and chemical‐free process for the fabrication of broadband, omnidirectional, antireflective glass, using laser nanostructuring, is demonstrated. Nanostructures are selectively textured on glass to mimic the morphology and the remarkable antireflection properties found on the Greta oto butterfly and Cicada wings. Bioinspired glass could revolutionize the antireflection technology and impact numerous applications, ranging from displays to optoelectronic devices. Abstract Here, a single‐step, biomimetic approach for the realization of omnidirectional transparent antireflective glass is reported. In particular, it is shown that circularly polarized ultrashort laser pulses produce self‐organized nanopillar structures on fused silica (SiO2). The laser‐induced nanostructures are selectively textured on the glass surface in order to mimic the spatial randomness, pillar‐like morphology, as well as the remarkable antireflection properties found on the wings of the glasswing butterfly, Greta oto, and various Cicada species. The artificial structures exhibit impressive antireflective properties, both in the visible and infrared frequency ranges, which are remarkably stable over time. Accordingly, the laser‐processed glass surfaces show reflectivity smaller than 1% for various angles of incidence in the visible spectrum for s–p linearly polarized configurations. However, in the near‐infrared spectrum, the laser‐textured glass shows higher transmittance compared to the pristine. It is envisaged that the current results will revolutionize the technology of antireflective transparent surfaces and impact numerous applications from glass displays to optoelectronic devices.

Rare‐Earth‐Element‐Ytterbium‐Substituted Lead‐Free Inorganic Perovskite Nanocrystals for Optoelectronic Applications

By Byung Joon Moon, Sang Jin Kim, Seungmin Lee, Aram Lee, Hyunjung Lee, Dong Su Lee, Tae‐Wook Kim, Seoung‐Ki Lee, Sukang Bae, Sang Hyun Lee from Wiley: Advanced Materials: Table of Contents. Published on Jun 23, 2019.

The rare‐earth element ytterbium (Yb) is substituted into the B site of a cubic ABX3 perovskite lattice in place of lead. The resulting CsYbI3 nanocrystals exhibit strong excitonic emission with high quantum yield and the potential for use in hybrid photodetectors as a photoactive layer. Such lead‐free CsYbI3 nanocrystals offer tremendous opportunities in optical and optoelectronic applications. Abstract Lead‐(Pb‐) halide perovskite nanocrystals (NCs) are interesting nanomaterials due to their excellent optical properties, such as narrow‐band emission, high photoluminescence (PL) efficiency, and wide color gamut. However, these NCs have several critical problems, such as the high toxicity of Pb, its tendency to accumulate in the human body, and phase instability. Although Pb‐free metal (Bi, Sn, etc.) halide perovskite NCs have recently been reported as possible alternatives, they exhibit poor optical and electrical properties as well as abundant intrinsic defect sites. For the first time, the synthesis and optical characterization of cesium ytterbium triiodide (CsYbI3) cubic perovskite NCs with highly uniform size distribution and high crystallinity using a simple hot‐injection method are reported. Strong excitation‐independent emission and high quantum yields for the prepared NCs are verified using photoluminescence measurements. Furthermore, these CsYbI3 NCs exhibit potential for use in organic–inorganic hybrid photodetectors as a photoactive layer. The as‐prepared samples exhibit clear on–off switching behavior as well as high photoresponsivity (2.4 × 103 A W−1) and external quantum efficiency (EQE, 5.8 × 105%) due to effective exciton dissociation and charge transport. These results suggest that CsYbI3 NCs offer tremendous opportunities in electronic and optoelectronic applications, such as chemical sensors, light emitting diodes (LEDs), and energy conversion and storage devices.

In vitro reconstitution of the biosynthetic pathway to the nitroimidazole antibiotic azomycin

By Katherine Ryan, Jason B. Hedges from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 23, 2019.

Nitroimidazoles are one of the most effective ways to treat anaerobic bacterial infections. Synthetic nitroimidazoles are inspired by the structure of azomycin, isolated from Streptomyces eurocidicus in 1953. Despite its foundational role, no biosynthetic gene cluster for azomycin has been found. Guided by bioinformatics, we identified a cryptic biosynthetic gene cluster in Streptomyces cattleya and then carried out in vitro reconstitution to deduce the enzymatic steps in the pathway linking L‐arginine to azomycin. The gene cluster we discover is widely distributed among soil‐dwelling actinobacteria and proteobacteria, suggesting that azomycin and related nitroimidazoles may play important ecological roles. Our work sets the stage for development of biocatalytic approaches to generate azomycin and related nitroimidazoles.

Engineering Donor‐acceptor Heterostructure Crystals for Photonic Logic Computation

By Xiao-Ting Liu, Kang Wang, Ze Chang, Ying-Hui Zhang, Jialiang Xu, Yong Sheng Zhao, Xian-He Bu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 23, 2019.

Photonic materials use photons as information carriers and offer the potential for unprecedented applications in optical and optoelectronic devices. Controllable photon manipulation can be achieved by construction of macroscopic crystalline heterostructures with tunable composition that can offer control over nanoscale structure and properties. In this study, we introduce a new strategy for photonic materials using metal‐organic frameworks (MOFs) as the host for the rational construction of donor‐acceptor (D‐A) heterostructure crystals. We have engineered a rich library of heterostructure crystals using the MOF NKU‐111 as a host. NKU‐111 is based upon an electron‐deficient tridentate ligand (acceptor, A) that can bind to various electron‐rich guests (donors, D). The resulting heterocrystals exhibit spatially segregated multi‐color emission resulting from the guest‐dependent charge‐transfer (CT) emission. In addition, the morphological characteristics of these crystalline D‐A heterostructures can be modulated based on their isotropic growth regularity. Spatially effective mono‐directional energy transfer has been achieved in these heterostructure crystals via rational design and tuning of the energy gradient between adjacent domains through the selection of donor guest molecules, which suggests potential applications in integrated optical circuit devices, e.g. photonic diodes, on‐chip signal processing, optical logic gates.

Wed 06 Nov 16:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 23, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Dirac-cone induced gating enhancement in single-molecule field-effect transistors

By Jianhui Liao from RSC - Nanoscale latest articles. Published on Jun 23, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01551E, Paper
Hantao Sun, Xunshan Liu, Yanjie Su, Bing Deng, Hailing Peng, Silvio Decurtins, Stefano Sanvito, Shi-Xia Liu, Shimin Hou, Jianhui Liao
Using graphene as electrodes provides an opportunity for fabricating stable single-molecule field-effect transistors (FETs) operating at room temperature. However, the role of the unique graphene band structure in charge transport...
The content of this RSS Feed (c) The Royal Society of Chemistry

Atomic‐Scale Insights into Surface Lattice Oxygen Activation at the Spinel/Perovskite interface of Co3O4/La0.3Sr0.7CoO3

By Xiyang Wang, Ziye Pan, Xuefeng Chu, Keke Huang, Yingge Cong, Rui Cao, Ritimukta Sarangi, Liping Li, Guangshe Li, Shouhua Feng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 22, 2019.

Emerging anionic redox chemistry has demonstrated that surface lattice oxygen in transition metal oxides plays a vital role in catalytic process. Mastering activation method of surface lattice oxygen and identifying activation mechanism at the atomic level are crucial for development and design of advanced catalysts. Herein, we develop a novel strategy that creating a spinel Co3O4/perovskite La0.3Sr0.7CoO3 interface by in‐situ reconstruction of surface Sr enrichment region in LSC to activate surface lattice oxygen. Experimentally, advanced XAS and XPS prove that the regulated chemical interface optimizes the hybridized orbital between Co 3d and O 2p and triggers more electrons in oxygen site of LSC transferred into lattice of Co3O4, leading to more inactive O2‐ transformed into active O2‐x. Furthermore, the activated Co3O4/LSC exhibits the best catalytic activities for CO oxidation, oxygen evolution and oxygen reduction. This work would provide a fundamental understanding to explain activation mechanism of surface oxygen sites.

Creation of well‐defined “mid‐sized” micropores in carbon molecular sieve membranes

By Yao Ma, Melinda L Jue, Fengyi Zhang, Ronita Mathias, Hye Youn Jang, Ryan Lively from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 22, 2019.

Carbon molecular sieve (CMS) membranes are candidates for the separation of organic molecules due to their stability, ability to be scaled at practical form factors, and the avoidance of expensive supports or complex multi‐step fabrication processes. A critical challenge is the creation of “mid‐range” (e.g., 5‐9 Å) microstructures that allow for facile permeation of organic solvents and selection between similarly‐sized guest molecules. Here, we create these microstructures via the pyrolysis of a microporous polymer (PIM‐1) under low concentrations of hydrogen gas. The introduction of H2 inhibits aromatization of the decomposing polymer and ultimately results in the creation of a well‐defined bimodal pore network that exhibits an ultramicropore size of 5.1 Å. The H2 assisted CMS dense membranes show a dramatic increase in p‐xylene ideal permeability (~15 times), with little loss in p‐xylene/o‐xylene selectivity (18.8 vs. 25.0) when compared to PIM‐1 membranes pyrolyzed under a pure argon atmosphere. This approach is successfully extended to hollow fiber membranes operating in organic solvent reverse osmosis mode, highlighting the potential of this approach to be translated from the laboratory to the field.

[ASAP] Ultrahigh Hot Carrier Transient Photocurrent in Nanocrystal Arrays by Auger Recombination

By Jianbo Gao?†‡#, Lyran Kidon?†§, Eran Rabani*†§?, and A. Paul Alivisatos*†‡§? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 22, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02374

[ASAP] Electron Compensation Effect Suppressed Silver Ion Release and Contributed Safety of Au@Ag Core–Shell Nanoparticles

By Yanlin Feng†‡, Guorui Wang§, Yun Chang†, Yan Cheng†, Bingbing Sun?, Liming Wang*?, Chunying Chen?, and Haiyuan Zhang*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 22, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01293

[ASAP] Correction to Electronic Modulation of Near-Field Radiative Transfer in Graphene Field Effect Heterostructures

By Nathan H. Thomas, Michelle C. Sherrott, Jeremy Broulliet, Harry A. Atwater, and Austin J. Minnich* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 22, 2019.

Nano Letters
DOI: 10.1021/acs.nanolett.9b02390

[ASAP] High-Performance and Rapid-Response Electrical Heaters Based on Ultraflexible, Heat-Resistant, and Mechanically Strong Aramid Nanofiber/Ag Nanowire Nanocomposite Papers

By Zhonglei Ma*†, Songlei Kang†, Jianzhong Ma*‡, Liang Shao†, Ajing Wei†, Chaobo Liang§, Junwei Gu*§, Bin Yang‡, Diandian Dong‡, Linfeng Wei‡, and Zhanyou Ji‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 22, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00434

[ASAP] Strand Breaks Induced by Very Low Energy Electrons: Product Analysis and Mechanistic Insight into the Reaction with TpT

By Ghazal Khorsandgolchin, Le´on Sanche, Pierre Cloutier, and J. Richard Wagner* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03295

[ASAP] Hierarchical Nanoassembly of MoS2/Co9S8/Ni3S2/Ni as a Highly Efficient Electrocatalyst for Overall Water Splitting in a Wide pH Range

By Yan Yang†, Huiqin Yao‡, Zihuan Yu†, Saiful M. Islam§?, Haiying He?, Mengwei Yuan†, Yonghai Yue#, Kang Xu#, Weichang Hao#, Genban Sun†, Huifeng Li†, Shulan Ma*†§, Peter Zapol*?, and Mercouri G. Kanatzidis*§? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 22, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04492

Salt induced silk gel derived N and trace Fe co-doped 3D porous carbon as oxygen reduction catalyst in microbial fuel cells

By Jianquan Shen from RSC - Nanoscale latest articles. Published on Jun 22, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03778K, Paper
Jianting Liu, Liling Wei, Chun Cao, Fengtao Zhang, Fengzheng Lang, Huiqiang Wang, Haijun Yang, Jianquan Shen
Less expensive and high-efficiency oxygen reduction reaction (ORR) catalysts played a great role in achieving the practical application of microbial fuel cells (MFCs). Hence, we synthesised a novel nitrogen (N)...
The content of this RSS Feed (c) The Royal Society of Chemistry

A Phase Regulation Strategy of Ammonium Ions Perovskite Nanocrystals from 1D Orthomorphic NH4PbI3 to 3D Cubic Phase by Cs Ions to Notedly Enhance Photoluminescence

By Chao Wang, Yue Liu, Xia Feng, Chenyang Zhou, Yalan Liu, Xi Yu, Guangjiu Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

In this work, we firstly synthesized 1D orthogonal NH4PbI3 perovskite NCs with considering the role of inorganic ammonium ions at the nanoscale. It can be found that the addition of bromide ions at the halogen site cannot improve the photoluminescence properties. Furthermore, we successfully synthesized 3D cubic phase of (NH4)0.5Cs0.5Pb(I0.5Br0.5)3 NCs with bright photoluminescence by adding Cs ions into the crystal lattice of (NH4)Pb(I0.5Br0.5)3. Moreover, the photophysical properties are obtained of different phase structures using femtosecond transient absorption (FTA) spectroscopy. The obvious ultrafast trap state capture process is a key factor in the change of photoluminescence properties and the cubic phase may be the best structure for photoluminescence. These results suggest that the ammonium ions perovskite (AIP) nanocrystals could be potential materials for optoelectronic applications through A‐site cation substitution strategy.

The Road Towards Planar Microbatteries and Micro‐Supercapacitors: From 2D to 3D Device Geometries

By Shuanghao Zheng, Xiaoyu Shi, Pratteek Das, Zhong‐Shuai Wu, Xinhe Bao from Wiley: Advanced Materials: Table of Contents. Published on Jun 21, 2019.

The development of and recent advances in planar microbatteries and micro‐supercapacitors from the fundamentals and design principle to 2D and 3D planar microdevices in both in‐plane and stacked geometries are highlighted. Additonally, a comprehensive analysis of the aspects that eventually affect the performance metrics of microscale energy storage devices, such as electrode materials, electrolyte, device architecture, and microfabrication techniques are explored. Abstract The rapid development and further modularization of miniaturized and self‐powered electronic systems have substantially stimulated the urgent demand for microscale electrochemical energy storage devices, e.g., microbatteries (MBs) and micro‐supercapacitors (MSCs). Recently, planar MBs and MSCs, composed of isolated thin‐film microelectrodes with extremely short ionic diffusion path and free of separator on a single substrate, have become particularly attractive because they can be directly integrated with microelectronic devices on the same side of one single substrate to act as a standalone microsized power source or complement miniaturized energy‐harvesting units. The development of and recent advances in planar MBs and MSCs from the fundamentals and design principle to the fabrication methods of 2D and 3D planar microdevices in both in‐plane and stacked geometries are highlighted. Additonally, a comprehensive analysis of the primary aspects that eventually affect the performance metrics of microscale energy storage devices, such as electrode materials, electrolyte, device architecture, and microfabrication techniques are presented. The technical challenges and prospective solutions for high‐energy‐density planar MBs and MSCs with multifunctionalities are proposed.

Nanostructured Back Reflectors for Efficient Colloidal Quantum‐Dot Infrared Optoelectronics

By Se‐Woong Baek, Pau Molet, Min‐Jae Choi, Margherita Biondi, Olivier Ouellette, James Fan, Sjoerd Hoogland, F. Pelayo Arquer, Agustín Mihi, Edward H. Sargent from Wiley: Advanced Materials: Table of Contents. Published on Jun 21, 2019.

A colloidal quantum‐dot solar cell with a patterned organic hole‐transport layer responsible for efficient light trapping in the near infrared is presented. The designed nano‐imprinted organic structure gives the device efficient backscattering electrodes that lead to a 22% power conversion efficiency increase, achieving power conversion efficiencies of 1.34% in the near infrared, beyond Si absorption. Abstract Colloidal quantum dots (CQDs) can be used to extend the response of solar cells, enabling the utilization of solar power that lies to the red of the bandgap of c‐Si and perovskites. To achieve largely complete absorption of infrared (IR) photons in CQD solids requires thicknesses on the micrometer range; however, this exceeds the typical diffusion lengths (≈300 nm) of photoexcited charges in these materials. Nanostructured metal back electrodes that grant the cell efficient IR light trapping in thin active layers with no deterioration of the electrical properties are demonstrated. Specifically, a new hole‐transport layer (HTL) is developed and directly nanostructured. Firstly, a material set to replace conventional rigid HTLs in CQD devices is developed with a moldable HTL that combines the mechanical and chemical requisites for nanoimprint lithography with the optoelectronic properties necessary to retain efficient charge extraction through an optically thick layer. The new HTL is nanostructured in a 2D lattice and conformally coated with MoO3/Ag. The photonic structure in the back electrode provides a record photoelectric conversion efficiency of 86%, beyond the Si bandgap, and a 22% higher IR power conversion efficiency compared to the best previous reports.

Lead Selenide (PbSe) Colloidal Quantum Dot Solar Cells with >10% Efficiency

By Waqar Ahmad, Jungang He, Zhitian Liu, Ke Xu, Zhuang Chen, Xiaokun Yang, Dengbing Li, Yong Xia, Jianbing Zhang, Chao Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 21, 2019.

Highly air‐stable PbSe colloidal quantum dots (CQDs) are produced via an in situ chloride and cadmium passivation technique. A high‐quality film is fabricated using solution‐phase ligand exchange and a one‐step deposition method. By using a PbS‐EDT hole‐transporting layer, a PbI2‐capped PbSe‐CQD‐based photovoltaic device shows a record efficiency of 10.68% with impressive air and light soaking stability. Abstract Low‐cost solution‐processed lead chalcogenide colloidal quantum dots (CQDs) have garnered great attention in photovoltaic (PV) applications. In particular, lead selenide (PbSe) CQDs are regarded as attractive active absorbers in solar cells due to their high multiple‐exciton generation and large exciton Bohr radius. However, their low air stability and occurrence of traps/defects during film formation restrict their further development. Air‐stable PbSe CQDs are first synthesized through a cation exchange technique, followed by a solution‐phase ligand exchange approach, and finally absorber films are prepared using a one‐step spin‐coating method. The best PV device fabricated using PbSe CQD inks exhibits a reproducible power conversion efficiency of 10.68%, 16% higher than the previous efficiency record (9.2%). Moreover, the device displays remarkably 40‐day storage and 8 h illuminating stability. This novel strategy could provide an alternative route toward the use of PbSe CQDs in low‐cost and high‐performance infrared optoelectronic devices, such as infrared photodetectors and multijunction solar cells.

Iridium‐Catalyzed Direct C4‐ and C7‐Selective Alkynylation of Indoles Using Sulfur‐Directing Groups

By Chandrababu Naidu Kona, Yuji Nishii, Masahiro Miura from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

S‐directed: An iridium‐catalyzed direct alkynylation for the indole C4‐ and C7‐positions was achieved with the assistance of sulfur directing groups. The transformation shows broad functional‐group tolerance with complete site selectivity, and the directing group can be either easily removed or transformed after the reaction. Abstract Indoles and their analogues have been one of the most ubiquitous heterocycles during the past century, and extensive studies have been conducted to establish practical synthetic methods for their derivatives. In particular, selective functionalization of the poorly reactive benzenoid core over the pyrrole ring has been a great challenge. Reported herein is an iridium‐catalyzed direct alkynylation of the indole C4‐ and C7‐positions with the assistance of sulfur directing groups. This transformation shows a wide range of functional‐group tolerance with exceptional site selectivity. The directing group can be either easily removed or transformed after catalysis. The synthetic utility of the alkyne fragment is demonstrated by the derivatization into the core structure of natural indole alkaloids.

Interplay between Short‐ and Long‐Ranged Forces Leading to the Formation of Ag Nanoparticle Superlattice

By Jaewon Lee, Elias Nakouzi, Dongdong Xiao, Zhigang Wu, Miao Song, Colin Ophus, Jaehun Chun, Dongsheng Li from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

The self‐assembly process of Ag nanoparticles is observed by in situ liquid transmission electron microscopy. The Ag nanoparticles self‐assembleinto a superlattice with short separation distance (

Revealing the distribution of metal carboxylates in oil paint from the micro‐ to nanoscale

By Xiao Ma, Victoria Beltran, Georg Ramer, Georges Pavlidis, Dilworthy Y. Parkinson, Mathieu Thoury, Tyler Meldrum, Andrea Centrone, Barbara Berrie from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

Oil paints comprise pigments, drying oils and additives that together confer desirable properties, but can react to form metal carboxylates (soaps) that may damage artworks over time. To obtain information on soap formation and aggregation, we introduce a new tapping‐mode measurement paradigm for the photothermal induced resonance (PTIR) technique that enables nanoscale IR spectroscopy and imaging on highly heterogenous and rough paint thin sections. PTIR is used in combination with µ‐computed tomography and IR microscopy to determine the distribution of metal carboxylates in a 23‐year old oil paint of known formulation. Results show that heterogeneous agglomerates of Al‐stearate and a Zn‐carboxylate complex with Zn‐stearate nano‐aggregates in proximity are distributed randomly in the paint. The gradients of zinc carboxylates are unrelated to the Al‐stearate distribution. These measurements open a new chemically sensitive nanoscale observation window on the distribution of metal soaps that can bring insights for understanding soap formation in oil paint.

In situ coupling of single molecules driven by Au‐catalyzed electrooxidation

By Yaping Zang, Ilana Stone, Michael Inkpen, Fay Ng, Tristan Lambert, Colin Nuckolls, Michael L. Steigerwald, Xavier Roy, Latha Venkataraman from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

Understanding how chemical bonds are formed and broken is the foundation of molecular design. Observing these processes in individual molecules promises levels of detail and precision beyond those achieved through traditional ensemble techniques. Here we develop a single‐molecule method based on the scanning tunneling microscope (STM) to selectively couple a series of aniline derivatives and create azobenzenes. The Au‐catalyzed oxidative coupling is driven by the local electrochemical potential at the nanostructured Au STM tip. The products are detected in situ by measuring the conductance and molecular junction elongation and compared with analogous measurements of the expected azobenzene derivatives prepared ex situ. This approach is robust, and it can quickly and reproducibly assess reactions for a variety of anilines. We further demonstrate the selective synthesis of geometric isomers and the assembly of complex molecular architectures by sequential coupling of complementary anilines demonstrating unprecedented control over bond formation at the nanoscale.

Thu 04 Jul 14:30: Aromatic foldamer based protein mimicry and recognition

From Materials Chemistry Research Interest Group. Published on Jun 21, 2019.

Aromatic foldamer based protein mimicry and recognition

Abstract not available

Add to your calendar or Include in your list

Thu 04 Jul 14:30: Aromatic foldamer based protein mimicry and recognition

From All Talks (aka the CURE list). Published on Jun 21, 2019.

Aromatic foldamer based protein mimicry and recognition

Abstract not available

Add to your calendar or Include in your list

Rhodium‐Catalyzed Asymmetric Intramolecular Hydroamination of Allenes

By Dino Berthold, Arne G. A. Geissler, Sabrina Giofré, Bernhard Breit from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

A rhodium‐catalyzed asymmetric intramolecular hydroamination of sulfonyl amides with terminal allenes provides enantioselective access to 5‐ and 6‐membered N‐heterocycles, scaffolds found in a wide variety of bioactive molecules. Moreover, gram scale reactions and transformations of suitable products into natural products or key intermediates thereof are demonstrated. Abstract The rhodium‐catalyzed asymmetric intramolecular hydroamination of sulfonyl amides with terminal allenes is reported. It provides selective access to 5‐ and 6‐membered N‐heterocycles, scaffolds found in a large range of different bioactive compounds. Moreover, gram scale reactions, as well as the application of suitable product transformations to natural products and key intermediates thereof are demonstrated.

Alternating Array Stacking of Ag26Au and Ag24Au Nanoclusters

By Lizhong He, Zibao Gan, Nan Xia, Lingwen Liao, Zhikun Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

A double nanocluster ion compound (DNIC) was synthesized that has a unique alternating stacking array of the cationic and anionic nanoclusters. A single nanocluster ion compound (SNIC), exhibiting a k‐vector‐differential crystallographic arrangement, was also obtained. The notable packing differences among the DNIC and the new and the existing SNICs indicate the dramatic influence of ligands and counterions on crystallographic arrangement. Abstract An assembly strategy for metal nanoclusters using electrostatic interactions with weak interactions, such as C−H⋅⋅⋅π and π⋅⋅⋅π interactions in which cationic [Ag26Au(2‐EBT)18(PPh3)6]+ and anionic [Ag24Au(2‐EBT)18]− nanoclusters gather and assemble in an unusual alternating array stacking structure is presented. [Ag26Au(2‐EBT)18(PPh3)6]+ [Ag24Au(2‐EBT)18]− is a new compound type, a double nanocluster ion compound (DNIC). A single nanocluster ion compound (SNIC) [PPh4]+ [Ag24Au(2‐EBT)18]− was also synthesized, having a k‐vector‐differential crystallographic arrangement. [PPh4]+ [Ag24Au(2,4‐DMBT)18]− adopts a different assembly mode from both [Ag26Au(2‐EBT)18(PPh3)6]+ [Ag24Au(2‐EBT)18]− and [PPh4]+ [Ag24Au(2‐EBT)18]−. Thus, the striking packing differences of [Ag26Au(2‐EBT)18(PPh3)6]+ [Ag24Au(2‐EBT)18]−, [PPh4]+ [Ag24Au(2‐EBT)18]− and the existing [PPh4]+ [Ag24Au(2,4‐DMBT)18]− from each other indicate the notable influence of ligands and counterions on the self‐assembly of nanoclusters.

Bioinspired Oxidative Cyclization of the Geissoschizine Skeleton for Enantioselective Total Synthesis of Mavacuran Alkaloids

By Maxime Jarret, Victor Turpin, Aurélien Tap, Jean‐François Gallard, Cyrille Kouklovsky, Erwan Poupon, Guillaume Vincent, Laurent Evanno from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

Skeleton assembly: The long‐standing problem of effecting the bioinspired oxidative cyclization of geissoschizine to the mavacuran skeleton has been resolved. The key N1−C16 bond was formed by locking in the cis conformation through quaternization of the aliphatic nitrogen atom, and allowed the total syntheses of (+)‐taberdivarine H, (+)‐16‐hydroxymethyl‐pleiocarpamine, and (+)‐16‐epi‐pleiocarpamine, and their postulated biosynthetic precursor 16‐formyl‐pleiocarpamine. Abstract Reported is the enantioselective total syntheses of mavacuran alkaloids, (+)‐taberdivarine H, (+)‐16‐hydroxymethyl‐pleiocarpamine, and (+)‐16‐epi‐pleiocarpamine, and their postulated biosynthetic precursor 16‐formyl‐pleiocarpamine. This family of monoterpene indole alkaloids is a target of choice since some of its members are subunits of intricate bisindole alkaloids such as bipleiophylline. Inspired by the biosynthetic hypothesis, an oxidative coupling approach from the geissoschizine framework to form the N1−C16 bond was explored. Quaternization of the aliphatic nitrogen center was key to achieving the oxidative coupling induced by KHMDS/I2 as it masks the nucleophilicity of the aliphatic nitrogen center and locks in the required cis conformation.

Dissipative Catalysis with a Molecular Machine

By Chiara Biagini, Stephen D. P. Fielden, David A. Leigh, Fredrik Schaufelberger, Stefano Di Stefano, Dean Thomas from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

An out‐of‐equilibrium state of a synthetic molecular machine is used to control catalysis. A rotaxane is transiently converted from a catalytically inactive state into an active form by CCl3CO2H. Deprotonation by the rotaxane promotes decarboxylation of the acid, thereby returning the system to its original state and stopping catalysis. This process allows temporal control of a coupled biomimetic reduction reaction. Abstract We report on catalysis by a fuel‐induced transient state of a synthetic molecular machine. A [2]rotaxane molecular shuttle containing secondary ammonium/amine and thiourea stations is converted between catalytically inactive and active states by pulses of a chemical fuel (trichloroacetic acid), which is itself decomposed by the machine and/or the presence of additional base. The ON‐state of the rotaxane catalyzes the reduction of a nitrostyrene by transfer hydrogenation. By varying the amount of fuel added, the lifetime of the rotaxane ON‐state can be regulated and temporal control of catalysis achieved. The system can be pulsed with chemical fuel several times in succession, with each pulse activating catalysis for a time period determined by the amount of fuel added. Dissipative catalysis by synthetic molecular machines has implications for the future design of networks that feature communication and signaling between the components.

An Isolable Silicon Analogue of a Ketone that Contains an Unperturbed Si=O Double Bond

By Ryo Kobayashi, Shintaro Ishida, Takeaki Iwamoto from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

Silicon analogues of ketones have remained elusive for more than 150 years. In their Communication (DOI: 10.1002/anie.201905198), T. Iwamoto and co‐workers report the first synthesis of an isolable silicon analogue of a ketone that exhibits a three‐coordinate silicon center and an unperturbed Si=O bond. This genuine silanone does not require coordination of Lewis bases and acids or the introduction of electron‐donating groups to stabilize the Si=O bond.

Key Role of Microtubule and Its Acetylation in a Zinc Oxide Nanoparticle–Mediated Lysosome–Autophagy System

By Jia Liu, Yiyuan Kang, Suhan Yin, Aijie Chen, Junrong Wu, Huimin Liang, Longquan Shao from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

The lysosome–autophagy system is debated utilizing zinc oxide nanoparticles (ZNPs). Lysosome‐based autophagic degradation is halted after ZNPs treatment, accompanied by blockage of lysophagy, which renews impaired lysosomes. The microtubule (MT) system participates in ZNP‐induced lysosome–autophagy system changes, especially in the fusion between autophagosomes and lysosomes. Moreover, MT acetylation is necessary for protecting from ZNP‐induced MT disruption. Abstract Autophagy is a biological process that has attracted considerable attention as a target for novel therapeutics. Recently, nanomaterials (NMs) have been reported to modulate autophagy, which makes them potential agents for the treatment of autophagy‐related diseases. In this study, zinc oxide nanoparticles (ZNPs) are utilized to evaluate NM‐induced autophagy and debate the mechanisms involved. It is found that ZNPs undergo pH‐dependent ion shedding and that intracellular zinc ions (Zn2+) play a crucial role in autophagy. Autophagy is activated with ZNPs treatment, which is inhibited after Zn2+ sequestration via ethylenediamine tetra‐acetic acid. Lysosome‐based autophagic degradation is halted after ZNPs treatment for more than 3 h and is accompanied by blockage of lysophagy, which renews impaired lysosomes. Furthermore, the microtubule (MT) system participates in ZNP‐induced lysosome–autophagy system changes, especially in the fusion between autophagosomes and lysosomes. MT acetylation is helpful for protecting from ZNP‐induced MT disruption, and it promotes the autophagic degradation process. In conclusion, this study provides valuable information on NM‐induced lysosome–autophagy system changes, particularly with respect to the role of lysophagy and the MT system, which point to some attractive targets for the design of engineered nanoparticles.

Improving Polysulfides Adsorption and Redox Kinetics by the Co4N Nanoparticle/N‐Doped Carbon Composites for Lithium‐Sulfur Batteries

By Kuikui Xiao, Jin Wang, Zhen Chen, Yuhong Qian, Zheng Liu, Lili Zhang, Xiaohua Chen, Jilei Liu, Xiaofeng Fan, Ze Xiang Shen from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

A highly efficient conductive network consisting of the metal–organic framework derived N‐doped porous carbon embedded with Co4N nanoparticles is prepared by a one‐step synthesis process. The uniform distribution of Co4N nanoparticles, the strong connection between Co4N and carbon matrix, and the catalytic effect of Co4N on the polysulfides redox boost the electrochemical performance significantly. Abstract Improved conductivity and suppressed dissolution of lithium polysulfides is highly desirable for high‐performance lithium‐sulfur (Li‐S) batteries. Herein, by a facile solvent method followed by nitridation with NH3, a 2D nitrogen‐doped carbon structure is designed with homogeneously embedded Co4N nanoparticles derived from metal organic framework (MOF), grown on the carbon cloth (MOF‐Co4N). Experimental results and theoretical simulations reveal that Co4N nanoparticles act as strong chemical adsorption hosts and catalysts that not only improve the cycling performance of Li‐S batteries via chemical bonding to trap polysulfides but also improve the rate performance through accelerating the conversion reactions by decreasing the polarization of the electrode. In addition, the high conductive nitrogen‐doped carbon matrix ensures fast charge transfer, while the 2D structure offers increased pathways to facilitate ion diffusion. Under the current density of 0.1C, 0.5C, and 3C, MOF‐Co4N delivers reversible specific capacities of 1425, 1049, and 729 mAh g−1, respectively, and retains 82.5% capacity after 400 cycles at 1C, as compared to the sample without Co4N (MOF‐C) values of 61.3% (200 cycles). The improved cell performance corroborates the validity of the multifunctional design of MOF‐Co4N, which is expected to be a potentially promising cathode host for Li‐S batteries.

A New Memristor with 2D Ti3C2Tx MXene Flakes as an Artificial Bio‐Synapse

By Xiaobing Yan, Kaiyang Wang, Jianhui Zhao, Zhenyu Zhou, Hong Wang, Jingjuan Wang, Lei Zhang, Xiaoyan Li, Zuoao Xiao, Qianlong Zhao, Yifei Pei, Gong Wang, Cuiya Qin, Hui Li, Jianzhong Lou, Qi Liu, Peng Zhou from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Two‐dimensional (2D) Ti3C2Tx is used as the functional layer of a memristor. Ti vacancies and partial oxidation are proposed as the origins of the physical mechanism of resistive switching behavior. The resistance can be modulated under the pulse sequence with 10 ns pulse width. On the nanosecond scale, the transition from short‐term plasticity to long‐term plasticity is achieved. Abstract Two‐dimensional (2D) materials have attracted extensive research interest in academia due to their excellent electrochemical properties and broad application prospects. Among them, 2D transition metal carbides (Ti3C2Tx) show semiconductor characteristics and are studied widely. However, there are few academic reports on the use of 2D MXene materials as memristors. In this work, reported is a memristor based on MXene Ti3C2Tx flakes. After electroforming, Al/Ti3C2Tx/Pt devices exhibit repeatable resistive switching (RS) behavior. More interestingly, the resistance of this device can be continuously modulated under the pulse sequence with 10 ns pulse width, and the pulse width of 10 ns is much lower than that in other reported work. Moreover, on the nanosecond scale, the transition from short‐term plasticity to long‐term plasticity is achieved. These two properties indicate that this device is favorable for ultrafast biological synapse applications and high‐efficiency training of neural networks. Through the exploration of the microstructure, Ti vacancies and partial oxidation are proposed as the origins of the physical mechanism of RS behavior. This work reveals that 2D MXene Ti3C2Tx flakes have excellent potential for use in memristor devices, which may open the door for more functions and applications.

Nanosilica‐Confined Synthesis of Orthogonally Active Catalytic Metal Nanocrystals in the Compartmentalized Carbon Framework

By Seon Hee Lee, Nitee Kumari, Soumen Dutta, Xing Jin, Amit Kumar, Jung Hun Koo, In Su Lee from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

A highly customizable nanosilica‐mediated and chemically directed confined endotemplating strategy toward compartmentalized carbon‐based nanocatalytic platforms for efficient cascade and multimodal catalytic reactions. Abstract Multifunctionalized porous catalytic nanoarchitectures are highly desirable for a variety of chemical transformations; however, selective installation of different catalysts with spatial and functional precision working synergistically and predictably, is highly challenging. Here, a synthetic strategy is developed toward the customizable combination of orthogonally reactive metal nanocrystals within interconnected carbon‐cavities as a compartmentalized framework by employing aminated‐silica‐directed thermal solid‐state nanoconfined synthesis of metal nanocrystals and endotemplating concomitant carbonization‐mediated interlocking, as key processes. The main advantage of the strategy is the facility to choose any combination of metals, which can be further employed according to the desired application. The strategically synthesized compartmentalized multifunctional catalytic architectures of Pd‐Pt@Com‐CF regulate the O2‐mediated selective cascade oxidation reaction converting alcohol to acid with high yield and selectivity; and another Pt‐Ir@Com‐CF platform is demonstrated as a bifunctional electrocatalyst for oxygen reduction/evolution reactions.

Independent Blue and Red Light Triggered Narcissistic Self‐Sorting Self‐Assembly of Colloidal Particles

By Oya Ilke Sentürk, Elizaveta Chervyachkova, Yuhao Ji, Seraphine V. Wegner from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Two different types of colloids self‐assemble orthogonally either under blue or red light and reversibly disassemble in the dark. Further, in a mixture these colloids self‐sort into separate clusters, a behavior known as narcissistic self‐sorting. This concept will allow for the assembly of addressable and adaptable materials into higher order tissue‐like structures. Abstract The ability of living systems to self‐sort different cells into separate assemblies and the ability to independently regulate different structures are one ingredient that gives rise to their spatiotemporal complexity. Here, this self‐sorting behavior is replicated in a synthetic system with two types of colloidal particles; where each particle type independently self‐assembles either under blue or red light into distinct clusters, known as narcissistic self‐sorting. For this purpose, each particle type is functionalized either with the light‐switchable protein VVDHigh or Cph1, which homodimerize under blue and red light, respectively. The response to different wavelengths of light and the high specificity of the protein interactions allows for the independent self‐assembly of each particle type with blue or red light and narcissistic self‐sorting. Moreover, as both of the photoswitchable protein interactions are reversible in the dark; also, the self‐sorting is reversible and dynamic. Overall, the independent blue and red light controlled self‐sorting in a synthetic system opens new possibilities to assemble adaptable, smart, and advanced materials similar to the complexity observed in tissues.

Fluorinated Polymer Mediated Transmucosal Peptide Delivery for Intravesical Instillation Therapy of Bladder Cancer

By Guangzhi Li, Qifang Lei, Fei Wang, Dashi Deng, Shupeng Wang, Longlong Tian, Wanwan Shen, Yiyun Cheng, Zhuang Liu, Song Wu from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

The fluorinated polymers like fluorinated polyethylenimine (F‐PEI) could be a promising type of transmucosal drug delivery carrier, which dramatically enhances cross‐membrane, transmucosal and intratumoral penetration abilities of peptides, and enables the effective use of peptide‐based therapeutics. This work extends the biomedical application of fluorinated polymers toward more clinically relevant directions, particularly promising for intravesical instillation therapy to treat bladder cancer. Abstract Surgical intervention combined with intravesical instillation of chemotherapeutics to clear residual cancer cells after operation is the current standard treatment method for bladder cancer. However, the poor bioavailability of active pharmaceutical ingredients for bladder cancer cells on account of the biological barriers of bladder mucosa, together with significant side effects of currently used intravesical medicine, have limited the clinical outcomes of localized adjuvant therapy for bladder cancer. Aiming at improved intravesical instillation therapy of bladder cancer, a fluorinated polyethylenimine (F‐PEI) is employed here for the transmucosal delivery of an active venom peptide, polybia‐mastoparan I (MPI), which shows selective antiproliferative effect against various bladder cancer cell lines. Upon simple mixing, MPI and F‐PET would coassemble to form stable nanoparticles, which show greatly improved cross‐membrane and transmucosal penetration capacities compared with MPI alone or nonfluorinated MPI/PEI nanoparticles. MPI/F‐PEI shows higher in vivo tumor growth inhibition efficacy for local treatment of a subcutaneous tumor model. More excitingly, as further demonstrated in an orthotopic bladder cancer model, MPI/F‐PEI offers remarkably improved therapeutic effects compared to those achieved by free MPI or the first‐line bladder cancer drug mitomycin C. This work presents a new transmucosal delivery carrier particularly promising for intravesical instillation therapy of bladder cancer.

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array

By Mohammad Mahdi Tavakoli, Hadi Tavakoli Dastjerdi, Jiayuan Zhao, Katherine E. Shulenberger, Chiara Carbonera, Riccardo Po, Alessandra Cominetti, Gabriele Bianchi, Nathan D. Klein, Moungi G. Bawendi, Silvija Gradecak, Jing Kong from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Light management using ZnO nanowire arrays and an antireflection layer can improve the absorption of organic semiconductors and enhance the performance of organic photovoltaics. Abstract Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as‐deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air‐stable active‐layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water‐repellent ability of the OPV device.

A Mussel‐Inspired Persistent ROS‐Scavenging, Electroactive, and Osteoinductive Scaffold Based on Electrochemical‐Driven In Situ Nanoassembly

By Ting Zhou, Liwei Yan, Chaoming Xie, Pengfei Li, Lili Jiang, Ju Fang, Cancan Zhao, Fuzeng Ren, Kefeng Wang, Yingbo Wang, Hongping Zhang, Tailin Guo, Xiong Lu from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

An electroactive, antioxidative, cell affinitive, and osteoinductive polypyrrole‐polydopamine‐hydroxyapatite (PPy‐PDA‐HA) film is prepared on porous scaffolds through a layer‐by‐layer pulse electrodeposition (LBL‐PED) method. During LBL‐PED, the PPy‐PDA nanoparticles (NPs) and HA NPs are in situ‐synthesized and uniformly assembled on the scaffolds from inside to outside. Abstract Conductive polymers are promising for bone regeneration because they can regulate cell behavior through electrical stimulation; moreover, they are antioxidative agents that can be used to protect cells and tissues from damage originating from reactive oxygen species (ROS). However, conductive polymers lack affinity to cells and osteoinductivity, which limits their application in tissue engineering. Herein, an electroactive, cell affinitive, persistent ROS‐scavenging, and osteoinductive porous Ti scaffold is prepared by the on‐surface in situ assembly of a polypyrrole‐polydopamine‐hydroxyapatite (PPy‐PDA‐HA) film through a layer‐by‐layer pulse electrodeposition (LBL‐PED) method. During LBL‐PED, the PPy‐PDA nanoparticles (NPs) and HA NPs are in situ synthesized and uniformly coated on a porous scaffold from inside to outside. PDA is entangled with and doped into PPy to enhance the ROS scavenging rate of the scaffold and realize repeatable, efficient ROS scavenging over a long period of time. HA and electrical stimulation synergistically promote osteogenic cell differentiation on PPy‐PDA‐HA films. Ultimately, the PPy‐PDA‐HA porous scaffold provides excellent bone regeneration through the synergistic effects of electroactivity, cell affinity, and antioxidative activity of the PPy‐PDA NPs and the osteoinductivity of HA NPs. This study provides a new strategy for functionalizing porous scaffolds that show great promise as implants for tissue regeneration.

Highly Porous Microcarriers for Minimally Invasive In Situ Skeletal Muscle Cell Delivery

By Ranjith Kumar Kankala, Jia Zhao, Chen‐Guang Liu, Xiao‐Jie Song, Da‐Yun Yang, Kai Zhu, Shi‐Bin Wang, Yu Shrike Zhang, Ai‐Zheng Chen from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Highly open porous microspheres (HOPMs) are conveniently designed using a microfluidic setup and evaluated for their feasibility toward minimally invasive cell delivery‐based tissue regeneration. These biocompatible HOPMs with interconnected paths facilitate a high cell proliferation rate, and partial differentiation of skeletal myoblasts. These modular cells‐laden microcarriers provide a convenient means for in situ repair of tissue defects and applications in regenerative medicine. Abstract Microscale cell carriers have recently garnered enormous interest in repairing tissue defects by avoiding substantial open surgeries using implants for tissue regeneration. In this study, the highly open porous microspheres (HOPMs) are fabricated using a microfluidic technique for harboring proliferating skeletal myoblasts and evaluating their feasibility toward cell delivery application in situ. These biocompatible HOPMs with particle sizes of 280–370 µm possess open pores of 10–80 µm and interconnected paths. Such structure of the HOPMs conveniently provide a favorable microenvironment, where the cells are closely arranged in elongated shapes with the deposited extracellular matrix, facilitating cell adhesion and proliferation, as well as augmented myogenic differentiation. Furthermore, in vivo results in mice confirm improved cell retention and vascularization, as well as partial myoblast differentiation. These modular cell‐laden microcarriers potentially allow for in situ tissue construction after minimally invasive delivery providing a convenient means for regeneration medicine.

Facile One Step Formation and Screening of Tumor Spheroids Using Droplet‐Microarray Platform

By Anna A. Popova, Tina Tronser, Konstantin Demir, P. Haitz, Karolina Kuodyte, Vytaute Starkuviene, Piotr Wajda, Pavel A. Levkin from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

In the current study, the Droplet Microarray platform utilizing hydrophilic–superhydrophobic micropatterns is used in combination with the method of hanging droplet for the formation of single‐spheroid‐microarrays. Formation of spheroids from several commonly used cell lines and on‐chip drug treatment is demonstrated. Established methodology can be adopted for miniaturized high‐throughput compound screenings using physiologically relevant 3D spheroids. Abstract Tumor spheroids or microtumors are important 3D in vitro tumor models that closely resemble a tumor's in vivo “microenvironment” compared to 2D cell culture. Microtumors are widely applied in the fields of fundamental cancer research, drug discovery, and precision medicine. In precision medicine tumor spheroids derived from patient tumor cells represent a promising system for drug sensitivity and resistance testing. Established and commonly used platforms for routine screenings of cell spheroids, based on microtiter plates of 96‐ and 384‐well formats, require relatively large numbers of cells and compounds, and often lead to the formation of multiple spheroids per well. In this study, an application of the Droplet Microarray platform, based on hydrophilic–superhydrophobic patterning, in combination with the method of hanging droplet, is demonstrated for the formation of highly miniaturized single‐spheroid‐microarrays. Formation of spheroids from several commonly used cancer cell lines in 100 nL droplets starting with as few as 150 cells per spheroid within 24–48 h is demonstrated. Established methodology carries a potential to be adopted for routine workflows of high‐throughput compound screening in 3D cancer spheroids or microtumors, which is crucial for the fields of fundamental cancer research, drug discovery, and precision medicine.

Schottky Barrier‐Controlled Black Phosphorus/Perovskite Phototransistors with Ultrahigh Sensitivity and Fast Response

By Xuming Zou, Yuanzhe Li, Guanqi Tang, Peng You, Feng Yan from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

High‐responsive photodetection of 2D layered materials can be achieved by employing a photogating mechanism. However, the corresponding response time is rather slow. Here, a Schottky barrier‐controlled phototransistor is reported. A fast response is obtained via a field‐assisted detrapping process of electrons in the perovskite layer. This provides the feasibility to achieve high‐performance photodetectors with both high responsivity and fast response time. Abstract Phototransistors are recognized as highly sensitive photodetectors owing to their high gain induced by a photogating effect. However, the response speed of a typical phototransistor is rather slow due to the long lifetime of trapped carriers in the channel. Here, a novel Schottky barrier‐controlled phototransistor that shows ultrahigh sensitivity as well as a fast response speed is reported. The device is based on a channel of few‐layer black phosphorous modified with a MAPbI3−xClx perovskite layer, whose channel current is limited by the Schottky barrier at the source electrode. The photoresponse speed of the device can be tuned by changing the drain voltage, which is attributed to a field‐assisted detrapping process of electrons in the perovskite layer close to the Schottky barrier. Under optimal conditions, the device exhibits a high responsivity of 106–108 A W−1, an ultrahigh specific detectivity up to 9 × 1013 Jones, and a response time of ≈10 ms.

3D Patternable Supercapacitors from Hierarchically Architected Porous Fiber Composites for Wearable and Waterproof Energy Storage

By Jianfeng Wen, Bingang Xu, Jinyun Zhou, Jiangtao Xu, Yuejiao Chen from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

3D patternable supercapactors (SCs) with a hierarchical architecture are designed and realized by decorating polypyrrole nanowires arrays and pseudocapacitive NiCoSe2 nanoparticles onto porous graphite felt fibers. Laser engraving and silicone sealing techniques are then employed for fabricating and encapsulating the SCs with various patterns, showing both stable electrochemical performance and effective waterproof properties. Abstract High‐performance wearable supercapactors (SCs) are gaining prominence as portable energy storage devices. To further enhance both energy and power density, the significant relationship between structure and performance inspires a delicate design of 3D patternable supercapacitors with a hierarchical architecture of porous conductive fibers composited with pseudocapacitive materials. In this work, the polypyrrole nanowires arrays decorated 3D graphite felt fiber assembly is initially fabricated as the conductive scaffold, followed by the distribution of the highly conductive and pseudocapacitive NiCoSe2 nanoparticles. Moreover, to realize the goal of standardized batch and pattern processing of the wearable SCs, laser engraving and silicone sealing techniques are employed, and SC devices with different patterns are successfully fabricated and encapsulated. Notably, the resulting SCs exhibit both stable electrochemical performance and effective waterproof properties, with the highest specific capacitance of 5.21 F cm−3 (113.36 F g−1) at the current density of 0.025 A cm−3 (0.5 F g−1), and the highest energy density of 1.09 mWh cm−3 (22.14 Wh kg−1) at a power density of 16.5 mW cm−3 (358.7 W kg−1).

Masthead: (Small 25/2019)

By from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Cell Delivery: Highly Porous Microcarriers for Minimally Invasive In Situ Skeletal Muscle Cell Delivery (Small 25/2019)

By Ranjith Kumar Kankala, Jia Zhao, Chen‐Guang Liu, Xiao‐Jie Song, Da‐Yun Yang, Kai Zhu, Shi‐Bin Wang, Yu Shrike Zhang, Ai‐Zheng Chen from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

In article number 1901397, Yu Shrike Zhang, Ai‐Zheng Chen, and co‐workers develop a new method for protein structure analysis. Atom probe tomography (APT) is used to simultaneously asses the 3D structure and chemical composition of proteins with high resolution. The key concept of the method is to embed proteins in an amorphous silicon oxide glass, from which ultra‐sharp needles are prepared and analyzed with APT.

MXene‐Based Nanocomposites: Surface Modified MXene‐Based Nanocomposites for Electrochemical Energy Conversion and Storage (Small 25/2019)

By Hong Yu, Yonghui Wang, Yao Jing, Jianmin Ma, Cheng‐Feng Du, Qingyu Yan from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

In article number 1901503, Cheng‐Feng Du, Qingyu Yan, and co‐workers summarize the recent developments of the synthesis methods, surface modification strategies, and the energy conversion and storage (ECS) applications of MXene materials. A comprehensive discussion is offered on the surface chemistry of this newly developed material family, which has a significant connection with the design and synthesis of MXene‐based heterostructures.

Compartmentalization: Nanosilica‐Confined Synthesis of Orthogonally Active Catalytic Metal Nanocrystals in the Compartmentalized Carbon Framework (Small 25/2019)

By Seon Hee Lee, Nitee Kumari, Soumen Dutta, Xing Jin, Amit Kumar, Jung Hun Koo, In Su Lee from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

In article number 1901280, In Su Lee and co‐workers develop a synthetic strategy toward customizable nanospatial grouping of orthogonally reactive nanocatalysts within interconnected carbon‐cavities as a compartmentalized framework, employing aminated‐silica‐directed thermal solid‐state nanoconfined nanocrystals synthesis and endotemplating concomitant carbonization‐mediated interlocking. The utility of the compartmentalized system shows an efficient cascade oxidation of cinnamyl alchohol → cinnamaldehyde → cinnamic acid using Pd and Pt catalytic nanocrystals (NCs), and also oxygen reduction reaction and oxygen evolution reaction using Pt and Ir NCs.

Alternatives to Cryogenic Distillation: Advanced Porous Materials in Adsorptive Light Olefin/Paraffin Separations

By Yuxiang Wang, Shing Bo Peh, Dan Zhao from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Adsorptive light olefin/paraffin separations facilitated by advanced porous materials such as zeolites and metal–organic frameworks are reviewed. Different separation mechanisms realized in these materials are highlighted, and constructive perspectives on future directions of the field are provided. Abstract As primary feedstocks in the petrochemical industry, light olefins such as ethylene and propylene are mainly obtained from steam cracking of naphtha and short chain alkanes (ethane and propane). Due to their similar physical properties, the separations of olefins and paraffins—pivotal processes to meet the olefin purity requirement of downstream processing—are typically performed by highly energy‐intensive cryogenic distillation at low temperatures and high pressures. To reduce the energy input and save costs, adsorptive olefin/paraffin separations have been proposed as promising techniques to complement or even replace cryogenic distillation, and growing efforts have been devoted to developing advanced adsorbents to fulfill this challenging task. In this Review, a holistic view of olefin/paraffin separations is first provided by summarizing how different processes have been established to leverage the differences between olefins and paraffins for effective separations. Subsequently, recent advances in the development of porous materials for adsorptive olefin/paraffin separations are highlighted with an emphasis on different separation mechanisms. Last, a perspective on possible directions to push the limit of the research in this field is presented.

Surface Modified MXene‐Based Nanocomposites for Electrochemical Energy Conversion and Storage

By Hong Yu, Yonghui Wang, Yao Jing, Jianmin Ma, Cheng‐Feng Du, Qingyu Yan from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Recently, MXenes have gained increasing attention in the field of energy conversion and storage (ECS). Meanwhile, the unique surface chemistry of MXenes endows them with great potential in the construction of 2D based nanocomposites. To this end, the present work offers a comprehensive summary of surface modified MXene‐based nanocomposites for ECS applications. Abstract In recent years, the rapidly growing attention on MXenes makes the material a rising star in the 2D materials family. Although most researchers' interests are still focused on the properties of bare MXenes, little attention has been paid to the surface chemistry of MXenes and MXene‐based nanocomposites. To this end, this Review offers a comprehensive discussion on surface modified MXene‐based nanocomposites for energy conversion and storage (ECS) applications. Based on the structure and reaction mechanism, the related synthesis methods toward MXenes are briefly summarized. After the discussion of existing surface modification techniques, the surface modified MXene‐based nanocomposites and their inherent chemical principles are presented. Finally, the application of these surface modified nanocomposites for supercapacitors (SCs), lithium/sodium–ion batteries (LIBs/SIBs), and electrocatalytic water splitting is discussed. The challenges and prospects of MXene‐based nanocomposites for future ECS applications are also presented.

Self‐Assembled Columnar Triazole‐Quartets ‐ an example of synergetic H‐bonding / Anion‐π Channels

By Shao-Ping Zheng, Yu-Hao Li, Ji-Jun Jiang, Arie van der Lee, Dan Dumitrescu, Mihail Barboiu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

The self‐assembly of triazole‐amphiphiles has been examined in homogenous solution, in the solid state and in bilayer membranes. Single‐crystal X‐ray diffraction structures show that stacked protonated Triazole‐quartets‐T4 quartets are mutually stabilized by strong regognition with two inner anions. Anion H‐ bonding / ion‐pairing recognition are combined with anion‐π recognition to produce columnar T4 architectures, resulted through anion‐π interactions between anions and triazole moieties of vicinal T4 quartets. In bilayer membranes, low transport activity is observed when the T4 channels are operated as H+/X‐ translocators, but higher transport activity is observed when X‐ translocation was performed in the presence of K+‐carrier valinomycin. The channel results are interpreted as arising from discrete stacks of T‐quartets where transport of anions would occur through the supramolecular macrocycles. These self‐assembled anion channels presenting amazing structural behaviors, directionality, strong anion encapsulation via H‐bonding supported with vicinal anion‐π interactions are proposed as artificial supramolecular channels that transport anions across lipid bilayer membranes.

Cyclobis(7,8‐(para‐quinodimethane)‐4,4'‐triphenylamine) and Its Cationic Species Showing Annulene‐like Global (Anti)Aromaticity

By Shaoqiang Dong, Tullimilli Y. Gopalakrishna, Yi Han, Chunyan Chi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

π‐Conjugated macrocycles containing all‐benzenoid rings usually show local aromaticity, but herein we report that a macrocycle (CBQT) containing alternating para‐quinodimethane and triphenylamine units displayed annulene‐like anti‐aromaticity at low temperatures due to structural rigidity and participation in π‐conjugation of the bridging nitrogen atoms. It was facilely synthesized by intermolecular Friedel‐Crafts alkylation followed by oxidative dehydrogenation. X‐ray crystallographic structures of CBQT as well as its dication, trication and tetracation were obtained. The dication and tetracation exhibited global aromaticity and antiaromaticity, respectively, as confirmed by NMR measurements and theoretic calculations. Both the dication and tetracation possess open‐shell singlet ground state, with a small singlet‐triplet gap.

Harvesting the Vibration Energy of BiFeO3 Nanosheets for Hydrogen Evolution

By huilin you, Zheng Wu, Luohong Zhang, Yiran Ying, Yan Liu, Linfeng Fei, Xinxin Chen, Yanmin Jia, Yaojin Wang, Feifei Wang, Sheng Ju, Jinli Qiao, Chi-Hang Lam, Haitao Huang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 21, 2019.

Vibration is one of the most prevalent energy sources in natural environment. Here, in this study, mechanical vibration is used for hydrogen generation and decomposition of dye molecules, with the help of BiFeO3 (BFO) square nanosheets. A high hydrogen production rate of ~124.1 µmol/g is achieved under mechanical vibration (100 W) for 1h at the resonant frequency of the BFO nanosheets. The decomposition ratio of Rhodamine B dye is up to ~94.1% after mechanically vibrating the BFO catalyst for 50 min. The vibration induced catalysis of the BFO square nanosheets may be attributed to the piezo‐catalytic properties of BFO and the high specific surface area of the nanosheets. The uncompensated piezoelectric charges on the surfaces of BFO nanosheets induced by mechanical vibration result in a built‐in electric field across the nanosheets. Unlike a photocatalyst for water splitting, which requires a proper band edge position for hydrogen evolution, such a requirement is not needed in piezo‐catalytic water splitting, where the band tilting under the induced piezoelectric field will make the conduction band of BFO more negative than the H2/H2O redox potential (0 V) for hydrogen generation. The observed piezo‐catalytic properties of BFO nanosheets pave the way towards a non‐toxic, highly efficient and sustainable technology for hydrogen generation or dye decomposition through harvesting waste vibration energy from the environment.

High‐Density Sb2Te3 Nanopillars Arrays by Templated, Bottom‐Up MOCVD Growth

By Raimondo Cecchini, Raja S. R. Gajjela, Christian Martella, Claudia Wiemer, Alessio Lamperti, Lucia Nasi, Laura Lazzarini, Luca G. Nobili, Massimo Longo from Wiley: Small: Table of Contents. Published on Jun 21, 2019.

Sb2Te3 nanostructures are grown by metal organic chemical vapor deposition (MOCVD) to form dense arrays: 20 nm single‐crystal Sb2Te3 nanopillars are grown by MOCVD inside high density (5 × 1010 cm−2) pores of aluminum oxide membranes. High‐density forests of freestanding Sb2Te3 nanopillars are also obtained. These methods can be used for different chalcogenide alloys and substrates. Abstract Sb2Te3 exhibits several technologically relevant properties, such as high thermoelectric efficiency, topological insulator character, and phase change memory behavior. Improved performances are observed and novel effects are predicted for this and other chalcogenide alloys when synthetized in the form of high‐aspect‐ratio nanostructures. The ability to grow chalcogenide nanowires and nanopillars (NPs) with high crystal quality in a controlled fashion, in terms of their size and position, can boost the realization of novel thermoelectric, spintronic, and memory devices. Here, it is shown that highly dense arrays of ultrascaled Sb2Te3 NPs can be grown by metal organic chemical vapor deposition (MOCVD) on patterned substrates. In particular, crystalline Sb2Te3 NPs with a diameter of 20 nm and a height of 200 nm are obtained in Au‐functionalized, anodized aluminum oxide (AAO) templates with a pore density of ≈5 × 1010 cm−2. Also, MOCVD growth of Sb2Te3 can be followed either by mechanical polishing and chemical etching to produce Sb2Te3 NPs arrays with planar surfaces or by chemical dissolution of the AAO templates to obtain freestanding Sb2Te3 NPs forests. The illustrated growth method can be further scaled to smaller pore sizes and employed for other MOCVD‐grown chalcogenide alloys and patterned substrates.

Fri 30 Aug 13:00: T cell tolerance: new thoughts on an old issue Hosted by Gillian Griffiths, Speaker Jonathan Sprent, Garvan Institute of Medical Research

From All Talks (aka the CURE list). Published on Jun 21, 2019.

T cell tolerance: new thoughts on an old issue

Abstract not available

Hosted by Gillian Griffiths, Speaker Jonathan Sprent, Garvan Institute of Medical Research

Add to your calendar or Include in your list

Fri 19 Jul 13:00: TBC Hosted by Andres Floto, Speaker Mihaela van der Schaar, The Alan Turing Institute

From All Talks (aka the CURE list). Published on Jun 21, 2019.

TBC

Abstract not available

Hosted by Andres Floto, Speaker Mihaela van der Schaar, The Alan Turing Institute

Add to your calendar or Include in your list

Fri 05 Jul 13:00: Comparative transcriptomics identifies a single SNP mutation that controls virulence of African Salmonella Hosted by Leo James, Speaker Jay Hinton, University of Liverpool

From All Talks (aka the CURE list). Published on Jun 21, 2019.

Comparative transcriptomics identifies a single SNP mutation that controls virulence of African Salmonella

With 3.4 million infections each year, invasive non-Typhoidal Salmonella (iNTS) is a major cause of illness worldwide. In Sub-Saharan Africa bloodstream infections with iNTS Salmonella enterica serovar Typhimurium are causing ~388,000 deaths annually. Co-infection with HIV or malaria in adults, and a young age (

Using a combination of comparative genomics and comparative transcriptomics, we discovered phenotypic differences that distinguish African from global Salmonella pathovariants (Canals et al., 2019).

Our analysis led us to identify a single core genome SNP responsible for the up-regulation of a single promoter in strain D23580 that controlled the expression of a Salmonella virulence factor (Hammarlöf et al., 2018), and offers part of the explanation of the pan-African epidemic of bloodstream infection.

All of the Salmonella transcriptomic data we have generated are now available online in a user-friendly website that allows intra-strain and inter-strain comparisons of gene expression: http://bioinf.gen.tcd.ie/cgi-bin/salcom_v2.pl

References

Canals et al. (2019) Adding function to the genome of African Salmonella Typhimurium ST313 strain D23580 . PLoS Biology 17(1): e3000059.

Hammarlöf et al. (2018) Role of a single noncoding nucleotide in the evolution of an epidemic African clade of Salmonella. Proc. Nat, Acad. Sci. USA 115 : E2614 – E2623 .

Hosted by Leo James, Speaker Jay Hinton, University of Liverpool

Add to your calendar or Include in your list

Thu 04 Jul 13:00: Genetic basis for immunoglobulin repertoire diversity and plasma cell differentiation Hosten by Ken Smith, Speaker Gunilla B. Karlsson Hedestam, Karolinska Institute

From All Talks (aka the CURE list). Published on Jun 21, 2019.

Genetic basis for immunoglobulin repertoire diversity and plasma cell differentiation

Abstract not available

Hosten by Ken Smith, Speaker Gunilla B. Karlsson Hedestam, Karolinska Institute

Add to your calendar or Include in your list

Mon 24 Jun 13:00: The pathogenesis and management of HIV-associated tuberculosis Hosted by Paul Lehner, Speaker Robert Wilkinson, The Francis Crick Institute

From All Talks (aka the CURE list). Published on Jun 21, 2019.

The pathogenesis and management of HIV-associated tuberculosis

Abstract not available

Hosted by Paul Lehner, Speaker Robert Wilkinson, The Francis Crick Institute

Add to your calendar or Include in your list

[ASAP] Carrier Recombination in the Base, Interior, and Surface of InAs/InAlAs Core–Shell Nanowires Grown on Silicon

By Kailing Zhang†‡, Xinxin Li†‡, Weitao Dai†‡, Fatima Toor†‡§, and J. P. Prineas*†‡§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00517

[ASAP] Generating Ultrabroadband Deep-UV Radiation and Sub-10 nm Gap by Hybrid-Morphology Gold Antennas

By Liping Shi*†‡@, Jose´ R. C. Andrade*†‡@, Ayhan Tajalli†‡, Jiao Geng*†, Juemin Yi§, Torsten Heidenblut‡?, Frans B. Segerink?, Ihar Babushkin†‡, Maria Kholodtsova#, Hamed Merdji#, Bert Bastiaens?, Uwe Morgner†‡, and Milutin Kovacev*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02100

[ASAP] Precision Nanomedicine Development Based on Specific Opsonization of Human Cancer Patient-Personalized Protein Coronas

By Jiayu Ren†?, Rong Cai†, Jing Wang‡, Muhammad Daniyal†?, Didar Baimanov†?, Ying Liu†, Dongtao Yin§, Yang Liu§, Qing Miao†, Yuliang Zhao†?, and Chunying Chen*†? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01774

[ASAP] Continuous, Ultra-lightweight, and Multipurpose Super-aligned Carbon Nanotube Tapes Viable over a Wide Range of Temperatures

By Xiang Jin‡†, Hengxin Tan‡†, Zipeng Wu‡†, Jiecun Liang?, Wentao Miao‡, Chao-Sheng Lian‡?, Jiangtao Wang‡, Kai Liu*#, Haoming Wei‡, Chen Feng‡, Peng Liu‡, Yang Wei‡, Qunqing Li‡, Jiaping Wang‡, Liang Liu‡, Xide Li*?, Shoushan Fan‡, Wenhui Duan*‡, and Kaili Jiang*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01629

[ASAP] Explaining the Unusual Photoluminescence of Semiconductor Nanocrystals Doped via Cation Exchange

By Abigail R. Freyer†, Peter C. Sercel§, Zhentao Hou†, Benjamin H. Savitzky‡#, Lena F. Kourkoutis??, Alexander L. Efros?, and Todd D. Krauss*†? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b02284

[ASAP] Recognition, Intervention, and Monitoring of Neutrophils in Acute Ischemic Stroke

By Chunming Tang, Cong Wang, Ying Zhang, Lingjing Xue, Yanyi Li, Caoyun Ju*, and Can Zhang* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01282

[ASAP] Highly Durable Nanofiber-Reinforced Elastic Conductors for Skin-Tight Electronic Textiles

By Hanbit Jin†§, Md Osman Goni Nayeem†, Sunghoon Lee†, Naoji Matsuhisa†, Daishi Inoue‡, Tomoyuki Yokota†, Daisuke Hashizume‡, and Takao Someya*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02297

[ASAP] A Wholly Degradable, Rechargeable Zn–Ti3C2 MXene Capacitor with Superior Anti-Self-Discharge Function

By Qi Yang†, Zhaodong Huang†, Xinliang Li†, Zhuoxin Liu†, Hongfei Li†, Guojin Liang†, Donghong Wang†, Qing Huang‡, Suojiang Zhang§, Shimou Chen*§, and Chunyi Zhi*†? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03650

[ASAP] Ligand Rigidification for Enhancing the Stability of Metal–Organic Frameworks

By Xiu-Liang Lv†, Shuai Yuan‡, Lin-Hua Xie†, Hannah F. Darke‡, Ya Chen†, Tao He†, Chen Dong†, Bin Wang†, Yong-Zheng Zhang†, Jian-Rong Li*†, and Hong-Cai Zhou*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02947

[ASAP] Fatty Acid Fueled Transmembrane Chloride Transport

By Ethan N. W. Howe and Philip A. Gale* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02116

[ASAP] Fluorescence Detection of Prostate Cancer by an Activatable Fluorescence Probe for PSMA Carboxypeptidase Activity

By Minoru Kawatani†?, Kyoko Yamamoto†?, Daisuke Yamada§?, Mako Kamiya*†?, Jimpei Miyakawa§, Yu Miyama?, Ryosuke Kojima†?, Teppei Morikawa?, Haruki Kume§, and Yasuteru Urano*†‡# from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04412

[ASAP] Traceless Electrophilic Amination for the Synthesis of Unprotected Cyclic ß-Amino Acids

By Jin-Sheng Yu, Miguel Espinosa, Hidetoshi Noda*, and Masakatsu Shibasaki* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05476

[ASAP] Understanding the Individual and Combined Effects of Solvent and Lewis Acid on CO2 Insertion into a Metal Hydride

By Jessica E. Heimann†, Wesley H. Bernskoetter‡, and Nilay Hazari*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05192

[ASAP] Modular Programming of Hierarchy and Diversity in Multivariate Polymer/Metal–Organic Framework Hybrid Composites

By Liang Feng†, Xiu-Liang Lv†‡, Tian-Hao Yan†, and Hong-Cai Zhou*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03707

[ASAP] Tuning the Negative Thermal Expansion Behavior of the Metal–Organic Framework Cu3BTC2 by Retrofitting

By Christian Schneider†, David Bodesheim†, Michael G. Ehrenreich†, Valentina Crocella`‡, Ja´nos Mink§?, Roland A. Fischer†, Keith T. Butler?, and Gregor Kieslich*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04755

[ASAP] Micellar Brønsted Acid Mediated Synthesis of DNA-Tagged Heterocycles

By M. Klika S?kopic´†, K. Go¨tte†, C. Gramse†, M. Dieter†, S. Pospich‡, S. Raunser‡, R. Weberskirch*†, and A. Brunschweiger*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05696

[ASAP] Bonding in 2D Donor–Acceptor Heterostructures

By Adam H. Woomer†, Daniel L. Druffel†, Jack D. Sundberg†, Jacob T. Pawlik†, and Scott C. Warren*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 21, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03155

Chemically synthesized anisotropic SmCo5 nanomagnets with a large energy product

By Ming Yue from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR03412A, Communication
Zhenhui Ma, Jingming Liang, Wen Ma, Liying Cong, Qiong Wu, Ming Yue
In this communication, we report a facile strategy to chemically synthesize anisotropic SmCo5 nanomagnets with a large magnetic energy product (BH).
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

Correction: CuCo2S4 nanocrystals as a nanoplatform for photothermal therapy of arterial inflammation

By Xinwu Lu from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR90141H, Correction
Open Access Open Access
Creative Commons Licence  This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Xing Zhang, Junchao Liu, Xinrui Yang, Guanjie He, Bo Li, Jinbao Qin, Paul R. Shearing, Dan J. L. Brett, Junqing Hu, Xinwu Lu
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

Window screen inspired fibrous materials with anisotropic thickness gradients for improving light transmittance

By Botao Song from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02810B, Paper
Nan Pan, Juanrong Qin, Pingping Feng, Botao Song
Fibrous materials with high light transmittance exhibit great potential in a wide range of applications; unfortunately, fabrication of such materials still remains a challenge due to the strong light scattering...
The content of this RSS Feed (c) The Royal Society of Chemistry

Flexible Bimodal Sensor Based on Electrospun Nanofibrous Structure for Simultaneous Pressure-Temperature Detection

By Chunzhong Li from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03098K, Paper
Zhihui Wang, Ling Zhang, Jin Liu, Chunzhong Li
We develop a flexible and multifunctional resistive sensor integrating uniform conductive coating layers with interlaced nanofibrous structure through a large-scale and cost-efficient strategy. Elastomer nanofiber framework not only endows superior...
The content of this RSS Feed (c) The Royal Society of Chemistry

In vivo clearable inorganic nanophotonic materials: designs, materials and applications

By Jianrong Qiu from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02083G, Review Article
Jianmin Nie, Yang Li, Gang Han, Jianrong Qiu
Inorganic nanophotonic materials (INPMs) have been considered to be promising diagnosis and therapeutic agents for in vivo applications, such as for bio-imaging, photoacoustic imaging and photothermal therapy. However, some concerns...
The content of this RSS Feed (c) The Royal Society of Chemistry

A scalable, self-healing and hot liquid repelling superamphiphobic spray coating with remarkable mechanochemical robustness for real-life applications

By Zhiguang Guo from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02893E, Paper
Yihan Sun, Zhiguang Guo
A simultaneous demonstration of scalability, mechanochemical robustness, self-healing and hot liquid repelling features is still a major challenge in fabricating superamphiphobic coatings. In this work, we developed a facile and...
The content of this RSS Feed (c) The Royal Society of Chemistry

Silver Fractal Dendrites for Highly Sensitive and Transparent Polymer Thermistors

By Youngu Lee from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04233D, Paper
Jongyoun Kim, Donghwa Lee, Kyu Tae Park, Hyeonjin Goh, Youngu Lee
Effective temperature measurement using non-invasive sensors finds applications in virtually every field of human life. Recently, significant efforts have been made toward developing polymer positive temperature coefficient (PTC) thermistors because...
The content of this RSS Feed (c) The Royal Society of Chemistry

Unravelling the polarity of InN Quantum Dots using a modified approach of negative-spherical-aberration imaging

By Somnath Bhattacharyya from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04146J, Paper
Piu Rajak, Mahabul Islam, Juan J. Jiménez, José Manuel M. Mánuel Delgado, P. Aseev, Zarco Gacevic, Enrique Calleja, Rafael García, F. Miguel Morales, Somnath Bhattacharyya
InN quantum dot (QD) is considered to be a promising nanostructure for different device applications. For any hexagonal AB-stacking semiconductor system, polarity is an important feature which affects electronic properties....
The content of this RSS Feed (c) The Royal Society of Chemistry

Mussel-inspired cryogels for promoting wound regeneration through photobiostimulation, modulating inflammatory response and suppressing bacterial invasion

By Xiong Lu from RSC - Nanoscale latest articles. Published on Jun 21, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03095F, Paper
Lu Han, Pengfei Li, Pengfei Tang, Xiao Wang, Ting Zhou, Kefeng Wang, Fuzeng Ren, Tailin Guo, Xiong Lu
Wound healing is a complex and dynamic process, and involves a series of events, which create a unique microenvironment at the wound sites. It is highly desirable to develop multi-functional...
The content of this RSS Feed (c) The Royal Society of Chemistry

The Power of Simplicity: Efficient and Selective Carboligation with Whole‐Cell Biocatalysts in Pickering Emulsion

By Robert Roellig, Christoph Plikat, Marion Ansorge-Schumacher from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 20, 2019.

Pickering emulsions are particle‐stabilized multiphase systems with promising features for synthetic application. We here describe a novel, simplified set‐up employing catalytic active whole‐cells for simultaneous emulsion stabilization and synthetic reaction. In the stereoselective carboligation of benzaldehyde to (R)‐benzoin catalyzed by a benzaldehyde lyase in E. coli, the set‐up yielded maximum substrate conversion within very short time, while economizing material demand and waste. Formation and activity of freshly produced PE were enhanced when the catalytic whole‐cells were covered with hydrophobic silicone prior to PE formation. Benchmarked against other easy‐to‐handle whole‐cell biocatalyses in pure organic solvent, neat substrate, an aqueous emulsion in substrate, and a micro‐aquatic system, respectively, the cell‐stabilized PE outperformed all other systems by far. Given the observed combination of synthetic performance and system’s simplicity we expect it to hold great potential for becoming a future platform technology for biocatalyzed multiphase synthesis.

Self‐Sorting of 10‐µm‐Long Single‐Walled Carbon Nanotubes in Aqueous Solution

By Peng Wang, Benjamin Barnes, Xiaojian Wu, Haoran Qu, Chiyu Zhang, Yang Shi, Robert J. Headrick, Matteo Pasquali, YuHuang Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

Ultralong carbon nanotubes self‐sort in a superacid–surfactant exchange process. This self‐sorting effect is driven by the length‐dependent phase behaviors of rigid rods in solution. The obtained nanotubes, with the longest approaching 13 µm, exhibit a carrier mobility as high as ≈90 cm2 V−1 s−1 in thin‐film transistors, which is ≈10 times higher than the short controls and approaches that of polycrystalline silicon. Abstract Single‐walled carbon nanotubes (SWCNTs) are a class of 1D nanomaterials that exhibit extraordinary electrical and optical properties. However, many of their fundamental studies and practical applications are stymied by sample polydispersity. SWCNTs are synthesized in bulk with broad structural (chirality) and geometrical (length and diameter) distributions; problematically, all known post‐synthetic sorting methods rely on ultrasonication, which cuts SWCNTs into short segments (typically 10 µm) SWCNTs can be efficiently separated from shorter ones through a solution‐phase “self‐sorting”. It is shown that thin‐film transistors fabricated from long semiconducting SWCNTs exhibit a carrier mobility as high as ≈90 cm2 V−1 s−1, which is ≈10 times higher than those which use shorter counterparts and well exceeds other known materials such as organic semiconducting polymers (

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 Jun 20, 2019.

Graphdiynes are 2D carbon materials that may be synthesized from organic monomers, such as hexaethynylbenzene, and significant interest of researchers is collected recently to the new 2D nanomaterial series. This work assembles comprehensive knowledge on graphdiynes: history, variations, syntheses, theoretical and experimental approaches for the physical properties, and 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.

Self‐Supported and Flexible Sulfur Cathode Enabled via Synergistic Confinement for High‐Energy‐Density Lithium–Sulfur Batteries

By Zhuosen Wang, Jiadong Shen, Jun Liu, Xijun Xu, Zhengbo Liu, Renzong Hu, Lichun Yang, Yuezhan Feng, Jun Liu, Zhicong Shi, Liuzhang Ouyang, Yan Yu, Min Zhu from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

A flexible sulfur cathode integrating sulfur, flexible carbon cloth, and N‐doped carbon nanoarrays with embedded CoP is successfully designed. Due to the artful structure and synergistic confinement for soluble lithium polysulfides, it displays an outstanding long‐term cycling performance and an ultralow decay of 0.016% per cycle during the whole 600 cycles at 2C. Abstract Lithium–sulfur (Li–S) batteries have attracted much attention in the field of electrochemical energy storage due to their high energy density and low cost. However, the “shuttle effect” of the sulfur cathode, resulting in poor cyclic performance, is a big barrier for the development of Li–S batteries. Herein, a novel sulfur cathode integrating sulfur, flexible carbon cloth, and metal–organic framework (MOF)‐derived N‐doped carbon nanoarrays with embedded CoP (CC@CoP/C) is designed. These unique flexible nanoarrays with embedded polar CoP nanoparticles not only offer enough voids for volume expansion to maintain the structural stability during the electrochemical process, but also promote the physical encapsulation and chemical entrapment of all sulfur species. Such designed CC@CoP/C cathodes with synergistic confinement (physical adsorption and chemical interactions) for soluble intermediate lithium polysulfides possess high sulfur loadings (as high as 4.17 mg cm–2) and exhibit large specific capacities at different C‐rates. Specially, an outstanding long‐term cycling performance can be reached. For example, an ultralow decay of 0.016% per cycle during the whole 600 cycles at a high current density of 2C is displayed. The current work provides a promising design strategy for high‐energy‐density Li–S batteries.

Sono‐Immunotherapeutic Nanocapturer to Combat Multidrug‐Resistant Bacterial Infections

By Xin Pang, Xue Liu, Yi Cheng, Chang Zhang, En Ren, Chao Liu, Yang Zhang, Jing Zhu, Xiaoyuan Chen, Gang Liu from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

A two‐birds‐with‐one‐stone nanocapturer is presented for bridging antibacterial sonodynamic therapy and antivirulence immunotherapy. A genetically engineered antibody on cell membrane nanovesicles (ANVs) potently reduces MRSA virulence. Upon ultrasound activation, sonosensitizers in the ANVs generate reactive oxygen species to kill bacteria and accelerate virulence clearance. Specific MRSA infection diagnosis is realized via fluorescence imaging and photoacoustic imaging. Abstract Antibiotic‐free methods hold particular promise for preventing and controlling multidrug‐resistant (MDR) bacterial infection via eradiation of bacteria and their pathogenic virulence. A facile and bioinspired strategy is presented for bridging antibacterial sonodynamic therapy and antivirulence immunotherapy. As a proof‐of‐concept, an antibody which neutralizes alpha‐toxin of methicillin‐resistant Staphylococcus aureus (MRSA) is genetically engineered on to the surface of cell membrane nanovesicles, which then undergo sonosensitizer encapsulation. Compared with conventional passive virulence absorption using natural red blood membrane, the highly active antibody–toxin interaction enables the nanovesicles to capture virulence more potently in vitro. Upon ultrasound activation, the sonosensitizers efficiently generate reactive oxygen species to kill bacteria and accelerate the virulence clearance. In vivo optical imaging shows that the antibody‐piloted nanocapturer can successfully locate MRSA infection and accurately distinguish the foci from sterile inflammation. In situ magnetic resonance imaging and oxyhemoglobin saturation detection visualize the treatment progression, revealing a complete sono‐immunotherapeutic eradication of MRSA myositis in mice. The first combination of antibacterial sonodynamic therapy and antivirulence immunotherapy, which promises a new way for antibiotic‐free nanotheranostics to robustly combat MDR bacterial infections, is presented.

Cancer‐Targeting Nanoparticles for Combinatorial Nucleic Acid Delivery

By Hannah J. Vaughan, Jordan J. Green, Stephany Y. Tzeng from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

Synthetic nanoparticles can be used for delivery of combinations of nucleic acid, with different materials conferring different advantages for safe and effective delivery. Targeting strategies can also be employed for cancer‐specific delivery, including passive targeting based on nanoparticle physical properties; active targeting using cancer‐specific ligands; transcriptional targeting using cancer‐specific promoters; and targeting of cancer‐specific proteins or signaling pathways. Abstract Nucleic acids are a promising type of therapeutic for the treatment of a wide range of conditions, including cancer, but they also pose many delivery challenges. For efficient and safe delivery to cancer cells, nucleic acids must generally be packaged into a vehicle, such as a nanoparticle, that will allow them to be taken up by the target cells and then released in the appropriate cellular compartment to function. As with other types of therapeutics, delivery vehicles for nucleic acids must also be designed to avoid unwanted side effects; thus, the ability of such carriers to target their cargo to cancer cells is crucial. Classes of nucleic acids, hurdles that must be overcome for effective intracellular delivery, types of nonviral nanomaterials used as delivery vehicles, and the different strategies that can be employed to target nucleic acid delivery specifically to tumor cells are discussed. Additonally, nanoparticle designs that facilitate multiplexed delivery of combinations of nucleic acids are reviewed.

Engineering Biomimetic Platesomes for pH‐Responsive Drug Delivery and Enhanced Antitumor Activity

By Guangna Liu, Xiao Zhao, Yinlong Zhang, Junchao Xu, Jiaqi Xu, Yao Li, Huan Min, Jian Shi, Ying Zhao, Jingyan Wei, Jing Wang, Guangjun Nie from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

A pH‐responsive platelet membrane–lipid hybrid drug carrier dubbed a “platesome” (PEOz‐platesome‐dox) is developed to simultaneously endow biomimetic nanoparticles with acid‐triggered drug release properties and tumor‐targeting capabilities. This tailor‐designed nanoplatform demonstrates enhanced in vivo chemotherapy antitumor activity. This strategy shows great promise towards a common approach for the development of biomimetic nanoparticles with useful functionalities. Abstract Biomimetic camouflage, i.e., using natural cell membranes for drug delivery, has demonstrated advantages over synthetic materials in both pharmacokinetics and biocompatibility, and so represents a promising solution for the development of safe nanomedicine. However, only limited efforts have been dedicated to engineering such camouflage to endow it with optimized or additional properties, in particular properties critical to a “smart” drug delivery system, such as stimuli‐responsive drug release. A pH‐responsive biomimetic “platesome” for specific drug delivery to tumors and tumor‐triggered drug release is described. This platesome nanovehicle is constructed by merging platelet membranes with functionalized synthetic liposomes and exhibits enhanced tumor affinity, due to its platelet membrane–based camouflage, and selectively releases its cargo in response to the acidic microenvironment of lysosomal compartments. In mouse cancer models, it shows significantly better antitumor efficacy than nanoformulations based on a platesome without pH responsiveness or those based on traditional pH‐sensitive liposomes. A convenient way to incorporate stimuli‐responsive features into biomimetic nanoparticles is described, demonstrating the potential of engineered cell membranes as biomimetic camouflages for a new generation of biocompatible and efficient nanocarriers.

Oral Delivery of Biologics for Precision Medicine

By Matilde Durán‐Lobato, Zhigao Niu, María José Alonso from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

Oral drug delivery technologies contribute to precision medicine by enabling the targeted delivery of biologics. The harsh environment of the gastrointestinal tract and the complex structure of macromolecules make their formulation a critical challenge. An overview of the current situation, future prospects, barriers to clinical translation, and identified opportunities for advancement in the field is provided. Abstract The emerging field of precision medicine is rapidly growing, fostered by the advances in genome mapping and molecular diagnosis. In general, the translation of these advances into precision treatments relies on the use of biological macromolecules, whose structure offers a high specificity and potency. Unfortunately, due to their complex structure and limited ability to overcome biological barriers, these macromolecules need to be administered via injection. The scientific community has devoted significant effort to making the oral administration of macromolecules plausible thanks to the implementation of drug delivery technologies. Here, an overview of the current situation and future prospects in the field of oral delivery of biologics is provided. Technologies in clinical trials, as well as recent and disruptive delivery systems proposed in the literature for local and systemic delivery of biologics including peptides, antibodies, and nucleic acids, are described. Strategies for the specific targeting of gastrointestinal regions—stomach, small bowel, and colon—cell populations, and internalization pathways, are analyzed. Finally, challenges associated with the clinical translation, future prospects, and identified opportunities for advancement in this field are also discussed.

MXenes for Plasmonic Photodetection

By Dhinesh Babu Velusamy, Jehad K. El‐Demellawi, Ahmed M. El‐Zohry, Andrea Giugni, Sergei Lopatin, Mohamed N. Hedhili, Ahmed E. Mansour, Enzo Di Fabrizio, Omar F. Mohammed, Husam N. Alshareef from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

Plasmonic photodetection in Mo2CTx MXene flexible thin films is demonstrated. The photocurrent generation in Mo2CTx is principally controlled by surface plasmon‐assisted hot electrons. The distribution of various surface plasmon modes over individual Mo2CTx nanosheets is visualized by the combination of scanning transmission electron microscopy and ultrahigh‐resolution electron energy‐loss spectroscopy. Abstract MXenes have recently shown impressive optical and plasmonic properties associated with their ultrathin‐atomic‐layer structure. However, their potential use in photonic and plasmonic devices has been only marginally explored. Photodetectors made of five different MXenes are fabricated, among which molybdenum carbide MXene (Mo2CTx) exhibits the best performance. Mo2CTx MXene thin films deposited on paper substrates exhibit broad photoresponse in the range of 400–800 nm with high responsivity (up to 9 A W−1), detectivity (≈5 × 1011 Jones), and reliable photoswitching characteristics at a wavelength of 660 nm. Spatially resolved electron energy‐loss spectroscopy and ultrafast femtosecond transient absorption spectroscopy of the MXene nanosheets reveal that the photoresponse of Mo2CTx is strongly dependent on its surface plasmon‐assisted hot carriers. Additionally, Mo2CTx thin‐film devices are shown to be relatively stable under ambient conditions, continuous illumination and mechanical stresses, illustrating their durable photodetection operation in the visible spectral range. Micro‐Raman spectroscopy conducted on bare Mo2CTx film and on gold electrodes allowing for surface‐enhanced Raman scattering demonstrates surface chemistry and a specific low‐frequency band that is related to the vibrational modes of the single nanosheets. The specific ability to detect and excite individual surface plasmon modes provides a viable platform for various MXene‐based optoelectronic applications.

Realizing 22.5% External Quantum Efficiency for Solution‐Processed Thermally Activated Delayed‐Fluorescence OLEDs with Red Emission at 622 nm via a Synergistic Strategy of Molecular Engineering and Host Selection

By Weixuan Zeng, Tao Zhou, Weimin Ning, Cheng Zhong, Jiawei He, Shaolong Gong, Guohua Xie, Chuluo Yang from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

Solution‐processed red fluorescent OLEDs with external quantum efficiencies of up to 22.5% are fabricated using a synergistic strategy of molecular engineering and host selection with thermally activated delayed‐fluorescence emitters. With this strategy, a good balance of critical photophysical parameters is realized by effectively fine tuning the excited states of the emitters, which is verified to support the record‐high efficiency reported. Abstract Developing high‐efficiency solution‐processable thermally activated delayed‐fluorescence (TADF) emitters, especially in longer wavelength regions, is a formidable challenge. Three red TADF emitters, namely NAI_R1, NAI_R2, and NAI_R3, are developed by phenyl encapsulation and tert‐butyl substitution on a prototypical 1,8‐naphthalimide‐acridine hybrid. This design strategy not only grants these molecules high solubility, excellent thermal stability, and good film‐forming ability, but also pulls down their charge‐transfer (CT) energy levels excited states. Furthermore, dispersing these emitters into two different host materials of mCP and mCPCN finely tailors their CT‐state energy levels. More importantly, a synergistic combination of molecular engineering and host selection can effectively manipulate the competition between the radiative and nonradiative decay rates of the CT singlet states of these emitters and the reverse intersystem crossing from their triplet to singlet states. Consequently, the optimal combination of NAI_R3 emitter and mCP host successfully results in a state‐of‐the‐art external quantum efficiency (EQE) of 22.5% for solution‐processed red TADF organic light‐emitting diodes (OLEDs) with an emission peak above 620 nm. This finding demonstrates that a synergistic strategy of molecular engineering and host selection with TADF emitters could provide a new pathway for developing efficient solution‐processable TADF systems.

Nature‐Inspired Design and Application of Lipidic Lyotropic Liquid Crystals

By Raffaele Mezzenga, John M. Seddon, Calum J. Drummond, Ben J. Boyd, Gerd E. Schröder‐Turk, Laurent Sagalowicz from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

The thermodynamics and physics underlying the self‐assembly of amphiphilic lipids are reviewed and then linked to Nature's deployment of these fascinating lyotropic liquid–crystalline phases for specific biological functions. The harnessing of the unique properties of these structures to enable a range of technological, biomedical, and food applications is reviewed. Abstract Amphiphilic lipids aggregate in aqueous solution into a variety of structural arrangements. Among the plethora of ordered structures that have been reported, many have also been observed in nature. In addition, due to their unique morphologies, the hydrophilic and hydrophobic domains, very high internal interfacial surface area, and the multitude of possible order−order transitions depending on environmental changes, very promising applications have been developed for these systems in recent years. These include crystallization in inverse bicontinuous cubic phases for membrane protein structure determination, generation of advanced materials, sustained release of bioactive molecules, and control of chemical reactions. The outstanding diverse functionalities of lyotropic liquid crystalline phases found in nature and industry are closely related to the topology, including how their nanoscopic domains are organized. This leads to notable examples of correlation between structure and macroscopic properties, which is itself central to the performance of materials in general. The physical origin of the formation of the known classes of lipidic lyotropic liquid crystalline phases, their structure, and their occurrence in nature are described, and their application in materials science and engineering, biology, medical, and pharmaceutical products, and food science and technology are exemplified.

A 3D and Stable Lithium Anode for High‐Performance Lithium–Iodine Batteries

By Kang Li, Ziyu Hu, Jizhen Ma, Song Chen, Dexu Mu, Jintao Zhang from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

The enhanced lithiophilicity of nitrogen/phosphorous‐doped carbon cloth facilitates uniform lithium coating on carbon fibers. This enables the construction of a 3D lithium anode with superior cycling stability for enhanced lithium–iodine battery performance. Abstract Lithium metal is considered as the most promising anode material due to its high theoretical specific capacity and the low electrochemical reduction potential. However, severe dendrite problems have to be addressed for fabricating stable and rechargeable batteries (e.g., lithium–iodine batteries). To fabricate a high‐performance lithium–iodine (Li–I2) battery, a 3D stable lithium metal anode is prepared by loading of molten lithium on carbon cloth doped with nitrogen and phosphorous. Experimental observations and theoretical calculation reveal that the N,P codoping greatly improves the lithiophilicity of the carbon cloth, which not only enables the uniform loading of molten lithium but also facilitates reversible lithium stripping and plating. Dendrites formation can thus be significantly suppressed at a 3D lithium electrode, leading to stable voltage profiles over 600 h at a current density of 3 mA cm−2. A fuel cell with such an electrode and a lithium–iodine cathode shows impressive long‐term stability with a capacity retention of around 100% over 4000 cycles and enhanced high‐rate capability. These results demonstrate the promising applications of 3D stable lithium metal anodes in next‐generation rechargeable batteries.

An Acidic‐Microenvironment‐Driven DNA Nanomachine Enables Specific ATP Imaging in the Extracellular Milieu of Tumor

By Zhenghan Di, Jian Zhao, Hongqian Chu, Wenting Xue, Yuliang Zhao, Lele Li from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

An intelligent DNA nanomachine for targeted imaging of extracellular ATP in the tumor microenvironment (TME) is designed. It can specifically anchor to the membrane of tumor cells in response to mild acidic TME, allowing for an “off–on” fluorescence imaging of extracellular ATP in both primary and metastatic tumors with high signal‐to‐background ratio. Abstract Extracellular ATP is an emerging target for cancer treatment because it is a key messenger for shaping the tumor microenvironment (TME) and regulating tumor progression. However, it remains a great challenge to design biochemical probes for targeted imaging of extracellular ATP in the TME. A TME‐driven DNA nanomachine (Apt‐LIP) that permits spatially controlled imaging of ATP in the extracellular milieu of tumors with ultrahigh signal‐to‐background ratio is reported. It operates in response to the mild acidity in the TME with the pH (low) insertion peptide (pHLIP) module, thus allowing the specific anchoring of the structure‐switching signaling aptamer unit to the membrane of tumor cells for “off–on” fluorescence imaging of the extracellular ATP. Apt‐LIP allows for acidity driven visualization of different extracellular concentrations of exogenous ATP, as well as the monitoring of endogenous ATP release from cells. Furthermore, it is demonstrated that Apt‐LIP represents a promising platform for the specific imaging of the extracellular ATP in both primary and metastatic tumors. Ultimately, since diverse aptamers are obtained through in vitro selection, this design strategy can be further applied for precise detection of various extracellular targets in the TME.

Strong and Tough Glass with Self‐Dispersed Nanoparticles via Solidification

By Qiang‐Guo Jiang, Chezheng Cao, Ting‐Chiang Lin, Shanghua Wu, Xiaochun Li from Wiley: Advanced Materials: Table of Contents. Published on Jun 20, 2019.

A strong and tough glass can be fabricated through a direct‐solidification process using a nanoparticle self‐dispersion mechanism, delivering a 6.1% strain limit and strength close to the theoretical limit. The fracture toughness of this glass is significantly higher than any other inorganic glasses. This new method opens up remarkable opportunities for glass and ceramic research, manufacturing, and applications. Abstract Glassy materials can be broadly defined as any amorphous solid, which are important in nature and have significant societal value for their applications in daily life and industry. Although many methods have been applied, the fracture toughness of traditional glasses is still very low due to intrinsic brittleness, significantly limiting their use for structural applications. While nanoelements may be added into glasses and ceramics to form nanocomposites with enhanced properties, it is extremely difficult to distribute and disperse them inside the liquid glass/ceramic matrix with traditional processing methods. It is shown that a strong and tough glass can be fabricated through a direct‐solidification process using a nanoparticle self‐dispersion mechanism in a glass melt (2MgO·2Al2O3·5SiO2) with the assistance of B2O3, delivering a 6.1% strain limit and strength up to E/14 (E is elastic modulus), which is close to the theoretical limit of E/10 and one of the highest among all materials reported so far. The fracture toughness of the glass with 30 vol% SiC nanoparticles is significantly higher than any other inorganic glass tested under similar conditions. This new method opens up remarkable opportunities for glass and ceramic research, manufacturing, and applications.

Wed 03 Jul 15:00: Mitochondrial dynamics in muscle physiopathology

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Mitochondrial dynamics in muscle physiopathology

Mitochondrial quality control is essential in highly structured cells such as neurons and muscles. In skeletal muscle the mitochondrial shaping machinery and mitophagy are altered in different physiopathological conditions that are characterized by muscle loss and weakness. The abnormal mitochondria signal to the nucleus to induce several signaling pathways that control proteostasis, inflammatory response and senescence. Importantly, the shape of the mitochondrial network more than mitochondrial function is an important factor for the activation of specific pathways that control peculiar phenotypes. Fusion defect triggers sarcopenia and systemic ageing while fission impairment causes myopathy. Here, I will present the latest data that connect mitochondrial network to signaling pathways that controls muscle mass.

Add to your calendar or Include in your list

Mercury Cyanides and Isocyanides: NCHgCN and CNHgNC. NCHgHgCN and CNHgHgNC: Simple Molecules with Short, Strong Hg‐Hg Bonds

By Lester Andrews, Han-Gook Cho from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 20, 2019.

Mercury atoms, laser ablated from an amalgam dental filling target, were reacted with cyanogen in excess argon during condensation at 4K to form two major products in the 2200 cyanide M‐C‐N stretching region of the infrared spectrum, which are assigned to the NCHgCN and NCHgHgCN molecules from their sharp antisymmetric C‐N stretching mode absorptions. Two broader bands in the 2100 isocyanide M‐N‐C stretching region are identified as the 87.6 and 113 kJ/m higher energy isocyanide isomers CNHgNC and CNHgHgNC. These assignments are confirmed by comparison with B3LYP and CCSD calculated frequencies and experimental frequencies observed with the same band patterns for the analogous Cd reaction products. Dissociation energy for the NCHgHgCN molecule giving two HgCN molecules is 283 kJ/mol and for CNHgHgNC to two HgNC is 291 kJ/mol calculated at the CCSD/aug‐cc‐pVTZ/SDD level of theory. These simple dimercury bearing molecules with two cyanide or two isocyanide ligands have two of the shortest and strongest known Hg‐Hg single bonds (calculated bond lengths 2.628 and 2.597 Å, respectively) as two electronegative CN ligands withdraw antibonding electron density from the bonding region relative to that for the isolated van der Waals Hg2 molecule (calculated CCSD(T) level as 4.092 Å). Although FHgHgF has a slightly shorter calculated Hg‐Hg bond (2.584 Å), its dissociation energy is less (276 kJ/m) than computed for the NCHgHgCN and CNHgHgNC molecules prepared in this matrix isolation investigation.

Mechanotropic Elastomers

By Brian Donovan, Hayden Fowler, Valentina Matavulj, Timothy J White from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 20, 2019.

Liquid crystal elastomers (LCEs) are anisotropic polymeric materials. When subjected to an applied stress, liquid crystalline (LC) mesogens within the elastomeric polymer network (re)orient to the loading direction. The (re)orientation during deformation results in considerable nonlinearity in stress‐strain response (referred to as soft elasticity) and strain hardening. Here, we uniquely explore mechanotropic phase transitions in elastomers with appreciable mesogenic content and compare these responses to LCEs in the polydomain orientation. The isotropic (amorphous) elastomers undergo significant directional orientation upon loading, evident in strong birefringence and x‐ray diffraction. Functionally, the mechanotropic displacement of the elastomers to load is also nonlinear, and shown to be similar to polydomain LCEs. However, in the compositions that are the focus of this work, the isotropic elastomers rapidly recover after deformation. The mechanotropic orientation of the mesogens in these materials increase the relative toughness by nearly 1300% relative to a chemically similar elastomer prepared from wholly isotropic precursors.

Thu 07 Nov 16:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

CatalySED! Neutral Organic Super Electron Donors Made Catalytic

By John Murphy, Simon Rohrbach, Rushabh S. Shah, Tell Tuttle from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 20, 2019.

Neutral organic super electron donors (SEDs) display impressive reducing power but, until now, it has not been possible to use them catalytically in radical chain reactions. This is because, following electron transfer, these donors form persistent radical cations that trap substrate‐derived radicals. This paper unlocks a conceptually new approach to super electron donors that overcomes this issue, leading to the first catalytic neutral organic super electron donor.

The proteome‐wide potential for reversible covalency at cysteine

By Kristine Senkane, Ekaterina Vinogradova, Radu Suciu, Vincent Crowley, Balyn Zaro, Michael Bradshaw, Ken Brameld, Benjamin Cravatt from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 20, 2019.

Reversible covalency, achieved with, for instance, highly electron‐deficient olefins, offers a compelling strategy to design chemical probes and drugs that benefit from the sustained target engagement afforded by irreversible compounds, while avoiding permanent protein modification that persists following unfolding and/or proteolytic processing. So far, reversible covalency has mainly been evaluated for cysteine residues in individual kinases and the broader potential for this strategy to engage cysteines across the proteome remains unexplored. Here we describe a mass‐spectrometry‐based platform that integrates gel filtration (GF) with activity‐based protein profiling (ABPP) to assess cysteine residues across the human proteome for both irreversible and reversible interactions with small‐molecule electrophiles. Using this method, we identify numerous cysteine residues from diverse protein classes that are reversibly engaged by cyanoacrylamide fragment electrophiles, revealing the broad potential for reversible covalency as a strategy for chemical probe discovery.

Wed 26 Jun 11:00: Learning via Data Compression: Bayesian Coresets and Sparse Variational Inference

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Learning via Data Compression: Bayesian Coresets and Sparse Variational Inference

We have reached a point in many fields of science and technology where we create data at a pace that far outstrips our capacity to process it. While a boon from a statistical perspective, this wealth of data presents a computational challenge: how might we design a model-based inference system that learns forever, retains important past information, doesn’t get bogged down by a persistent stream of new data, and makes inferences with guaranteed statistical quality? The human nervous system provides inspiration; to handle the astounding amount of perceptual data it constantly receives, the nervous system filters and compresses the data significantly before passing it along to the brain where learning occurs. Although a seemingly simple solution, it does raise interesting questions for the design of a computational inference system: how should we decide what data to retain, how should we compress it, and what degree of compression should we apply before learning from it?

This talk will cover recent work on Bayesian coresets (“core of a dataset”), a methodology for statistical inference via data compression. Coresets achieve compression by forming a small weighted subset of data that replaces the full dataset during inference, leading to significant computational gains with provably minimal loss in inferential quality. In particular, the talk will present numerous methods for Bayesian coreset construction, from previously-developed subsampling, greedy, and sparse linear regression-based techniques to novel algorithms based on sparse variational inference (VI). In contrast to past algorithms, the sparse VI-based algorithms are fully automated, requiring only the dataset and probabilistic model specification as inputs. The talk will additionally provide a unifying view and statistical analysis of these methods using the theory of exponential families and Riemannian information geometry. The talk will conclude with empirical results showing that despite requiring much less user input than past methods, sparse VI coreset construction provides state-of-the-art data summarization for Bayesian inference.

Add to your calendar or Include in your list

Tue 16 Jul 12:30: Integrating T cell Signals Note unusual time, (Tuesday 1230) (12.15 Refreshments available)

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Integrating T cell Signals

Abstract not available

Note unusual time, (Tuesday 1230) (12.15 Refreshments available)

Add to your calendar or Include in your list

Thu 14 Nov 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Thu 21 Nov 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 16 Oct 16:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 20, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

[ASAP] Electrical Double Layer of Supported Atomically Thin Materials

By Sun Sang Kwon†?, Jonghyun Choi‡?, Mohammad Heiranian‡, Yerim Kim‡, Won Jun Chang†, Peter M. Knapp‡, Michael Cai Wang‡, Jin Myung Kim§, Narayana R. Aluru‡, Won Il Park*†, and SungWoo Nam*‡§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01563

[ASAP] Multifunctional Two-Dimensional PtSe2-Layer Kirigami Conductors with 2000% Stretchability and Metallic-to-Semiconducting Tunability

By Emmanuel Okogbue†‡?, Sang Sub Han†§?, Tae-Jun Ko†, Hee-Suk Chung?, Jinwoo Ma§, Mashiyat Sumaiya Shawkat†‡, Jung Han Kim†, Jong Hun Kim§, Eunji Ji¶, Kyu Hwan Oh§, Lei Zhai†?#, Gwan-Hyoung Lee§, and Yeonwoong Jung*†‡# from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01726

[ASAP] Correction to Optimized Assembly of a Multifunctional RNA-Protein Nanostructure in a Cell-Free Gene Expression System

By Matthaeus Schwarz-Schilling, Aurore Dupin, Fabio Chizzolini, Swati Krishnan, Sheref S. Mansy, and Friedrich C. Simmel* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

Nano Letters
DOI: 10.1021/acs.nanolett.9b02419

[ASAP] Carbogenic Nanozyme with Ultrahigh Reactive Nitrogen Species Selectivity for Traumatic Brain Injury

By Xiaoyu Mu†?, Hua He‡?, Junying Wang†?, Wei Long§, Qifeng Li?, Haile Liu†, Yalong Gao?, Lufei Ouyang†, Qinjuan Ren†, Si Sun†, Jingya Wang§, Jiang Yang?, Qiang Liu§, Yuanming Sun§, Changlong Liu†, Xiao-Dong Zhang*†#, and Wenping Hu†# from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01333

[ASAP] Phonon Engineering in Twinning Superlattice Nanowires

By Marta De Luca†, Claudia Fasolato†‡, Marcel A. Verheijen§, Yizhen Ren§, Milo Y. Swinkels†, Sebastian Ko¨lling§, Erik P. A. M. Bakkers§, Riccardo Rurali*?, Xavier Cartoixa`?, and Ilaria Zardo*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01775

[ASAP] Fractional and Symmetry-Broken Chern Insulators in Tunable Moiré Superlattices

By Bin Cheng†#, Cheng Pan†#, Shi Che†‡, Peng Wang†, Yong Wu†, Kenji Watanabe§, Takashi Taniguchi§, Supeng Ge?, Roger Lake?, Dmitry Smirnov?, Chun Ning Lau‡, and Marc Bockrath*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00811

[ASAP] Si Doping of Vapor–Liquid–Solid GaAs Nanowires: n-Type or p-Type?

By Hadi Hijazi*†, Guillaume Monier†, Evelyne Gil*†, Agne`s Trassoudaine†, Catherine Bougerol‡, Christine Leroux§, Dominique Castellucci†, Christine Robert-Goumet†, Philip E. Hoggan†, Yamina Andre´†, Nebile Isik Goktas?, Ray R. LaPierre?, and Vladimir G. Dubrovskii? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01308

[ASAP] Defect Dynamics in Self-Catalyzed III–V Semiconductor Nanowires

By James A. Gott†, Richard Beanland*†, H. Aruni Fonseka†, Jonathan J. P. Peters†, Yunyan Zhang‡, Huiyun Liu‡, and Ana M. Sanchez*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01508

[ASAP] Spatiotemporally Super-Resolved Volumetric Traction Force Microscopy

By Huw Colin-York†?, Yousef Javanmardi‡?, Liliana Barbieri†, Di Li§, Kseniya Korobchevskaya?, Yuting Guo§?, Chloe Hall‡, Aaron Taylor#, Satya Khuon#, Graham K. Sheridan¶?, Teng-Leong Chew#, Dong Li*§?, Emad Moeendarbary*‡?, and Marco Fritzsche*†? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01196

[ASAP] A Magneto-Optical Nanoplatform for Multimodality Imaging of Tumors in Mice

By Guosheng Song†‡, Xianchuang Zheng‡, Youjuan Wang†, Xin Xia†, Steven Chu§, and Jianghong Rao*‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01436

[ASAP] Timesaving, High-Efficiency Approaches To Fabricate Aramid Nanofibers

By Bin Yang*, Lin Wang, Meiyun Zhang*, Jingjing Luo, and Xueyao Ding from ACS Nano: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02258

[ASAP] Continuous Heteroepitaxy of Two-Dimensional Heterostructures Based on Layered Chalcogenides

By Yu Kobayashi†, Shoji Yoshida‡, Mina Maruyama‡, Hiroyuki Mogi‡, Kota Murase‡, Yutaka Maniwa†, Osamu Takeuchi‡, Susumu Okada‡, Hidemi Shigekawa‡, and Yasumitsu Miyata*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.8b07991

[ASAP] Sn-Triggered Two-Dimensional Fast Protein Assembly with Emergent Functions

By Bassam Saif†, Wenxin Zhang‡, Xu Zhang‡, Quan Gu*†, and Peng Yang*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01392

[ASAP] Plasmonic Ti3C2Tx MXene Enables Highly Efficient Photothermal Conversion for Healable and Transparent Wearable Device

By Xiangqian Fan†?, Yan Ding†?, Yang Liu†, Jiajie Liang*†‡§, and Yongsheng Chen†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03161

[ASAP] Josephson Field-Effect Transistors Based on All-Metallic Al/Cu/Al Proximity Nanojunctions

By Giorgio De Simoni*†, Federico Paolucci†‡, Claudio Puglia†§, and Francesco Giazotto*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02209

[ASAP] Developing a Predictive Solubility Model for Monomeric and Oligomeric Cyclopropenium-Based Flow Battery Catholytes

By Sophia G. Robinson†§?, Yichao Yan‡§?, Koen H. Hendriks§?, Melanie S. Sanford*‡§, and Matthew S. Sigman*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04270

[ASAP] Dioxygen-Derived Nonheme Mononuclear FeIII(OH) Complex and Its Reactivity with Carbon Radicals

By Vishal Yadav, Jesse B. Gordon, Maxime A. Siegler, and David P. Goldberg* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03329

[ASAP] Hydration-Shell Vibrational Spectroscopy

By Dor Ben-Amotz* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02742

[ASAP] New Horizons of Nonclassical Crystallization

By Marie Jehannin*†?, Ashit Rao*‡?, and Helmut Co¨lfen*†§? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01883

[ASAP] Interplay of Three G-Quadruplex Units in the KIT Promoter

By Cosimo Ducani*†, Giulio Bernardinelli†, Bjo¨rn Ho¨gberg†, Bernhard K. Keppler‡, and Alessio Terenzi*‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.8b12753

[ASAP] Nonenzymatic Template-Directed Synthesis of Mixed-Sequence 3'-NP-DNA up to 25 Nucleotides Long Inside Model Protocells

By Derek K. O’Flaherty†‡?, Lijun Zhou†‡?, and Jack W. Szostak*†‡§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04858

[ASAP] Electrochemiluminescence-Based Capacitance Microscopy for Label-Free Imaging of Antigens on the Cellular Plasma Membrane

By Jingjing Zhang†‡, Rong Jin†, Dechen Jiang*†, and Hong-Yuan Chen† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03007

[ASAP] Molecular Mechanisms of Membrane Curvature Sensing by a Disordered Protein

By Wade F. Zeno†, Ajay S. Thatte†, Liping Wang‡, Wilton T. Snead†, Eileen M. Lafer‡, and Jeanne C. Stachowiak*†§ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 20, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03927

Patching Laser-Reduced Graphene Oxide with Carbon Nanodots

By Richard B Kaner from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR01719D, Paper
Volker Strauss, Mit Muni, Arie Borenstein, Bolortuya Badamdorj, Tobias Heil, Matthew D. Kowal, Richard B Kaner
Three-dimensional graphenes are versatile materials for a range of electronic applications and considered among the most promising candidates for electrodes in future electric double layer capacitors (EDLCs) as they are...
The content of this RSS Feed (c) The Royal Society of Chemistry

Promoting Pt catalysis for CO oxidation via the Mott−Schottky effect

By Huiyuan Zhu from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04055B, Paper
Peiwen Wu, Zili Wu, David Mullins, Shize Yang, Xue Han, Yafen Zhang, Guo Shiou Foo, Huaming Li, Wenshuai Zhu, Sheng Dai, Huiyuan Zhu
CO oxidation is an important reaction both experimentally and industrially, and its performance is usually dominated by the surface charge state. For example, CO oxidation on platinum (Pt) surface requires...
The content of this RSS Feed (c) The Royal Society of Chemistry

Anomalous Lattice Vibrations of CVD-grown Monolayer MoS2 Probed by Linear Polarized Excitation Light

By Junjie Qi from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03203G, Communication
Feng Li, Teng-De Huang, YannWen Lan, Ting-Hua Lu, Bryan Simbulan Kristan, Tao Shen, Junjie Qi
Novel physical phenomenon and advanced application have been explored in 2D low-dimensional Van der Waals layered materials due to their reduced in-plane symmetry. Light-matter interaction is observed upon rapid characterization...
The content of this RSS Feed (c) The Royal Society of Chemistry

Interface charge-transfer induced intralayer excited-state biexciton in graphene/WS2 van der Waals heterostructures

By Jiannong Wang from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02862E, Paper
Yang Li, Nore Stolte, Baikui Li, Li Hui, Guanghui Cheng, Ding Pan, Jiannong Wang
The monolayer transition metal dichalcogenides (TMDCs) are ideal platform for multi-carriers bound states of which the excitons and trions have been well identified and investigated. However, the formation and identification...
The content of this RSS Feed (c) The Royal Society of Chemistry

Monoclinic VO2(D) hollow nanospheres with super-long cycle life for aqueous zinc ion batteries

By Yaoguo Huang from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR03129D, Paper
Linlin Chen, Zhanhong Yang, Yaoguo Huang
Vanadium dioxide (VO2) is a very promising cathode material for aqueous zinc ion batteries (AZIBs) because of their high reversible specific capacity, excellent rate performance and fast diffusion kinetics. However,...
The content of this RSS Feed (c) The Royal Society of Chemistry

Transition from Vesicles to Nanofibres in the Enzymatic Self-Assemblies of an Amphiphilic Peptide as an Antitumour Drug Carrier

By Jingkun Bai from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR02874A, Paper
Zhongying Gong, Xiaoying Liu, Jinhua Dong, Weifen Zhang, Yuanfei Jiang, Jinhui Zhang, Weiguo Feng, Kun Chen, Jingkun Bai
Amphiphilic peptides modified by molecular design can self-assemble into specific nanostructures with interesting applications in the fields of biomedicine and biotechnology. Lysyl oxidase (LO) is ubiquitous in human serum. However,...
The content of this RSS Feed (c) The Royal Society of Chemistry

Crystallographic Characterization of Er3N@C2n (2n = 80, 82, 84, 88): The Importance of a Planar Er3N Cluster

By Takeshi Akasaka from RSC - Nanoscale latest articles. Published on Jun 20, 2019.

Nanoscale, 2019, Accepted Manuscript
DOI: 10.1039/C9NR04330F, Paper
Xing Lu, Shuaifeng Hu, Pei Zhao, Wangqiang Shen, Pengyuan Yu, wenhuan Huang, Masahiro Ehara, Yun-Peng Xie, Takeshi Akasaka
A series of Er-based nitride clusterfullerenes (NCFs), Er3N@C80-88, have been successfully synthesized and isolated. In particular, Er3N@Ih(7)-C80, Er3N@D5h(6)-C80, Er3N@C2v(9)-C82, Er3N@Cs(51365)-C84, and Er3N@D2(35)-C88 have been characterized by single-crystal X-ray diffraction (XRD)...
The content of this RSS Feed (c) The Royal Society of Chemistry

A Perspective on Fluorescent Nanodiamond Bioimaging

By Marco D. Torelli, Nicholas A. Nunn, Olga A. Shenderova from Wiley: Small: Table of Contents. Published on Jun 19, 2019.

The field of fluorescent nanodiamonds (FNDs) has advanced greatly over the past few years. This Review summarizes the advances made in the synthesis, functionalization, and application of FNDs to bioimaging. Highlights range from super‐resolution microscopy, through cellular and whole animal imaging, up to constantly emerging fields including sensing and hyperpolarized magnetic resonance imaging. Abstract The field of fluorescent nanodiamonds (FNDs) has advanced greatly over the past few years. Though historically limited primarily to red fluorescence, the wavelengths available for nanodiamonds have increased due to continuous technical advancement. This Review summarizes the strides made in the synthesis, functionalization, and application of FNDs to bioimaging. Highlights range from super‐resolution microscopy, through cellular and whole animal imaging, up to constantly emerging fields including sensing and hyperpolarized magnetic resonance imaging.

Fabrication of Lamellar Nanosphere Structure for Effective Stress‐Management in Large‐Volume‐Variation Anodes of High‐Energy Lithium‐Ion Batteries

By Jaekyung Sung, Jiyoung Ma, Seong‐Hyeon Choi, Jaehyung Hong, Namhyung Kim, Sujong Chae, Yeonguk Son, Sung Youb Kim, Jaephil Cho from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

A SiOx ‐interlayer within the nanosphere anode, synthesized via a one‐pot chemical vapor deposition (CVD) method, enhances the cyclability of a Li‐ion battery system by sustaining its morphological integrity through mitigating stress intensification. Tested under industrial protocols, this anode exhibits a 1.7 times higher average energy density than conventional graphite. This breakthrough technology sheds light on the practical implementation of large‐volume‐change anodes. Abstract The use of high‐capacity anode materials to overcome the energy density limits imposed by the utilization of low‐theoretical‐capacity conventional graphite has recently drawn increased attention. Until now, stress management (including strategies relying on size, surface coating, and free volume control) has been achieved by addressing the critical problems originating from significant anode volume expansion upon lithiation. However, commercially viable alternatives to graphite have not yet been found. A new stress‐management strategy relying on the use of a lamellar nanosphere Si anode is proposed. Specifically, nanospheres comprising ≈50 nm Si nanoparticles encapsulated by SiOx /Si/SiOx /C layers with thicknesses of

Fast and Efficient CRISPR/Cas9 Genome Editing In Vivo Enabled by Bioreducible Lipid and Messenger RNA Nanoparticles

By Ji Liu, Jin Chang, Ying Jiang, Xiandi Meng, Tianmeng Sun, Lanqun Mao, Qiaobing Xu, Ming Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

A bioreducible lipid nanoparticle integrated with disulfide bonds can efficiently deliver Cas9 messenger RNA (mRNA) and single‐guide RNA into cells, while releasing mRNA in response to the reductive intracellular environment for genome editing as fast as 24 h post mRNA delivery. The leading lipid nanoparticle, BAMEA‐O16B, represents one of the most efficient CRISPR/Cas9 delivery nanocarriers reported so far. Abstract A main challenge to broaden the biomedical application of CRISPR/Cas9 (clustered regularly interspaced short palindromic repeat (CRISPR) associated protein 9) genome editing technique is the delivery of Cas9 nuclease and single‐guide RNA (sgRNA) into the specific cell and organ. An effective and very fast CRISPR/Cas9 genome editing in vitro and in vivo enabled by bioreducible lipid/Cas9 messenger RNA (mRNA) nanoparticle is reported. BAMEA‐O16B, a lipid nanoparticle integrated with disulfide bonds, can efficiently deliver Cas9 mRNA and sgRNA into cells while releasing RNA in response to the reductive intracellular environment for genome editing as fast as 24 h post mRNA delivery. It is demonstrated that the simultaneous delivery of Cas9 mRNA and sgRNA using BAMEA‐O16B knocks out green fluorescent protein (GFP) expression of human embryonic kidney cells with efficiency up to 90%. Moreover, the intravenous injection of BAMEA‐O16B/Cas9 mRNA/sgRNA nanoparticle effectively accumulates in hepatocytes, and knocks down proprotein convertase subtilisin/kexin type 9 level in mouse serum down to 20% of nontreatment. The leading lipid nanoparticle, BAMEA‐O16B, represents one of the most efficient CRISPR/Cas9 delivery nanocarriers reported so far, and it can broaden the therapeutic promise of mRNA and CRISPR/Cas9 technique further.

A Nature‐Inspired, Flexible Substrate Strategy for Future Wearable Electronics

By Chuang Zhu, Evelyn Chalmers, Liming Chen, Yuqi Wang, Ben Bin Xu, Yi Li, Xuqing Liu from Wiley: Small: Table of Contents. Published on Jun 19, 2019.

A nature‐inspired approach for manufacturing durable bending sensors is reported. A traditional mordant, tannic acid, is precoated as adherent layers for textiles and PU sponges and captures Pd2+ catalysts for subsequent metal layer formation on the surface of flexible substrates, with application in arm‐monitoring sensors. The Kelvin structure model to understand the mechanism of cluster growth and to optimize conductivity and flexibility is introduced. Abstract Flexibility plays a vital role in wearable electronics. Repeated bending often leads to the dramatic decrease of conductivity because of the numerous microcracks formed in the metal coating layer, which is undesirable for flexible conductors. Herein, conductive textile‐based tactile sensors and metal‐coated polyurethane sponge‐based bending sensors with superior flexibility for monitoring human touch and arm motions are proposed, respectively. Tannic acid, a traditional mordant, is introduced to attach to various flexible substrates, providing a perfect platform for catalyst absorbing and subsequent electroless deposition (ELD). By understanding the nucleation, growth, and structure of electroless metal deposits, the surface morphology of metal nanoparticles can be controlled in nanoscale with simple variation of the plating time. When the electroless plating time is 20 min, the normalized resistance (R/R0) of as‐made conductive fibers is only 1.6, which is much lower than a 60 min ELD sample at the same conditions (R/R0 ≈ 5). This is because a large number of unfilled gaps between nanoparticles prevent metal films from cracking under bending. Importantly, the Kelvin problem is relevant to deposited conductive coatings because metallic cells have a honeycomb‐like structure, which is a rationale to explain the relationships of conductivity and flexibility.

High‐Performance Polymeric Materials through Hydrogen‐Bond Cross‐Linking

By Pingan Song, Hao Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

Hydrogen‐bond cross‐linking has recently emerged as a promising strategy for creating high‐performance polymeric materials via self‐association of multiple hydrogen bonds or the addition of external cross‐linkers. These polymers exhibit a unique combination of high strength, large extensibility, thermostability, and even healable capability. Such a performance portfolio enables these polymeric materials to find many potential applications in the electronics and gas‐separation fields. Abstract It has always been critical to develop high‐performance polymeric materials with exceptional mechanical strength and toughness, thermal stability, and even healable properties for meeting performance requirements in industry. Conventional chemical cross‐linking leads to enhanced mechanical strength and thermostability at the expense of extensibility due to mutually exclusive mechanisms. Such major challenges have recently been addressed by using noncovalent cross‐linking of reversible multiple hydrogen‐bonds (H‐bonds) that widely exist in biological materials, such as silk and muscle. Recent decades have witnessed the development of many tailor‐made high‐performance H‐bond cross‐linked polymeric materials. Here, recent advances in H‐bond cross‐linking strategies are reviewed for creating high‐performance polymeric materials. H‐bond cross‐linking of polymers can be realized via i) self‐association of interchain multiple H‐bonding interactions or specific H‐bond cross‐linking motifs, such as 2‐ureido‐4‐pyrimidone units with self‐complementary quadruple H‐bonds and ii) addition of external cross‐linkers, including small molecules, nanoparticles, and polymer aggregates. The resultant cross‐linked polymers normally exhibit tunable high strength, large extensibility, improved thermostability, and healable capability. Such performance portfolios enable these advanced polymers to find many significant cutting‐edge applications. Major challenges facing existing H‐bond cross‐linking strategies are discussed, and some promising approaches for designing H‐bond cross‐linked polymeric materials in the future are also proposed.

Tailorable Dynamics in Nonlinear Optical Metasurfaces

By Mengxin Ren, Wei Cai, Jingjun Xu from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

Finding a material with tailorable nonlinearities would be a major breakthrough in nonlinear optics, which in turn promises a bright future for developing multifunctional nonlinear optical devices based on monolithic material frameworks. Recent progress in tailorable nonlinear optical dynamics in metasurfaces is reviewed, and the development trends of nonlinear metasurfaces for weak‐light nonlinear photonics and devices are explored. Abstract Controlling light with light is essential for all‐optical switching, data processing in optical communications and computing. Until now, all‐optical control of light has relied almost exclusively on nonlinear optical interactions in materials. Achieving giant nonlinearities under low light intensity is essential for weak‐light nonlinear optics. In the past decades, such weak‐light nonlinear phenomena have been demonstrated in photorefractive and photochromic materials. However, their bulky size and slow speed have hindered practical applications. Metasurfaces, which enhance light–matter interactions at the nanoscale, provide a new framework with tailorable nonlinearities for weak‐light nonlinear dynamics. Current advances in nonlinear metasurfaces are introduced, with a special emphasis on all‐optical light controls. The tuning of the nonlinearity values using metasurfaces, including enhancement and sign reversal is presented. The tailoring of the transient behaviors of nonlinearities in metasurfaces to achieve femtosecond switching speed is also discussed. Furthermore, the impact of quantum effects from the metasurface on the nonlinearities is introduced. Finally, an outlook on the future development of this energetic field is offered.

Artificial Muscles Powered by Glucose

By Fariba Mashayekhi Mazar, Jose G. Martinez, Manav Tyagi, Mahdi Alijanianzadeh, Anthony P. F. Turner, Edwin W. H. Jager from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

An autonomously powered soft artificial muscle is presented. Enzymes integrated in the actuator catalytically convert glucose in the presence of oxygen into electrical power that powers the electroactive polymer polypyrrole, resulting in a reversible bending. This autonomous artificial muscle is of great interest for soft (micro‐)robotics and implantable or ingestible medical devices that need to maneuver throughout the body. Abstract Untethered actuation is important for robotic devices to achieve autonomous motion, which is typically enabled by using batteries. Using enzymes to provide the required electrical charge is particularly interesting as it will enable direct harvesting of fuel components from a surrounding fluid. Here, a soft artificial muscle is presented, which uses the biofuel glucose in the presence of oxygen. Glucose oxidase and laccase enzymes integrated in the actuator catalytically convert glucose and oxygen into electrical power that in turn is converted into movement by the electroactive polymer polypyrrole causing the actuator to bend. The integrated bioelectrode pair shows a maximum open‐circuit voltage of 0.70 ± 0.04 V at room temperature and a maximum power density of 0.27 μW cm−2 at 0.50 V, sufficient to drive an external polypyrrole‐based trilayer artificial muscle. Next, the enzymes are fully integrated into the artificial muscle, resulting in an autonomously powered actuator that can bend reversibly in both directions driven by glucose and O2 only. This autonomously powered artificial muscle can be of great interest for soft (micro‐)robotics and implantable or ingestible medical devices manoeuvring throughout the body, for devices in regenerative medicine, wearables, and environmental monitoring devices operating autonomously in aqueous environments.

Interface Engineering V2O5 Nanofibers for High‐Energy and Durable Supercapacitors

By Wenchao Bi, Jichao Wang, Evan P. Jahrman, Gerald T. Seidler, Guohua Gao, Guangming Wu, Guozhong Cao from Wiley: Small: Table of Contents. Published on Jun 19, 2019.

Interface modification of V2O5 nanofibers is achieved by inducing oxygen vacancies in one‐step polymerization of polyaniline (PANI) for use in supercapacitors. Charge transfer kinetics of the obtained Vö‐V2O5/PANI nanocables is synergistically enhanced by the local electric field caused by oxygen vacancies and porous PANI shells, leading to an excellent energy density and long cycling life. Abstract A local electric field is induced to engineer the interface of vanadium pentoxide nanofibers (V2O5‐NF) to manipulate the charge transport behavior and obtain high‐energy and durable supercapacitors. The interface of V2O5‐NF is modified with oxygen vacancies (Vö) in a one‐step polymerization process of polyaniline (PANI). In the charge storage process, the local electric field deriving from the lopsided charge distribution around Vö will provide Coulombic forces to promote the charge transport in the resultant Vö‐V2O5/PANI nanocable electrode. Furthermore, an ≈7 nm porous PANI coating serves as the external percolated charge transport pathway. As the charge transfer kinetics are synergistically enhanced by the dual modifications, Vö‐V2O5/PANI‐based supercapacitors exhibit an excellent specific capacitance (523 F g−1) as well as a long cycling lifespan (110% of capacitance remained after 20 000 cycles). This work paves an effective way to promote the charge transfer kinetics of electrode materials for next‐generation energy storage systems.

Enhanced Charge Transport by Incorporating Formamidinium and Cesium Cations for Two‐Dimensional Perovskite Solar Cells

By Kai Zhu, Liguo Gao, Fei Zhang, Xihan Chen, Chuanxiao Xiao, Bryon Larson, Sean Dunfield, Joseph Berry from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 19, 2019.

Organic‐inorganic hybrid two‐dimensional (2D) perovskites (n≤5) have recently attracted significant attention due to their promising stability and optoelectronic properties. Normally, 2D perovskites contain a mono cation (e.g., methylammonium (MA+) or formamidinium (FA+)). Here, we report for the first time on fabricating 2D perovskites (n=5) with mixed cations of MA+, FA+, and cesium (Cs+). The use of these triple cations leads to the formation of a smooth, compact surface morphology with larger grain size and fewer grain boundaries compared to the conventional MA‐based counterpart. The resulting perovskite also exhibits longer carrier lifetime and higher conductivity in triple‐cation 2D perovskite solar cells (PSCs). The power conversion efficiency (PCE) of 2D PSCs with triple cations was enhanced by more than 80% (from 7.80% to 14.23%) compared to PSCs fabricated with a mono cation; the PCE is also higher than that of PSCs based on binary‐cation (MA+‐FA+ or MA+‐Cs+) 2D structures.

Tue 23 Jul 14:00: Deploying Differential Privacy for the 2020 Census of Population and Housing

From All Talks (aka the CURE list). Published on Jun 19, 2019.

Deploying Differential Privacy for the 2020 Census of Population and Housing

When differential privacy was created more than a decade ago, the motivating example was statistics published by an official statistics agency. In theory there is no difference between theory and practice, but in practice there is.

In attempting to transition differential privacy from the theory to practice, and in particular for the 2020 Census of Population and Housing, the U.S. Census Bureau has encountered many challenges unanticipated by differential privacy’s creators. Many of these challenges had less to do with the mathematics of differential privacy and more to do with operational requirements that differential privacy’s creators had not discussed in their writings. These challenges included obtaining qualified personnel and a suitable computing environment, the difficulty of accounting for all uses of the confidential data, the lack of release mechanisms that align with the needs of data users, the expectation on the part of data users that they will have access to micro-data, the difficulty in setting the value of the privacy-loss parameter, ε (epsilon), and the lack of tools and trained individuals to verify the correctness of differential privacy, and push-back from same members of the data user community.

Addressing these concerns required developing a novel hierarchical algorithm that makes extensive use of a high-performance commercial optimizer; transitioning the computing environment to the cloud; educating insiders about differential privacy; engaging with academics, data users, and the general public; and redesigning both data flows inside the Census Bureau and some of the final data publications to be in line with the demands of formal privacy.

Bio: Simson Garfinkel is the Senior Computer Scientist for Confidentiality and Data Access at the US Census Bureau. He holds seven US patents and has published more than 50 research articles in computer security and digital forensics. He is a fellow of the Association for Computing Machinery (ACM) and the Institute of Electrical and Electronics Engineers (IEEE), and a member of the National Association of Science Writers. His most recent book is The Computer Book, which features 250 chronologically arranged milestones in the history of computing. As a journalist, he has written about science, technology, and technology policy in the popular press since 1983, and has won several national journalism awards.

Garfinkel received three Bachelor of Science degrees from MIT in 1987, a Master’s of Science in Journalism from Columbia University in 1988, and a Ph.D. in Computer Science from MIT in 2005.

https://simson.net/bio/

Add to your calendar or Include in your list

A switchable domino process for the construction of novel CO2‐sourced sulfur‐containing building blocks and polymers

By Farid Ouhib, Bruno Grignard, Elias Van Den Broeck, André Luxen, Koen Robeyns, Veronique Van Speybroeck, Christine Jerome, Christophe Detrembleur from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 19, 2019.

α‐alkylidene cyclic carbonates (αCCs) recently emerged as attractive CO2‐sourced synthons for the construction of complex organic molecules. Herein, we report the transformation of αCCs into novel families of sulfur‐containing compounds by organocatalyzed chemoselective addition of thiols, following a domino process that is switched on/off depending on the desired product. The process is extremely fast, versatile in substrate scope, provides selectively linear thiocarbonates or elusive tetrasubstituted ethylene carbonates with high yields following a 100% atom economy reaction, and valorizes CO2 as a renewable feedstock. It is also exploited to produce a large diversity of unprecedented functional polymers. It constitutes a robust platform for the design of new sulfur‐containing organic synthons and important families of polymers.

Sub‐micromolar pulse dipolar EPR spectroscopy reveals increasing CuII‐labelling of double‐histidine motifs with lower temperature.

By Joshua Wort, Katrin Ackermann, Angeliki Giannoulis, Alan Stewart, David Norman, Bela E. Bode from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 19, 2019.

Electron paramagnetic resonance (EPR) distance measurements are making increasingly important contributions to studies of biomolecules underpinning health and disease by providing highly accurate and precise geometric constraints. Combining double‐histidine motifs with Cu(II) spin labels shows promise for further increasing the precision of distance measurements. It also appeals in proteins containing essential cysteines which can interfere with thiol‐specific labelling. However, the non‐covalent Cu(II) coordination approach is vulnerable to low binding‐affinity. Here, dissociation constants (KD) are investigated directly from the cryoprotectant of relaxation induced dipolar modulation enhancement (RIDME) EPR distance experiments. The superb sensitivity of these experiments reveals low‐ to sub‐μM Cu(II) KDs under EPR distance measurement conditions at cryogenic temperatures. We show the feasibility of exploiting the double histidine motif for EPR applications even at sub‐μM protein concentrations in orthogonally‐labelled Cu(II) ‐nitroxide systems using a commercial Q‐band EPR instrument.nd EPR instrument.

Highly Diastereoselective Synthesis of Syn‐1,3‐Dihydroxyketone Motifs from Propargylic Alcohols via Unusual Spiroepoxide Intermediates

By Margaret Anne Brimble, Xiaobo Ding, Daniel Furkert from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 19, 2019.

Syn dihydroxyketone motifs are embedded in a wide range of biologically active natural products, however development of stereoselective synthetic methods to assemble these structures has proven a challenging task to date. We report here a highly diastereoselective method for synthesis of complex syn dihydroxyketones from propargylic alcohols, with wide scope for application in natural product synthesis. The reaction sequence involves regioselective cyclisation of propargylic alcohols with incorporation of a triketone to give enol dioxolanes that are then diastereoselectively epoxidised to form unusual spiroepoxide intermediates. Hydrolysis affords syn dihydroxyketones as essentially single diastereomers. The reaction sequence is operationally simple, of wide substrate scope and remarkably can be efficiently carried out as a one‐pot process with no loss of overall yield or diastereoselectivity.

Active Template Synthesis of Protein Heterocatenanes

By Xiao-Di Da, Wenbin Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 19, 2019.

Covalent bond–forming protein domains can be versatile tools for creating unconventional protein topologies. In this study, through rewiring SpyTag‐SpyCatcher complex to induce rationally designed chain entanglement, we developed a biologically enabled active template for concise, modular and programmable synthesis of protein heterocatenanes both in vitro and in vivo. It is a general and good‐yielding reaction for forming heterocatenanes with precisely controlled ring sizes and broad structural diversity. More importantly, such hetero‐catenation not only provides an efficient means of bioconjugation for integrating multiple native bio‐functions, but also enhances the component proteins’ stability against proteolytic digestion, thermal unfolding, and freeze/thaw–induced mechanical denaturation, thus opening up a versatile path in the nascent field of protein topological engineering.

Formation of CX Bonds in CO2 Chemical Fixation Catalyzed by Metal−Organic Frameworks

By Sheng‐Li Hou, Jie Dong, Bin Zhao from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

The transformation of CO2 into value‐added chemicals has received particular attention in recent years. The formation of covalent bonds between CO2 and substrates catalyzed by metal‐organic frameworks are summarized. The catalytic mechanism of generating different CX bonds is discussed. The critical challenges and potential solutions, future opportunities and prospects in this field are also covered. Abstract Transformation of CO2 based on metal−organic framework (MOF) catalysts is becoming a hot research topic, not only because it will help to reduce greenhouse gas emission, but also because it will allow for the production of valuable chemicals. In addition, a large number of impressive products have been synthesized by utilizing CO2. In fact, it is the formation of new covalent bonds between CO2 and substrate molecules that successfully result in CO2 solidly inserting into the products, and only four types of new CX bonds, including CH, CC, CN, and CO bonds, are observed in this exploration. An overview of recent progress in constructing CX bonds for CO2 conversion catalyzed by various MOF catalysts is provided. The catalytic mechanism of generating different CX bonds is further discussed according to both structural features of MOFs and the interactions among CO2, substrates, as well as MOFs. The future opportunities and challenges in this field are also tentatively covered.

Toward Cluster Materials with Ordered Structures via Self‐Assembly of Heterocluster Janus Molecules

By Li‐Jun Ren, Hong‐Kai Liu, Han Wu, Min‐Biao Hu, Wei Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 19, 2019.

Inspired by lipid self‐assembly and nanocluster functionalities, the design and subsequent creation of a series of heterocluster Janus molecules (HCJMs) are pioneered. Owing to efficient shape control, HCJMs self‐assemble into nanostructures that can go beyond those of predicated nanoaggregates of traditional amphiphiles. Thus, an efficient strategy for bridging the gap between clusters and cluster materials is established. Abstract Cluster materials have attracted much attention because of their unique chemical and physical properties, hitherto unseen in bulk materials. Inspired by the lipid self‐assembly principle, a series of heterocluster Janus molecules (HCJMs) with atomic precision have been rationally designed and synthesized by connecting different clusters via covalent bonds for the construction of nanomaterials and nano‐objects. Due to their amphiphilicity, HCJMs self‐assemble into cluster‐containing nanomaterials or nano‐objects with versatile ordered structures beyond those observed in conventional crystals. Their hybrid composition and nanoscale size are also greatly advantageous in the study of their fine structure by electron microscopy techniques, and enable their formation mechanisms to be unraveled. Finally, the influence of the characteristics of the HCJMs on the structure and properties of the self‐assembled nano‐objects are explored comprehensively. This synthesis strategy will promote further development of cluster materials with advanced functions via rational molecular design toward the construction of hierarchical nanostructures via molecular self‐assembly.

Dendrimer conjugation enables multiphoton chemical neurophysiology with an extended π‐electron caging chromophore

By Matthew T. Richers, Stefan Passlick, Hitesh Agarwal, Graham Ellis-Davies from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 19, 2019.

We have developed a caged neurotransmitter using an extended π‐electron chromophore for efficient multiphoton uncaging on living neurons. Widely studied in a chemical context, such chromophores are inherently bioincompatible due to their highly lipophilic character. Attachment of two polycarboxylate dendrimers, a method we call "cloaking", to a bisstyrylthiophene (or BIST) core effectively transformed the chromophore into a water‐soluble optical bioprobe, whilst maintaining the high two‐photon absorption of >500 GM. Importantly, the cloaked caged compound was biologically inert at high concentrations required for multiphoton chemical physiology. Thus, in contrast to non‐cloaked BIST compounds, this allowed safe delivery of a BIST‐caged neurotransmitter onto neurons in acutely isolated brain slices, enabling high‐resolution two‐photon uncaging without any side effects. We expect that our cloaking method will enable the development of new classes of cell‐compatible photolabile probes using a wide variety of extended π‐electron caging chromophores.

Wed 06 Nov 16:00: TBC

From All Talks (aka the CURE list). Published on Jun 19, 2019.

TBC

Abstract not available

Add to your calendar or Include in your list

Fri 20 Mar 09:00: The Futures of Medicine - One Day meeting ONE DAY MEETING FREE ENTRY NO BOOKING REQUIRED

From All Talks (aka the CURE list). Published on Jun 19, 2019.

The Futures of Medicine - One Day meeting

Abstract not available

ONE DAY MEETING FREE ENTRY NO BOOKING REQUIRED

Add to your calendar or Include in your list

Thu 27 Jun 14:30: Microbes as medicines: the emergence of live biotherapeutics To register to attend: https://microbes-as-medicines.eventbrite.co.uk

From All Talks (aka the CURE list). Published on Jun 19, 2019.

Microbes as medicines: the emergence of live biotherapeutics

The human gut microbiome is essential to our health and imbalances in the microbiota are thought to underpin many human diseases. Advances in microbiology and genomics in recent years have made the microbiome more accessible to scientists who want to exploit it for the development of new drugs. This talk will discuss the human gut microbiota, how it influences our health, and how it can be targeted and leveraged for the development of new medicines to treat human diseases.

To register to attend: https://microbes-as-medicines.eventbrite.co.uk

Add to your calendar or Include in your list

[ASAP] Antioxidative Lithium Reservoir Based on Interstitial Channels of Carbon Nanotube Bundles

By Seok-Kyu Cho†, Gwan Yeong Jung†, Keun-Ho Choi‡, Jiyun Lee†, JongTae Yoo*§, Sang Kyu Kwak*†, and Sang-Young Lee*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01334

[ASAP] Liquid-Phase Electron Microscopy with Controllable Liquid Thickness

By Sercan Keskin†, Peter Kunnas†, and Niels de Jonge*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01576

[ASAP] Thermal Expansion Coefficient of Monolayer Molybdenum Disulfide Using Micro-Raman Spectroscopy

By Lenan Zhang, Zhengmao Lu, Youngsup Song, Lin Zhao, Bikram Bhatia, Kevin R. Bagnall, and Evelyn N. Wang* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01829

[ASAP] Correction to In Situ X-ray Absorption Spectroscopic Investigation of the Capacity Degradation Mechanism in Mg/S Batteries

By Yan Xu, Yifan Ye, Shuyang Zhao, Jun Feng, Jia Li, Hao Chen, Ankun Yang, Feifei Shi, Lujie Jia, Yang Wu, Xiaoyun Yu, Per-Anders Glans-Suzuki, Yi Cui, Jinghua Guo*, and Yuegang Zhang* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 19, 2019.

Nano Letters
DOI: 10.1021/acs.nanolett.9b02364

[ASAP] Interfacial Junctions Control Electrolyte Transport through Charge-Patterned Membranes

By Feng Gao, Aaron Hunter, Siyi Qu, John R. Hoffman, Peng Gao, and William A. Phillip* from ACS Nano: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00780

[ASAP] End-Bonded Metal Contacts on WSe2 Field-Effect Transistors

By Chun-Hao Chu†, Ho-Chun Lin‡§, Chao-Hui Yeh†, Zheng-Yong Liang†, Mei-Yin Chou‡§, and Po-Wen Chiu*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03250

[ASAP] Controlled Patterning of Carbon Nanotube Energy Levels by Covalent DNA Functionalization

By Yu Zheng†, Sergei M. Bachilo†, and R. Bruce Weisman*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03488

[ASAP] Dehydroxymethylation of Alcohols Enabled by Cerium Photocatalysis

By Kaining Zhang†, Liang Chang†, Qing An, Xin Wang, and Zhiwei Zuo* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05932

[ASAP] Nanorg Microbial Factories: Light-Driven Renewable Biochemical Synthesis Using Quantum Dot-Bacteria Nanobiohybrids

By Yuchen Ding†‡§?, John R. Bertram§??, Carrie Eckert§?, Rajesh Reddy Bommareddy#, Rajan Patel#, Alex Conradie?, Samantha Bryan?, and Prashant Nagpal*†§? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02549

[ASAP] Rapid Structure Determination of Molecular Solids Using Chemical Shifts Directed by Unambiguous Prior Constraints

By Albert Hofstetter†, Martins Balodis†, Federico M. Paruzzo†, Cory M. Widdifield§, Gabriele Stevanato†, Arthur C. Pinon†, Peter J. Bygrave‡, Graeme M. Day‡, and Lyndon Emsley*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03908

[ASAP] Catalytic and Asymmetric Process via PIII/PV-O Redox Cycling: Access to (Trifluoromethyl)cyclobutenes via a Michael Addition/Wittig Olefination Reaction

By Charlotte Lorton, Thomas Castanheiro, and Arnaud Voituriez* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02539

[ASAP] Synthesis of (±)-Idarubicinone via Global Functionalization of Tetracene

By David G. Dennis, Mikiko Okumura, and David Sarlah* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05370

[ASAP] Stereochemical Revision, Total Synthesis, and Solution State Conformation of the Complex Chlorosulfolipid Mytilipin B

By Philipp Sondermann and Erick M. Carreira* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05013

[ASAP] Freestanding Cubic ZrN Single-Crystalline Films with Two-Dimensional Superconductivity

By Yuqiao Guo§†, Jing Peng§†, Wei Qin‡, Jiang Zeng‡, Jiyin Zhao†, Jiajing Wu†, Wangsheng Chu?, Linjun Wang†, Changzheng Wu*†, and Yi Xie† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05114

[ASAP] Off-Pathway Assembly: A Broad-Spectrum Mechanism of Action for Drugs That Undermine Controlled HIV-1 Viral Capsid Formation

By Alexander J. Pak, John M. A. Grime, Alvin Yu, and Gregory A. Voth* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01413

[ASAP] Harnessing Dielectric Confinement on Tin Perovskites to Achieve Emission Quantum Yield up to 21%

By Jin-Tai Lin†, Chen-Cheng Liao‡, Chia-Shuo Hsu†, Deng-Gao Chen†, Hao-Ming Chen*†, Ming-Kang Tsai*‡, Pi-Tai Chou*†§, and Ching-Wen Chiu*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03148

[ASAP] An Efficient Modular One-Pot Synthesis of Heparin-Based Anticoagulant Idraparinux

By Supriya Dey†, Hong-Jay Lo†, and Chi-Huey Wong*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03266

[ASAP] Generation of N-Centered Radicals via a Photocatalytic Energy Transfer: Remote Double Functionalization of Arenes Facilitated by Singlet Oxygen

By Vineet Kumar Soni†, Ho Seong Hwang†, Yu Kyung Moon‡, Sung-Woo Park§, Youngmin You*‡, and Eun Jin Cho*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b05572

[ASAP] Native Ion Mobility-Mass Spectrometry Reveals the Formation of ß-Barrel Shaped Amyloid-ß Hexamers in a Membrane-Mimicking Environment

By Nicklas O¨sterlund†, Rani Moons‡, Leopold L. Ilag§, Frank Sobott*‡??, and Astrid Gra¨slund*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04596

[ASAP] Activatable NIR Fluorescence/MRI Bimodal Probes for in Vivo Imaging by Enzyme-Mediated Fluorogenic Reaction and Self-Assembly

By Runqi Yan†?, Yuxuan Hu†?, Fei Liu†, Shixuan Wei†, Daqing Fang‡, Adam J. Shuhendler§, Hong Liu‡, Hong-Yuan Chen†, and Deju Ye*†? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03649

[ASAP] Spotlights on Recent JACS Publications

By ACS Contributing Correspondents from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 19, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06488

Bridging the gap

By Bartel Van Waeyenberge from Nature Materials - Issue - nature.com science feeds. Published on Jun 19, 2019.

Nature Materials, Published online: 19 June 2019; doi:10.1038/s41563-019-0411-7

The chiral magnetic exchange interaction, or Dzyaloshinskii–Moriya interaction, is found to propagate through dozens of atomic layers and also to be present in inhomogeneous amorphous alloys. These discoveries extend the parameter space available for realizing magnetic structures with chiral character.

New dating agency for artists

By Philip Ball from Nature Materials - Issue - nature.com science feeds. Published on Jun 19, 2019.

Nature Materials, Published online: 19 June 2019; doi:10.1038/s41563-019-0417-1

New dating agency for artists

Rydberg spectroscopy of indirect excitons

By Steven T. Cundiff from Nature Materials - Issue - nature.com science feeds. Published on Jun 19, 2019.

Nature Materials, Published online: 19 June 2019; doi:10.1038/s41563-019-0410-8

Measuring the 1s–2p splitting of direct and indirect excitons in van der Waals heterostructures allows their binding energy and dynamics to be determined.

Platelet mechanosensing axis revealed

By Xuanhong Cheng from Nature Materials - Issue - nature.com science feeds. Published on Jun 19, 2019.

Nature Materials, Published online: 19 June 2019; doi:10.1038/s41563-019-0393-5

An intermediate affinity state of integrin αIIBβ3 has been identified to be a key player in platelet mechanosignalling.

Catalytic sites are finally in sight

By E. Charles H. Sykes from Nature Materials - Issue - nature.com science feeds. Published on Jun 19, 2019.

Nature Materials, Published online: 19 June 2019; doi:10.1038/s41563-019-0400-x

Controlled Pt loading on TiO2 nanoparticles enables single-site catalysts. With this, the coordination environment and catalytic activity can be obtained, allowing extraction of structure-function information.

The magnetic landscape

From Nature Materials - Issue - nature.com science feeds. Published on Jun 19, 2019.

Nature Materials, Published online: 19 June 2019; doi:10.1038/s41563-019-0420-6

Synergy between materials and methods is helping to address open questions in magnetism and superconductivity.

High‐Performance Hierarchical Black‐Phosphorous‐Based Soft Electrochemical Actuators in Bioinspired Applications

By Guan Wu, Xingjiang Wu, Yijun Xu, Hengyang Cheng, Jinku Meng, Qiang Yu, Xinyiao Shi, Kai Zhang, Wei Chen, Su Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A new electrochemical actuator based on hierarchically structured and covalently bridged black phosphorous/carbon nanotube hybrid electrodes is developed. Due to the hierarchically structured materials with ordered lamellar‐framework and large redox activity for ions' smooth diffusion and flooding accommodation, the actuator displays higher electromechanical performance, including low power consumption/strain, large peak‐to‐peak strain, faster strain and stress rates, high power and energy densities, and biomimetic applications. Abstract Bioinspired methods allowing artificial actuators to perform controllably are potentially important for various principles and may offer fundamental insight into chemistry and engineering. To date, the main challenges persist regarding the achievement of large deformation in fast response‐time and potential‐engineering applications in which electrode materials and structures limit ion diffusion and accumulation processes. Herein, a novel electrochemical actuator is developed that presents both higher electromechanical performances and biomimetic applications based on hierachically structured covalently bridged black phosphorous/carbon nanotubes. The new actuator demonstrates astonishing actuation properties, including low power consumption/strain (0.04 W cm−2 %−1), a large peak‐to‐peak strain (1.67%), a controlled frequency response (0.1–20 Hz), faster strain and stress rates (11.57% s−1; 28.48 MPa s−1), high power (29.11 kW m−3), and energy (8.48 kJ m−3) densities, and excellent cycling stability (500 000 cycles). More importantly, bioinspired applications such as artificial‐claw, wings‐vibrating, bionic‐flower, and hand actuators have been realized. The key to high performances stems from hierachically structured materials with an ordered lamellar structure, large redox activity, and electrochemical capacitance (321.4 F g−1) for ions with smooth diffusion and flooding accommodation, which will guide substantial progress of next‐generation electrochemical actuators.

Manipulating the Mixed‐Perovskite Crystallization Pathway Unveiled by In Situ GIWAXS

By Minchao Qin, Kinfai Tse, Tsz‐Ki Lau, Yuhao Li, Chun‐Jen Su, Guang Yang, Jiehuan Chen, Junyi Zhu, U‐Ser Jeng, Gang Li, Hongzheng Chen, Xinhui Lu from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

The crystallization pathways of mixed perovskites under spin‐coating are investigated via in situ grazing‐incidence wide‐angle X‐ray scattering (GIWAXS), which reveals the existence of an “annealing window”. The as‐cast film should be timely annealed within the annealing window to achieve a high‐quality perovskite film. The incorporation of Cs+ can remarkably extend the annealing window, thereby improving the device performance and reproducibility. Abstract Mixed perovskites have achieved substantial successes in boosting solar cell efficiency, but the complicated perovskite crystal formation pathway remains mysterious. Here, the detailed crystallization process of mixed perovskites (FA0.83MA0.17Pb(I0.83Br0.17)3) during spin‐coating is revealed by in situ grazing‐incidence wide‐angle X‐ray scattering measurements, and three phase‐formation stages are identified: I) precursor solution; II) hexagonal δ‐phase (2H); and III) complex phases including hexagonal polytypes (4H, 6H), MAI–PbI2–DMSO intermediate phases, and perovskite α‐phase. The correlated device performance and ex situ characterizations suggest the existence of an “annealing window” covering the duration of stage II. The spin‐coated film should be annealed within the annealing window to avoid the formation of hexagonal polytypes during the perovskite crystallization process, thus achieving a good device performance. Remarkably, the crystallization pathway can be manipulated by incorporating Cs+ ions in mixed perovskites. Combined with density functional theory calculations, the perovskite system with sufficient Cs+ will bypass the formation of secondary phases in stage III by promoting the formation of α‐phase both kinetically and thermodynamically, thereby significantly extending the annealing window. This study provides underlying reasons of the time sensitivity of fabricating mixed‐perovskite devices and insightful guidelines for manipulating the perovskite crystallization pathways toward higher performance.

Integration of Electrochemical Microsupercapacitors with Thin Film Electronics for On‐Chip Energy Storage

By Mrinal K. Hota, Qiu Jiang, Zhenwei Wang, Zhong Lin Wang, Khaled N. Salama, Husam N. Alshareef from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

On‐chip electrochemical energy storage is integrated with thin‐film electronics at the transistor level. A single electrode material (RuO2) is used for transistors, rectifiers, and microsupercapacitors. The functionality of the integrated devices is successfully demonstrated, and used to power several electronic devices. Abstract The development of self‐powered electronic systems requires integration of on‐chip energy‐storage units to interface with various types of energy harvesters, which are intermittent by nature. Most studies have involved on‐chip electrochemical microsupercapacitors that have been interfaced with energy harvesters through bulky Si‐based rectifiers that are difficult to integrate. This study demonstrates transistor‐level integration of electrochemical microsupercapacitors and thin film transistor rectifiers. In this approach, the thin film transistors, thin film rectifiers, and electrochemical microsupercapacitors share the same electrode material for all, which allows for a highly integrated electrochemical on‐chip storage solution. The thin film rectifiers are shown to be capable of rectifying AC signal input from either triboelectric nanogenerators or standard function generators. In addition, electrochemical microsupercapacitors exhibit exceptionally slow self‐discharge rate (≈18.75 mV h−1) and sufficient power to drive various electronic devices. This study opens a new avenue for developing compact on‐chip electrochemical micropower units integrated with thin film electronics.

Curvature‐Controlled Wrinkling Surfaces for Friction

By Haozhi Yuan, Kai Wu, Jinyu Zhang, Yaqiang Wang, Gang Liu, Jun Sun from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Curvature‐controlled wrinkling surfaces are fabricated on spherical metal/polymer systems by sputtering methods. The wrinkled surfaces exhibit controlled friction, depending on wrinkling patterns and length scales. The dimple patterns and labyrinth patterns show almost isotropic friction, while the herringbone patterns exhibit apparent friction anisotropy with respect to topographic orientation. This study provides a strategy to tune friction by harnessing substrate curvature. Abstract Topographical patterns endow material surfaces with unique and intriguing physical and chemical properties. Spontaneously formed wrinkling has been harnessed to generate surface topography for various functionalities. Despite promising applications in biomedical devices and robot engineering, the friction behavior of wrinkling on curved surfaces remains unclear. Herein, wrinkled surfaces are induced by sputtering metals on soft polymer microspheres. The wrinkle morphologies and length scales can be controlled precisely by tailoring the microsphere radius (substrate curvature) and film thickness. The wrinkled surfaces exhibit controlled friction property, depending on the wrinkling patterns and length scales. An increase in friction force with increasing surface roughness is generally found for dimple patterns and labyrinth patterns. The dimple patterns show the lowest friction due to strong curvature constraint. The herringbone patterns exhibit apparent friction anisotropy with respect to topographic orientation. These results will guide future design of wrinkled surfaces for friction by harnessing substrate curvature.

Conical Hollow Microhelices with Superior Swimming Capabilities for Targeted Cargo Delivery

By Chen Xin, Liang Yang, Jiawen Li, Yanlei Hu, Dongdong Qian, Shengying Fan, Kai Hu, Ze Cai, Hao Wu, Dawei Wang, Dong Wu, Jiaru Chu from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A designable conical hollow microhelix is rapidly fabricated by femtosecond vortex beams along helical scanning. The conical microhelices demonstrate faster forward velocity for fast cargo delivery and reduce drift velocity for precise guiding compared with straight microhelices. Their applications in transportation of nano/microcargoes for chemical microreaction and biomedical research are realized. Abstract Inspired by flagellate microorganisms in nature, the microhelix is considered as an ideal model for transportation in fluid environment with low Reynolds number. However, how to promote the swimming and loading capabilities of microhelices with controllable geometries remains challenging. In this study, a novel kind of conical hollow microhelices is proposed and a method is developed to rapidly fabricate these microhelices with controllable parameters by femtosecond vortex beams generated from spatial light modulation along helical scanning. Conical hollow microhelices with designable heights (H = 45–75 µm), diameters (D = 6–18 µm), pitch numbers (Pi = 2–4), taper angles (T = 0.1–0.6 rad), and pitch periods (ΔP = 10–30 µm) are efficiently fabricated. In addition, compared with straight microhelices, the forward swimming capability of conical microhelices increases by 50% and the lateral drift of the conical hollow microhelices is reduced by 70%. Finally, the capabilities of these conical hollow microhelices for nanocargo loading and release by the inner hollow core, as well as transportation of neural stem cells by the outer surface are demonstrated. This work provides new insights into faster and simultaneous transportation of multicargoes for hybrid drug delivery, targeted therapy, and noninvasive surgery in vivo.

Zinc‐Tiered Synthesis of 3D Graphene for Monolithic Electrodes

By Xiang‐Fen Jiang, Ruiqing Li, Ming Hu, Zheng Hu, Dmitri Golberg, Yoshio Bando, Xue‐Bin Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A novel mechanism of impregnation‐and‐delamination of a solid char into multiple membranes by zinc is proposed for yielding graphene in pyrolysis of glucose. The produced all‐membrane 3D graphene monolith possesses superior surface area, conductivity, stability, and morphological purity. It is further applied to supercapacitors with high energy, power, and life, which illuminates a versatile porous monolithic electrochemical electrode. Abstract A high‐surface‐area conductive cellular carbon monolith is highly desired as the optimal electrode for achieving high energy, power, and lifetime in electrochemical energy storage. 3D graphene can be regarded as a first‐ranking member of cellular carbons with the pore‐wall thickness down to mono/few‐atomic layers. Current 3D graphenes, derived from either gelation or pyrolysis routes, still suffer from low surface area, conductivity, stability, and/or yield, being subjected to methodological inadequacies including patchy assembly, wet processing, and weak controllability. Herein, a strategy of zinc‐assisted solid‐state pyrolysis to produce a superior 3D graphene is established. Zinc unprecedentedly impregnates and delaminates a solid (“nonhollow”) char into multiple membranes, which eliminates the morphological impurities ever‐present in the previous pyrolyses using solid‐state carbon precursors. Zinc also catalyzes the carbonization and graphitization, and its in situ thermal extraction and recycling enables the scaled‐up production. The created 3D graphene network consists integrally of morphologically and chemically pure graphene membranes. It possesses unrivaled surface area, outstanding stability, and conductivity both in air and electrolyte, exceeding preexisting 3D graphenes. The advanced 3D graphene thus equips a porous monolithic electrode with unparalleled energy density, power density, and lifetime in electric‐double‐layer capacitive devices.

A Hypoxia‐Responsive Albumin‐Based Nanosystem for Deep Tumor Penetration and Excellent Therapeutic Efficacy

By Guangbao Yang, Soo Zeng Fiona Phua, Wei Qi Lim, Rui Zhang, Liangzhu Feng, Guofeng Liu, Hongwei Wu, Anivind Kaur Bindra, Deblin Jana, Zhuang Liu, Yanli Zhao from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A hypoxia‐responsive albumin‐based nanosystem can be dissociated into individual therapeutic agents with sizes below 10 nm for increased intratumoral permeability under a tumor's hypoxic environment. The photoactivity of the loaded chlorin e6 is activated with recovered fluorescence and increased singlet oxygen production, achieving superior antitumor treatment on animal models through combined photodynamic therapy and chemotherapy. Abstract Uncontrolled cancer cell proliferation, insufficient blood flow, and inadequate endogenous oxygen lead to hypoxia in tumor tissues. Herein, a unique type of hypoxia‐responsive human serum albumin (HSA)‐based nanosystem (HCHOA) is reported, prepared by cross‐linking the hypoxia‐sensitive azobenzene group between photosensitizer chlorin e6 (Ce6)‐conjugated HSA (HC) and oxaliplatin prodrug‐conjugated HSA (HO). The HCHOA nanosystem is stable under normal oxygen partial pressure with a size of 100–150 nm. When exposed to the hypoxic tumor microenvironment, the nanosystem can quickly dissociate into ultrasmall HC and HO therapeutic nanoparticles with a diameter smaller than 10 nm, significantly enabling their enhanced intratumoral penetration. After the dissociation, the quenched fluorescence of Ce6 in the produced HC nanoparticles can be recovered for bioimaging. At the same time, the production of singlet oxygen is increased because of the enhancement in the photoactivity of the photosensitizer. On account of these improvements, combined photodynamic therapy and chemotherapy is realized to display superior antitumor efficacy in vivo. Based on this simple strategy, it is possible to achieve the dissociation of hypoxic‐responsive nanosystem to enhance the tumor penetration and therapeutic effect.

Perovskite Grains Embraced in a Soft Fullerene Network Make Highly Efficient Flexible Solar Cells with Superior Mechanical Stability

By Meng Li, Ying‐Guo Yang, Zhao‐Kui Wang, Tin Kang, Qiong Wang, Silver‐Hamill Turren‐Cruz, Xing‐Yu Gao, Chain‐Shu Hsu, Liang‐Sheng Liao, Antonio Abate from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Embracing perovskite grains in a soft fullerene network represents a new and scalable approach, to make perovskite mechanically stable and thus compatible with flexible substrates. The method is demonstrated to prepare flexible perovskite solar cells with the highest ever reported power conversion efficiency. The superior mechanical stability from device performance under working conditions is characterized in situ. Abstract Halide perovskite films processed from solution at low‐temperature offer promising opportunities to make flexible solar cells. However, the brittleness of perovskite films is an issue for mechanical stability in flexible devices. Herein, photo‐crosslinked [6,6]‐phenylC61‐butyric oxetane dendron ester (C‐PCBOD) is used to improve the mechanical stability of methylammonium lead iodide (MAPbI3) perovskite films. Also, it is demonstrated that C‐PCBOD passivates the grain boundaries, which reduces the formation of trap states and enhances the environmental stability of MAPbI3. Thus, MAPbI3 perovskite solar cells are prepared on solid and flexible substrates with record efficiencies of 20.4% and 18.1%, respectively, which are among the highest ever reported for MAPbI3 on both flexible and solid substrates. The result of this work provides a step improvement toward stable and efficient flexible perovskite solar cells.

Quantifying Quasi‐Fermi Level Splitting and Mapping its Heterogeneity in Atomically Thin Transition Metal Dichalcogenides

By Mike Tebyetekerwa, Jian Zhang, Kun Liang, The Duong, Guru Prakash Neupane, Linglong Zhang, Boqing Liu, Thien N. Truong, Rabin Basnet, Xiaojing Qiao, Zongyou Yin, Yuerui Lu, Daniel Macdonald, Hieu T. Nguyen from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

2D atomically thin transition metal dichalcogenides (TMDs) show a remarkable light–matter interaction and atomic thickness. The possible maximum open‐circuit voltages, one of the most important photovoltaic parameters, of monolayer TMD‐based solar cells are quantified. The values determined from this work reveal the potential of atomically thin TMDs for high‐voltage, ultralight, flexible, and eye‐transparent future photovoltaic devices. Abstract One of the most fundamental parameters of any photovoltaic material is its quasi‐Fermi level splitting (∆µ) under illumination. This quantity represents the maximum open‐circuit voltage (Voc) that a solar cell fabricated from that material can achieve. Herein, a contactless, nondestructive method to quantify this parameter for atomically thin 2D transition metal dichalcogenides (TMDs) is reported. The technique is applied to quantify the upper limits of Voc that can possibly be achieved from monolayer WS2, MoS2, WSe2, and MoSe2‐based solar cells, and they are compared with state‐of‐the‐art perovskites. These results show that Voc values of ≈1.4, ≈1.12, ≈1.06, and ≈0.93 V can be potentially achieved from solar cells fabricated from WS2, MoS2, WSe2, and MoSe2 monolayers at 1 Sun illumination, respectively. It is also observed that ∆µ is inhomogeneous across different regions of these monolayers. Moreover, it is attempted to engineer the observed ∆µ heterogeneity by electrically gating the TMD monolayers in a metal‐oxide‐semiconductor structure that effectively changes the doping level of the monolayers electrostatically and improves their ∆µ heterogeneity. The values of ∆µ determined from this work reveal the potential of atomically thin TMDs for high‐voltage, ultralight, flexible, and eye‐transparent future solar cells.

Phase‐Tunable Synthesis of Ultrathin Layered Tetragonal CoSe and Nonlayered Hexagonal CoSe Nanoplates

By Huifang Ma, Zhong Wan, Jia Li, Ruixia Wu, Zhengwei Zhang, Bo Li, Bei Zhao, Qi Qian, Yuan Liu, Qinglin Xia, Guanghua Guo, Xidong Duan, Xiangfeng Duan from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Ultrathin CoSe nanoplates with tunable structure phases are synthesized by a chemical vapor deposition route. Electrical transport studies reveal that both types of CoSe nanoplates show strong thickness‐tunable electrical properties, excellent breakdown current density, yet distinct conductance trends with the decreasing temperature. The tetragonal CoSe nanoplates show angle‐dependent magnetoresistance and weak antilocalization at lower field. Abstract Multiple structural phases in transition metal dichalcogenides have attracted considerable recent interest for their tunable chemical and electronic properties. Herein, a chemical vapor deposition route to ultrathin CoSe nanoplates with tunable structure phases is reported. By precisely tailoring the growth temperature, ultrathin 2D layered tetragonal CoSe nanoplates and nonlayered hexagonal CoSe nanoplates can be selectively prepared as square or hexagonal geometries, with thickness as thin as 2.3 and 3.7 nm, respectively. X‐ray diffraction, transmission electron microscopy, and selected area electron diffraction studies show that both types of nanoplates are high‐quality single crystals. Electrical transport studies reveal that both the tetragonal and hexagonal CoSe nanoplates show strong thickness‐tunable electrical properties and excellent breakdown current density. The 2D hexagonal CoSe nanoplates display metallic behavior with an excellent conductivity up to 6.6 × 105 S m−1 and an extraordinary breakdown current density up to 3.9 × 107 A cm−2, while the square tetragonal nanoplates show considerably lower conductivity up to 8.2 × 104 S m−1 with angle‐dependent magnetoresistance and weak antilocalization effect at lower field. This study offers a tunable material system for exploring multiphase 2D materials and their potential applications for electronic and magnetoelectronic devices.

Zero‐Field Nernst Effect in a Ferromagnetic Kagome‐Lattice Weyl‐Semimetal Co3Sn2S2

By Satya N. Guin, Praveen Vir, Yang Zhang, Nitesh Kumar, Sarah J. Watzman, Chenguang Fu, Enke Liu, Kaustuv Manna, Walter Schnelle, Johannes Gooth, Chandra Shekhar, Yan Sun, Claudia Felser from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A zero‐field Nernst effect in the ferromagnetic Weyl‐semimetal Co3Sn2S2 is reported. A maximum Nernst thermopower of ≈3 µV K−1 at 80 K in zero field is achieved. This study shows the potential of the search for new hard magnets from the library of topological materials for the generation of larger and potentially useful levels of Nernst thermopower. Abstract The discovery of magnetic topological semimetals has recently attracted significant attention in the field of topology and thermoelectrics. In a thermoelectric device based on the Nernst geometry, an external magnet is required as an integral part. Reported is a zero‐field Nernst effect in a newly discovered hard‐ferromagnetic kagome‐lattice Weyl‐semimetal Co3Sn2S2. A maximum Nernst thermopower of ≈3 µV K−1 at 80 K in zero field is achieved in this magnetic Weyl‐semimetal. The results demonstrate the possibility of application of topological hard magnetic semimetals for low‐power thermoelectric devices based on the Nernst effect and are thus valuable for the comprehensive understanding of transport properties in this class of materials.

Promoting the Transformation of Li2S2 to Li2S: Significantly Increasing Utilization of Active Materials for High‐Sulfur‐Loading Li–S Batteries

By Xiaofei Yang, Xuejie Gao, Qian Sun, Sara Panahian Jand, Ying Yu, Yang Zhao, Xia Li, Keegan Adair, Liang‐Yin Kuo, Jochen Rohrer, Jianneng Liang, Xiaoting Lin, Mohammad Norouzi Banis, Yongfeng Hu, Hongzhang Zhang, Xianfeng Li, Ruying Li, Huamin Zhang, Payam Kaghazchi, Tsun‐Kong Sham, Xueliang Sun from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Amorphous CoS3 are developed to promote the solid–solid conversion from solid‐state intermediate product Li2S2 to the final discharge product Li2S, which significantly increased the sulfur utilizations for over 20% for high loading electrodes. Abstract Lithium–sulfur (Li–S) batteries with high sulfur loading are urgently required in order to take advantage of their high theoretical energy density. Ether‐based Li–S batteries involve sophisticated multistep solid–liquid–solid–solid electrochemical reaction mechanisms. Recently, studies on Li–S batteries have widely focused on the initial solid (sulfur)–liquid (soluble polysulfide)–solid (Li2S2) conversion reactions, which contribute to the first 50% of the theoretical capacity of the Li–S batteries. Nonetheless, the sluggish kinetics of the solid–solid conversion from solid‐state intermediate product Li2S2 to the final discharge product Li2S (corresponding to the last 50% of the theoretical capacity) leads to the premature end of discharge, resulting in low discharge capacity output and low sulfur utilization. To tackle the aforementioned issue, a catalyst of amorphous cobalt sulfide (CoS3) is proposed to decrease the dissociation energy of Li2S2 and propel the electrochemical transformation of Li2S2 to Li2S. The CoS3 catalyst plays a critical role in improving the sulfur utilization, especially in high‐loading sulfur cathodes (3–10 mg cm−2). Accordingly, the Li2S/Li2S2 ratio in the discharge products increased to 5.60/1 from 1/1.63 with CoS3 catalyst, resulting in a sulfur utilization increase of 20% (335 mAh g−1) compared to the counterpart sulfur electrode without CoS3.

SupraCells: Living Mammalian Cells Protected within Functional Modular Nanoparticle‐Based Exoskeletons

By Wei Zhu, Jimin Guo, Shahrouz Amini, Yi Ju, Jacob Ongudi Agola, Andreas Zimpel, Jin Shang, Achraf Noureddine, Frank Caruso, Stefan Wuttke, Jonas G. Croissant, C. Jeffrey Brinker from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A new concept of “SupraCells,” which are mammalian cells encapsulated within modular nanoparticle‐based exoskeletons, is introduced. A SupraCell induces a spore‐like state, wherein cells do not replicate or spread but are endowed with extremophile properties, for example, resistance to osmotic stress, reactive oxygen species, and pH, along with abiotic properties like magnetism, conductivity, and multifluorescence, which are foreign to native cells. Abstract Creating a synthetic exoskeleton from abiotic materials to protect delicate mammalian cells and impart them with new functionalities could revolutionize fields like cell‐based sensing and create diverse new cellular phenotypes. Herein, the concept of “SupraCells,” which are living mammalian cells encapsulated and protected within functional modular nanoparticle‐based exoskeletons, is introduced. Exoskeletons are generated within seconds through immediate interparticle and cell/particle complexation that abolishes the macropinocytotic and endocytotic nanoparticle internalization pathways that occur without complexation. SupraCell formation is shown to be generalizable to wide classes of nanoparticles and various types of cells. It induces a spore‐like state, wherein cells do not replicate or spread on surfaces but are endowed with extremophile properties, for example, resistance to osmotic stress, reactive oxygen species, pH, and UV exposure, along with abiotic properties like magnetism, conductivity, and multifluorescence. Upon decomplexation cells return to their normal replicative states. SupraCells represent a new class of living hybrid materials with a broad range of functionalities.

3D Pixel Mechanical Metamaterials

By Fei Pan, Yilun Li, Zhaoyu Li, Jialing Yang, Bin Liu, Yuli Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A mechanical pixel design strategy for 3D metamaterials is proposed. Similar to a screen that displays images by adjusting the colors of pixels, using this strategy, the metamaterials can form and reconfigure complex 3D morphologies by tuning the heights (lengths) of the mechanical pixels, and thus gain extremely large shear deformation, ultrarich programmability, and efficient shape‐reconfigurability. Abstract Metamaterials have unprecedented properties that facilitate the development of advanced devices and machines. However, their interconnected building structures limit their applications, especially in the fields that require large deformation, rich programmability and efficient shape‐reconfigurability. To break this limit and exploit more potentialities of metamaterials, an innovative material design strategy is proposed, named mechanical pixel (MP) array design. Similar to a screen that displays images by adjusting the colors of pixels, the metamaterials can form and reconfigure 3D morphologies by tuning the heights (lengths) of the MPs in the array. The strategy is demonstrated in a multistable metamaterial by experimental tests, theoretical analysis, and numerical simulations. Using this strategy, a large macroscopic shear deformation is obtained, and remarkable enhancements in the mechanical programmability, shape‐reconfigurability and adaptability, and reusable shock‐resistance are exhibited. Moreover, mechanical design and property prediction for the metamaterials are both greatly simplified due to the pixelated design. For a piece of the 3D pixel metamaterial with m n‐unit MPs, the number of programmable displacement–force curves increases from n+1 to 2m∙n+1, and the number of stable morphologies grows from n+1 to at least (n+1)m. This strategy can be used to enhance the merits and further excavate the potential of versatile metamaterials.

A Hierarchical Nanoparticle‐in‐Micropore Architecture for Enhanced Mechanosensitivity and Stretchability in Mechanochromic Electronic Skins

By Jonghwa Park, Youngoh Lee, Meredith H. Barbee, Soowon Cho, Seungse Cho, Ravi Shanker, Jinyoung Kim, Jinyoung Myoung, Minsoo P. Kim, Chunggi Baig, Stephen L. Craig, Hyunhyub Ko from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

A hierarchical nanoparticle‐in‐micropore architecture in porous mechanochromic polymers enhances the mechanosensitivity and stretchability of mechanochromic electronic skins. In this device structure, stress‐concentration‐induced mechanochemical activation of mechanophores significantly improves the mechanochromic sensitivity for both tensile strain and normal force stimuli. This architecture also enables a dual‐mode mechanochromic electronic skin for detecting static/dynamic forces via mechanochromism and triboelectricity. Abstract Biological tissues are multiresponsive and functional, and similar properties might be possible in synthetic systems by merging responsive polymers with hierarchical soft architectures. For example, mechanochromic polymers have applications in force‐responsive colorimetric sensors and soft robotics, but their integration into sensitive, multifunctional devices remains challenging. Herein, a hierarchical nanoparticle‐in‐micropore (NP‐MP) architecture in porous mechanochromic polymers, which enhances the mechanosensitivity and stretchability of mechanochromic electronic skins (e‐skins), is reported. The hierarchical NP‐MP structure results in stress‐concentration‐induced mechanochemical activation of mechanophores, significantly improving the mechanochromic sensitivity to both tensile strain and normal force (critical tensile strain: 50% and normal force: 1 N). Furthermore, the porous mechanochromic composites exhibit a reversible mechanochromism under a strain of 250%. This architecture enables a dual‐mode mechanochromic e‐skin for detecting static/dynamic forces via mechanochromism and triboelectricity. The hierarchical NP‐MP architecture provides a general platform to develop mechanochromic composites with high sensitivity and stretchability.

Finite Size Effects on the Switching Dynamics of Spin‐Crossover Thin Films Photoexcited by a Femtosecond Laser Pulse

By Karl Ridier, Alin‐Ciprian Bas, Victoria Shalabaeva, William Nicolazzi, Lionel Salmon, Gábor Molnár, Azzedine Bousseksou, Maciej Lorenc, Roman Bertoni, Eric Collet, Hervé Cailleau from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Size reduction effects are evidenced on the room temperature photoswitching dynamics of spin‐crossover thin films induced by femtosecond laser excitations. A thermally activated switching is observed on the 20–40 ns timescale, governed by the intramolecular energy barrier between the two spin states. This additional switching step is suppressed in the thinnest films. Abstract Using ultrafast optical absorption spectroscopy, the room‐temperature spin‐state switching dynamics induced by a femtosecond laser pulse in high‐quality thin films of the molecular spin‐crossover (SCO) complex [Fe(HB(tz)3)2] (tz = 1,2,4‐triazol‐1‐yl) are studied. These measurements reveal that the early, sub‐picosecond, low‐spin to high‐spin photoswitching event, with linear response to the laser pulse energy, can be followed under certain conditions by a second switching process occurring on a timescale of tens of nanoseconds, enabling nonlinear amplification. This out‐of‐equilibrium dynamics is discussed in light of the characteristic timescales associated with the different switching mechanisms, i.e., the electronic and structural rearrangements of photoexcited molecules, the propagation of strain waves at the material scale, and the thermal activation above the molecular energy barrier. Importantly, the additional, nonlinear switching step appears to be completely suppressed in the thinnest (50 nm) film due to the efficient heat transfer to the substrate, allowing the system to retrieve the thermal equilibrium state on the 100 ns timescale. These results provide a first milestone toward the assessment of the physical parameters that drive the photoresponse of SCO thin films, opening up appealing perspectives for their use as high‐frequency all‐optical switches working at room temperature.

Guided Assembly of Microporous/Mesoporous Manganese Phosphates by Bifunctional Organophosphonic Acid Etching and Templating

By Yating Hu, Yu Zhang, Changjian Li, Ling Wang, Yonghua Du, Guang Mo, Xu Li, Anthony K. Cheetham, John Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

The challenges in synthesizing porous manganese phosphates using the soft‐templating method are overcome by using n‐hexylphosphonic acid as both the etching and the templating agent, with high‐vacuum‐assisted annealing. Benefitting from its high surface area (304.1 m2 g−1) and ultrafine pore size, highly ordered microporous manganese phosphate is found to be a promising candidate for energy storage and electrocatalysis applications, such as the oxygen evolution reaction. Abstract Manganese (Mn)‐based compounds are important materials for both energy conversion and energy storage. Unfortunately, it has been a significant challenge to develop highly ordered microporous/mesoporous structures for them to provide more active sites for these applications. In order to do so using the soft‐templating method, three conditions have to be met, namely, a strong interaction between the inorganic precursor and the organic templates; eliminating the formation of bulk manganese phosphate; and the preservation of the manganese phosphate framework without it collapsing upon template removal. Herein, a soft‐templating approach is reported using an organophosphonic acid (n‐hexylphosphonic acid) as both the etching and the templating agent, followed by high‐vacuum‐assisted annealing. This approach simultaneously satisfies the above conditions. Both microporous and mesoporous manganese phosphates with uniform pore sizes and well‐defined pore structures are obtained. The utilization of the organophosphonic acid is shown to be the key in the transformation from bulk manganese oxide into a highly ordered microporous phosphate. A very high surface area of 304.1 m2 g−1 is obtained for the microporous manganese phosphate, which is the highest among the reported values for Mn‐based compounds. The ultrafine micropores and high specific surface area of our manganese phosphate promote electrocatalytic activity for the oxygen evolution reaction.

Encrypted Thermal Printing with Regionalization Transformation

By Run Hu, Shiyao Huang, Meng Wang, Xiaobing Luo, Junichiro Shiomi, Cheng‐Wei Qiu from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Heat conduction has long been considered in an omnidirectional diffusive way. Such a stereotype is successfully broken in this work and extreme heat flow manipulation is achieved, based on which encrypted thermal printing and regionalization transformation for structuring thermal metamaterial‐strokes as infrared signatures are proposed, enabling the writing of letters, the drawing of paintings, and the display of information. Abstract Artificially structured thermal metamaterials provide an unprecedented possibility of molding heat flow that is drastically distinct from the conventional heat diffusion in naturally conductive materials. The Laplacian nature of heat conduction makes the transformation thermotics, as a design principle for thermal metadevices, compatible with transformation optics. Various functional thermal devices, such as thermal cloaks, concentrators, and rotators, have been successfully demonstrated. How far can it possible go beyond just realizing a heat‐distribution function in a thermal metadevice? Herein, the concept of encrypted thermal printing is proposed and experimentally validated, which could conceal encrypted information under natural light and present static or dynamic messages in an infrared image. Regionalization transformation is developed for structuring thermal metamaterial‐strokes as infrared signatures, enabling letters of the alphabet to be written, paintings to be drawn, movies to be made, and information to be displayed. This strategy successfully demonstrates an extreme level of manipulation of heat flow for encryption, illusions, and messaging.

Hydrophobic Hydrogels with Fruit‐Like Structure and Functions

By Hui Guo, Tasuku Nakajima, Dominique Hourdet, Alba Marcellan, Costantino Creton, Wei Hong, Takayuki Kurokawa, Jian Ping Gong from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Hydrophobic networks containing omniphilic organic solvents are found to abnormally swell in water to form hydrophobic hydrogels with high water content. The hydrophobic hydrogels, having a fruit‐like structure with a semipermeable skin layer and water‐trapped micropores, display unique properties, including enhanced strength, surface hydrophobicity, and antidrying, despite their extremely high water content. The abnormal swelling is applied to extract water from saline solution. Abstract Normally, a polymer network swells in a good solvent to form a gel but the gel shrinks in a poor solvent. Here, an abnormal phenomenon is reported: some hydrophobic gels significantly swell in water, reaching water content as high as 99.6 wt%. Such abnormal swelling behaviors in the nonsolvent water are observed universally for various hydrophobic organogels containing omniphilic organic solvents that have a higher affinity to water than to the hydrophobic polymers. The formation of a semipermeable skin layer due to rapid phase separation, and the asymmetric diffusion of water molecules into the gel driven by the high osmotic pressure of the organic solvent–water mixing, are found to be the reasons. As a result, the hydrophobic hydrogels have a fruit‐like structure, consisting of hydrophobic skin and water‐trapped micropores, to display various unique properties, such as significantly enhanced strength, surface hydrophobicity, and antidrying, despite their extremely high water content. Furthermore, the hydrophobic hydrogels exhibit selective water absorption from concentrated saline solutions and rapid water release at a small pressure like squeezing juices from fruits. These novel functions of hydrophobic hydrogels will find promising applications, e.g., as materials that can automatically take the fresh water from seawater.

A Fermi‐Level‐Pinning‐Free 1D Electrical Contact at the Intrinsic 2D MoS2–Metal Junction

By Zheng Yang, Changsik Kim, Kwang Young Lee, Myeongjin Lee, Samudrala Appalakondaiah, Chang‐Ho Ra, Kenji Watanabe, Takashi Taniguchi, Kyeongjae Cho, Euyheon Hwang, James Hone, Won Jong Yoo from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Polarity control of MoS2 is realized without extrinsic doping by employing a Fermi‐level‐pinning‐free 1D metal contact design. The use of high‐work‐function metals such as Pd and Au gives rise to high‐performance p‐type MoS2 with hole mobility exceeding 400 cm2 V−1 s−1 at 300 K. The pinning factor obtained from MoS2 1D contact devices approaches the ideal Schottky–Mott limit. Abstract Currently 2D crystals are being studied intensively for use in future nanoelectronics, as conventional semiconductor devices face challenges in high power consumption and short channel effects when scaled to the quantum limit. Toward this end, achieving barrier‐free contact to 2D semiconductors has emerged as a major roadblock. In conventional contacts to bulk metals, the 2D semiconductor Fermi levels become pinned inside the bandgap, deviating from the ideal Schottky–Mott rule and resulting in significant suppression of carrier transport in the device. Here, MoS2 polarity control is realized without extrinsic doping by employing a 1D elemental metal contact scheme. The use of high‐work‐function palladium (Pd) or gold (Au) enables a high‐quality p‐type dominant contact to intrinsic MoS2, realizing Fermi level depinning. Field‐effect transistors (FETs) with Pd edge contact and Au edge contact show high performance with the highest hole mobility reaching 330 and 432 cm2 V−1 s−1 at 300 K, respectively. The ideal Fermi level alignment allows creation of p‐ and n‐type FETs on the same intrinsic MoS2 flake using Pd and low‐work‐function molybdenum (Mo) contacts, respectively. This device acts as an efficient inverter, a basic building block for semiconductor integrated circuits, with gain reaching 15 at VD = 5 V.

High‐Efficiency Cryo‐Thermocells Assembled with Anisotropic Holey Graphene Aerogel Electrodes and a Eutectic Redox Electrolyte

By Guangyong Li, Dapeng Dong, Guo Hong, Lifeng Yan, Xuetong Zhang, Wenhui Song from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Highly efficient cylindrical cryo‐thermocells, working in a wide operation window of cold temperatures, are developed via the combination of anisotropic holey graphene aerogel electrodes and a eutectic redox electrolyte. Abstract Thermocells, capable of converting temperature‐dependent electrochemical redox potentials into electrical power, can harvest waste or low‐grade heat in an economical and continuous approach with zero carbon emission. However, the power density and conversion efficiency of thermocells are hindered by a narrow operation window and low ion conductivity of the electrodes, especially in freezing weather conditions. Herein, highly efficient cylindrical thermocells, working in a wide operation window of cold temperatures, are developed. A eutectic electrolyte consisting of formamide and water is formulated with a high ion conductivity, which is retained at a significantly extended lower limit of the operation window from conventional 0 to −40 °C. In parallel, an electrode material based on anisotropic holey graphene aerogel is synthesized with improved ion conductivity, especially at temperatures below 0 °C, due to its aligned graphene sheets and pores. By taking the advantages of both components, the power density and the Seebeck coefficient of a single‐cylinder thermocell reaches an exceptionally high value, i.e., 3.6 W m−2 and 1.3 mV K−1, respectively. Moreover, assembled thermocells in series packaging substantially enhance the voltage of the open‐circuit, i.e., from 140 mV (1‐cylinder thermocell) to 2.1 V (15‐cylinder thermocells).

Surface‐Halogenation‐Induced Atomic‐Site Activation and Local Charge Separation for Superb CO2 Photoreduction

By Lin Hao, Lei Kang, Hongwei Huang, Liqun Ye, Keli Han, Songqiu Yang, Hongjian Yu, Munkhbayar Batmunkh, Yihe Zhang, Tianyi Ma from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Surface‐halogenation‐induced atomic site activation and local charge separation of layered Bi2O2(OH)(NO3) is presented. Br−‐modified Bi2O2(OH)(NO3) shows the most prominent CO2 activation activity with a CO production rate of 8.12 µmol g−1 h−1, which is 73 times higher than that of bulk Bi2O2(OH)(NO3), exceeding that of most previously reported state‐of‐the‐art photocatalysts. Abstract Solar‐energy‐driven CO2 conversion into value‐added chemical fuels holds great potential in renewable energy generation. However, the rapid recombination of charge carriers and deficient reactive sites, as two major obstacles, severely hampers the photocatalytic CO2 reduction activity. Herein, a desirable surface halogenation strategy to address the aforementioned concerns over a Sillén‐related layer‐structured photocatalyst Bi2O2(OH)(NO3) (BON) is demonstrated. The surface halogen ions that are anchored on the Bi atoms by replacing surface hydroxyls on the one hand facilitate the local charge separation, and, on the other hand, activate the hydroxyls that profoundly boost the adsorption of CO2 molecules and protons and facilitate the CO2 conversion process, as evidenced by experimental and theoretical results collectively. Among the three series of BON‐X (X = Cl, Br, and I) catalysts, BON‐Br shows the most substantially enhanced CO production rate (8.12 µmol g−1 h−1) without any sacrificial agents or cocatalysts, ≈73 times higher than that of pristine Bi2O2(OH)(NO3), also exceeding that of the state‐of‐the‐art photocatalysts reported to date. This work presents a surface polarization protocol for engineering charge behavior and reactive sites to promote photocatalysis, which shows great promise to the future design of high‐performance materials for clean energy production.

High‐Resolution 3D NIR‐II Photoacoustic Imaging of Cerebral and Tumor Vasculatures Using Conjugated Polymer Nanoparticles as Contrast Agent

By Bing Guo, Jingqin Chen, Ningbo Chen, Eshu Middha, Shidang Xu, Yutong Pan, Min Wu, Ke Li, Chengbo Liu, Bin Liu from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

An NIR‐II conjugated polymer is synthesized and formulated into uniform nanoparticles via microfluidics. The nanoparticles exhibit strong light absorbance, high photoacoustic sensitivity, excellent photoacoustic stability, and good biocompatibility, which facilitate 3D wide‐field deciphering of tumor margins and brain vasculatures with deep penetration to millimeter, large signal‐to‐background ratio, and high maximum imaging depth to depth resolution ratio. Abstract Exogenous contrast‐agent‐assisted NIR‐II optical‐resolution photoacoustic microscopy imaging (ORPAMI) holds promise to decipher wide‐field 3D biological structures with deep penetration, large signal‐to‐background ratio (SBR), and high maximum imaging depth to depth resolution ratio. Herein, NIR‐II conjugated polymer nanoparticle (CP NP) assisted ORPAMI is reported for pinpointing cerebral and tumor vasculatures. The CP NPs exhibit a large extinction coefficient of 48.1 L g−1 at the absorption maximum of 1161 nm, with an ultrahigh PA sensitivity up to 2 µg mL−1. 3D ORPAMI of wide‐field mice ear allows clear visualization of regular vasculatures with a resolution of 19.2 µm and an SBR of 29.3 dB at the maximal imaging depth of 539 µm. The margin of ear tumor composed of torsional dense vessels among surrounding normal regular vessels can be clearly delineated via 3D angiography. In addition, 3D whole‐cortex cerebral vasculatures with large imaging area (48 mm2), good resolution (25.4 µm), and high SBR (22.3 dB) at a depth up to 1001 µm are clearly resolved through the intact skull. These results are superior to the recently reported 3D NIR‐II fluorescence confocal vascular imaging, which opens up new opportunities for NIR‐II CP‐NP‐assisted ORPAMI in various biomedical applications.

Masthead: (Adv. Mater. 25/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Contents: (Adv. Mater. 25/2019)

By from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

On‐Chip Energy Storage: Integration of Electrochemical Microsupercapacitors with Thin Film Electronics for On‐Chip Energy Storage (Adv. Mater. 25/2019)

By Mrinal K. Hota, Qiu Jiang, Zhenwei Wang, Zhong Lin Wang, Khaled N. Salama, Husam N. Alshareef from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

In article number 1807450, Khaled N. Salama, Husam N. Alshareef, and co‐workers describe the integration of on‐chip electrochemical microsupercapacitors with thin‐film electronics at the transistor level using a single electrode material (RuO2) for both. The functionality of the integrated devices is successfully demonstrated using alternating signals, which are properly stored, and used to power several electronic devices. Highly miniaturized microsupercapacitor–rectifier micropower units are produced as a result, which are suitable for self‐powered sensor applications.

Hydrophobic Hydrogels: Hydrophobic Hydrogels with Fruit‐Like Structure and Functions (Adv. Mater. 25/2019)

By Hui Guo, Tasuku Nakajima, Dominique Hourdet, Alba Marcellan, Costantino Creton, Wei Hong, Takayuki Kurokawa, Jian Ping Gong from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

In article number 1900702, Jian Ping Gong and co‐workers discover that hydrophobic networks containing omniphilic organic solvents abnormally swell in water to form hydrophobic hydrogels with high water content (99.6 wt% at most). The hydrophobic hydrogels, having a fruit‐like structure with a semipermeable skin layer and water‐trapped micropores, display unique properties, including enhanced strength, surface hydrophobicity, and antidrying properties, despite their extremely high water content. The abnormal swelling is applied to extract water from saline solution.

Solar Cells: Quantifying Quasi‐Fermi Level Splitting and Mapping its Heterogeneity in Atomically Thin Transition Metal Dichalcogenides (Adv. Mater. 25/2019)

By Mike Tebyetekerwa, Jian Zhang, Kun Liang, The Duong, Guru Prakash Neupane, Linglong Zhang, Boqing Liu, Thien N. Truong, Rabin Basnet, Xiaojing Qiao, Zongyou Yin, Yuerui Lu, Daniel Macdonald, Hieu T. Nguyen from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Two‐dimensional atomically thin transition metal dichalcogenides (TMDs) show a remarkable light–matter interaction and atomic thickness. In article number 1900522, Mike Tebyetekerwa, Yuerui Lu, Daniel Macdonald, Hieu T. Nguyen, and co‐workers quantify the possible maximum open‐circuit voltages, one of the most important photovoltaic parameters, of monolayer TMD‐based solar cells. The values they determine reveal the potential of atomically thin TMDs for high‐voltage, ultralight, flexible, and eye‐transparent future photovoltaic devices.

Actuators: High‐Performance Hierarchical Black‐Phosphorous‐Based Soft Electrochemical Actuators in Bioinspired Applications (Adv. Mater. 25/2019)

By Guan Wu, Xingjiang Wu, Yijun Xu, Hengyang Cheng, Jinku Meng, Qiang Yu, Xinyiao Shi, Kai Zhang, Wei Chen, Su Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

In article number 1806492, Guan Wu, Su Chen, and co‐workers demonstrate a new electrochemical actuator based on hierarchically structured black‐phosphorous/carbon‐nanotube nanocomposite electrodes. Due to the ordered lamellar structure and large redox activity for ions with smooth diffusion and flooding accommodation, the actuator displays high electromechanical performance, including low power‐consumption/strain, large peak‐to‐peak strain, fast strain and stress rates, and biomimetic applications.

Micro‐/Mesoporous Materials: Guided Assembly of Microporous/Mesoporous Manganese Phosphates by Bifunctional Organophosphonic Acid Etching and Templating (Adv. Mater. 25/2019)

By Yating Hu, Yu Zhang, Changjian Li, Ling Wang, Yonghua Du, Guang Mo, Xu Li, Anthony K. Cheetham, John Wang from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Porous transition‐metal compounds that are highly redox‐active show excellent potential as active components for applications, such as electrocatalysts for energy conversion and electrodes for energy storage. In article number 1901124, John Wang and co‐workers obtain highly ordered microporous and uniform mesoporous manganese phosphates. By using n‐hexylphosphonic acid as both the etching and templating agents, and with high‐vacuum‐assisted annealing, they overcome the challenges in synthesizing porous manganese phosphate with the soft‐templating method.

Defect and Contact Passivation for Perovskite Solar Cells

By Erkan Aydin, Michele Bastiani, Stefaan Wolf from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Defects in metal halide perovskites contribute to nonradiative recombination of photo‐carriers. On device level, such recombination undesirably inflates the open‐circuit voltage deficit and acts as a significant roadblock toward the theoretical efficiency limit of 30% perovskite solar cells. Such voltage‐limiting mechanisms are assessed by focusing on their origin and possible mitigation strategies. Abstract Metal‐halide perovskites are rapidly emerging as an important class of photovoltaic absorbers that may enable high‐performance solar cells at affordable cost. Thanks to the appealing optoelectronic properties of these materials, tremendous progress has been reported in the last few years in terms of power conversion efficiencies (PCE) of perovskite solar cells (PSCs), now with record values in excess of 24%. Nevertheless, the crystalline lattice of perovskites often includes defects, such as interstitials, vacancies, and impurities; at the grain boundaries and surfaces, dangling bonds can also be present, which all contribute to nonradiative recombination of photo‐carriers. On device level, such recombination undesirably inflates the open‐circuit voltage deficit, acting thus as a significant roadblock toward the theoretical efficiency limit of 30%. Herein, the focus is on the origin of the various voltage‐limiting mechanisms in PSCs, and possible mitigation strategies are discussed. Contact passivation schemes and the effect of such methods on the reduction of hysteresis are described. Furthermore, several strategies that demonstrate how passivating contacts can increase the stability of PSCs are elucidated. Finally, the remaining key challenges in contact design are prioritized and an outlook on how passivating contacts will contribute to further the progress toward market readiness of high‐efficiency PSCs is presented.

Metal‐Complex/Semiconductor Hybrid Photocatalysts and Photoelectrodes for CO2 Reduction Driven by Visible Light

By Kazuhiko Maeda from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Metal‐complex/semiconductor hybrid materials have attracted attention as new photocatalysts and photoelectrodes for visible‐light CO2 reduction to carbon feedstocks, because they can utilize both the outstanding electrochemical (and/or photocatalytic) activity of metal complexes for CO2 reduction and the strong photo‐oxidation ability of semiconductors. A critical overview of the development of hybrid photocatalysts and photoelectrodes for visible‐light CO2 reduction is presented. Abstract CO2 reduction to carbon feedstocks using heterogeneous photocatalysts is an attractive means of addressing both climate change and the depletion of fossil fuels. Of particular importance is the development of a photosystem capable of functioning in response to visible light, which accounts for the majority of the solar spectrum, representing a kind of artificial photosynthesis. Hybrid systems comprising a metal complex and a semiconductor are promising because of the excellent electrochemical (and/or photocatalytic) activity of metal complexes during CO2 reduction and the ability of semiconductors to efficiently oxidize water to molecular O2. Here, the development of hybrid photocatalysts and photoelectrodes for CO2 reduction in combination with water oxidation is described.

Heavy‐Metal‐Free Colloidal Semiconductor Nanorods: Recent Advances and Future Perspectives

By Guohua Jia, Yingping Pang, Jiajia Ning, Uri Banin, Botao Ji from Wiley: Advanced Materials: Table of Contents. Published on Jun 18, 2019.

Heavy‐metal‐free semiconductor nanorods are potential alternatives to the toxic cadmium‐chalcogenide‐based materials and hold promise for application in optoelectronics, catalysis, and biomedicine. Recent advances in the synthesis, growth mechanism, and structural engineering of these materials are discussed, and various emerging applications are highlighted. Abstract Quasi‐1D colloidal semiconductor nanorods (NRs) are at the forefront of nanoparticle (NP) research owing to their intriguing size‐dependent and shape‐dependent optical and electronic properties. The past decade has witnessed significant advances in both fundamental understanding of the growth mechanisms and applications of these stimulating materials. Herein, the state‐of‐the‐art of colloidal semiconductor NRs is reviewed, with special emphasis on heavy‐metal‐free materials. The main growth mechanisms of heavy‐metal‐free colloidal semiconductor NRs are first elaborated, including anisotropic‐controlled growth, oriented attachment, solution–liquid–solid method, and cation exchange. Then, structural engineering and properties of semiconductor NRs are discussed, with a comprehensive overview of core/shell structures, alloying, and doping, as well as semiconductor–metal hybrid nanostructures, followed by highlighted practical applications in terms of photocatalysis, photodetectors, solar cells, and biomedicine. Finally, challenges and future opportunities in this fascinating research area are proposed.

Untangling Cooperative Effects of Pyridinic and Graphitic Nitrogen Sites at Metal‐Free N‐Doped Carbon Electrocatalysts for the Oxygen Reduction Reaction

By James A. Behan, Eric Mates‐Torres, Serban N. Stamatin, Carlota Domínguez, Alessandro Iannaci, Karsten Fleischer, Md. Khairul Hoque, Tatiana S. Perova, Max García‐Melchor, Paula E. Colavita from Wiley: Small: Table of Contents. Published on Jun 18, 2019.

Co‐presence of pyridinic and graphitic N‐sites in metal‐free carbon electrodes modulates the binding energy of hydroperoxide/hydroperoxyl intermediates and promotes selectivity toward 4e‐reduction in the oxygen reduction reaction. Abstract Metal‐free carbon electrodes with well‐defined composition and smooth topography are prepared via sputter deposition followed by thermal treatment with inert and reactive gases. X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy show that three carbons of similar N/C content that differ in N‐site composition are thus prepared: an electrode consisting of almost exclusively graphitic‐N (NG), an electrode with predominantly pyridinic‐N (NP), and one with ≈1:1 NG:NP composition. These materials are used as model systems to investigate the activity of N‐doped carbons in the oxygen reduction reaction (ORR) using voltammetry. Results show that selectivity toward 4e‐reduction of O2 is strongly influenced by the NG/NP site composition, with the material possessing nearly uniform NG/NP composition being the only one yielding a 4e‐reduction. Computational studies on model graphene clusters are carried out to elucidate the effect of N‐site homogeneity on the reaction pathway. Calculations show that for pure NG‐doping or NP‐doping of model graphene clusters, adsorption of hydroperoxide and hydroperoxyl radical intermediates, respectively, is weak, thus favoring desorption prior to complete 4e‐reduction to hydroxide. Clusters with mixed NG/NP sites display synergistic effects, suggesting that co‐presence of these sites improves activity and selectivity by achieving high theoretical reduction potentials while facilitating retention of intermediates.

Fluorescent Isoindole Crosslink (FlICk) Chemistry ‐ A Rapid, User‐friendly Stapling Reaction

By Mihajlo Todorovic, Katerina D. Schwab, Jutta Zeisler, Chengcheng Zhang, Francois Benard, David Perrin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

The stabilization of peptide secondary structure via stapling is a ubiquitous goal for creating new probes, imaging agents, and drugs. Inspired by indole‐derived crosslinks found in natural peptide toxins, we employed ortho‐phthalaldehydes to create isoindole staples, thus transforming inactive linear and monocyclic precursors into bioactive monocyclic and bicyclic products. Mild, metal‐free conditions give an array of macrocyclic α‐MSH derivatives, of which several isoindole‐stapled α‐MSH analogs (Ki ~ 1 nM) are found to be as potent as α‐MSH. Analogously, late‐stage intra‐annular isoindole stapling furnished a bicyclic peptide mimic of α‐amanitin that is cytotoxic to CHO cells (IC50 = 70 µM). Given its user‐friendliness, we have termed this approach FlICk (fluorescent isoindole crosslink) chemistry.

Bio‐inspired Design and Additive Manufacturing of Soft Materials, Machines, Robots, and Haptic Interfaces

By Shuo Li, Hedan Bai, Robert F. Shepherd, Huichan Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

The soft side of robots: This Review gives an overview of current advances in materials with intrinsic softness as well as soft machines, robots, and haptic interfaces. The focus lies on two specific topics: bio‐inspired design and additive manufacturing. Abstract Soft materials possess several distinctive characteristics, such as controllable deformation, infinite degrees of freedom, and self‐assembly, which make them promising candidates for building soft machines, robots, and haptic interfaces. In this Review, we give an overview of recent advances in these areas, with an emphasis on two specific topics: bio‐inspired design and additive manufacturing. Biology is an abundant source of inspiration for functional materials and systems that mimic the function or mechanism of biological tissues, agents, and behaviors. Additive manufacturing has enabled the fabrication of materials and structures prevalent in biology, thereby leading to more‐capable soft robots and machines. We believe that bio‐inspired design and additive manufacturing have been, and will continue to be, important tools for the design of soft robots.

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

By Takashi Takeda, Masataka Ozawa, Tomoyuki Akutagawa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

HOF, step, jump! The cooperative motion of twisted π units serve to develop a thermo‐responsive jumping molecular crystal with a hydrogen‐bonded organic framework (HOF) of tetra[2,3]thienylene tetracarboxylic acid. The change in the molecular structure triggered by the desolvation of THF in the channels of the HOF induces not only a change in the HOF structure but also a mechanical force. Abstract There is a limited number of reports on mechanically responsive molecular crystals, including thermo‐responsive and light‐responsive crystals. Rigid ordered molecular crystals with a close‐packing structure are less able to accept distortion, which hampers the development of such molecular crystals. The thermosalient effect, or “crystal jumping”, refers to a thermo‐responsive system that converts heat into mechanical force by thermally induced phase transition. While they have recently attracted attention as potential highly efficient molecular actuators, less than two dozens of thermosalient molecular crystals have been reported to date, and the design of such molecules as well as how they assemble to express a thermosalient effect are unknown. Herein, we demonstrate how the cooperative molecular motion of twisted π units could serve to develop a thermo‐responsive jumping molecular crystal with a hydrogen‐bonded organic framework (HOF) of tetra[2,3]thienylene tetracarboxylic acid (1). The cooperative change in the molecular structure triggered by the desolvation of THF in the channel of the HOF structure induced not only a change in the structure of HOF but also mechanical force. Hydrogen bonding interactions contributed significant thermal stability to maintain the HOF assembly even with a dynamic structural change.

An Isolable Silicon Analogue of a Ketone that Contains an Unperturbed Si=O Double Bond

By Ryo Kobayashi, Shintaro Ishida, Takeaki Iwamoto from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Good to Si you: The first example of a genuine silanone, that is, an isolable silicon analogue of a ketone that contains an unperturbed Si=O bond, was synthesized. The structure and properties of this silanone were examined by a single‐crystal XRD analysis, NMR spectroscopy, and theoretical calculations. Bimolecular reactions revealed high electrophilicity on the Si atom and high nucleophilicity on the O atom of the Si=O bond. Abstract Despite tremendous efforts to synthesize isolable compounds with an Si=O bond, silicon analogues of ketones that contain an unperturbed Si=O bond have remained elusive for more than 100 years. Herein, we report the synthesis of an isolable silicon analogue of a ketone that exhibits a three‐coordinate silicon center and an unperturbed Si=O bond, thus representing the first example of a genuine silanone. Most importantly, this silanone does not require coordination by Lewis bases and acids and/or the introduction of electron‐donating groups to stabilize the Si=O bond. The structure and properties of this unperturbed Si=O bond were examined by a single‐crystal X‐ray diffraction analysis, NMR spectroscopy, and theoretical calculations. Bimolecular reactions revealed high electrophilicity on the Si atom and high nucleophilicity on the O atom of this genuine Si=O bond.

Plasmonic Switching of the Reaction Pathway: Visible‐Light Irradiation Varies the Reactant Concentration at the Solid–Solution Interface of a Gold–Cobalt Catalyst

By Erandi Peiris, Sarina Sarina, Eric R. Waclawik, Godwin A. Ayoko, Pengfei Han, Jianfeng Jia, Huai‐Yong Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Flicking the switch: The product selectivity of two competing reactions—alkyne hydroamination and alkyne–alkyne homo‐coupling—occuring on catalyst Au2Co alloy nanoparticles can be switched by visible‐light irradiation. Light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross‐coupling by several orders of magnitude, while in the dark, homo‐coupling of two alkyne molecules is preferred. Abstract Product selectivity of alkyne hydroamination over catalytic Au2Co alloy nanoparticles (NPs) can be made switchable by a light‐on/light‐off process, yielding imine (cross‐coupling product of aniline and alkyne) under visible‐light irradiation, but 1,4‐diphenylbutadiyne in the dark. The low‐flux light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross‐coupling by several orders of magnitude even at a very low overall aniline concentrations (1.0×10−3 mol L−1). A tentative mechanism is that Au2Co NPs absorb light, generating an intense fringing electromagnetic field and hot electrons. The sharp field‐gradient (plasmonic optical force) can selectively enhance adsorption of light‐polarizable aniline molecules on the catalyst. The light irradiation thereby alters the aniline/alkyne ratio at the NPs surface, switching product selectivity. This represents a new paradigm to modify a catalysis process by light.

Hierarchical Assembly of Peptoid‐Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution

By Fang Jiao, Xuepeng Wu, Tengyue Jian, Shuai Zhang, Haibao Jin, Pingang He, Chun-Long Chen, James J DeYoreo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Developing synthetic systems for which self‐assembly of hierarchical structures can be programmed through interactions between sequence‐specific domains is critical to achieving bioinspired materials exhibiting complex functions. Here we show that by appending bulky cyclodextrin groups onto sheet‐forming peptoids, we obtain cylindrical micelles that further assembly into membranes and intertwined ribbons on substrates in aqueous solution, depending on the choice of solution and substrate conditions. In‐situ atomic force microscopy shows that micelle assembly occurs in two steps, starting with “precursor” particles that transform into worm‐like micelles, which extend and coalesce to form the higher order structures with a rate and a degree of cooperativity dependent on pH and Ca2+ concentration. After co‐assembly with hydrophobic 4‐(2‐hydroxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole donors that occupy the hydrophobic core, followed by exposure to hydrophilic Rhodamine B as acceptors that insert into cyclodextrin, the micelles exhibit highly efficient Förster resonance energy transfer efficiency in aqueous solution, thereby mimicking natural light harvesting systems.

Regioselective Formal [3+2] Cycloadditions of Ureas with Activated and Unactivated Olefins for Intermolecular Olefin Aminooxygenation

By Fan Wu, Nur-E Alom, Jeewani Poornima Ariyarathna, Johannes Naß, Wei Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Abstract: A new class of intermolecular olefin aminooxygenation reaction is described. This reaction utilizes the classic halonium intermediate, as a regio‐ and stereochemical template, to accomplish the selective oxyamination of both activated and unactivated alkenes. Notably, urea chemical feedstock can be directly introduced as the N‐ and O‐source and simple iodide salt can be utilized as the catalyst. This formal [3+2] cycloaddition process provides a highly modular entry to a range of useful heterocyclic products with excellent selectivities and functional group tolerance.

X‐ray Magnetic Circular Dichroism Spectroscopy Applied to Nitrogenase and Related Models: Experimental Evidence for a Spin‐Coupled Molybdenum(III) Center

By Joanna K. Kowalska, Justin T. Henthorn, Casey Van Stappen, Christian Trncik, Oliver Einsle, David Keavney, Serena DeBeer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Spin states: A combination of Fe L2,3‐edge and Mo L3‐edge X‐ray magnetic circular dichroism (XMCD) spectroscopy was utilized to examine the FeMo cofactor of nitrogenase enzyme and an electronically related model complex. The results provide experimental support for a non‐Hund configuration at the Mo atom. Abstract Nitrogenase enzymes catalyze the reduction of atmospheric dinitrogen to ammonia utilizing a Mo‐7Fe‐9S‐C active site, the so‐called FeMoco cluster. FeMoco and an analogous small‐molecule (Et4N)[(Tp)MoFe3S4Cl3] cubane have both been proposed to contain unusual spin‐coupled MoIII sites with an S(Mo)=1/2 non‐Hund configuration at the Mo atom. Herein, we present Fe and Mo L3‐edge X‐ray magnetic circular dichroism (XMCD) spectroscopy of the (Et4N)[(Tp)MoFe3S4Cl3] cubane and Fe L2,3‐edge XMCD spectroscopy of the MoFe protein (containing both FeMoco and the 8Fe‐7S P‐cluster active sites). As the P‐clusters of MoFe protein have an S=0 total spin, these are effectively XMCD‐silent at low temperature and high magnetic field, allowing for FeMoco to be selectively probed by Fe L2,3‐edge XMCD within the intact MoFe protein. Further, Mo L3‐edge XMCD spectroscopy of the cubane model has provided experimental support for a local S(Mo)=1/2 configuration, demonstrating the power and selectivity of XMCD.

Photoinduced Reversible Solid‐to‐Liquid Transitions for Photoswitchable Materials

By Wen‐Cong Xu, Shaodong Sun, Si Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Light switch: Azobenzene‐containing materials that show photoinduced reversible solid‐to‐liquid transitions are reviewed. These materials show trans‐to‐cis and cis‐to‐trans isomerization under UV and visible light irradiation. The trans isomers are solid and cis isomers are liquid. Thus, light can induce reversible solid‐to‐liquid transitions. Photoinduced reversible solid‐to‐liquid transitions are promising for many applications. Abstract Heating and cooling can induce reversible solid‐to‐liquid transitions of matter. In contrast, athermal photochemical processes can induce reversible solid‐to‐liquid transitions of some newly developed azobenzene compounds. Azobenzene is photoswitchable. UV light induces trans‐to‐cis isomerization; visible light or heat induces cis‐to‐trans isomerization. Trans and cis isomers usually have different melting points (Tm) or glass transition temperatures (Tg). If Tm or Tg of an azobenzene compound in trans and cis forms are above and below room temperature, respectively, light may induce reversible solid‐to‐liquid transitions. In this Review, we introduce azobenzene compounds that exhibit photoinduced reversible solid‐to‐liquid transitions, discuss the mechanisms and design principles, and show their potential applications in healable coatings, adhesives, transfer printing, lithography, actuators, fuels, and gas separation. Finally, we discuss remaining challenges in this field.

Negative Charging of Au Nanoparticles during Methanol Synthesis from CO2/H2 on a Au/ZnO Catalyst: Insights from Operando IR and Near‐Ambient‐Pressure XPS and XAS Measurements

By Ali M. Abdel‐Mageed, Alexander Klyushin, Azita Rezvani, Axel Knop‐Gericke, Robert Schlögl, R. Jürgen Behm from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Put in charge: Methanol synthesis activity has been demonstrated to coincide with the formation of O vacancies during the initial activation period. These vacancies result in a negative charging of the Au nanoparticles during the reaction. Abstract The electronic and structural properties of Au/ZnO under industrial and idealized methanol synthesis conditions have been investigated. This was achieved by kinetic measurements in combination with time‐resolved operando infrared (DRIFTS) as well as in situ near‐ambient pressure X‐ray photoelectron spectroscopy (NAP‐XPS) and X‐ray absorption near‐edge spectroscopy (XANES) measurements at the O K‐edge together with high‐resolution electron microscopy. The adsorption of CO during the reaction revealed the presence of negatively charged Au nanoparticles/Au sites during the initial phase of the reaction. Near‐ambient‐pressure XPS and XANES demonstrate the build‐up of O vacancies during the reaction, which goes along with a substantial increase in the rate of methanol formation. The results are discussed in comparison with previous findings for Cu/ZnO and Au/ZnO catalysts.

Efficient Separation of cis‐ and trans‐1,2‐Dichloroethene Isomers by Adaptive Biphen[3]arene Crystals

By Yiliang Wang, Kaidi Xu, Bin Li, Lei Cui, Jian Li, Xueshun Jia, Hongbin Zhao, Jianhui Fang, Chunju Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Keep it separated: The separation of cis‐ and trans‐1,2‐dichloroethene (DCE) isomers by activated crystalline biphen[3]arene materials, MeBP3α, is demonstrated. MeBP3α highly selectively adsorbs cis‐DCE from a 50:50 (v/v) cis/trans‐isomer mixture, yielding cis‐DCE with a purity of 96.4 % in a single adsorption cycle. The uptake of cis‐DCE triggers a solid‐state structural transformation of the activated MeBP3α crystals. Abstract Reported here is the highly efficient separation of industrially important cis‐ and trans‐1,2‐dichloroethene (cis‐DCE and trans‐DCE) isomers by activated crystalline 2,2′,4,4′‐tetramethoxyl biphen[3]arene (MeBP3) materials, MeBP3α. MeBP3 can be synthesized in excellent yield (99 %), and a cyclic pentamer is also obtained when using 1,2‐dichloroethane as the solvent. The structure of MeBP3 in the CH3CN@MeBP3 crystal displays a triangle‐shape topology, forming 1D channels through window‐to‐window packing. Desolvated crystalline MeBP3 materials, MeBP3α, preferentially adsorb cis‐DCE vapors over its trans isomer. MeBP3α is able to separate cis‐DCE from a 50:50 (v/v) cis/trans‐isomer mixture, yielding cis‐DCE with a purity of 96.4 % in a single adsorption cycle. Single‐crystal structures and powder X‐ray diffraction patterns indicate that the uptake of cis‐DCE triggers a solid‐state structural transformation of MeBP3, suggesting the adaptivity of MeBP3α materials during the sorption process. Moreover, the separation can be performed over multiple cycles without loss of separation selectivity and capacity.

Gonçalo J. L. Bernardes

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

“My favorite molecule is cysteine because of its key structural and many, yet unknown, functional roles. My favorite saying is ‘Luck takes a damn lot of work’ …” Find out more about Gonçalo Bernardes in his Author Profile.

Syntheses and Catalytic Hydrogenation Performance of Cationic Bis(phosphine) Cobalt(I) Diene and Arene Compounds

By Hongyu Zhong, Max R. Friedfeld, Paul J. Chirik from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Schrock–Osborn type cationic rhodium phosphine complexes, discovered and extensively studied since the 1970s, have formed the foundation of modern homogeneous and asymmetric catalysis. Cobalt, the first‐row congener of rhodium, is an attractive surrogate for this privileged class of catalysts, yet their cobalt analogues have remained elusive for over 40 years. In their Communication (DOI: 10.1002/anie.201903766), P. J. Chirik and co‐workers report the first syntheses and characterization of these sought‐after cobalt complexes and their performance in asymmetric hydrogenation reactions.

A Single‐Atom Iridium Heterogeneous Catalyst in Oxygen Reduction Reaction

By Meiling Xiao, Jianbing Zhu, Gaoran Li, Na Li, Shuang Li, Zachary Paul Cano, Lu Ma, Peixin Cui, Pan Xu, Gaopeng Jiang, Huile Jin, Shun Wang, Tianpin Wu, Jun Lu, Aiping Yu, Dong Su, Zhongwei Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Ir‐N‐C: Single‐atom catalysts (SACs) combine the advantages of homogeneous and heterogeneous catalysts. A single‐atom iridium catalyst coordinated with four nitrogen atoms has been designed and synthesized to mimic homogeneous iridium porphyrins for high‐efficiency oxygen reduction reaction catalysis. Abstract Combining the advantages of homogeneous and heterogeneous catalysts, single‐atom catalysts (SACs) are bringing new opportunities to revolutionize ORR catalysis in terms of cost, activity and durability. However, the lack of high‐performance SACs as well as the fundamental understanding of their unique catalytic mechanisms call for serious advances in this field. Herein, for the first time, we develop an Ir‐N‐C single‐atom catalyst (Ir‐SAC) which mimics homogeneous iridium porphyrins for high‐efficiency ORR catalysis. In accordance with theoretical predictions, the as‐developed Ir‐SAC exhibits orders of magnitude higher ORR activity than iridium nanoparticles with a record‐high turnover frequency (TOF) of 24.3 e− site−1 s−1 at 0.85 V vs. RHE) and an impressive mass activity of 12.2 A mg−1Ir, which far outperforms the previously reported SACs and commercial Pt/C. Atomic structural characterizations and density functional theory calculations reveal that the high activity of Ir‐SAC is attributed to the moderate adsorption energy of reaction intermediates on the mononuclear iridium ion coordinated with four nitrogen atom sites.

Nanocatalyst/Nanoplasmon‐Enabled Detection of Organic Mercury: A One‐Minute Visual Test

By Paolo Donati, Mauro Moglianetti, Marina Veronesi, Mirko Prato, Giuseppina Tatulli, Tiziano Bandiera, Pier Paolo Pompa from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

An ultrafast (1 min) and sensitive (20 ppb LOD) colorimetric nanosensor for organic mercury is presented, based on the combined use of the catalytic and plasmonic properties of gold nanoparticles. The method is one‐step, completely instrument‐free, and has ambient conditions operation with clear visual readout. Abstract We present a fast and sensitive nanosensor that can detect organic mercury, exploiting the combination of the catalytic and plasmonic properties of gold nanoparticles (AuNPs). The method is one‐step and completely instrument‐free, and has a colorimetric readout clearly detectable by simple visual inspection. The AuNPs catalyze efficient organic mercury reduction to the metallic form (Hg0), allowing its nucleation and amalgam formation on particle surface, with consequent aggregation‐induced plasmon shift. This leads to very rapid (1 min) and specific colorimetric detection of mercury species. The achieved limit of detection (20 ppb) is compliant with current regulatory limits in food.

Design and Use of de novo Cascades for the Biosynthesis of New Benzylisoquinoline Alkaloids

By Yu Wang, Nadine Tappertzhofen, Daniel Méndez‐Sánchez, Maria Bawn, Boyu Lyu, John M. Ward, Helen C. Hailes from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Cascades to alkaloids: One‐pot in vitro enzyme cascades to give tetrahydroisoquinolines from low‐cost starting materials were developed based the combination of tyrosinase, tyrosine decarboxylase, transaminase and norcoclaurine synthase enzymes. By introducing substrates or enzymes at different stages in the cascades, this “mix and match” strategy was used to synthesise a range of non‐natural alkaloids in good yields and with high stereoselectivity. Abstract The benzylisoquinoline alkaloids (BIAs) are an important group of secondary metabolites from higher plants and have been reported to show significant biological activities. The production of BIAs through synthetic biology approaches provides a higher‐yielding strategy than traditional synthetic methods or isolation from plant material. However, the reconstruction of BIA pathways in microorganisms by combining heterologous enzymes can also give access to BIAs through cascade reactions. Most importantly, non‐natural BIAs can be generated through such artificial pathways. In the current study, we describe the use of tyrosinases and decarboxylases and combine these with a transaminase enzyme and norcoclaurine synthase for the efficient synthesis of several BIAs, including six non‐natural alkaloids, in cascades from l‐tyrosine and analogues.

De Novo Synthesis of Highly Functionalized Benzimidazolones and Benzoxazolones through an Electrochemical Dehydrogenative Cyclization Cascade

By Fan Xu, Hao Long, Jinshuai Song, Hai‐Chao Xu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Electricity powers the synthesis of highly substituted benzimidazolone and benzoxazolone derivatives through de novo construction of the benzene and heterocyclic rings from acyclic substrates, as described by H.‐C. Xu and co‐workers in their Communication (DOI: 10.1002/anie.201904931). At the anode [阳极 (yang pole)], the substrate gives up 4 electrons and 4 protons to afford the benzo‐fused heterocyclic product. At the cathode [阴极 (yin pole)], electrons and protons are combined to generate H2.

Metal‐organic Framework‐Activated Carbon Composite Materials for the Removal of Ammonia from Contaminated Airstreams.

By Lauren Nicole McHugh, Angela Terracina, Paul Stewart Wheatley, Gianpiero Buscarino, Martin William Smith, Russell Edward Morris from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Metal‐organic frameworks (MOFs) are a class of porous materials that show promise in the removal of Toxic Industrial Chemicals (TICs) from contaminated airstreams, though their development for this application has so far been hindered by issues of water stability and the wide availability and low cost of traditionally used activated carbons. Here a series of three MOF‐activated carbon composite materials with different MOF to carbon ratios are prepared by growing STAM‐17‐OEt crystals inside the commercially available BPL activated carbon. The composite materials display excellent water stability and increased uptake of ammonia gas when compared to unimpregnated carbon. Such properties make these composites very promising in the fields of air purification and personal protective equipment.

In‐situ chemiluminescence driven Reversible Addition‐Fragmentation chain Transfer Photopolymerization

By Nethmi De Alwis Watuthanthrige, Michael L. Allegrezza, Madison T Dolan, Alex J Kloster, Marina Kovaliov, Saadyah Averick, Dominik Konkolewicz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

The power of chemical light generation (chemiluminescence) is used to drive polymerization reactions. A biphasic reaction is developed such that light generating reactions are confined to the organic phase, and photopolymerization occurs in the aqueous phase. Well‐defined RAFT‐capped polymers are synthesized and the kinetics are shown to be dictated by light generation.

Formic Acid Mediated Direct Z‐Selective Reductive Coupling of Dienes and Aldehydes

By Christopher Cooze, Raphael Dada, Rylan J. Lundgren from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Methods for the addition of unsaturated nucleophiles to carbonyls to generate Z‐olefin products remain rare and often require alkyl borane or zinc reductants, limiting their utility. We demonstrate that formic acid mediates the Rh‐catalyzed, Z‐selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active Rh‐intermediate by ligand dissociation is the rate determining step. The rapid generation and trapping of Rh‐allyl intermediates is key to preventing chain‐walking isomerization events that plague related protocols. Insights gained through this study may have wider implications in selective metal‐catalyzed hydrofunctionalization reactions.

Critical Switching of Cyclization Modes of Polyepoxides in Acidic Aqueous Media and Neutral Water: Synthesis and Revised Structure of a Nerolidol‐Type Sesquiterpenoid

By Keisuke Nishikawa, Kengo Morita, Subaru Hashimoto, Akihiro Hoshino, Takumi Ikeuchi, Momochika Kumagai, Yoshiki Morimoto from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Biomimetic epoxide‐opening cascades of polyepoxides enable efficient and rapid construction of polyether frameworks. Here, we show that the epoxide‐opening cascade cyclization affording tetrahydrofuran products in acidic aqueous media switches the mode to tetrahydropyran (THP) formation in neutral water. The THP formation proceeded by simply heating polyepoxides in neutral water and a different cyclization mode from the ones so far. The novel cascade cyclization in H₂O was applied to the synthesis of a new nerolidol‐type sesquiterpenoid, resulting in revision of the proposed structure and determination of the absolute configuration.

Superior Hydrogen Evolution Reaction Performance in 2H‐MoS2 to that of 1T Phase

By Wencui Zhang, Xiaobin Liao, Xuelei Pan, Mengyu Yan, Yanxi Li, Xiaocong Tian, Yan Zhao, Lin Xu, Liqiang Mai from Wiley: Small: Table of Contents. Published on Jun 18, 2019.

The significant influence of the Fermi level on the thermodynamic limitation of electrocatalysis performance is demonstrated. In particular, with the Fermi level position approaching the conduction band, the 2H‐MoS2 can achieve a better hydrogen evolution reaction activity (74 mV at 10 mA cm−2 in 0.5 mol L−1 H2SO4) than 1T‐MoS2. Abstract In the hydrogen evolution reaction (HER), energy‐level matching is a prerequisite for excellent electrocatalytic activity. Conventional strategies such as chemical doping and the incorporation of defects underscore the complicated process of controlling the doping species and the defect concentration, which obstructs the understanding of the function of band structure in HER catalysis. Accordingly, 2H‐MoS2 and 1T‐MoS2 are used to create electrocatalytic nanodevices to address the function of band structure in HER catalysis. Interestingly, it is found that the 2H‐MoS2 with modulated Fermi level under the application of a vertical electric field exhibits excellent electrocatalytic activity (as evidenced by an overpotential of 74 mV at 10 mA cm−2 and a Tafel slope of 99 mV per decade), which is superior to 1T‐MoS2. This unexpected excellent HER performance is ascribed to the fact that electrons are injected into the conduction band under the condition of back‐gate voltage, which leads to the increased Fermi level of 2H‐MoS2 and a shorter Debye screen length. Hence, the required energy to drive electrons from the electrocatalyst surface to reactant will decrease, which activates the 2H‐MoS2 thermodynamically.

Template‐Free, Surfactant‐Mediated Orientation of Self‐Assembled Supercrystals of Metal–Organic Framework Particles

By Civan Avci, Yang Liu, Jose Angel Pariente, Alvaro Blanco, Cefe Lopez, Inhar Imaz, Daniel Maspoch from Wiley: Small: Table of Contents. Published on Jun 18, 2019.

Control on the mesoscale self‐assembly of (111)‐, (100)‐, and (110)‐oriented face‐centered cubic supercrystals of metal–organic framework (MOF) particles by adjusting the amount of surfactant (cetyltrimethylammonium bromide) used is described. By controlling the orientation of supercrystals made of polyhedral MOF ZIF‐8, porous ZIF‐8 crystals on surfaces are oriented. Furthermore, these supercrystals behave as photonic crystals whose properties depend on their growth orientation. Abstract Mesoscale self‐assembly of particles into supercrystals is important for the design of functional materials such as photonic and plasmonic crystals. However, while much progress has been made in self‐assembling supercrystals adopting diverse lattices and using different types of particles, controlling their growth orientation on surfaces has received limited success. Most of the latter orientation control has been achieved via templating methods in which lithographic processes are used to form a patterned surface that acts as a template for particle assembly. Herein, a template‐free method to self‐assemble (111)‐, (100)‐, and (110)‐oriented face‐centered cubic supercrystals of the metal–organic framework ZIF‐8 particles by adjusting the amount of surfactant (cetyltrimethylammonium bromide) used is described. It is shown that these supercrystals behave as photonic crystals whose properties depend on their growth orientation. This control on the orientation of the supercrystals dictates the orientation of the composing porous particles that might ultimately facilitate pore orientation on surfaces for designing membranes and sensors.

A Facile and Effective Method for Patching Sulfur Vacancies of WS2 via Nitrogen Plasma Treatment

By Jianfeng Jiang, Qinghua Zhang, Aizhu Wang, Yu Zhang, Fanqi Meng, Congcong Zhang, Xianjin Feng, Yuanping Feng, Lin Gu, Hong Liu, Lin Han from Wiley: Small: Table of Contents. Published on Jun 18, 2019.

There are formidable challenges to essentially improve carrier scattering during the transmission of devices and distinct contact barrier between metal and semiconductors, which are caused by inevitable vacancies in transition metal dichalcogenides. To address these issues, a facile and effective defect patching approach is developed via nitrogen plasma doping, and the effective vacancies patching events are confirmed by a high‐resolution spherical aberration correction transmission electron microscopy. Abstract Although transition metal dichalcogenides (TMDs) are attractive for the next‐generation nanoelectronic era due to their unique optoelectronic and electronic properties, carrier scattering during the transmission of electronic devices, and the distinct contact barrier between the metal and the semiconductors, which is caused by inevitable defects in TMDs, remain formidable challenges. To address these issues, a facile, effective, and universal patching defect approach that uses a nitrogen plasma doping protocol is developed, via which the intrinsic vacancies are repaired effectively. To reveal sulfur vacancies and the nature of the nitrogen doping effects, a high‐resolution spherical aberration corrected scanning transmission electron microscopy is used, which confirms the N atoms doping in sulfur vacancies. In this study, a typical TMD material, namely tungsten disulfide, is employed to fabricate field‐effect transistors (FETs) as a preliminary paradigm to demonstrate the patching defects method. This doping method endows FETs with high electrical performance and excellent contact interface properties. As a result, an electron mobility of up to 184.2 cm2 V−1 s−1 and a threshold voltage of as low as 3.8 V are realized. This study provides a valuable approach to improve the performance of electronic devices that are based on TMDs in practical electronic applications.

Total Synthesis of 1‐Hydroxytaxinine

By Yusuke Imamura, Shun Yoshioka, Masanori Nagatomo, Masayuki Inoue from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

1‐Hydroxytaxinine (1) is a cytotoxic taxane diterpenoid. Its central 8‐membered B‐ring possesses four oxygen‐functionalized centers (C1, 2, 9, and 10) and two quaternary carbons (C8 and 15), and is fused with 6‐membered A‐ and C‐rings. The densely functionalized and intricately fused structure of 1 makes it a highly challenging synthetic target. We developed an efficient radical‐based strategy for assembling 1 from A‐ and C‐ring fragments. A‐ring 5 bearing the a‐alkoxyacyl telluride moiety underwent intermolecular coupling with C‐ring 6 via a Et3B/O2‐promoted decarbonylative radical formation. After construction of the C8‐quaternary stereocenters, a pinacol coupling reaction of 4 using a low‐valent titanium reagent formed the B‐ring of 3 with stereoselective installation of the C1,2‐diol system. Subsequent manipulations at the A‐ and C‐rings furnished 1 in 26 total steps.

What is XNA?

By John C. Chaput, Piet Herdewijn from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

The term ‘xeno‐nucleic acids’, abbreviated XNA, has grown in popularity to the point that it has become a catch‐all phrase for almost any unnatural nucleic acid, raising the question: what is XNA and how does it differ from chemically modified DNA?

Significant Difference in Semiconducting Properties of Isomeric All‐Acceptor Polymers Synthesized via Direct Arylation Polycondensation

By Yang Wang, Tsukasa Hasegawa, Hidetoshi Matsumoto, Tsuyoshi Michinobu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

All‐acceptor polymers have been of significant fundamental and technical interests. However, their challenging synthesis by Stille or Suzuki polycondensations has prevented the development and understanding of such polymers. Alternatively, direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers without using the tin or boric acid ester precursors. However, the conventional DArP often requires monomers with an orienting or activating group for the reactive carbon‐hydrogen (C‐H) bonds, which limits the choice of acceptor units. In this study, we describe the successful example of DArP for producing high‐molecular‐weight all‐acceptor polymers comprised of the acceptor monomers without any orienting or activating groups for C‐H bonds via a modified protocol using Pd/Cu co‐catalysts. By employing this DArP, we obtain two isomeric all‐acceptor polymers, P1 and P2, which have the same backbone and side‐chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing and charge‐transport properties. Interestingly, while P1 possesses a more planar backbone based on density functional theory (DFT) calculations, it shows lower electron mobilities (μe) in organic thin‐film transistors. In contrast, P2 with a greater backbone torsion in DFT calculations exhibits a remarkable μe of 2.55 cm2 V−1 s−1, which is among the highest values for unipolar n‐type polymers synthesized by DArP. Moreover, P2‐based transistors show an excellent shelf‐storage stability in air. The μe of P2‐based transistors is 1.0 cm2 V−1 s−1 even after the storage for 1 month, suggesting the potential use as a benchmark n‐type semiconducting polymer in organic electronics. Overall, our new DArP protocol can open the door for developing exceptional electron‐transporting polymers that cannot be obtained by the traditional Suzuki or Stille polycondensations.

Breaking Parallel Orientation of Rods via Dendritic Architecture toward Diverse Supramolecular Structures

By Ruimeng Zhang, Xueyan Feng, Rui Zhang, Wenpeng Shan, Zebin Su, Jialin Mao, Chrys Wesdemiotis, Jiahao Huang, Xiao-Yun Yan, Tong Liu, Tao Li, Mingjun Huang, Zhiwei Lin, An-Chang Shi, Stephen Z. D. Cheng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Self‐assembled nanostructures of rod‐like molecules are commonly limited to nematic or layered smectic structures dominated by parallel arrangement of the rod‐like components. We report distinct self‐assembly behavior of four categories of dendritic rods constructed by placing a tri(hydroxyl) group at the apex of dendritic oligo‐fluorenes. Designed hydrogen bonding and dendritic architecture break the parallel arrangement of the rods, resulting in molecules with specific (fan‐like or cone‐like) shapes. While the fan‐shaped molecules tend to form hexagonal packing cylindrical phases, the cone‐shaped molecules could form various spherical motifs to pack into ordered structures including the Frank‐Kasper A15 phase and dodecagonal quasicrystal. This study provides a model system to engineer diverse supramolecular structures by rod‐like molecules and sheds new light into the mechanisms of the formation of unconventional spherical packing structures in soft matter.

The crystal structure of orthocetamol solved by 3D electron diffraction

By Iryna Andrusenko, Victoria Hamilton, Enrico Mugnaioli, Arianna Lanza, Charlie Hall, Jason Potticary, Simon R. Hall, Mauro Gemmi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Orthocetamol is a regioisomer of the well‐known pain medication paracetamol and a promising analgesic and an anti‐arthritic medicament itself. However, orthocetamol cannot be grown as single crystals suitable for X‐ray diffraction, so its crystal structure has remained a mystery for more than a century. We report here the ab‐initio structure determination of orthocetamol obtained by 3D electron diffraction, combining a low dose acquisition method and a dedicated single electron detector for recording the diffracted intensities. The structure is monoclinic, with a pseudo‐tetragonal cell that favors multiple twinning on a scale of a few tens of nanometers. The successful application of 3D electron diffraction to orthocetamol introduces a new gold standard of total structure solution in all cases where X‐ray diffraction and electron microscope imaging methods fail.

Developing a “polysulfide‐phobic” strategy to restrain shuttle effect in lithium‐sulfur batteries

By Yibo He, Yu Qiao, Zhi Chang, Xin Cao, Min Jia, Ping He, Haoshen Zhou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 18, 2019.

Inspired by hydrophobic interface, a novel design of “polysulfide‐phobic” interface was proposed and developed to restrain shuttle effect in lithium‐sulfur batteries. Two‐dimensional VOPO4 sheets with adequate active sites were employed to immobilize the polysulfides via the formation of V‐S bond. Moreover, owing to the intrinsic Coulomb repulsion between polysulfide anions, the surface anchored with polysulfides can be further evolved into a “polysulfide‐phobic” interface, which was demonstrated by the advanced time/space‐resolved operando Raman evidences. In particular, by introducing the “polysulfide‐phobic” surface design into separator fabrication, the lithium‐sulfur battery performed a superior long‐term cycling stability. This work expands a novel strategy to build a “polysulfide‐phobic” surface by “self‐defense” mechanism for suppressing polysulfides shuttle, which provides new insights and opportunities to develop advanced lithium‐sulfur batteries.

[ASAP] Hierarchical Assembly of Plasmonic Nanoparticle Heterodimer Arrays with Tunable Sub-5 nm Nanogaps

By Jiajing Li†, Tian-Song Deng‡§, Xiaoying Liu†, James A. Dolan†??, Norbert F. Scherer‡§, and Paul F. Nealey*†?? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00792

[ASAP] An in Vivo Nanosensor Measures Compartmental Doxorubicin Exposure

By Jackson D. Harvey†‡?, Ryan M. Williams†?, Kathryn M. Tully†‡, Hanan A. Baker†‡, Yosi Shamay†§, and Daniel A. Heller*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00956

[ASAP] NIR-Responsive Polypeptide Nanocomposite Generates NO Gas, Mild Photothermia, and Chemotherapy to Reverse Multidrug-Resistant Cancer

By Yue Ding, Chang Du, Jiwen Qian, and Chang-Ming Dong* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00975

[ASAP] Direct Measurement of the Electron Beam Spatial Intensity Profile via Carbon Nanotube Tomography

By Matthew D. Zotta, Sharadh Jois, Prathamesh Dhakras, Miguel Rodriguez, and Ji Ung Lee* from Nano Letters: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01228

[ASAP] The Role of Oxygen Atoms on Excitons at the Edges of Monolayer WS2

By Zhenliang Hu†‡, Jose Avila?, Xinyun Wang†‡, Jin Feng Leong†, Qi Zhang†, Yanpeng Liu#, Maria C. Asensio?, Junpeng Lu*§, Alexandra Carvalho*‡, Chorng Haur Sow*†‡, and Antonio Helio Castro Neto*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01670

[ASAP] Structure Control of a p-Conjugated Oligothiophene-Based Liquid Crystal for Enhanced Mixed Ion/Electron Transport Characteristics

By Ban Xuan Dong†, Ziwei Liu‡, Mayank Misra§, Joseph Strzalka?, Jens Niklas?, Oleg G. Poluektov?, Fernando A. Escobedo*§, Christopher K. Ober*‡, Paul F. Nealey*†#, and Shrayesh N. Patel*†? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01055

[ASAP] Highly Compressive Boron Nitride Nanotube Aerogels Reinforced with Reduced Graphene Oxide

By Mingmei Wang†‡?, Tao Zhang†?, Dasha Mao†§, Yimin Yao†§, Xiangliang Zeng†‡, Linlin Ren†, Qiran Cai?, Srikanth Mateti?, Lu Hua Li?, Xiaoliang Zeng*†, Guoping Du*‡, Rong Sun*†, Ying Chen*?, Jian-Bin Xu?, and Ching-Ping Wong# from ACS Nano: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03225

[ASAP] Plasmon Nanocavity Array Lasers: Cooperating over Losses and Competing for Gain

By A. Femius Koenderink* from ACS Nano: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b04091

[ASAP] Microphysiological Engineering of Self-Assembled and Perfusable Microvascular Beds for the Production of Vascularized Three-Dimensional Human Microtissues

By Jungwook Paek†?, Sunghee E. Park†?, Qiaozhi Lu†, Kyu-Tae Park†, Minseon Cho†, Jeong Min Oh†, Keon Woo Kwon†, Yoon-suk Yi†, Joseph W. Song†, Hailey I. Edelstein‡, Jeff Ishibashi§?, Wenli Yang‡, Jacob W. Myerson?, Raisa Y. Kiseleva?, Pavel Aprelev?, Elizabeth D. Hood?, Dwight Stambolian#, Patrick Seale§?, Vladimir R. Muzykantov?, and Dongeun Huh*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00686

[ASAP] Defect-Mediated Charge-Carrier Trapping and Nonradiative Recombination in WSe2 Monolayers

By Lesheng Li† and Emily A. Carter*‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04663

[ASAP] Spiro-Functionalized Diphenylethenes: Suppression of a Reversible Photocyclization Contributes to the Aggregation-Induced Emission Effect

By Zhibiao Zhou†#, Sheng Xie‡#, Xian Chen†, Yujie Tu‡, Jiannan Xiang†, Jianguo Wang‡?, Zikai He§, Zebing Zeng*†, and Ben Zhong Tang*‡|| from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04426

[ASAP] Squeezing All Elements in the Periodic Table: Electron Configuration and Electronegativity of the Atoms under Compression

By Martin Rahm*†, Roberto Cammi‡, N. W. Ashcroft§, and Roald Hoffmann? from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02634

[ASAP] Enabling Room-Temperature Mechanochromic Activation in a Glassy Polymer: Synthesis and Characterization of Spiropyran Polycarbonate

By Yuval Vidavsky†?, Steven J. Yang†?, Brooks A. Abel‡, Iris Agami§, Charles E. Diesendruck§, Geoffrey W. Coates‡, and Meredith N. Silberstein*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 18, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04229

The changing phase of data storage

By Robert E. Simpson from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 18, 2019.

Nature Nanotechnology, Published online: 18 June 2019; doi:10.1038/s41565-019-0491-1

The combination of ferroelectrics and phase-change materials provides a route towards phase-change data storage at room temperature, without heating.

Soft, Skin‐Interfaced Microfluidic Systems with Passive Galvanic Stopwatches for Precise Chronometric Sampling of Sweat

By Amay J. Bandodkar, Jungil Choi, Stephen P. Lee, William J. Jeang, Prophecy Agyare, Philipp Gutruf, Siqing Wang, Rebecca A. Sponenburg, Jonathan T. Reeder, Stephanie Schon, Tyler R. Ray, Shulin Chen, Sunita Mehta, Savanna Ruiz, John A. Rogers from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

A combination of materials, device layouts, and passive time‐tracking principles forms the foundations for a class of soft, skin‐interfaced microfluidic devices that can capture sequences of pristine sweat samples with time‐stamped information for comprehensive analysis of sweat chemistry and dynamics. Abstract Comprehensive analysis of sweat chemistry provides noninvasive health monitoring capabilities that complement established biophysical measurements such as heart rate, blood oxygenation, and body temperature. Recent developments in skin‐integrated soft microfluidic systems address many challenges associated with standard technologies in sweat collection and analysis. However, recording of time‐dependent variations in sweat composition requires bulky electronic systems and power sources, thereby constraining form factor, cost, and modes of use. Here, presented are unconventional design concepts, materials, and device operation principles that address this challenge. Flexible galvanic cells embedded within skin‐interfaced microfluidics with passive valves serve as sweat‐activated “stopwatches” that record temporal information associated with collection of discrete microliter volumes of sweat. The result allows for precise measurements of dynamic sweat composition fluctuations using in situ or ex situ analytical techniques. Integrated electronics based on near‐field communication (NFC) protocols or docking stations equipped with standard electronic measurement tools provide means for extracting digital timing results from the stopwatches. Human subject studies of time‐stamped sweat samples by in situ colorimetric methods and ex situ techniques based on inductively coupled plasma mass spectroscopy (ICP‐MS) and chlorodimetry illustrate the ability to quantitatively capture time‐dynamic sweat chemistry in scenarios compatible with field use.

Kinetic Stabilization of the Sol–Gel State in Perovskites Enables Facile Processing of High‐Efficiency Solar Cells

By Kai Wang, Ming‐Chun Tang, Hoang X. Dang, Rahim Munir, Dounya Barrit, Michele De Bastiani, Erkan Aydin, Detlef‐M. Smilgies, Stefaan Wolf, Aram Amassian from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

The role of cation and halide mixing is revealed using in situ X‐ray scattering measurements during spin‐coating. Modulating the cation/halide composition directly impacts the lifetime of the sol–gel precursor film and its easy and reproducible conversion to the perovskite phase to yield solar cells with 20% power conversion efficiency. Abstract Perovskite solar cells increasingly feature mixed‐halide mixed‐cation compounds (FA1−x−yMAxCsyPbI3−zBrz) as photovoltaic absorbers, as they enable easier processing and improved stability. Here, the underlying reasons for ease of processing are revealed. It is found that halide and cation engineering leads to a systematic widening of the anti‐solvent processing window for the fabrication of high‐quality films and efficient solar cells. This window widens from seconds, in the case of single cation/halide systems (e.g., MAPbI3, FAPbI3, and FAPbBr3), to several minutes for mixed systems. In situ X‐ray diffraction studies reveal that the processing window is closely related to the crystallization of the disordered sol–gel and to the number of crystalline byproducts; the processing window therefore depends directly on the precise cation/halide composition. Moreover, anti‐solvent dripping is shown to promote the desired perovskite phase with careful formulation. The processing window of perovskite solar cells, as defined by the latest time the anti‐solvent drip yields efficient solar cells, broadened with the increasing complexity of cation/halide content. This behavior is ascribed to kinetic stabilization of sol–gel state through cation/halide engineering. This provides guidelines for designing new formulations, aimed at formation of the perovskite phase, ultimately resulting in high‐efficiency perovskite solar cells produced with ease and with high reproducibility.

Biomimetic Nanotechnology toward Personalized Vaccines

By Jiarong Zhou, Ashley V. Kroll, Maya Holay, Ronnie H. Fang, Liangfang Zhang from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

Personalized medicine is transforming how diseases are managed in the clinic. At the same time, biomimetic nanotechnology offers many advantages that can be leveraged toward the design of more effective medical interventions. Recent developments in biomimetic nanovaccines against cancer and bacterial infections are discussed, with a specific emphasis on potential avenues for personalization. Abstract While traditional approaches for disease management in the era of modern medicine have saved countless lives and enhanced patient well‐being, it is clear that there is significant room to improve upon the current status quo. For infectious diseases, the steady rise of antibiotic resistance has resulted in super pathogens that do not respond to most approved drugs. In the field of cancer treatment, the idea of a cure‐all silver bullet has long been abandoned. As a result of the challenges facing current treatment and prevention paradigms in the clinic, there is an increasing push for personalized therapeutics, where plans for medical care are established on a patient‐by‐patient basis. Along these lines, vaccines, both against bacteria and tumors, are a clinical modality that could benefit significantly from personalization. Effective vaccination strategies could help to address many challenging disease conditions, but current vaccines are limited by factors such as a lack of potency and antigenic breadth. Recently, researchers have turned toward the use of biomimetic nanotechnology as a means of addressing these hurdles. Recent progress in the development of biomimetic nanovaccines for antibacterial and anticancer applications is discussed, with an emphasis on their potential for personalized medicine.

Bayesian Network Resource for Meta‐Analysis: Cellular Toxicity of Quantum Dots

By Muhammad Bilal, Eunkeu Oh, Rong Liu, Joyce C. Breger, Igor L. Medintz, Yoram Cohen from Wiley: Small: Table of Contents. Published on Jun 17, 2019.

A Bayesian networks (BNs) approach is developed for meta‐analysis of nanomaterials' toxicity. The BN based models are demonstrated for exploring the cellular toxicity of quantum dots (QDs) for i) causal analysis of cellular toxicity, ii) identification of the relevant attributes, iii) intelligent query of the body of evidence, iv) quantification of data uncertainties, and v) identification of toxicity association rules. Abstract A web‐based resource for meta‐analysis of nanomaterials toxicity is developed whereby the utility of Bayesian networks (BNs) is illustrated for exploring the cellular toxicity of Cd‐containing quantum dots (QDs). BN models are developed based on a dataset compiled from 517 publications comprising 3028 cell viability data samples and 837 IC50 values. BN QD toxicity (BN‐QDTox) models are developed using both continuous (i.e., numerical) and categorical attributes. Using these models, the most relevant attributes identified for correlating IC50 are: QD diameter, exposure time, surface ligand, shell, assay type, surface modification, and surface charge, with the addition of QD concentration for the cell viability analysis. Data exploration via BN models further enables identification of possible association rules for QDs cellular toxicity. The BN models as web‐based applications can be used for rapid intelligent query of the available body of evidence for a given nanomaterial and can be readily updated as the body of knowledge expands.

Oxidative Amide Coupling from Functionally Diverse Alcohols and Amines using Aerobic Copper/Nitroxyl Catalysis

By Paige E. Piszel, Aristidis Vasilopoulos, Shannon S Stahl from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

The aerobic Cu/ABNO catalyzed oxidative coupling of alcohols and amines is highlighted here in the synthesis of amide bonds in diverse drug‐like molecules (ABNO = 9‐azabicyclo[3.3.1]nonane N‐oxyl). The robust method leverages the privileged reactivity of alcohols bearing electronegative heteroatoms (O, F, N, Cl) in the β‐position. The reaction tolerates over 20 unique functional groups and is demonstrated on a 15 mmol scale under air. Steric constraints of the catalyst allow for chemoselective amidation of primary amines in the presence of secondary amines. All catalyst components are commercially available, and the reaction proceeds under mild conditions with retention of stereocenters in both reaction partners, while producing only water as a by‐product.

σ‐Noninnocence Masked Phenyl Cation Transfer at Formal Ni(IV)

By Jelte S. Steen, Gerald Knizia, Johannes E. M. N. Klein from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of ‐2 at a transition metal center. For a series of formal high‐valent Ni(IV) complexes, aryl‐CF₃ bond forming reductive elimination was reported to occur readily by Sanford and co‐workers (Bour et al. J. Am. Chem. Soc. 2015, 137, 8034‐8037.). We here report a detailed computational analysis of this reaction. Unexpectedly, we find that the formal Ni(IV) centers in these complexes are better described as approaching the +II oxidation state for the Ni center, originating from highly covalent metal‐ligand bonds, a phenomenon attributable to σ‐noninnocence. A direct consequence of this unusual bonding scenario is that elimination of aryl‐CF₃ products occurs in an essentially redox neutral fashion, rather than a regular reductive elimination. This is also supported by an electron flow analysis of the reaction, which shows that an anionic CF₃ group is transferred to an electrophilic aryl group. The uncovered role of σ‐noninnocence in metal‐ligand bonding, and of an essentially redox neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry.

A Stable Tetrathiophene Diradical by Cross‐Conjugation

By Juan Casado, Cheng Zhang, Samara Medina Rivero, Wuyue Liu, David Casanova, Xiaozhang Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A tetracyano quinoidal tetrathiophene having a central bi(thieno[3,4‐c]pyrrole‐4,6‐dione) acceptor has been studied. The aromaticity recovery of the thiophenes produces the formation of a diradical species and cross‐conjugation between the inter‐dicyano and the inter‐dione acceptor paths originates a diradical character of y0 = 0.61 and a singlet‐triplet gap of ‐2.76 kcal/mol. Competition between the two cross‐conjugated paths enhances the disjoint character of the SOMOs and provokes the “confinement” of the diradical in the molecular center enabling a thermodynamic diradical stabilization featured by a half‐life of 262 hours. Cross‐conjugation effects have been also addressed in the anionic species, (up to a radical trianion).

Efficient innate immune killing of cancer cells triggered by cell surface anchoring of multivalent antibody‐recruiting polymers

By Annemiek Uvyn, Ruben De Coen, Mandy Gruijs, Cees Tuk, Jana De Vrieze, Marjolein van Egmond, Bruno de Geest from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Rewiring innate immune defence to eradicate cancer is one of the mechanisms of action of several monoclonal antibodies (mAbs) used in the clinic. Binding of mAbs onto a cell surface triggers antibody‐mediated effector killing by innate immune cells and through complement activation. As an alternative to mAbs, which face inherent issues with costs of production and stability, synthetic systems that can recruit endogenous antibodies from the blood stream to a cancer cell surface could be of great relevance. Here we explore antibody‐recruiting polymers (ARPs) as a novel class of immunotherapy. ARPs consist of a cell binding motif linked to a polymer that contains multiple small molecule antibody‐binding motifs along its backbone. As a proof of concept, we employ a lipid anchor that inserts into the phospholipid cell membrane and make use of a polymeric activated ester scaffold onto which we substitute dinitrophenol as antibody‐binding motif. We demonstrate that ARPs allow for high avidity antibody binding and are able to drive antibody recruitment to treated cells for up to several days. Further we show that ARP‐treated cancer cells are prone to antibody‐mediated killing of cancer cells through phagocytosis by macrophages.

Iron‐Catalyzed C–H Activation with Propargyl Acetates: Mechanistic Insights on Iron(II) by Experiment, Kinetics, Mössbauer Spectroscopy and Computation

By Jiayu Mo, Thomas Müller, João Carlos Agostinho de Oliveira, Serhiy Demeshko, Franc Meyer, Lutz Ackermann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

The iron‐catalyzed C–H/N–H alkyne annulation was realized by a customizable click‐triazole‐amide under exceedingly mild reaction conditions. A unifying mechanistic approach by experiment, spectroscopy, kinetics and computation provided strong support for facile C–H activation by a ligand‐to‐ligand hydrogen transfer (LLHT) mechanism. Combined Mössbauer spectroscopic analysis and DFT calculations were indicative of high‐spin iron(II) species as the key intermediates in the C–H activation manifold.

Reversing Chemoselectivity: Simultaneous Positive and Negative Catalysis by Chemically Equivalent Rims of Cucurbit[7]uril Host

By Nazar Rad, Oksana Danylyuk, Volodymyr Sashuk from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Enzyme catalysis has always been an inspiration and an unattainable pursuit for chemists due to features such as high specificity, selectivity, and efficiency. Here, we disclose a feature neither common in enzymes nor ever described for enzyme mimics, but one that could prove crucial for the catalytic performance of the latter, namely the ability to catalyze and inhibit two different reactions at the same time. Remarkably, this can be realized by two identical, spatially resolved catalytic sites. In the future, such a synchronized catalyst action could be used not only for controlling chemoselectivity, as in the present case, but also for regulating other types of chemical reactivity.

Influencing epigenetic information with a hydrolytically stable carbocyclic 5 aza‐2’‐deoxycytidine

By Thomas Carell, Thomas Wildenhof, Sarah Schiffers, Franziska Regine Traube, Peter Mayer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

5‐Aza‐2’ deoxycytidine (AzadC) is an antimetabolite in clinical use, which reduces the level of the epigenetic modification 5 methyl‐2’ deoxycytidine (mdC). AzadC is incorporated into the genome of proliferating cells, where it inhibits the DNA methyltransferases (DNMTs) in a suicide process leading to a reduction of mdC. The loss of mdC, which is a transcriptional silencer in promoters, leads to the reactivation of genes including tumor suppressor genes, which elicits a beneficial effect. The problem associated with AzadC is that the compound is hydrolytically unstable. It decomposes during treatment to a variety of poorly characterized hydrolysis products. After its incorporation into the genome, this hydrolytic instability generates abasic sites. It is consequently difficult to dissect if the activity of the compound is caused by DNMT inhibition or more generally by DNA lesion formation. We now discovered that a disarmed version of AzadC, in which the ribose oxygen was replaced by a CH2‐group, is surprisingly stable under a variety of pH values while keeping the epigenetic activity against the DNMTs.

A Very Strong Methylation Agent: [Me2Cl][Al(OTeF5)4]

By Sebastian Hämmerling, Günther Thiele, Simon Steinhauer, Helmut Beckers, Carsten Müller, Sebastian Riedel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A chloronium‐containing salt, [Me2Cl][Al(OTeF5)4], was synthesized on multigram scale by means of a simple one‐pot procedure. The isolated product can be handled at room temperature and used as a strong electrophilic methylation agent. This is demonstrated by the methylation of the very weak bases P(CF3)3, PF3, MeI, and MeBr. Abstract A new chloronium‐containing salt, [Me2Cl][Al(OTeF5)4], was synthesized on multigram scale by means of a simple one‐pot procedure. The isolated product can be handled at room temperature and used as a strong electrophilic methylation agent. This is demonstrated by the methylation of the very weak bases P(CF3)3, PF3, MeI, and MeBr.

In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a C −C Stille Coupling

By Julia Holz, Camilla Pfeffer, Hualiang Zuo, Dennis Beierlein, Gunther Richter, Elias Klemm, René Peters from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Black gold: In situ formed Au metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C −C bonds. Turnover numbers up to 29 000 could be achieved by using active carbon as solid support, which allowed for convenient catalyst recovery and reuse. This is a rare case where a Au catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent. Abstract Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C −C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C −C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent.

A Giant Dy76 Cluster: A Fused Bi‐Nanopillar Structural Model for Lanthanide Clusters

By Xiao‐Yu Li, Hai‐Feng Su, Quan‐Wen Li, Rui Feng, Hui‐Yun Bai, Hua‐Yu Chen, Jian Xu, Xian‐He Bu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

We go together: Two dysprosium clusters with 48 and 76 metal atoms, respectively, were generated under solvothermal conditions by using 3‐furancarboxylic acid. The bi‐nanopillar Dy76 was formed by the fusion of two Dy48 nanopillars. Abstract Although great achievements have been made in the synthesis of giant lanthanide clusters, novel structural models are still scarce. Herein, we report a giant lanthanide cluster Dy76, constructed from [Dy3(μ3‐OH)4] and [Dy5(μ4‐O)(μ3‐OH)8] building blocks. As the largest known Dy cluster, the structure of Dy76 can be seen as arising from the fusion of two Dy48 clusters; these clusters can be isolated under various synthetic conditions and were characterized by single‐crystal X‐ray diffraction. This new, fused structural model of the pillar motif has not been found in Ln clusters. Furthermore, the successful conversion of Dy76 back into Dy48 in a retrosynthetic manner supports the proposed fusion formation mechanism of Dy76. Electrospray ionization mass spectrometry (ESI‐MS) analysis suggests that the metal cluster skeleton of Dy76 shows good stability in various solvents. This work not only reveals a new structural type of Ln clusters but also provides insight into the novel fusion assembly process.

Hyperpolarising Pyruvate through Signal Amplification by Reversible Exchange (SABRE)

By Wissam Iali, Soumya S. Roy, Ben J. Tickner, Fadi Ahwal, Aneurin J. Kennerley, Simon B. Duckett from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Signal amplification by reversible exchange (SABRE) can provide strong 13C pyruvate signal enhancements in seconds through the formation of the novel polarisation transfer catalyst [Ir(H)2(η2‐pyruvate)(DMSO)(IMes)]. By harnessing SABRE, strong signals for [1‐13C]‐ and [2‐13C]pyruvate are readily created. Abstract Hyperpolarisation methods that premagnetise agents such as pyruvate are currently receiving significant attention because they produce sensitivity gains that allow disease tracking and interrogation of cellular metabolism by magnetic resonance. Here, we communicate how signal amplification by reversible exchange (SABRE) can provide strong 13C pyruvate signal enhancements in seconds through the formation of the novel polarisation transfer catalyst [Ir(H)2(η2‐pyruvate)(DMSO)(IMes)]. By harnessing SABRE, strong signals for [1‐13C]‐ and [2‐13C]pyruvate in addition to a long‐lived singlet state in the [1,2‐13C2] form are readily created; the latter can be observed five minutes after the initial hyperpolarisation step. We also demonstrate how this development may help with future studies of chemical reactivity.

Oxygen Isotope Labeling Experiments Reveal Different Reaction Sites for the Oxygen Evolution Reaction on Nickel and Nickel Iron Oxides

By Seunghwa Lee, Karla Banjac, Magalí Lingenfelder, Xile Hu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

On active duty: In situ Raman spectroscopic analysis of 18O‐labeled ultrathin layered double hydroxide has provided evidence for the different active sites of Fe‐free and Fe‐doped Ni oxides for the oxygen evolution reaction. Whereas lattice oxygen atoms are the active sites in Fe‐free Ni‐containing oxides, highly reactive surface sites lead to the dramatically increased catalytic activity of Fe‐doped Ni oxides. Abstract Nickel iron oxide is considered a benchmark nonprecious catalyst for the oxygen evolution reaction (OER). However, the nature of the active site in nickel iron oxide is heavily debated. Here we report direct spectroscopic evidence for the different active sites in Fe‐free and Fe‐containing Ni oxides. Ultrathin layered double hydroxides (LDHs) were used as defined samples of metal oxide catalysts, and 18O‐labeling experiments in combination with in situ Raman spectroscopy were employed to probe the role of lattice oxygen as well as an active oxygen species, NiOO−, in the catalysts. Our data show that lattice oxygen is involved in the OER for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. Moreover, NiOO− is a precursor to oxygen for Ni and NiCo LDHs, but not for NiFe and NiCoFe LDHs. These data indicate that bulk Ni sites in Ni and NiCo oxides are active and evolve oxygen via a NiOO− precursor. Fe incorporation not only dramatically increases the activity, but also changes the nature of the active sites.

Highly Efficient CO2 Utilization via Aqueous Zinc– or Aluminum–CO2 Systems for Hydrogen Gas Evolution and Electricity Production

By Changmin Kim, Jeongwon Kim, Sangwook Joo, Yejin Yang, Jeeyoung Shin, Meilin Liu, Jaephil Cho, Guntae Kim from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

CO2 power: Zn/Al–CO2 systems utilize CO2 to produce electricity and hydrogen gas. As a novel electrochemical reaction, a hydrogen evolution reaction (HER) utilizing acidity contributed by the spontaneous dissolution of CO2, is the cathodic reaction. The system sequesters CO2 and simultaneously generates electrical energy and H2 from the electrochemical oxidation of Zn and Al metals. Abstract Atmospheric carbon dioxide (CO2) has increased from 278 to 408 parts per million (ppm) over the industrial period and has critically impacted climate change. In response to this crisis, carbon capture, utilization, and storage/sequestration technologies have been studied. So far, however, the economic feasibility of the existing conversion technologies is still inadequate owing to sluggish CO2 conversion. Herein, we report an aqueous zinc– and aluminum–CO2 system that utilizes acidity from spontaneous dissolution of CO2 in aqueous solution to generate electrical energy and hydrogen (H2). The system has a positively shifted onset potential of hydrogen evolution reaction (HER) by 0.4 V compared to a typical HER under alkaline conditions and facile HER kinetics with low Tafel slope of 34 mV dec−1. The Al–CO2 system has a maximum power density of 125 mW cm−2 which is the highest value among CO2 utilization electrochemical system.

Regioselective Functionalization of Stable BN‐Modified Luminescent Tetraphenes for High‐Resolution Fingerprint Imaging

By Huanan Huang, Ying Zhou, Meng Wang, Jianying Zhang, Xiaohua Cao, Shitao Wang, Dapeng Cao, Chunming Cui from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

New tool for forensic science: Polycyclic aromatic hydrocarbons modified with a BN unit show outstanding luminescence properties. In powdered form, these compounds can be used for fast and high‐resolution imaging of latent fingerprints under simple operating conditions. Even the second level of unique details of the fingerprint can be visualized. Abstract A series of novel BN tetraphene derivatives have been prepared successfully for the first time via a post‐functionalization strategy. The optical and electronic properties of these derivatives could be tuned systematically by the incorporation of different substituents on the main skeleton. The functionalized BN‐containing luminogens have been explored for the detection of latent fingerprints (LFPs) on different substrates, including glass, aluminum foil, plastic, and ironware. This strategy provides great versatility in LFP imaging and good potential in elucidating the chemical information within LFPs, making the strategy valuable in forensic investigations.

Decorated Traditional Zeolites with Subunits of Metal–Organic Frameworks for CH4/N2 Separation

By Yaqi Wu, Danhua Yuan, Dawei He, Jiacheng Xing, Shu Zeng, Shutao Xu, Yunpeng Xu, Zhongmin Liu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Subunits of MOFs were introduced into traditional zeolite frameworks to obtain applicable adsorbents with advantages of both zeolites and MOFs. The subunits of ZIFs were introduced into zeolite Y and zeolite ZSM‐5 for CH4/N2 separation. Both the molecular simulation and experimental results validated that the IAST CH4/N2 selectivity of the resulting samples greatly improved. Abstract Metal–organic frameworks (MOF) materials are promising materials for gas separation, but their application still faces various challenges. A strategy is now reported for introducing subunits of MOFs into traditional zeolite frameworks to obtain applicable adsorbents with advantages of both zeolites and MOFs. The subunits of ZIFs were introduced into zeolite Y and zeolite ZSM‐5 for CH4/N2 separation. Both the molecular simulation and experimental results validated that the IAST CH4/N2 selectivity of the resulting samples greatly improved (above 8, at 100 kPa and 25 °C) with the incorporation of ZIF subunits into zeolites structure, and the selectivities were obviously higher than that of zeolites and even better than that of ZIFs. This strategy not only gave rise to an efficient adsorbent for CH4/N2 separation but also provided ideas for design of other adsorption and separation materials.

Copper‐Catalyzed 1,2‐Methoxy Methoxycarbonylation of Alkenes with Methyl Formate

By Balázs Budai, Alexandre Leclair, Qian Wang, Jieping Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A generous donor: Methyl formate acts as a donor of both methoxycarbonyl and methoxy groups in the Cu‐catalyzed alkene difunctionalization reaction. Formation of a diketiminato‐CuI‐styrene ternary complex (1), fully characterized, is proposed to accelerate the addition of the nucleophilic methoxycarbonyl radical. TBPA=tert‐butyl peroxyacetate, Tf=trifluoromethanesulfonyl. Abstract Reported here is a copper‐catalyzed 1,2‐methoxy methoxycarbonylation of alkenes by an unprecedented use of methyl formate as a source of both the methoxy and the methoxycarbonyl groups. This reaction transforms styrene and its derivatives into value‐added β‐methoxy alkanoates and cinnamates, as well as medicinally important five‐membered heterocycles, such as functionalized tetrahydrofurans, γ‐lactones, and pyrrolidines. A ternary β‐diketiminato‐CuI‐styrene complex, fully characterized by NMR spectroscopy and X‐ray crystallographic analysis, is capable of catalyzing the same transformation. These findings suggest that pre‐coordination of electron‐rich alkenes to copper might play an important role in accelerating the addition of nucleophilic radicals to electron‐rich alkenes, and could have general implications in the design of novel radical‐based transformations.

Utilizing the Space‐charge Region of FeNi‐LDH/CoP p‐n Junction to Promote the Performance in Oxygen Evolution Electrocatalysis

By Kai He, Tsegaye Tadesse Tsega, Xi Liu, Jiantao Zai, Xin-Hao Li, Xuejiao Liu, Wenhao Li, Nazakat Ali, Xuefeng Qian from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Further exploring optimal path to develop efficient alternative electrocatalysts are urgent. The modulation of electron density is turned out to be one of effective options. Herein, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode. The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs RHE) of FeNi‐LDH/CoP/CC achieves ~10‐fold and ~100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH‐ has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities.

Programmable On‐Chip Artificial Cell Producing Post‐Translationally Modified Ubiquitinated Protein

By Shai Zilberzwige‐Tal, Aviad Levin, Zenon Toprakcioglu, Tuomas P.J. Knowles, Ehud Gazit, Johann Elbaz from Wiley: Small: Table of Contents. Published on Jun 17, 2019.

Artificial cell‐on‐a‐chip, which allows the production of modified proteins by programming transcription, translation and post‐translational modifications (PTMs) in a discrete and highly precise manner has been developed. The modular nature of microfluidics grants significant advantages to control a wide range of cell‐free processes and to study the effect of individual steps in protein expression and modifications. Abstract In nature, intracellular microcompartments have evolved to allow the simultaneous execution of tightly regulated complex processes within a controlled environment. This architecture serves as the blueprint for the construction of a wide array of artificial cells. However, such systems are inadequate in their ability to confine and sequentially control multiple central dogma activities (transcription, translation, and post‐translational modifications) resulting in a limited production of complex biomolecules. Here, an artificial cell‐on‐a‐chip comprising hierarchical compartments allowing the processing and transport of products from transcription, translation, and post‐translational modifications through connecting channels is designed and fabricated. This platform generates a tightly controlled system, yielding directly a purified modified protein, with the potential to produce proteoform of choice. Using this platform, the full ubiquitinated form of the Parkinson's disease‐associated α‐synuclein is generated starting from DNA, in a single device. By bringing together all central dogma activities in a single controllable platform, this approach will open up new possibilities for the synthesis of complex targets, will allow to decipher diverse molecular mechanisms in health and disease and to engineer protein‐based materials and pharmaceutical agents.

Nitrogen Engineering on 3D Dandelion‐Flower‐Like CoS2 for High‐Performance Overall Water Splitting

By Na Yao, Peng Li, Zirui Zhou, Ran Meng, Gongzhen Cheng, Wei Luo from Wiley: Small: Table of Contents. Published on Jun 17, 2019.

Tailoring the electronic structure of 3D dandelion‐flower‐like CoS2 via nitrogen engineering can optimize both the adsorption free energies of hydrogen (∆G*H) and water , resulting in boosting hydrogen evolution reaction performance, with an overpotential of 28 mV to achieve 10 mA cm−2 in 1.0 m KOH. Besides, the N‐CoS2 also exhibits remarkable oxygen evolution reaction performance, making it a high‐performance bifunctional electrocatalyst toward water splitting. Abstract Searching for highly efficient and stable bifunctional electrocatalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is highly desirable for the practical application of water electrolysis under alkaline electrolyte. Although electrocatalysts based on transition metal sulfides (TMSs) are widely studied as efficient (pre)catalysts toward OER under alkaline media, their HER performances are far less than the state‐of‐the‐art Pt catalyst. Herein, the synthesis of nitrogen doped 3D dandelion‐flower‐like CoS2 architecture directly grown on Ni foam (N‐CoS2/NF) is reported that possesses outstanding HER activity and durability, with an overpotential of 28 mV to obtain the current density of 10 mA cm−2, exceeding almost all the documented TMS‐based electrocatalysts. Density functional theory calculations and experimental results reveal that the d‐band center of CoS2 could be efficiently tailored by N doping, resulting in optimized adsorption free energies of hydrogen (ΔG*H) and water , which can accelerate the HER process in alkaline electrolyte. Besides, the resulting N‐CoS2/NF also displays excellent performance for OER, making it a high‐performance bifunctional electrocatalyst toward overall water splitting, with a cell voltage of 1.50 V to achieve 10 mA cm−2.

Zwitterion‐Functionalized Detonation Nanodiamond with Superior Protein Repulsion and Colloidal Stability in Physiological Media

By Viktor Merz, Julian Lenhart, Yvonne Vonhausen, Maria E. Ortiz‐Soto, Jürgen Seibel, Anke Krueger from Wiley: Small: Table of Contents. Published on Jun 17, 2019.

The covalent functionalization of nanodiamond particles with a combination of a triglycol linker and zwitterionic headgroups ensures the colloidal stability of the nanoparticles in physiological media such as fetal bovine serum and Dulbecco's modified Eagle medium. It simultaneously prevents nonspecific adsorption of serum proteins and thus the formation of a hard protein corona—an essential prerequisite for biomedical applications. Abstract Nanodiamond (ND) is a versatile and promising material for bioapplications. Despite many efforts, agglomeration of nanodiamond and the nonspecific adsorption of proteins on the ND surface when exposed to biofluids remains a major obstacle for biomedical applications. Here, the functionalization of detonation nanodiamond with zwitterionic moieties in combination with tetraethylene glycol (TEG) moieties immobilized by click chemistry to improve the colloidal dispersion in physiological media with strong ion background and for the simultaneous prevention of nonspecific interactions with proteins is reported. Based on five building blocks, a series of ND conjugates is synthesized and their performance is compared in biofluids, such as fetal bovine serum (FBS) and Dulbecco's modified Eagle medium (DMEM). The adsorption of proteins is investigated via dynamic light scattering (DLS) and thermogravimetric analysis. The colloidal stability is tested with DLS monitoring over prolonged periods of time in various ratios of water/FBS/DMEM and at different pH values. The results show that zwitterions efficiently promote the anti‐fouling properties, whereas the TEG linker is essential for the enhanced colloidal stability of the particles.

Constructing Patch‐Ni‐Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li‐S Batteries

By Yang Liu, Wei Kou, Xiangcun Li, Chuqing Huang, Ruobing Shui, Gaohong He from Wiley: Small: Table of Contents. Published on Jun 17, 2019.

A Pt@Ni core‐shell catalyst with a synergic effect in confined nanoreactors shows dual functions for catalytic oxidation of insoluble products to soluble polysulfides by effectively reducing the energy barrier with strong adsorption. Electronic migration from Ni to Pt becomes a driving force to activate Li2S molecules to form Ni‐S‐Li, the presence of ‐S‐Li is more active to oxidize Li2S2/Li2S to polysulfides. Abstract Reducing the deposit of discharge products and suppressing the polysulfide shuttle are critical to enhancing reaction kinetics in Li‐S batteries. Herein, a Pt@Ni core–shell bimetallic catalyst with a patch‐like or complete Ni shell based on a confined catalysis reaction in porous carbon spheres is reported. The Pt nanodots can effectively direct and catalyze in situ reduction of Ni2+ ions to form core–shell catalysts with a seamless interface that facilitates the charge transfer between the two metals. Thus, the bimetallic catalysts offer a synergic effect on catalyzing reactions, which shows dual functions for catalytic oxidation of insoluble polysulfides to soluble polysulfides by effectively reducing the energy barrier with simultaneous strong adsorption, ensuring a high reversible capacity and cycling stability. A novel process based on the Pt@Ni core–shell bimetallic catalyst with a patch‐like Ni shell is proposed: electronic migration from Ni to Pt forces Ni to activate Li2S2/Li2S molecules by promoting the transformation of Li‐S‐Li to Ni‐S‐Li, consequently releasing Li+ and free electrons, simultaneously enhancing protonic/electronic conductivity. The presence of the intermediate state Ni‐S‐Li is more active to oxidize Li2S to polysulfides. The Li2S bound to adjacent Pt sites reacts with abundant ‐S‐Li species and then releases the Pt sites for the next round of reactions.

Construction of Single‐Iron‐Atom Nanocatalysts for Highly Efficient Catalytic Antibiotics

By Minfeng Huo, Liying Wang, Haixian Zhang, Linlin Zhang, Yu Chen, Jianlin Shi from Wiley: Small: Table of Contents. Published on Jun 17, 2019.

Remarkable peroxidase‐like activity of single‐atom Fe nanocatalysts (SAF NCs) is first investigated for antibacterial performance in vitro and in vivo. The physical contact membrane destruction, peroxidase‐like hydroxyl radical‐generating oxidative damage, and the photothermal effect synergistically contribute to the dominant bacteria ablation effectively with high biocompatibility. Abstract Bacterial infection caused by pathogenic bacteria has long been an intractable issue that threatens human health. Herein, the fact that nanocatalysts with single iron atoms anchored in nitrogen‐doped amorphous carbon (SAF NCs) can effectively induce peroxidase‐like activities in the presence of H2O2, generating abundant hydroxyl radicals for highly effective bacterial elimination (e.g., Escherichia coli and Staphylococcus aureus), is reported. In combination with the intrinsic photothermal performance of the nanocatalysts, noticeable bacterial‐killing effects are extensively investigated. Especially, the antibacterial mechanism of critical cell membrane destruction induced by SAF NCs is unveiled. Based on the bactericidal properties of SAF NCs, in vivo bacterial infections propagated at wounds by E. coli and S. aureus pathogens can be effectively eradicated, resulting in better wound healing. Collectively, the present study highlights the highly efficient in vitro antibacterial and in vivo anti‐infection performances by the single‐iron‐atom‐containing nanocatalysts.

1,2‐(Bis)trifluoromethylation of Alkynes: A One‐Step Reaction to Install an Underutilized Functional Group

By Shuo Guo, Deyaa AbuSalim, Silas Cook from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Modifying the electronic properties of olefins represents the quintessential approach to tuning alkene reactivity. In this context, the exploration of trifluoromethyl groups as divergent electronic modifiers has not been considered. Here, we describe a copper‐mediated 1,2‐(bis)trifluoromethylation of acetylenes to create—in a single step—E‐hexafluorobutenes (E‐HFBs). The reaction proceeds with high yield and E/Z selectivity. Since the alkyne captures two trifluoromethyl groups from each molecule of bpyCu(CF3)3, mechanistic studies were conducted to illuminate the role of reactants. Interestingly, E‐HFBs exhibit remarkable stability to standard olefin functionalization reactions in spite of the pendant trifluoromethyl groups. This finding has significant implications for medicine, agroscience, and materials.

Elucidating the Doping Effect on the Electronic Structure of Thiolate‐Protected Silver Superatoms by Photoelectron Spectroscopy

By Kuenhee Kim, Keisuke Hirata, Katsunosuke Nakamura, Hirokazu Kitazawa, Shun Hayashi, Kiichirou Koyasu, Tatsuya Tsukuda from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Silver clusters protected by thiolates represent a new class of chemically modified superartoms and have gained attention due to their unique properties such as photoluminescence. Doping of heteroatom(s) is a promising strategy to tuning and improving their properties. Effect of a single atom doping on the electronic structures has been conventionally studied by optical spectroscopy and voltammetry. This work aims to answer the question of how and why the energy levels of the superatomic orbitals are shifted upon doping by gas‐phase photoelectron spectroscopy (PES). The target systems chosen were [XAg24(SPhMe2)18]– (X = Ag, Au) and [YAg24(SPhMe2)18]2– (Y = Pd, Pt), having a common structural motif in which an icosahedral core (X@Ag12)5+ (X = Ag, Au) or (Y@Ag12)4+ (Y = Pd, Pt), respectively, is protected by six bidentate oligomers Ag2(SPhMe2)3–. PE spectrum of [AuAg24(SPhMe2)18]– was similar to that of [Ag25(SPhMe2)18]–, whereas those of [YAg24(SPhMe2)18]2– were shifted by ~1.4 eV toward lower binding energy with respect to that of [Ag25(SPhMe2)18]–, without any significant change in the spectral profiles. These results together with theoretical calculation indicate that superatomic orbitals in the (X@Ag12)5+ (X = Ag, Au) core shifted upwards by replacing the central X+ atom with a Pt or Pd atom. The higher‐energy shift of the superatomic orbitals was ascribed to (1) the weaker binding of valence electrons in Y@(Ag+)12 (Y = Pd, Pt) compared to that in X+@(Ag+)12 (X = Ag, Au) due to the reduction in formal charge of the core potential and (2) the upward shift of the apparent vacuum level by the presence of a repulsive Coulomb barrier for Y@(Ag+)12.

Oxygen Vacancies on Layered Niobic Acid Weaken the Catalytic Conversion of Polysulfides in Lithium Sulfur Battery

By Lingling Xu, Hongyang Zhao, Bolong Huang, Jianwei Wang, Jiale Xia, Na Li, Dandan Yin, Meng Luo, Feng Luo, Yaping Du, Chunhua Yan from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Oxygen vacancies are usually considered as beneficial in catalytic conversion of polysulfides in lithium sulfur battery. In this work, we demonstrated that the conversion of polysulfides was hindered by creating oxygen vacancies on ultrathin layered niobic acid. The inferior performance induced by oxygen vacancy was mainly attributed to the decreased electric conductivity as well as the weakened adsorption of polysulfides on catalyst surface. This work showed that the care should be taken when designing a new catalyst for lithium‐sulfur battery using defect‐engineering strategy.

Reduction of a Tetrafluoroterephthalonitrile‐β‐Cyclodextrin Polymer to Remove Anionic Micropollutants and Perfluorinated Alkyl Substances from Water.

By Max J. Klemes, Yuhan Ling, Casey Ching, Vicki Wu, Damian E. Helbling, William R. Dichtel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Organic micropollutants (MPs) are anthropogenic substances that contaminate water resources at trace concentrations. Many MPs, including per‐ and polyfluorinated alkyl substances (PFASs), have come under increased scrutiny because of their environmental persistence and association with various health problems. A β‐cyclodextrin polymer linked with tetrafluoroterephthalonitrile (TFN‐CDP) has high affinity for cationic and many neutral MPs from contaminated water because of anionic groups incorporated during the polymerization. But TFN‐CDP does not bind many anionic MPs strongly, including anionic PFASs. To address this shortcoming, we reduced the nitrile groups in TFN‐CDP to primary amines, which reverses its affinity towards charged MPs. TFN‐CDP exhibits adsorption distribution coefficients (log KD values) of 2‐3 for cationic MPs and ‐0.5‐1.5 for anionic MPs, whereas the reduced TFN‐CDP exhibits log KD values of ‐0.5‐1.5 for cationic MPs and 2‐4 for anionic MPs, with especially high affinity towards anionic PFASs. Kinetic studies of the removal of 10 anionic PFASs at environmentally relevant concentrations showed 80‐98% removal of all contaminants after 30 min and was superior to commercial granular activated carbon. These findings demonstrate the scope and tunability of CD‐based adsorbents derived from a single polymerization and the promise of novel adsorbents constructed from molecular receptors.

Ternary CoPtAu Nanoparticles as a General Catalyst for Highly Efficient Electro‐Oxidation of Liquid Fuels

By Junrui Li, Safia Z. Jilani, Honghong Lin, Xiaoming Liu, Kecheng Wei, Yukai Jia, Peng Zhang, Miaofang Chi, Yuye J. Tong, Zheng Xi, Shouheng Sun from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Efficient electro‐oxidation of formic acid, methanol and especially ethanol, is challenging due to the multiple chemical reaction steps required to accomplish full oxidation into CO₂. Herein, we report a ternary CoPtAu nanoparticle catalyst system, in which Co and Pt form an intermetallic L1₀‐structure and Au segregates on the surface to alloy with Pt. The L1₀‐structure stabilizes Co and significantly enhances the catalysis of the PtAu surface towards electro‐oxidation of ethanol, methanol and formic acid, with mass activities of 1.55 A/mgPt, 1.49 A/mgPt and 11.97 A/mgPt respectively in 0.1 M HClO₄. The L1₀‐CoPtAu catalyst is also stable with negligible degradation in mass activities and no obvious Co/Pt/Au composition changes after 10,000 potential cycles. The in‐situ surface‐enhanced infrared absorption spectroscopy study indicates that the ternary catalyst activates the C‐C bond more efficiently for the ethanol oxidation. The L1₀‐CoPtAu holds great promise as a general fuel cell anode catalyst for renewable energy applications.

Flat Boron: A New Cousin of Graphene

By Sheng‐Yi Xie, Yeliang Wang, Xian‐Bin Li from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

The successful synthesis of borophene on metal substrates marks a milestone for the synthesis of 2D materials without layered bulk structures, just as graphene is the cornerstone for synthesizing 2D materials with layered bulk structures. The exotic properties and wide applications of borophene make it a new cousin of graphene in the family of 2D materials. Abstract The mechanical exfoliation of graphene from graphite provides the cornerstone for the synthesis of other 2D materials with layered bulk structures, such as hexagonal boron nitride, transition metal dichalcogenides, black phosphorus, and so on. However, the experimental production of 2D flat boron is challenging because bulk boron has very complex spatial structures and a rich variety of chemical properties. Therefore, the realization of 2D flat boron marks a milestone for the synthesis of 2D materials without layered bulk structures. The historical efforts in this field, particularly the most recent experimental progress, such as the growth of 2D flat boron on a metal substrate by chemical vapor deposition and molecular beam epitaxy, or liquid exfoliation from bulk boron, are described.

The Future of Neuroimplantable Devices: A Materials Science and Regulatory Perspective

By Nikita Obidin, Farita Tasnim, Canan Dagdeviren from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

Recent progress in the development of existing neuroimplantable devices such as electrocorticography (ECoG) systems, multielectrode arrays (MEAs), Stentrode, and deep brain probes is reviewed. Furthermore, the materials science and regulatory perspective on such devices, with regards to their relationship with biological, mechanical, and material risk factors, are highlighted. Abstract The past two decades have seen unprecedented progress in the development of novel materials, form factors, and functionalities in neuroimplantable technologies, including electrocorticography (ECoG) systems, multielectrode arrays (MEAs), Stentrode, and deep brain probes. The key considerations for the development of such devices intended for acute implantation and chronic use, from the perspective of biocompatible hybrid materials incorporation, conformable device design, implantation procedures, and mechanical and biological risk factors, are highlighted. These topics are connected with the role that the U.S. Food and Drug Administration (FDA) plays in its regulation of neuroimplantable technologies based on the above parameters. Existing neuroimplantable devices and efforts to improve their materials and implantation protocols are first discussed in detail. The effects of device implantation with regards to biocompatibility and brain heterogeneity are then explored. Topics examined include brain‐specific risk factors, such as bacterial infection, tissue scarring, inflammation, and vasculature damage, as well as efforts to manage these dangers through emerging hybrid, bioelectronic device architectures. The current challenges of gaining clinical approval by the FDA—in particular, with regards to biological, mechanical, and materials risk factors—are summarized. The available regulatory pathways to accelerate next‐generation neuroimplantable devices to market are then discussed.

Stretchable Transparent Conductors: from Micro/Macromechanics to Applications

By Zhi Hong Chen, Rui Fang, Wei Li, Jianguo Guan from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

Stretchable transparent conductors (STCs) are key components of stretchable electronics. The conducting element–substrate interaction is systematically correlated with the structural stability of conducting networks, properties, and device applications of STCs. Special focus is put on the micromechanics of conducting elements on elastomers and the macromechanics of conducting networks. Conclusions and the outlook in this field are also presented. Abstract Stretchable transparent conductors (STCs), generally consisting of conducting networks and stretchable transparent elastomers, can maintain stable conductivity and transparency even at large tensile strain, beyond the reach of rigid/flexible transparent conductors. They are essential components in stretchable/wearable electronics for using on irregular 3D conformable surfaces and have attracted tremendous attention in recent years. This review aims to provide systematical correlation of the conducting element–substrate interaction with the structural stability of conducting networks, as well as the properties and device applications of STCs. It starts with the micromechanics for stretching of conducting elements on substrates, including the mechanical mismatch, distribution/level of interfacial shear stress, and the deformation behavior of conducting elements on substrates. The macromechanics for stretching of conducting networks on substrates are then further illustrated from a more statistical point of view, namely sliding/preferred orientation of percolation networks, unfolding of buckled structures, and unit cell distortion/distributed rupture of nanomeshes. The structure‐dependent properties as well as the state‐of‐the‐art applications of STCs are summarized before ending with the conclusions and outlooks for STCs.

An Organic Afterglow Protheranostic Nanoassembly

By Shasha He, Chen Xie, Yuyan Jiang, Kanyi Pu from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

An organic afterglow protheranostic nanoassembly is developed to specifically activate both pharmaceutical drug and diagnostic afterglow signals in the tumor microenvironment by a tumor‐associated chemical mediator (H2O2) for cancer theranostics. Abstract Cancer theranostics holds potential promise for precision medicine; however, most existing theranostic nanoagents are simply developed by doping both therapeutic agents and imaging agent into one particle entity, and thus have an “always‐on” pharmaceutical effect and imaging signals regardless of their in vivo location. Herein, the development of an organic afterglow protheranostic nanoassembly (APtN) that specifically activates both the pharmaceutical effect and diagnostic signals in response to a tumor‐associated chemical mediator (hydrogen peroxide, H2O2) is reported. APtN comprises an amphiphilic macromolecule and a near‐infrared (NIR) dye acting as the H2O2‐responsive afterglow prodrug and the afterglow initiator, respectively. Such a molecular architecture allows APtN to passively target tumors in living mice, specifically release the anticancer drug in the tumor, and spontaneously generate the uncaged afterglow substrate. Upon NIR light preirradiation, the afterglow initiator generates singlet oxygen to react and subsequently transform the uncaged afterglow substrate into an active self‐luminescent form. Thus, the intensity of generated afterglow luminescence is correlated with the drug release status, permitting real‐time in vivo monitoring of prodrug activation. This study proposes a background‐free design strategy toward activatable cancer theranostics.

Recent Advances in Fiber Supercapacitors: Materials, Device Configurations, and Applications

By Di Chen, Kai Jiang, Tingting Huang, Guozhen Shen from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

Cutting edge advances in fiber supercapacitor research are summarized. Particular emphasis is placed on the electrode materials, a number of device configurations, system integration, and possible applications. Abstract Fiber supercapacitors (SCs), with their small size and weight, excellent flexibility and deformability, and high capacitance and power density, are recognized as one of the most robust power supplies available for wearable electronics. They can be woven into breathable textiles or integrated into different functional materials to fit curved surfaces for use in day‐to‐day life. A comprehensive review on recent important development and progress in fiber SCs is provided, with respect to the active electrode materials, device configurations, functions, integrations. Active electrode materials based on different electrochemical mechanisms and intended to improve performance including carbon‐based materials, metal oxides, and hybrid composites, are first summarized. The three main types of fiber SCs, namely parallel, twist, and coaxial structures, are then discussed, followed by the exploration of some functions including stretchability and self‐healing. Miniaturized integration of fiber SCs to obtain flexible energy fibers and integrated sensing systems is also discussed. Finally, a short conclusion is made, combining with comments on the current challenges and potential solutions in this field.

Fiber‐Based Energy Conversion Devices for Human‐Body Energy Harvesting

By Liang Huang, Shizhe Lin, Zisheng Xu, He Zhou, Jiangjiang Duan, Bin Hu, Jun Zhou from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

Fiber shaped energy conversion devices can directly harvest the mechanical or thermal energy from the human body, and convert into electric energy. These nanogenerators could supply power for wearable electronics and act as self‐powered sensors to monitor human health signals. Abstract Following the rapid development of lightweight and flexible smart electronic products, providing energy for these electronics has become a hot research topic. The human body produces considerable mechanical and thermal energy during daily activities, which could be used to power most wearable electronics. In this context, fiber‐based energy conversion devices (FBECD) are proposed as candidates for effective conversion of human‐body energy into electricity for powering wearable electronics. Herein, functional materials, fiber fabrication techniques, and device design strategies for different classes of FBECD based on piezoelectricity, triboelectricity, electrostaticity, and thermoelectricity are comprehensively reviewed. An overview of fiber‐based self‐powered systems and sensors according to their superior flexibility and cost‐effectiveness is also presented. Finally, the challenges and opportunities in the field of fiber‐based energy conversion are discussed.

Tuneable Surface Area, Porosity and Function in Conjugated Microporous Polymers

By Jie Chen, Wei Yan, Esther J Townsend, Jiangtao Feng, Long Pan, Veronica Del Angel Hernandez, Charl FJ Faul from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A novel method using salts to tune N‐containing conjugated microporous materials synthesized by Buchwald‐Hartwig (BH) cross‐coupling reactions is reported. The surface area and the porosity of the poly(triphenylamine) (PTPA) are optimized by the addition of inorganic salts, which provides, for the first time, a route to radically improve the BET surface area from 58 m2/g to 1152 m2/g. PTPA initially shows a broad distribution of micropores, mesopores and macropores. However, the addition of salts narrows the pore size distribution to the microporous range only, mimicking COFs and MOFs. We furthermore show the ability to fine‐tune the surface area of PTPA using salts with different sized anions (including NaF, NaCl, NaBr, NaI) or cations (LiNO3, NaNO3, KNO3, Ba(NO3)2); the surface area shows a gradual decrease with an increase in the ionic radius of salts. We propose that the effect of the salt on the physical properties of the polymer is mainly owing to adjusting and optimizing the Hansen solubility parameters (HSPs) of solvents for the growing polymer, resulting in the phase separation of the product during polymerization at a much later stage. This approach, named the Bristol‐Xi’an Jiaotong (BXJ) approach, results in N‐containing polymers possessing a lower average pore diameter and larger surface area, with overall highly desirable and tuneable properties.

Rubbery Electronics Fully Made of Stretchable Elastomeric Electronic Materials

By Kyoseung Sim, Zhoulyu Rao, Faheem Ershad, Cunjiang Yu from Wiley: Advanced Materials: Table of Contents. Published on Jun 17, 2019.

Compared to conventional rigid and bulky electronics, stretchable electronics have substantial advantages for various situations where large mechanical deformations are required. Recent progress shows stretchable electronics from all rubber‐like components are excellent candidates to substitute electronics developed using architectural engineering for eliminating strain. This work briefly reviews the current development in rubbery electronics and suggests future directions for the field. Abstract Stretchable electronics outperform existing rigid and bulky electronics and benefit a wide range of species, including humans, machines, and robots, whose activities are associated with large mechanical deformation and strain. Due to the nonstretchable nature of most electronic materials, in particular semiconductors, stretchable electronics are mostly realized through the strategies of architectural engineering to accommodate mechanical stretching rather than imposing strain into the materials directly. On the other hand, recent development of stretchable electronics by creating them entirely from stretchable elastomeric electronic materials, i.e., rubbery electronics, suggests a feasible a venue. Rubbery electronics have gained increasing interest due to the unique advantages that they and their associated manufacturing technologies have offered. This work reviews the recent progress in developing rubbery electronics, including the crucial stretchable elastomeric materials of rubbery conductors, rubbery semiconductors, and rubbery dielectrics. Thereafter, various rubbery electronics such as rubbery transistors, integrated electronics, rubbery optoelectronic devices, and rubbery sensors are discussed.

Guanitrypmycin Biosynthetic Pathways Imply Cytochrome P450‐mediated Regio‐ and Stereospecific Guaninyl Transfer Reactions

By Jing Liu, xiulan Xie, Shu-Ming Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Mining microbial genomes including those of Streptomyces reveals the presence of a large number of biosynthetic gene clusters. Unraveling this genetic potential was proven to be a useful approach for novel compound discovery. Here, we report the heterologous expression of two similar P450‐associated cyclodipeptide synthases‐containing gene clusters in Streptomyces coelicolor and identification of eight rare and novel natural products, C3‐guaninyl indole alkaloids guanitrypmycins. Expression of different gene combinations proved that the cyclodipeptide synthases assemble cyclo‐L‐Trp‐L‐Phe and cyclo‐L‐Trp‐L‐Tyr, which are consecutively and regiospecifically modified by cyclodipeptide oxidases, cytochrome P450 enzymes, and N‐methyltransferases. In vivo and in vitro results proved that the P450 enzymes function as key biocatalysts and catalyze the regio‐ and stereospecific 3α‐guaninylation at the indole ring of the tryptophanyl moiety. Isotope exchange experiments provided evidence for the non‐enzymatic epimerization of the biosynthetic pathway products via keto‐enol tautomerism. This post‐pathway modification during cultivation increases furthermore the structural diversity of guanitrypmycins.

Diagonally Related s‐ and p‐Block Metals Join Forces: Synthesis and Characterization of Complexes with Covalent Beryllium‐Aluminum Bonds

By Cameron Jones, Albert Paparo, Cory Smith from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Additions of beryllium‐halide bonds in the simple beryllium dihalide adducts, [BeX2(tmeda)] (X = Br ot I), across the metal center of a neutral aluminum(I) heterocycle, [:Al(DipNacnac)] (DipNacnac = [(DipNCMe)2CH]‐, Dip = 2,6‐diisopropylphenyl), have yielded the first examples of compounds with beryllium‐aluminum bonds, [(DipNacnac)(X)Al−Be(X)(tmeda)] (tmeda = N,N,N',N'‐tetramethylethylenediamine). For sake of comparison, isostructural Mg−Al and Zn−Al analogues of these complexes, viz. [(DipNacnac)(X)Al−M(X)(tmeda)] (M = Mg or Zn, X = I or Br) have been prepared and structurally characterized. DFT calculations reveal all compounds to have high s‐character metal‐metal bonds, the polarity of which is consistent with the electronegativities of the metals involved. Preliminary reactivity studies of [(DipNacnac)(Br)Al−Be(Br)(tmeda)] are reported.

Emergence of Function and Selection from Recursively Programmed Polymerisation Reactions in Mineral Environments

By Lee Cronin, David Doran, Yousef Abul-Haija from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Living systems are characterised by an ability to sustain chemical reaction networks far‐from‐equilibrium. It is likely that life first arose through a process of continual disruption of equilibrium states in recursive reaction networks, driven by periodic environmental changes allowing the emergence of a memory. Herein, we report the emergence of proto‐enzymatic function from recursive polymerisation reactions using amino acids and glycolic acid over four wet‐dry cycles. Reactions are kept out of equilibrium by diluting products 9:1 in fresh starting solution at the end of each recursive cycle, and the development of complex high molecular weight species is explored using a new metric, the Mass Index, which allows the complexity of the system to be explored as a function of cycle. This process is carried out on a range of different mineral environments. We explore the hypothesis that disrupting equilibrium via recursive cycling imposes a selection pressure and subsequent boundary conditions on products, which may otherwise be prone to uncontrolled combinatorial explosion. After just four reaction cycles, product mixtures from recursive reactions exhibit greater catalytic activity and truncation of product space towards higher molecular weight species compared to non‐recursive controls.

Structural Engineering of Luminogens with High Emission Efficiency both in Solution and the Solid State

By Yanli Zhao, Hongwei Wu, Zhao Chen, Weijie Chi, Bindra Anivind Kaur, Long Gu, Cheng Qian, Bing Wu, Bingbing Yue, Guofeng Liu, Guangbao Yang, Liangliang Zhu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

Developing molecules with high emission efficiency both in solution and the solid state is still a great challenge, since most organic luminogens are either aggregation‐caused quenching or aggregation‐induced emission molecules. We overcame this dilemma via integrating planar and distorted structures with long alkyl side chains to achieve DAπAD type emitters. Linear diphenyl‐diacetylene core and charge transfer effect ensure considerable planarity of these molecules in excited state, allowing strong emission in dilute solution (quantum yield up to 98.2 %). On the other hand, intermolecular interactions of two distorted cyanostilbene units restrict molecular vibration and rotation, and long alkyl chains reduce the quenching effect from π‐π stacking, eventually leading to strong emission in the solid state (quantum yield up to 60.7 %). Thus, multiple bioimaging upon carrying the concentration of the emitters was well established, which may provide a new vision for applying bright luminescent materials in a variety of environments.

Inhibition of Pathogen Adhesion by Bacterial Outer Membrane‐Coated Nanoparticles

By Yue Zhang, Yijie Chen, Christopher Lo, Jia Zhuang, Pavimol Angsantikul, Qiangzhe Zhang, Xiaoli Wei, Zhidong Zhou, Marygorret Obonyo, Ronnie Fang, Weiwei Gao, Liangfang Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

The treatment of bacterial infection is increasingly challenged by the rapid emergence of antibiotic resistance. Among various alternatives, anti‐adhesion therapies that interfere with the bacterial adhesion to the host are attractive, as they avoid direct disruption of bacterial cycles for killing and thus may alleviate resistance development. Herein, an anti‐adhesion nanomedicine platform is made by wrapping synthetic polymeric cores with bacterial outer membranes. The resulting bacterium‐mimicking nanoparticles (denoted ‘OM‐NPs’) compete with source bacteria for binding to the host, overcome network complexity of bacterial virulence, and ultimately inhibit bacterial adhesion. The ‘top‐down’ fabrication of OM‐NPs avoids the identification of the adhesins and bypasses the design of agonists targeting these adhesins. In this study, OM‐NPs are made with membrane of Helicobacter pylori (H. pylori) and shown to bind with gastric epithelial cells (e.g., AGS cells). Treatment of AGS cells with OM‐NPs reduces H. pylori adhesion and such anti‐adhesion efficacy is dependent on OM‐NP concentration as well as the dosing sequence in relation to that of H. pylori. In addition, OM‐NPs displace H. pylori pre‐bound to AGS monolayers. In a mouse stomach model, OM‐NPs reduce H. pylori adherence. These results together demonstrate that OM‐NP confer an anti‐adhesion property with potential as an anti‐adhesion approach against bacterial infections.

When Nanozymes Meet Single‐Atom Catalysis

By Lei Jiao, Hongye Yan, Yu Wu, Wenling Gu, Chengzhou Zhu, Dan Du, Yuehe Lin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

The limitation of enzymes encourages us to seek for the alternatives. Nanomaterials with enzyme‐like activities, defined as nanozymes, have been widely investigated, possessing unparalleled features in different fields owing to their advantages of low cost, superior activity and high stability. The complex structures and composition lead to the extensive investigation of the catalytic sites at atomic scale and in‐depth understanding of the nature of the biocatalysis. Recently, single‐atom catalysts (SACs) characterized by atomically dispersive activity sites provide great opportunities to mimic metalloprotease, demonstrating great potential for the understanding of the catalytic mechanism and bridging the gap between natural enzyme and nanozyme. In this review, we briefly demonstrate the unique properties and the recent advances in the synthesis, characterization, and applications of SACs. Then, we will mainly cover the impressive progress in single‐atom nanozymes and their applications in sensing, organic pollutants degradation and therapy. Finally, the major challenges and opportunities for further research on the marriage of nanozyme and SACs are presented.

Asymmetric Hydrocyanation of Alkenes without HCN

By Xiuxiu Li, Cai You, Jiaxin Yang, Shuailong Li, Dequan Zhang, Hui Lv, Xumu Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A general and efficient rhodium‐catalyzed asymmetric cyanide‐free hydrocyanation of alkenes has been developed. Based on the asymmetric hydroformylation/condensation/aza‐Cope elimination sequences, a broad scope of substrates including mono‐substituted, 1,2‐ and 1,1‐disubstituted alkenes (involving natural product R‐ and S‐limonene) were employed, and a series of valuable chiral nitriles are prepared with high yields (up to 95%) and enantioselectivities (up to 98% ee). Notably, the critical factor to achieve high enantioseletivies is the addition of catalytic amount of benzoic acid. This novel methodology provides an efficient and concise synthetic route to the intermediate of vildagliptin and anagliptin.

A Triangular Platinum(II) Multi‐nuclear Complex with Impressive Cytotoxicity Towards Breast Cancer Stem Cells

By Arvin Eskandari, Arunangshu Kundu, Sushobhan Ghosh, Kogularamanan Suntharalingam from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

The preparation of multi‐nuclear metal complexes offers a route to novel anticancer agents and delivery systems. The potency of a novel triangular multi‐nuclear complex containing three platinum atoms, Pt‐3, towards breast cancer stem cells (CSCs) is reported. The tri‐nuclear platinum(II) complex, Pt‐3 exhibits selectivity toxicity towards breast CSCs over bulk breast cancer cells and non‐tumorigenic breast cells. Remarkably, Pt‐3 inhibits the formation, size, and viability of mammospheres to a better extent than salinomycin, an established CSC‐potent agent, and cisplatin and carboplatin, clinically used platinum drugs. Mechanism of action studies show that Pt‐3 effectively enters breast CSCs, penetrates the nucleus, induces genomic DNA damage, and prompts caspase‐dependent apoptosis. To the best of our knowledge, Pt‐3 is the first multi‐nuclear platinum complex to selectivity kill breast CSCs over other breast cell types.

Formation of a Pillar[5]arene based 2D Poly‐pseudo‐rotaxane via “Threading and Crosslinking” by the Same Guest Molecules

By Eunji Lee, In-Hyeok Park, Huiyeong Ju, Seulgi Kim, Jong Hwa Jung, Yoichi Habata, Shim Sung Lee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A one‐pot reaction of A1/A2‐thiopyridyl pillar[5]arene (L) with silver(I) trifluoroacetate in the presence of the linear dinitrile guest C8, [CN(CH2)nCN, n = 8], afforded the first example of a two‐dimensional (2D) poly‐pseudo‐rotaxane {[(μ4‐Ag)2(C8@L)2(μ‐C8)](CF3CO2)2}n. Surprisingly, in this structure the C8 guest not only “threads” into the pillar[5]arene unit but also “crosslinks” the 1D coordinative polymeric arrays. The formation of the 2D poly‐pseudo‐rotaxane is driven by an adaptive rearrangement of the components that minimizes the steric hindrance not only between the threaded guests but also between the threaded and crosslinked guests where crosslinking occurs. A pathway for the formation of the 2D poly‐pseudo‐rotaxane is proposed.

Visible light‐promoted Fe‐catalyzed Csp2‐Csp3 Kumada cross‐coupling in flow

By Xiao-Jing Wei, Irini Abdiaj, Carlo Sambiagio, Chenfei Li, Eli Zysman-Colman, Jesus Alcazar, Timothy Noel from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

A continuous‐flow, visible light‐promoted method has been developed to overcome the limitations of Fe‐catalyzed Kumada‐Corriu cross‐couplings. A variety of strongly electron‐rich aryl chlorides, previously hardly reactive, could be efficiently coupled with aliphatic Grignard reagents at room temperature, in high yields and within a few minutes residence time, considerably enhancing the applicability of this Fe‐catalyzed reaction. The robustness of this protocol was demonstrated on the multi‐gram scale, providing the potential for future pharmaceutical application.

REI₅O₁₄ (RE= Y and Gd): Promising SHG Materials Featuring the Semi‐Circle Shaped I₅O₁₄³¯ Polyiodate Anion

By Jin Chen, Chun-Li Hu, Fei-Fei Mao, Bing-Ping Yang, Xiao-Han Zhang, Jiang-Gao Mao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 17, 2019.

First examples of rare‐earth polyiodates, namely, REI5O14 (RE = Y and Gd), have been prepared by hydrothermal reactions of RE2O3 and H5IO6 in H3PO4 (≥85 wt. % in H2O), with extremely high yields (> 95%). They crystalize in polar space group Cm, and feature a brand‐new semi‐circle shaped [I5O14]3‐ pentameric polyiodate anion composed of two IO3 and three IO4 polyhedra. Remarkably, both compounds exhibit very large SHG signals (14 × and 15 × KH2PO4 (KDP) on 1064 nm laser radiation for Y and Gd compounds, respectively). Our work shows that the hydrothermal reaction under phosphoric acid medium facilitates the formation of rare‐earth polyiodates.

Mon 05 Aug 14:00: Dispersion Interactions in Density-Functional Theory and Application to Molecular Crystal-Structure Prediction

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Dispersion Interactions in Density-Functional Theory and Application to Molecular Crystal-Structure Prediction

The exchange-hole dipole moment (XDM) method is a density-functional model of London dispersion based upon second-order perturbation theory. The XDM dispersion coefficients are non-empirical and depend directly on the electron density and related properties, allowing variation of the atomic dispersion coefficients with changing chemical environment. XDM offers simultaneous high accuracy for a diverse range of chemical systems, such as intermolecular complexes, layered materials, surface adsorption, and molecular crystals. In this talk, recent applications of XDM will be presented, with a focus on the use of low-cost and composite approaches for molecular crystal-structure prediction (CSP). In particular, the application of composite methods to chiral helicenes, which have applications in organic electronics, and to four pharmaceutical compounds: 5-fluorouracil, naproxen, carbamanzapine, and olanzapine, will be illustrated. Finally, the effect of the density-functional delocalisation error on CSP is highlighted for organic acid-base co-crystals.

Add to your calendar or Include in your list

Mon 29 Jul 14:00: Nutrition sensing pathways regulate transmission of mutant mitochondrial genomes

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Nutrition sensing pathways regulate transmission of mutant mitochondrial genomes

Hundreds to thousands of mitochondrial genome copies are normally present in each cell. However, a fraction of these genomes can acquire pathogenic mutations and coexist with wildtype copies. We sought to determine the cellular forces that allow mutant genomes to persist. Given the central role of mitochondria in metabolism, we reasoned that mitochondrial genome dynamics might be sensitive to nutritional conditions. Using model system C. elegans, we find that mutant genomes lose their competitive advantage over wildtype genomes within the female germline under conditions of caloric restriction. Our subsequent genetic and cellular analyses show that this is because mutant genomes sense and exploit nutrition sensing pathways. We are currently exploring the molecular mechanisms that underlie the ability of mutant genomes to exploit nutrition. Taken together, our work suggests that environmental context of diet and nutrition can play an important role in modulating the mitochondrial genotype.

Add to your calendar or Include in your list

Wed 30 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 30 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 17 Jul 15:00: Mitochondrial membrane musings

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Mitochondrial membrane musings

Beyond energy, the mitochondrion is also a powerhouse of phospholipid biosynthesis. The mitochondrion is the home for one of the two major phosphatidylethanolamine (PE) biosynthetic pathways in cells and is the sole site of production of the dimeric phospholipid, cardiolipin (CL). Mutations that specifically impair normal mitochondrial phospholipid metabolism represent an emerging class of mitochondrial disease. Barth syndrome, an X-linked childhood cardiomyopathy caused by mutations in the gene that encodes the CL remodeling enzyme TAZ , was the founding member of this new category of human disease. More recently, mutations in the gene that encodes the mitochondrial enzyme that makes PE, PISD , have been determined to cause a novel mitochondrial chaperonopathy. Thus, human genetics has made it clear that normal mitochondrial phospholipid metabolism as a whole is clinically important. Our goal is to obtain a detailed mechanistic understanding of how individual phospholipids support the myriad of proteins, protein complexes, and functions that occur within and across mitochondrial membranes. Such information is needed to fully understand the numerous roles played by phospholipids in both healthy and disease states.

Add to your calendar or Include in your list

Wed 09 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 20 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 25 Sep 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 02 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 16 Oct 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 27 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 11 Sep 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Wed 13 Nov 15:00: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 17, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

[ASAP] Bi(OH)3/PdBi Composite Nanochains as Highly Active and Durable Electrocatalysts for Ethanol Oxidation

By Xiaolei Yuan†?, Yong Zhang†?, Muhan Cao†?, Tong Zhou‡, Xiaojing Jiang†, Jinxing Chen†§, Fenglei Lyu†, Yong Xu†, Jun Luo‡, Qiao Zhang*†, and Yadong Yin*§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01843

[ASAP] Mechanical Behavior of InP Twinning Superlattice Nanowires

By Zhilin Liu†‡, Ioannis Papadimitriou‡, Miguel Castillo-Rodri´guez‡, Chuanyun Wang‡, Gustavo Esteban-Manzanares‡, Xiaoming Yuan*§, Hark H. Tan?, Jon M. Molina-Aldaregui´a‡, and Javier Llorca*‡? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01300

[ASAP] Directional Excitation of Surface Plasmon Polaritons via Molecular Through-Bond Tunneling across Double-Barrier Tunnel Junctions

By Wei Du†?, Yingmei Han†?, Hongting Hu†, Hong-Son Chu‡, Harshini V. Annadata†, Tao Wang†¶, Nikodem Tomczak†§, and Christian A. Nijhuis*†? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01665

[ASAP] Spatial Variations in Femtosecond Field Dynamics within a Plasmonic Nanoresonator Mode

By Matthias Hensen†?, Bernhard Huber†?, Daniel Friedrich‡, Enno Krauss‡, Sebastian Pres†, Philipp Grimm‡, Daniel Fersch†, Julian Lu¨ttig†, Victor Lisinetskii†, Bert Hecht*‡, and Tobias Brixner*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01672

[ASAP] Precise Size Control of the Growth of Fe3O4 Nanocubes over a Wide Size Range Using a Rationally Designed One-Pot Synthesis

By Javier Muro-Cruces*†‡, Alejandro G. Roca*†, Alberto Lo´pez-Ortega§, Elvira Fantechi?, Daniel del-Pozo-Bueno?, So`nia Estrade´?, Francesca Peiro´?, Borja Sepu´lveda†, Francesco Pineider?, Claudio Sangregorio#?, and Josep Nogues†¶ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01281

[ASAP] Molecular Signature of Asthma-Enhanced Sensitivity to CuO Nanoparticle Aerosols from 3D Cell Model

By Ingeborg Kooter†, Marit Ilves‡?, Mariska Gro¨llers-Mulderij†?, Evert Duistermaat§, Peter C. Tromp†, Frieke Kuper†, Pia Kinaret??, Kai Savolainen#, Dario Greco??, Piia Karisola‡, Joseph Ndika‡, and Harri Alenius*‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01823

[ASAP] Cancer-Cell-Activated Photodynamic Therapy Assisted by Cu(II)-Based Metal–Organic Framework

By Yuanbo Wang†?, Wenbo Wu†?, Jingjing Liu†, Purnima Naresh Manghnani†, Fang Hu†, Dou Ma‡, Cathleen Teh§, Bo Wang‡, and Bin Liu*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01665

[ASAP] Nanotube-Mediated Path to Protocell Formation

By Elif S. Ko¨ksal†, Susanne Liese‡, Ilayda Kantarci†, Ragni Olsson†, Andreas Carlson‡, and Irep Go¨zen*†§? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01646

[ASAP] Tri-Stable Structural Switching in 2D Molecular Assembly at the Liquid/Solid Interface Triggered by External Electric Field

By Shu-Ying Li†‡, Xue-Qing Yang†§, Ting Chen*†, Dong Wang†?, Sheng-Fu Wang§, and Li-Jun Wan† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01337

[ASAP] Increasing the Efficacy of Stem Cell Therapy via Triple-Function Inorganic Nanoparticles

By Fang Chen†‡, Eric Ruike Zhao†, Ghanim Hableel†, Tao Hu§, Taeho Kim†?, Jingting Li?, Natalia Isabel Gonzalez-Pech#, David J. Cheng†, Jeanne E. Lemaster†, Yijun Xie‡#, Vicki H. Grassian†#¶, George L. Sen?, and Jesse V. Jokerst*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00653

[ASAP] Sulfur-Based Intramolecular Hydrogen-Bond: Excited-State Hydrogen-Bond On/Off Switch with Dual Room-Temperature Phosphorescence

By Zong-Ying Liu†?, Jiun-Wei Hu‡?, Chun-Hao Huang§?, Teng-Hsing Huang‡, Deng-Gao Chen†, Ssu-Yu Ho†, Kew-Yu Chen*‡, Elise Y. Li*§, and Pi-Tai Chou*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02765

[ASAP] Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation

By Viktoriia Morad†‡, Yevhen Shynkarenko†‡, Sergii Yakunin†‡, Alexandra Brumberg§, Richard D. Schaller§?, and Maksym V. Kovalenko*†‡ from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b02365

[ASAP] Geometric and Electronic Structure Contributions to O–O Cleavage and the Resultant Intermediate Generated in Heme-Copper Oxidases

By Andrew W. Schaefer, Antonio C. Roveda Jr., Anex Jose, and Edward I. Solomon* from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b04271

[ASAP] Two-Step Carbothermal Welding To Access Atomically Dispersed Pd1 on Three-Dimensional Zirconia Nanonet for Direct Indole Synthesis

By Yafei Zhao†?, Huang Zhou†?, Wenxing Chen§?, Yujing Tong†, Chao Zhao†, Yue Lin†, Zheng Jiang?, Qingwei Zhang†, Zhenggang Xue†, Weng-Chon Cheong‡, Benjin Jin†, Fangyao Zhou†, Wenyu Wang†, Min Chen†, Xun Hong†, Juncai Dong?, Shiqiang Wei#, Yadong Li‡, and Yuen Wu*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b03182

[ASAP] New Catalytic Asymmetric Formation of Oxygen Heterocycles Bearing Nucleoside Bases at the Anomeric Carbon

By Barry M. Trost*, Shiyan Xu, and Ehesan U. Sharif from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b06050

[ASAP] Structure Elucidation of 2D Polymer Monolayers Based on Crystallization Estimates Derived from Tip-Enhanced Raman Spectroscopy (TERS) Polymerization Conversion Data

By Wei Wang†, Feng Shao‡, Martin Kro¨ger§, Renato Zenobi‡, and A. Dieter Schlu¨ter*† from Journal of the American Chemical Society: Latest Articles (ACS Publications). Published on Jun 17, 2019.

TOC Graphic

Journal of the American Chemical Society
DOI: 10.1021/jacs.9b01765

Defect induced, layer-modulated magnetism in ultrathin metallic PtSe2

By Andras Kis from Nature Nanotechnology - Issue - nature.com science feeds. Published on Jun 17, 2019.

Nature Nanotechnology, Published online: 17 June 2019; doi:10.1038/s41565-019-0467-1

Magneto-transport measurements on thin metallic crystals of the transition metal dichalcogenide PtSe2 show signatures of ferro- and antiferromagnetic order depending on the number of layers and first-principles calculations suggest Pt vacancies at the surface as a plausible cause.

News: Carbon Journal Prize 2019 winners Announced

From Carbon. Published on Jun 17, 2019.

This annual award aims to recognize recent graduates with "an outstanding Ph.D. thesis in carbon material science and technology”.

Aligned carbon nanotube morphogenesis predicts physical properties of their polymer nanocomposites

By Brian L. Wardle from RSC - Nanoscale latest articles. Published on Jun 17, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR03317C, Paper
Open Access Open Access
Bharath Natarajan, Itai Y. Stein, Noa Lachman, Namiko Yamamoto, Douglas S. Jacobs, Renu Sharma, J. Alexander Liddle, Brian L. Wardle
Tomography derived nanoscale 3D morphological information is combined with modeling and simulation to explain anisotropy and scaling of experimental mechanical, thermal, and electrical properties of aligned carbon nanotube polymer composites.
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

Mon 24 Jun 14:00: Regularized linear autoencoders, the Morse theory of loss, and backprop in the brain

From All Talks (aka the CURE list). Published on Jun 15, 2019.

Regularized linear autoencoders, the Morse theory of loss, and backprop in the brain

When trained to minimize the distance between the data and its reconstruction, linear autoencoders (LAEs) learn the subspace spanned by the top principal directions but cannot learn the principal directions themselves. We prove that L2-regularized LAEs are symmetric at all critical points and learn the principal directions as the left singular vectors of the decoder. We smoothly parameterize the critical manifold and relate the minima to the MAP estimate of probabilistic PCA . Finally, we consider implications for PCA algorithms, computational neuroscience, and the algebraic topology of deep learning.

ICML 2019 .

Add to your calendar or Include in your list

Mon 01 Jul 13:00: Deriving a Theory of the Perceived Motion Direction of Plaids

From All Talks (aka the CURE list). Published on Jun 15, 2019.

Deriving a Theory of the Perceived Motion Direction of Plaids

Based on prior work, we know that at an early stage the visual system has three different systems that independently extract visual motion information from visual inputs. At later stages, these systems combine their outputs. Here, we consider a much studied (>650 publications) class of visual stimuli, plaids, which are combinations of two sine waves. Currently, there is no quantitative theory to explain the perceived motion of plaids. With an important methodological improvement, we obtained a large set of data exploring the various dimensions in which same-spatial-frequency plaids differ. We found that only two of the three motion systems are active in plaid processing. With this clue, we were able to formulate a pure theory for the outputs of the first-order and third-order motion systems and how they combine. With zero parameters estimated from the data, the theory captures the essence of the full range of our plaid data and supports some surprising, counter-intuitive conjectures about how vision works.

Add to your calendar or Include in your list

Thu 05 Dec 14:30: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 15, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

Thu 07 Nov 14:30: Intersection sizes of linear subspaces with the hypercube

From All Talks (aka the CURE list). Published on Jun 15, 2019.

Intersection sizes of linear subspaces with the hypercube

What are the possible intersection sizes that a k-dimensional subspace can have with the vertices of the n-dimensional hypercube (in Euclidean space)? Melo and Winter [arXiv:1712.01763, 2017] conjectured that all intersection sizes larger than 2 to the {k-1} (the “large” sizes) are of the form 2 to the {k-1} + 2 to the i. We show that this is almost true: the large intersection sizes are either of this form or of the form 35·2 to the {k-6} . We also disprove a second conjecture of Melo and Winter by proving that a positive fraction of the “small” values is missing. Joint work with Tom Johnson

Add to your calendar or Include in your list

Ordered Structures with Functional Units as a Paradigm of Material Design

By Kexin Chen, Liang Li from Wiley: Advanced Materials: Table of Contents. Published on Jun 14, 2019.

Ordered structures not only exist naturally in nature, but also in artificial materials. Summarizing previous research results, a “paradigm” of material research based on ordered structures with functional units (OSFU) in the form of compositions, phases, domains, and twins, is proposed. Researchers can pay more attention to this concept and produce some original research results. Abstract Realizing new functions through the construction of ordered structures not only exists naturally in nature, but also in artificial materials. However, much research focuses more on the relationship between structure and performance rather than on the impact of functional units themselves. Reviewing previous research findings, a “paradigm” of material research is proposed, which is based on ordered structures with functional units (OSFU) such as compositions, phases, domains, and twins. The goal is to draw more intensive attention of researchers to this concept and thus to promote the development of this field toward a deeper and broader direction, producing highly influential research results.

Nanotransducers for Near‐Infrared Photoregulation in Biomedicine

By Jingchao Li, Hongwei Duan, Kanyi Pu from Wiley: Advanced Materials: Table of Contents. Published on Jun 14, 2019.

Near‐infrared (NIR) photoregulation provides a promising approach for remote control of biological events and innovation of new therapeutic modalities. The recent development of optical nanotransducers for NIR photoregulation applications, including photoregulation of neural activity, gene expression, and visual systems, as well as photochemical tissue bonding, are summarized. Abstract Photoregulation, which utilizes light to remotely control biological events, provides a precise way to decipher biology and innovate in medicine; however, its potential is limited by the shallow tissue penetration and/or phototoxicity of ultraviolet (UV)/visible light that are required to match the optical responses of endogenous photosensitive substances. Thereby, biologically friendly near‐infrared (NIR) light with improved tissue penetration is desired for photoregulation. Since there are a few endogenous biomolecules absorbing or emitting light in the NIR region, the development of molecular transducers is essential to convert NIR light into the cues for regulation of biological events. In this regard, optical nanomaterials able to convert NIR light into UV/visible light, heat, or free radicals are suitable for this task. Here, the recent developments of optical nanotransducers for NIR‐light‐mediated photoregulation in medicine are summarized. The emerging applications, including photoregulation of neural activity, gene expression, and visual systems, as well as photochemical tissue bonding, are highlighted, along with the design principles of nanotransducers. Moreover, the current challenges and perspectives in this field are discussed.

Molecular Beam Epitaxy Scalable Growth of Wafer‐Scale Continuous Semiconducting Monolayer MoTe2 on Inert Amorphous Dielectrics

By Qingyuan He, Pengji Li, Zhiheng Wu, Bin Yuan, Zhongtao Luo, Wenlong Yang, Jie Liu, Guoqin Cao, Wenfeng Zhang, Yonglong Shen, Peng Zhang, Suilin Liu, Guosheng Shao, Zhiqiang Yao from Wiley: Advanced Materials: Table of Contents. Published on Jun 14, 2019.

Two‐inch atomically flat 2H‐MoTe2 monolayers with tunable coverage from 40 to 100% are directly grown on inert SiO2 dielectrics by molecular beam epitaxy. A single‐step nucleation and growth strategy is developed to promote lateral growth under low Mo‐flux. The effective layer‐by‐layer growth is controlled solely by the molecular beam dynamics rather than the assistance of catalysts, seeding promoters, and epitaxial templates. Abstract Monolayer MoTe2, with the narrowest direct bandgap of ≈1.1 eV among Mo‐ and W‐based transition metal dichalcogenides, has attracted increasing attention as a promising candidate for applications in novel near‐infrared electronics and optoelectronics. Realizing 2D lateral growth is an essential prerequisite for uniform thickness and property control over the large scale, while it is not successful yet. Here, layer‐by‐layer growth of 2 in. wafer‐scale continuous monolayer 2H‐MoTe2 films on inert SiO2 dielectrics by molecular beam epitaxy is reported. A single‐step Mo‐flux controlled nucleation and growth process is developed to suppress island growth. Atomically flat 2H‐MoTe2 with 100% monolayer coverage is successfully grown on inert 2 in. SiO2/Si wafer, which exhibits highly uniform in‐plane structural continuity and excellent phonon‐limited carrier transport behavior. The dynamics‐controlled growth recipe is also extended to fabricate continuous monolayer 2H‐MoTe2 on atomic‐layer‐deposited Al2O3 dielectric. With the breakthrough in growth of wafer‐scale continuous 2H‐MoTe2 monolayers on device compatible dielectrics, batch fabrication of high‐mobility monolayer 2H‐MoTe2 field‐effect transistors and the three‐level integration of vertically stacked monolayer 2H‐MoTe2 transistor arrays for 3D circuitry are successfully demonstrated. This work provides novel insights into the scalable synthesis of monolayer 2H‐MoTe2 films on universal substrates and paves the way for the ultimate miniaturization of electronics.

Single Fe Atom on Hierarchically Porous S, N‐Codoped Nanocarbon Derived from Porphyra Enable Boosted Oxygen Catalysis for Rechargeable Zn‐Air Batteries

By Jiting Zhang, Meng Zhang, Yan Zeng, Jisheng Chen, Lingxi Qiu, Hua Zhou, Chengjun Sun, Ying Yu, Chengzhou Zhu, Zhihong Zhu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

The effect of sulfur doping on the structure–activity relationship toward high‐efficiency oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is intensively investigated for the first time by a FeCl3‐encapsulated‐porphyra precursor pyrolysis route. The assembled Zn–air battery device comprising this synthetic catalyst shows excellent battery performance, implying its tremendous application potential in rechargeable energy conversion and storage devices. Abstract Iron–nitrogen–carbon materials (Fe–N–C) are known for their excellent oxygen reduction reaction (ORR) performance. Unfortunately, they generally show a laggard oxygen evolution reaction (OER) activity, which results in a lethargic charging performance in rechargeable Zn–air batteries. Here porous S‐doped Fe–N–C nanosheets are innovatively synthesized utilizing a scalable FeCl3‐encapsulated‐porphyra precursor pyrolysis strategy. The obtained electrocatalyst exhibits ultrahigh ORR activity (E1/2 = 0.84 V vs reversible hydrogen electrode) and impressive OER performance (Ej = 10 = 1.64 V). The potential gap (ΔE = Ej = 10 − E1/2) is 0.80 V, outperforming that of most highly active bifunctional electrocatalysts reported to date. Furthermore, the key role of S involved in the atomically dispersed Fe–Nx species on the enhanced ORR and OER activities is expounded for the first time by ultrasound‐assisted extraction of the exclusive S source (taurine) from porphyra. Moreover, the assembled rechargeable Zn–air battery comprising this bifunctional electrocatalyst exhibits higher power density (225.1 mW cm−2) and lower charging–discharging overpotential (1.00 V, 100 mA cm−2 compared to Pt/C + RuO2 catalyst). The design strategy can expand the utilization of earth‐abundant biomaterial‐derived catalysts, and the mechanism investigations of S doping on the structure–activity relationship can inspire the progress of other functional electrocatalysts.

Inkjet Printed Nanopatterned Aptamer‐Based Sensors for Improved Optical Detection of Foodborne Pathogens

By Susana Díaz‐Amaya, Min Zhao, Li‐Kai Lin, Carlos Ostos, Jan P. Allebach, George T.‐C. Chiu, Amanda J. Deering, Lia A. Stanciu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

For the first time a controlled nano‐patterning of novel carboxyl‐functionalized aptameric ink on nitrocellulose, for the highly efficient whole cell detection of E. coli O157:H7 in pure culture (25 colony forming units (CFU) mL‐1) and ground beef (233 CFU mL‐1), with high specificity at genus, species, strain and serotype level. This approach may potentially be applied to a wide variety of targets. Abstract The increasing incidence of infectious outbreaks from contaminated food and water supply continues imposing a global burden for food safety, creating a market demand for on‐site, disposable, easy‐to‐use, and cost‐efficient devices. Despite of the rapid growth of biosensors field and the generation of breakthrough technologies, more than 80% of the platforms developed at lab‐scale never will get to meet the market. This work aims to provide a cost‐efficient, reliable, and repeatable approach for the detection of foodborne pathogens in real samples. For the first time an optimized inkjet printing platform is proposed taking advantage of a carefully controlled nanopatterning of novel carboxyl‐functionalized aptameric ink on a nitrocellulose substrate for the highly efficient detection of E. coli O157:H7 (25 colony forming units (CFU) mL−1 in pure culture and 233 CFU mL−1 in ground beef) demonstrating the ability to control the variation within ±1 SD for at least 75% of the data collected even at very low concentrations. From the best of the knowledge this work reports the lowest limit of detection of the state of the art for paper‐based optical detection of E. coli O157:H7, with enough evidence (p > 0.05) to prove its high specificity at genus, species, strain, and serotype level.

Biologically Inspired Scaffolds for Heart Valve Tissue Engineering via Melt Electrowriting

By Navid T. Saidy, Frederic Wolf, Onur Bas, Hans Keijdener, Dietmar W. Hutmacher, Petra Mela, Elena M. De‐Juan‐Pardo from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

The unique capabilities of melt electrowriting allow to create functional scaffolds recapitulating the complex biomechanical behavior of native heart valve leaflets. Scaffolds with precise serpentine architectures mimicking the wavy collagen fibers present a tailorable J‐shaped strain stiffening response, anisotropy, and viscoelastic behavior, support the growth of human vascular SMCs, and display excellent acute hydrodynamic performance under aortic physiological conditions. Abstract Heart valves are characterized to be highly flexible yet tough, and exhibit complex deformation characteristics such as nonlinearity, anisotropy, and viscoelasticity, which are, at best, only partially recapitulated in scaffolds for heart valve tissue engineering (HVTE). These biomechanical features are dictated by the structural properties and microarchitecture of the major tissue constituents, in particular collagen fibers. In this study, the unique capabilities of melt electrowriting (MEW) are exploited to create functional scaffolds with highly controlled fibrous microarchitectures mimicking the wavy nature of the collagen fibers and their load‐dependent recruitment. Scaffolds with precisely‐defined serpentine architectures reproduce the J‐shaped strain stiffening, anisotropic and viscoelastic behavior of native heart valve leaflets, as demonstrated by quasistatic and dynamic mechanical characterization. They also support the growth of human vascular smooth muscle cells seeded both directly or encapsulated in fibrin, and promote the deposition of valvular extracellular matrix components. Finally, proof‐of‐principle MEW trileaflet valves display excellent acute hydrodynamic performance under aortic physiological conditions in a custom‐made flow loop. The convergence of MEW and a biomimetic design approach enables a new paradigm for the manufacturing of scaffolds with highly controlled microarchitectures, biocompatibility, and stringent nonlinear and anisotropic mechanical properties required for HVTE.

One‐Step Synthesis of Silica‐Coated Carbon Dots with Controllable Solid‐State Fluorescence for White Light‐Emitting Diodes

By Yuan Zhan, Bin Shang, Min Chen, Limin Wu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Multiple‐color‐emissive solid‐state silica‐coated carbon dots (silica/CDots) composites are synthesized by a one‐step solvothermal approach. The emission of the resultant silica/CDots composites can be tailored from blue to orange by controlling CDots loading fraction and composite morphology, accompanied with high photoluminescence quantum yields and good thermal stability for blue, yellow, and orange emitting, and thus supply widespread potential in solid‐state lighting devices. Abstract Carbon dots (CDots)‐based solid‐state luminescent materials have important applications in light‐emitting devices owing to their outstanding optical properties. However, it still remains a challenge to develop multiple‐color‐emissive solid‐state CDots, due to the serious self‐quenching of the CDots in the aggregation or solid state. Herein, a one‐step synthesis of multiple‐color‐emissive solid‐state silica‐coated CDots (silica/CDots) composites by controlling CDots loading fraction and composite morphology to realize the adjustment of emitting color is reported. The emission of resultant silica/CDots composites shifts from blue to orange with the photoluminescence quantum yields of 57.9%, 34.3%, and 32.7% for blue, yellow, and orange emitting, respectively. Furthermore, the yellow emitting silica/CDots composites exhibit an excellent fluorescence thermal stability, and further have been applied to fabricate white‐light‐emitting devices with a high color rendering index of above 80.

Vacancy‐Induced Synaptic Behavior in 2D WS2 Nanosheet–Based Memristor for Low‐Power Neuromorphic Computing

By Xiaobing Yan, Qianlong Zhao, Andy Paul Chen, Jianhui Zhao, Zhenyu Zhou, Jingjuan Wang, Hong Wang, Lei Zhang, Xiaoyan Li, Zuoao Xiao, Kaiyang Wang, Cuiya Qin, Gong Wang, Yifei Pei, Hui Li, Deliang Ren, Jingsheng Chen, Qi Liu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

A low‐power memristor comprised of 2D layered WS2 nanosheets is designed and tested. Its switching mechanism differs from the conventional mechanisms based on oxygen vacancies or metal‐ion conductive filaments. The memristor is used to efficiently realize simulated biological synapse functionality, which is promising for low‐power neuromorphic computing applications. Abstract Memristors with nonvolatile memory characteristics have been expected to open a new era for neuromorphic computing and digital logic. However, existing memristor devices based on oxygen vacancy or metal‐ion conductive filament mechanisms generally have large operating currents, which are difficult to meet low‐power consumption requirements. Therefore, it is very necessary to develop new materials to realize memristor devices that are different from the mechanisms of oxygen vacancy or metal‐ion conductive filaments to realize low‐power operation. Herein, high‐performance and low‐power consumption memristors based on 2D WS2 with 2H phase are demonstrated, which show fast ON (OFF) switching times of 13 ns (14 ns), low program current of 1 µA in the ON state, and SET (RESET) energy reaching the level of femtojoules. Moreover, the memristor can mimic basic biological synaptic functions. Importantly, it is proposed that the generation of sulfur and tungsten vacancies and electron hopping between vacancies are dominantly responsible for the resistance switching performance. Density functional theory calculations show that the defect states formed by sulfur and tungsten vacancies are at deep levels, which prevent charge leakage and facilitate the realization of low‐power consumption for neuromorphic computing application.

Near‐Infrared Activated Black Phosphorus as a Nontoxic Photo‐Oxidant for Alzheimer's Amyloid‑β Peptide

By Yang Li, Zhi Du, Xinping Liu, Mengmeng Ma, Dongqin Yu, Yao Lu, Jinsong Ren, Xiaogang Qu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Photoexcited black phosphorus (BP) is used as a nontoxic photooxidant of amyloid‐β (Aβ) for Alzheimer's disease (AD) treatment. Under near‐infrared illumination, the BP‐based hybrid nanosheets generate singlet oxygen (1O2), thereby inhibiting aggregation of Aβ by selectively oxidizing the β‐sheet aggregates. Moreover, the nanoplatform can attenuate Aβ‐triggered toxicity to prolong the life‐span of AD model Caenorhabditis elegans CL2006 strain. Abstract The inhibition of amyloid‐β (Aβ) aggregation by photo‐oxygenation has become an effective way of treating Alzheimer's disease (AD). New near‐infrared (NIR) activated treatment agents, which not only possess high photo‐oxygenation efficiency, but also show low biotoxicity, are urgently needed. Herein, for the first time, it is demonstrated that NIR activated black phosphorus (BP) could serve as an effective nontoxic photo‐oxidant for amyloid‑β peptide in vitro and in vivo. The nanoplatform BP@BTA (BTA: one of thioflavin‐T derivatives) possesses high affinity to the Aβ peptide due to specific amyloid selectivity of BTA. Importantly, under NIR light, BP@BTA can significantly generate a high quantum yield of singlet oxygen (1O2) to oxygenate Aβ, thereby resulting in inhibiting the aggregation and attenuating Aβ‐induced cytotoxicity. In addition, BP could finally degrade into nontoxic phosphate, which guarantees the biosafety. Using transgenic Caenorhabditis elegans CL2006 as AD model, the results demonstrate that the 1O2‐generation system could dramatically promote life‐span extension of CL2006 strain by decreasing the neurotoxicity of Aβ.

Preparation and Characterization of Dentin Phosphophoryn‐Derived Peptide‐Functionalized Lignin Nanoparticles for Enhanced Cellular Uptake

By Patrícia Figueiredo, Mika H. Sipponen, Kalle Lintinen, Alexandra Correia, Alexandros Kiriazis, Jari Yli‐Kauhaluoma, Monika Österberg, Anne George, Jouni Hirvonen, Mauri A. Kostiainen, Hélder A. Santos from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

In this study, a novel dentin phosphophoryn‐derived peptide (DSS) is used to decorate lignin nanoparticles (LNPs). PC3‐MM2, MDA‐MB‐231, and A549 are cultured, using the conventional 2D model and the 3D cell spheroids, and the cellular internalization of the DSS‐functionalized LNPs (LNPs‐DSS) into the three different cancer cell lines is evaluated and compared for their efficacy with iRGD. Abstract The surface modification of nanoparticles (NPs) using different ligands is a common strategy to increase NP−cell interactions. Here, dentin phosphophoryn‐derived peptide (DSS) lignin nanoparticles (LNPs) are prepared and characterized, the cellular internalization of the DSS‐functionalized LNPs (LNPs‐DSS) into three different cancer cell lines is evaluated, and their efficacy with the widely used iRGD peptide is compared. It is shown that controlled extent of carboxylation of lignin improves the stability at physiological conditions of LNPs formed upon solvent exchange. Functionalization with DSS and iRGD peptides maintains the spherical morphology and moderate polydispersity of LNPs. The LNPs exhibit good cytocompatibility when cultured with PC3‐MM2, MDA‐MB‐231, and A549 in the conventional 2D model and in the 3D cell spheroid morphology. Importantly, the 3D cell models reveal augmented internalization of peptide‐functionalized LNPs and improve antiproliferative effects when the LNPs are loaded with a cytotoxic compound. Overall, LNPs‐DSS show equal or even superior cellular internalization than the LNPs‐iRGD, suggesting that DSS can also be used to enhance the cellular uptake of NPs into different types of cells, and release different cargos intracellularly.

Atom Probe Tomography for 3D Structural and Chemical Analysis of Individual Proteins

By Gustav Sundell, Mats Hulander, Astrid Pihl, Martin Andersson from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

This study describes a methodology using atom probe tomography (APT) for direct high‐resolution 3D visualization of proteins, here exemplified by the antibody IgG. The APT technique is based on spatially resolved mass spectroscopy with equal sensitivity for all elements across the periodic table, and near‐atomic resolution, hence the technique simultaneously provides both structural information and a chemical fingerprint. Abstract Determination of the 3D structure of proteins and other biomolecules is a major goal in structural biology, to provide insights to their biological function. Such structures are historically unveiled experimentally by X‐ray crystallography or NMR spectroscopy, and in recent years using cryo‐electron microscopy. Here, a method for structural analysis of individual proteins on the sub‐nanometer scale using atom probe tomography is described. This technique offers a combination of high‐resolution analysis of biomolecules in 3D, and the chemical sensitivity of mass spectrometry. As a model protein, the well‐characterized antibody IgG is used. IgG is encapsulated in an amorphous solid silica matrix via a sol–gel process to provide the requisite support for atom probe analysis. The silica synthesis is tuned to resemble physiological conditions. The 3D reconstructions show good agreement with the protein databank IgG crystal structure. This suggests that the silica‐embedding strategy can open the field of atom probe tomography to the analysis of biological molecules. In addition to high‐resolution structural information, the technique may potentially provide chemical information on the atomic scale using isotopic labeling. It is envisaged that this method may constitute a useful complement to existing tools in structural biology, particularly for the examination of proteins with low propensity for crystallization.

Synthesis Process of CoSeO3 Microspheres for Unordinary Li‐ion Storage Performances and Mechanism of Their Conversion Reaction with Li ions

By Gi Dae Park, Jeong Hoo Hong, Jae Hun Choi, Jong‐Heun Lee, Yang Soo Kim, Yun Chan Kang from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Herein, a synthesis process of phase‐pure CoSeO3 microspheres with high porosity through the use of cobalt selenide is introduced. Then, the Li‐ion storage mechanism of the CoSeO3 microspheres is systematically studied. CoSeO3 microspheres with heterostructures via coupling of nanocrystals of cobalt oxide and selenide show unordinary Li‐ion storage performances as anode materials of lithium‐ion batteries. Abstract Multicomponent materials with various double cations have been studied as anode materials of lithium‐ion batteries (LIBs). Heterostructures formed by coupling different‐bandgap nanocrystals enhance the surface reaction kinetics and facilitate charge transport because of the internal electric field at the heterointerface. Accordingly, metal selenites can be considered efficient anode materials of LIBs because they transform into metal selenide and oxide nanocrystals in the first cycle. However, few studies have reported synthesis of uniquely structured metal selenite microspheres. Herein, synthesis of high‐porosity CoSeO3 microspheres is reported. Through one‐pot oxidation at 400 °C, CoSex–C microspheres formed by spray pyrolysis transform into CoSeO3 microspheres showing unordinary cycling and rate performances. The conversion mechanism of CoSeO3 microspheres for lithium‐ion storage is systematically studied by cyclic voltammetry, in situ X‐ray diffraction and electrochemical impedance spectroscopy, and transmission electron microscopy. The reversible reaction mechanism of the CoSeO3 phase from the second cycle onward is evaluated as CoO + xSeO2 + (1 − x)Se + 4(x + 1)Li++ 4( x + 1)e− ↔ Co + (2x + 1)Li2O + Li2Se. The CoSeO3 microspheres show a high reversible capacity of 709 mA h g−1 for the 1400th cycle at a current density of 3 A g−1 and a high reversible capacity of 526 mA h g−1 even at an extremely high current density of 30 A g−1.

Synergistic Amplification of Oxidative Stress–Mediated Antitumor Activity via Liposomal Dichloroacetic Acid and MOF‐Fe2+

By Lei Sun, Yurui Xu, Ya Gao, Xinyu Huang, Shujun Feng, Jianmei Chen, Xuekun Wang, Leilei Guo, Meng Li, Xia Meng, Jikang Zhang, Junliang Ge, Xueying An, Dang Ding, Yadong Luo, Yu Zhang, Qing Jiang, Xinghai Ning from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

A liposomal formulation of metal–organic framework (MOF)‐Fe2+ and dichloroacetic acid (DCA), named MD@Lip, is developed for improving reactive oxygen species‐based anticancer treatment. MD@Lip can not only stimulate DCA‐mediated H2O2 generation, but also effectively promote MOF‐Fe2+‐associated Fenton reaction to produce cytotoxic hydroxyl radicals, thereby inducing cancer cell apoptosis and inhibiting tumor growth with negligible adverse effects. Abstract Cancer cells are susceptible to oxidative stress; therefore, selective elevation of intracellular reactive oxygen species (ROS) is considered as an effective antitumor treatment. Here, a liposomal formulation of dichloroacetic acid (DCA) and metal–organic framework (MOF)‐Fe2+ (MD@Lip) has been developed, which can efficiently stimulate ROS‐mediated cancer cell apoptosis in vitro and in vivo. MD@Lip can not only improve aqueous solubility of octahedral MOF‐Fe2+, but also generate an acidic microenvironment to activate a MOF‐Fe2+‐based Fenton reaction. Importantly, MD@Lip promotes DCA‐mediated mitochondrial aerobic oxidation to increase intracellular hydrogen peroxide (H2O2), which can be consequently converted to highly cytotoxic hydroxyl radicals (•OH) via MOF‐Fe2+, leading to amplification of cancer cell apoptosis. Particularly, MD@Lip can selectively accumulate in tumors, and efficiently inhibit tumor growth with minimal systemic adverse effects. Therefore, liposome‐based combination therapy of DCA and MOF‐Fe2+ provides a promising oxidative stress–associated antitumor strategy for the management of malignant tumors.

Light‐Directed Liquid Manipulation in Flexible Bilayer Microtubes

By Bo Xu, Chongyu Zhu, Lang Qin, Jia Wei, Yanlei Yu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Photocontrollable flexible microtubes (PFMs) are fabricated from commercially available soft microtubes coated with a photodeformable linear liquid crystal polymer (PABBP). Various liquids in the PFMs are manipulated upon mild visible light irradiation. The PABBP coating of the PFMs are self‐healable upon UV light irradiation. Light‐directed liquid manipulation in a PFM attached on a finger works well and is achieved in different gestures. Abstract Flexible microfluidic systems have potential in wearable and implantable medical applications. Directional liquid transportation in these systems typically requires mechanical pumps, gas tanks, and magnetic actuators. Herein, an alternative strategy is presented for light‐directed liquid manipulation in flexible bilayer microtubes, which are composed of a commercially available supporting layer and the photodeformable layer of a newly designed azobenzene‐containing linear liquid crystal copolymer. Upon moderate visible light irradiation, various liquid slugs confined in the flexible microtubes are driven in the preset direction over a long distance due to photodeformation‐induced asymmetric capillary forces. Several light‐driven prototypes of parallel array, closed‐loop channel, and multiple micropump are established by the flexible bilayer microtubes to achieve liquid manipulation. Furthermore, an example of a wearable device attached to a finger for light‐directed liquid motion is demonstrated in different gestures. These unique photocontrollable flexible microtubes offer a novel concept of wearable microfluidics.

Efficient Nitrogen‐Doped Carbon for Zinc–Bromine Flow Battery

By Hong‐Xin Xiang, Ai‐Dong Tan, Jin‐Hua Piao, Zhi‐Yong Fu, Zhen‐Xing Liang from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

A facile method is developed to synthesize heteroatom‐doped carbon, which yields a superior electrocatalytic activity toward the redox Br2/Br−. As the positive electrode material in a zinc–bromine flow battery, the optimal carbon exhibits a voltage efficiency of 83.0% and an energy efficiency of 82.5% at the current density of 80 mA cm−2. Abstract The zinc–bromine flow battery (ZBFB) is one of the most promising technologies for large‐scale energy storage. Here, nitrogen‐doped carbon is synthesized and investigated as the positive electrode material in ZBFBs. The synthesis includes the carbonization of the glucose precursor and nitrogen doping by etching in ammonia gas. Physicochemical characterizations reveal that the resultant carbon exhibits high electronic conductivity, large specific surface area, and abundant heteroatom‐containing functional groups, which benefit the formation and exposure of the active sites toward the Br2/Br− redox couple. As a result, the assembled ZBFB achieves a voltage efficiency of 83.0% and an energy efficiency of 82.5% at a current density of 80 mA cm−2, which are among the top values in literature. Finally, the ZBFB does not yield any detectable degradation in performance after a 200‐cycle charging/discharging test, revealing its high stability. In summary, this work provides a highly efficient electrode material for the zinc–bromine flow battery.

Sequential Targeting TGF‐β Signaling and KRAS Mutation Increases Therapeutic Efficacy in Pancreatic Cancer

By Yuanyuan Pei, Liang Chen, Yukun Huang, Jiahao Wang, Jingxian Feng, Minjun Xu, Yu Chen, Qingxiang Song, Gan Jiang, Xiao Gu, Qian Zhang, Xiaoling Gao, Jun Chen from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Fraxinellone‐loaded CGKRK‐modified nanoparticles are prepared for regulating transforming growth factor beta signals in the suppressive tumor microenvironment. Based on this, the dense stroma is modulated and the intratumor blood perfusion is enhanced, meaning the delivery barrier of the following siRNA‐loaded lipid‐coated calcium phosphate (LCP) biomimetic high‐density lipoprotein nanoparticles (siKras‐LCP‐ApoE3) are internalized and specifically silence KRAS mutation and kill cancer cells. Abstract Pancreatic cancer is a highly aggressive malignancy that strongly resists extant treatments. The failure of existing therapies is majorly attributed to the tough tumor microenvironment (TME) limiting drug access and the undruggable targets of tumor cells. The formation of suppressive TME is regulated by transforming growth factor beta (TGF‐β) signaling, while the poor response and short survival of almost 90% of pancreatic cancer patients results from the oncogenic KRAS mutation. Hence, simultaneously targeting both the TGF‐β and KRAS pathways might dismantle the obstacles of pancreatic cancer therapy. Here, a novel sequential‐targeting strategy is developed, in which antifibrotic fraxinellone‐loaded CGKRK‐modified nanoparticles (Frax‐NP‐CGKRK) are constructed to regulate TGF‐β signaling and siRNA‐loaded lipid‐coated calcium phosphate (LCP) biomimetic nanoparticles (siKras‐LCP‐ApoE3) are applied to interfere with the oncogenic KRAS. Frax‐NP‐CGKRK successfully targets the tumor sites through the recognition of overexpressed heparan sulfate proteoglycan, reverses the activated cancer‐associated fibroblasts (CAFs), attenuates the dense stroma barrier, and enhances tumor blood perfusion. Afterward, siKras‐LCP‐ApoE3 is efficiently internalized by the tumor cells through macropinocytosis and specifically silencing KRAS mutation. Compared with gemcitabine, this sequential‐targeting strategy significantly elongates the lifespans of pancreatic tumor‐bearing animals, hence providing a promising approach for pancreatic cancer therapy.

Masthead: (Small 24/2019)

By from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

A 3‐Fluoro‐4‐hexylthiophene‐Based Wide Bandgap Donor Polymer for 10.9% Efficiency Eco‐Friendly Nonfullerene Organic Solar Cells

By Jeong Eun Yu, Sung Jae Jeon, Jun Young Choi, Yong Woon Han, Eui Jin Ko, Doo Kyung Moon from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Characterization Tools: Atom Probe Tomography for 3D Structural and Chemical Analysis of Individual Proteins (Small 24/2019)

By Gustav Sundell, Mats Hulander, Astrid Pihl, Martin Andersson from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

In article number 1900316, Martin Andersson and co‐workers develop a new method for protein structure analysis. Atom probe tomography (APT) is used to simultaneously asses the 3D structure and chemical composition of proteins with high resolution. The key concept of the method is to embed proteins in an amorphous silicon oxide glass, from which ultra‐sharp needles are prepared and analyzed with APT.

Photocontrollable Flexible Microtubes: Light‐Directed Liquid Manipulation in Flexible Bilayer Microtubes (Small 24/2019)

By Bo Xu, Chongyu Zhu, Lang Qin, Jia Wei, Yanlei Yu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Water control has always been essential from ancient times to modern life. The Chinese mythical hero, Da Yu, established a flood control system for the Yellow River and successfully protected the Chinese civilization. In article number 1901847, Yanlei Yu and co‐workers develop a strategy for light‐directed liquid manipulation in a flexible photodeformable microchannel, offering a novel concept of optofluidics.

Bio‐Nanopatterning: Inkjet Printed Nanopatterned Aptamer‐Based Sensors for Improved Optical Detection of Foodborne Pathogens (Small 24/2019)

By Susana Díaz‐Amaya, Min Zhao, Li‐Kai Lin, Carlos Ostos, Jan P. Allebach, George T.‐C. Chiu, Amanda J. Deering, Lia A. Stanciu from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

In article number 1805342, Susana Díaz‐Amaya, Lia A. Stanciu, and co‐workers study the performance of an optimized inkjet printing‐approach for nanopatterning of aptameric inks on nitrocellulose. The achieved optical detection of E. coli O157:H7 in real complex samples represents the lowest limit of detection reported to date.

Mesoporous Silica‐Based Materials with Bactericidal Properties

By Andrea Bernardos, Elena Piacenza, Félix Sancenón, Mehrdad Hamidi, Aziz Maleki, Raymond J. Turner, Ramón Martínez‐Máñez from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

Bacteria are the main cause of chronic infections and the emergence of antibiotic resistance has become a major concern worldwide. This review discusses the design and synthesis of multifunctional/controllable drug delivery systems based on mesoporous silica nanoparticles (MSNs) to combat bacterial infections. A comprehensive analysis of all the papers published dealing with the use of MSMs for delivery of antibacterial chemicals is provided. Abstract Bacterial infections are the main cause of chronic infections and even mortality. In fact, due to extensive use of antibiotics and, then, emergence of antibiotic resistance, treatment of such infections by conventional antibiotics has become a major concern worldwide. One of the promising strategies to treat infection diseases is the use of nanomaterials. Among them, mesoporous silica materials (MSMs) have attracted burgeoning attention due to high surface area, tunable pore/particle size, and easy surface functionalization. This review discusses how one can exploit capacities of MSMs to design and fabricate multifunctional/controllable drug delivery systems (DDSs) to combat bacterial infections. At first, the emergency of bacterial and biofilm resistance toward conventional antimicrobials is described and then how nanoparticles exert their toxic effects upon pathogenic cells is discussed. Next, the main aspects of MSMs (e.g., physicochemical properties, multifunctionality, and biosafety) which one should consider in the design of MSM‐based DDSs against bacterial infections are introduced. Finally, a comprehensive analysis of all the papers published dealing with the use of MSMs for delivery of antibacterial chemicals (antimicrobial agents functionalized/adsorbed on mesoporous silica (MS), MS‐loaded with antimicrobial agents, gated MS‐loaded with antimicrobial agents, MS with metal‐based nanoparticles, and MS‐loaded with metal ions) is provided.

3D Bioprinting in Skeletal Muscle Tissue Engineering

By Serge Ostrovidov, Sahar Salehi, Marco Costantini, Kasinan Suthiwanich, Majid Ebrahimi, Ramin Banan Sadeghian, Toshinori Fujie, Xuetao Shi, Stefano Cannata, Cesare Gargioli, Ali Tamayol, Mehmet Remzi Dokmeci, Gorka Orive, Wojciech Swieszkowski, Ali Khademhosseini from Wiley: Small: Table of Contents. Published on Jun 14, 2019.

3D bioprinting in skeletal muscle tissue engineering (SMTE) is discussed in this Review. After a short state‐of‐the‐art on SMTE with “conventional methods,” 3D bioprinting methods are in focus, and an overview of the bioink formulations and properties are provided. Different advances made in SMTE with 3D bioprinting are highlighted, and future needs and a short perspective are provided. Abstract Skeletal muscle tissue engineering (SMTE) aims at repairing defective skeletal muscles. Until now, numerous developments are made in SMTE; however, it is still challenging to recapitulate the complexity of muscles with current methods of fabrication. Here, after a brief description of the anatomy of skeletal muscle and a short state‐of‐the‐art on developments made in SMTE with “conventional methods,” the use of 3D bioprinting as a new tool for SMTE is in focus. The current bioprinting methods are discussed, and an overview of the bioink formulations and properties used in 3D bioprinting is provided. Finally, different advances made in SMTE by 3D bioprinting are highlighted, and future needs and a short perspective are provided.

[ASAP] Highly Efficient Spin–Orbit Torque and Switching of Layered Ferromagnet Fe3GeTe2

By Mohammed Alghamdi†?, Mark Lohmann†?, Junxue Li†?, Palani R. Jothi‡, Qiming Shao§, Mohammed Aldosary†#, Tang Su?†, Boniface P. T. Fokwa‡, and Jing Shi*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01043

[ASAP] Dimensional Crossover and Topological Nature of the Thin Films of a Three-Dimensional Topological Insulator by Band Gap Engineering

By Zhenyu Wang*†‡#, Tong Zhou†, Tian Jiang†?, Hongyi Sun??, Yunyi Zang§, Yan Gong§, Jianghua Zhang§#, Mingyu Tong?, Xiangnan Xie†, Qihang Liu*??, Chaoyu Chen*?, Ke He§#, and Qi-Kun Xue§# from Nano Letters: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01641

[ASAP] Curvature- and Phase-Induced Protein Sorting Quantified in Transfected Cell-Derived Giant Vesicles

By Guillermo Moreno-Pescador†, Christoffer D. Florentsen†, Henrik Østbye‡, Stine L. Sønder§, Theresa L. Boye§, Emilie L. Veje†, Alexander K. Sonne†, Szabolcs Semsey†, Jesper Nylandsted§?, Robert Daniels‡, and Poul Martin Bendix*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01052

[ASAP] Tuning Transport Properties in Thermoelectric Nanocomposites through Inorganic Ligands and Heterostructured Building Blocks

By Maria Iba´n~ez*†‡§, Aziz Genc¸??, Roger Hasler‡§, Yu Liu†, Oleksandr Dobrozhan#, Olga Nazarenko‡§, Mari´a de la Mata?¶, Jordi Arbiol??, Andreu Cabot#?, and Maksym V. Kovalenko*‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00346

[ASAP] Memory Distance for Interfacial Chemical Bond-Induced Friction at the Nanoscale

By Kaiwen Tian†#, Zhuohan Li‡#, Nitya N. Gosvami§?, David L. Goldsby?, Izabela Szlufarska‡, and Robert W. Carpick*§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.8b09714

[ASAP] Equipartition of Energy Defines the Size–Thickness Relationship in Liquid-Exfoliated Nanosheets

By Claudia Backes*†, Davide Campi‡, Beata M. Szydlowska†§, Kevin Synnatschke†, Ezgi Ojala†, Farnia Rashvand†, Andrew Harvey§, Aideen Griffin§, Zdenek Sofer?, Nicola Marzari‡, Jonathan N. Coleman*§, and David D. O’Regan*§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02234

[ASAP] Bias-Voltage Driven Switching of the Charge-Density-Wave and Normal Metallic Phases in 1T-TaS2 Thin-Film Devices

By Adane K. Geremew†, Sergey Rumyantsev†?, Fariborz Kargar†, Bishwajit Debnath‡, Adrian Nosek§, Matthew A. Bloodgood¶, Marc Bockrath§, Tina T. Salguero¶, Roger K. Lake‡, and Alexander A. Balandin*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02870

[ASAP] In Situ Nanoadjuvant-Assembled Tumor Vaccine for Preventing Long-Term Recurrence

By Quoc-Viet Le†, Juhan Suh†, Jin Joo Choi†, Gyu Thae Park†, Jung Weon Lee†‡§, Gayong Shim*†, and Yu-Kyoung Oh*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02071

[ASAP] Harnessing Heat Beyond 200 °C from Unconcentrated Sunlight with Nonevacuated Transparent Aerogels

By Lin Zhao, Bikram Bhatia, Sungwoo Yang†, Elise Strobach, Lee A. Weinstein, Thomas A. Cooper‡, Gang Chen*, and Evelyn N. Wang* from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02976

[ASAP] Shape Engineering of InP Nanostructures by Selective Area Epitaxy

By Naiyin Wang†, Xiaoming Yuan*‡, Xu Zhang*†§, Qian Gao†?, Bijun Zhao†, Li Li?, Mark Lockrey?#, Hark Hoe Tan†, Chennupati Jagadish†, and Philippe Caroff†@ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02985

[ASAP] Robust Piezo-Phototronic Effect in Multilayer ?-InSe for High-Performance Self-Powered Flexible Photodetectors

By Mingjin Dai†‡#, Hongyu Chen‡§#, Fakun Wang?, Yunxia Hu†‡, Shuai Wei‡, Jia Zhang‡, Zhiguo Wang?, Tianyou Zhai?, and PingAn Hu*†‡ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03278

[ASAP] Anisotropic Plasmonic CuS Nanocrystals as a Natural Electronic Material with Hyperbolic Optical Dispersion

By R. Margoth Co´rdova-Castro*†, Marianna Casavola†, Mark van Schilfgaarde, Alexey V. Krasavin, Mark A. Green, David Richards, and Anatoly V. Zayats from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b00282

[ASAP] Negative Gauge Factor Piezoresistive Composites Based on Polymers Filled with MoS2 Nanosheets

By Sonia Biccai†, Conor S. Boland†, Daniel P. O’Driscoll†, Andrew Harvey†, Cian Gabbett†, Domhnall R. O’Suilleabhain†, Aideen J. Griffin†, Zheling Li‡, Robert J. Young‡, and Jonathan N. Coleman*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01613

[ASAP] Tailor-Made Semiconducting Polymers for Second Near-Infrared Photothermal Therapy of Orthotopic Liver Cancer

By Tingting Sun†, Jinfeng Han†, Shi Liu†, Xin Wang‡, Zhi Yuan Wang*†, and Zhigang Xie*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03910

[ASAP] Dynamic Origin of Chirality Transfer between Chiral Surface and Achiral Ligand in Au38 Clusters

By Laura Riccardi†, Federico De Biasi‡, Marco De Vivo†, Thomas Bu¨rgi*§, Federico Rastrelli*‡, and Giovanni Salassa*§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 14, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02552

Accelerating, guiding, and compressing skyrmions by defect rails

By Carles Navau from RSC - Nanoscale latest articles. Published on Jun 14, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR02171J, Paper
Josep Castell-Queralt, Leonardo González-Gómez, Nuria Del-Valle, Alvaro Sanchez, Carles Navau
Magnetic skyrmions can be guided along rails made by line defects while their speed increased by a factor of ten.
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

Chlorine-additive-promoted incorporation of Mn2+ dopants into CsPbCl3 perovskite nanocrystals

By Daqin Chen from RSC - Nanoscale latest articles. Published on Jun 14, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR04663A, Communication
Su Zhou, Yiwen Zhu, Jiasong Zhong, Feifan Tian, Hai Huang, Jiangkun Chen, Daqin Chen
Chlorine-promoted doping of Mn(II) in CsPbCl3 perovskites is achieved by employing manganese acetate as a Mn(II) precursor for the first time.
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

Measurements of aptamer–protein binding kinetics using graphene field-effect transistors

By Qiao Lin from RSC - Nanoscale latest articles. Published on Jun 14, 2019.

Nanoscale, 2019, Advance Article
DOI: 10.1039/C9NR02797A, Paper
Xuejun Wang, Zhuang Hao, Timothy R. Olsen, Wenjun Zhang, Qiao Lin
Kinetics of aptamer-protein binding at different ionic strengths and temperatures are characterized using graphene field-effect transistors.
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

Enabling Tailorable Optical Properties and Markedly Enhanced Stability of Perovskite Quantum Dots by Permanently Ligating with Polymer Hairs

By Young Jun Yoon, Yajing Chang, Shuguang Zhang, Meng Zhang, Shuang Pan, Yanjie He, Chun Hao Lin, Shengtao Yu, Yihuang Chen, Zewei Wang, Yong Ding, Jaehan Jung, Naresh Thadhani, Vladimir V. Tsukruk, Zhitao Kang, Zhiqun Lin from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

A general amphiphilic star‐like block copolymer nanoreactor strategy for in situ crafting a set of hairy perovskite quantum dots (QDs) with precisely tunable size and exceptionally high water and colloidal stabilities is presented. Intriguingly, the readily alterable length of the permanently bound outer hydrophobic polymers renders remarkable control over the stability enhancement of hairy perovskite QDs. Abstract Instability of perovskite quantum dots (QDs) toward humidity remains one of the major obstacles for their long‐term use in optoelectronic devices. Herein, a general amphiphilic star‐like block copolymer nanoreactor strategy for in situ crafting a set of hairy perovskite QDs with precisely tunable size and exceptionally high water and colloidal stabilities is presented. The selective partition of precursors within the compartment occupied by inner hydrophilic blocks of star‐like diblock copolymers imparts in situ formation of robust hairy perovskite QDs permanently ligated by outer hydrophobic blocks via coprecipitation in nonpolar solvent. These size‐ and composition‐tunable perovskite QDs reveal impressive water and colloidal stabilities as the surface of QDs is intimately and permanently ligated by a layer of outer hydrophobic polymer hairs. More intriguingly, the readily alterable length of outer hydrophobic polymers renders the remarkable control over the stability enhancement of hairy perovskite QDs.

Nitrogen Vacancies on 2D Layered W2N3: A Stable and Efficient Active Site for Nitrogen Reduction Reaction

By Huanyu Jin, Laiquan Li, Xin Liu, Cheng Tang, Wenjie Xu, Shuangming Chen, Li Song, Yao Zheng, Shi‐Zhang Qiao from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Nitrogen vacancies on 2D layered W2N3 reveals stable and efficient nitrogen reduction performance. The activity and selectivity of the unique active sites are confirmed by mutually corroborating electrochemical experiments and theoretical computation. The nitrogen vacancies on W2N3 have an electron deficient environment for the acceptance of the lone‐pair electrons of N2, which can facilitate dinitrogen molecule adsorption and activation. Abstract Electrochemical nitrogen reduction reaction (NRR) under ambient conditions provides an avenue to produce carbon‐free hydrogen carriers. However, the selectivity and activity of NRR are still hindered by the sluggish reaction kinetics. Nitrogen Vacancies on transition metal nitrides are considered as one of the most ideal active sites for NRR by virtue of their unique vacancy properties such as appropriate adsorption energy to dinitrogen molecule. However, their catalytic performance is usually limited by the unstable feature. Herein, a new 2D layered W2N3 nanosheet is prepared and the nitrogen vacancies are demonstrated to be active for electrochemical NRR with a steady ammonia production rate of 11.66 ± 0.98 µg h−1 mgcata−1 (3.80 ± 0.32 × 10−11 mol cm−2 s−1) and Faradaic efficiency of 11.67 ± 0.93% at −0.2 V versus reversible hydrogen electrode for 12 cycles (24 h). A series of ex situ synchrotron‐based characterizations prove that the nitrogen vacancies on 2D W2N3 are stable by virtue of the high valence state of tungsten atoms and 2D confinement effect. Density function theory calculations suggest that nitrogen vacancies on W2N3 can provide an electron‐deficient environment which not only facilitates nitrogen adsorption, but also lowers the thermodynamic limiting potential of NRR.

Immunogold FIB‐SEM: Combining Volumetric Ultrastructure Visualization with 3D Biomolecular Analysis to Dissect Cell–Environment Interactions

By Sahana Gopal, Ciro Chiappini, James P. K. Armstrong, Qu Chen, Andrea Serio, Chia‐Chen Hsu, Christoph Meinert, Travis J. Klein, Dietmar W. Hutmacher, Stephen Rothery, Molly M. Stevens from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Focused ion beam scanning electron microscopy (FIB‐SEM) has recently emerged as a powerful tool for obtaining volumetric and nanoscale structural information at the cell–material interface. However, obtaining functional biomolecular information at the same resolution using FIB‐SEM is yet to be achieved. This study reports the first immunogold labeling approach for FIB‐SEM, allowing simultaneous volumetric acquistion of ultrastructural and functional information. Abstract Volumetric imaging techniques capable of correlating structural and functional information with nanoscale resolution are necessary to broaden the insight into cellular processes within complex biological systems. The recent emergence of focused ion beam scanning electron microscopy (FIB‐SEM) has provided unparalleled insight through the volumetric investigation of ultrastructure; however, it does not provide biomolecular information at equivalent resolution. Here, immunogold FIB‐SEM, which combines antigen labeling with in situ FIB‐SEM imaging, is developed in order to spatially map ultrastructural and biomolecular information simultaneously. This method is applied to investigate two different cell–material systems: the localization of histone epigenetic modifications in neural stem cells cultured on microstructured substrates and the distribution of nuclear pore complexes in myoblasts differentiated on a soft hydrogel surface. Immunogold FIB‐SEM offers the potential for broad applicability to correlate structure and function with nanoscale resolution when addressing questions across cell biology, biomaterials, and regenerative medicine.

High‐Throughput Growth of Microscale Gold Bicrystals for Single‐Grain‐Boundary Studies

By Lucia T. Gan, Rui Yang, Rachel Traylor, Wei Cai, William D. Nix, Jonathan A. Fan from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Studies of single grain boundaries are enabled through the preparation of microscale gold bicrystals via rapid melt growth. This material platform supports the high‐throughput and high‐yield growth of gold bicrystals on amorphous oxide. Crystallization is mediated by platinum doping, which decouples crystal nucleation from growth. These bicrystals offer model systems for the systematic study of individual defect properties. Abstract The study of grain boundaries is the foundation to understanding many of the intrinsic physical properties of bulk metals. Here, the preparation of microscale thin‐film gold bicrystals, using rapid melt growth, is presented as a model system for studies of single grain boundaries. This material platform utilizes standard fabrication tools and supports the high‐yield growth of thousands of bicrystals per wafer, each containing a grain boundary with a unique tilt character. The crystal growth dynamics of the gold grains in each bicrystal are mediated by platinum gradients, which originate from the gold–platinum seeds responsible for gold crystal nucleation. This crystallization mechanism leads to a decoupling between crystal nucleation and crystal growth, and it ensures that the grain boundaries form at the middle of the gold microstructures and possess a uniform distribution of misorientation angles. It is envisioned that these bicrystals will enable the systematic study of the electrical, optical, chemical, thermal, and mechanical properties of individual grain boundary types.

Systematic Control of the Orientation of Organic Phosphorescent Pt Complexes in Thin Films for Increased Optical Outcoupling

By Jongchan Kim, Thilini Batagoda, Jaesang Lee, Daniel Sylvinson, Kan Ding, PatrickJ.G. Saris, Ushasree Kaipa, Iain W. H. Oswald, Mohammad A. Omary, Mark E. Thompson, Stephen R. Forrest from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Pt(II) complex orientation is controlled by modifying the molecular structure and structural templating. Molecules with modified structures show ≈20% increased fraction of horizontally aligned transition dipole moments (TDMs) when doped into a host. Alternatively, a highly ordered molecular template drives the alignment of a subsequently deposited polycrystalline emissive layer, showing a 60% increase in horizontally aligned TDMs versus without template. Abstract Orienting light‐emitting molecules relative to the substrate is an effective method to enhance the optical outcoupling of organic light‐emitting devices. Platinum(II) phosphorescent complexes enable facile control of the molecular alignment due to their planar structures. Here, the orientation of Pt(II) complexes during the growth of emissive layers is controlled by two different methods: modifying the molecular structure and using structural templating. Molecules whose structures are modified by adjusting the diketonate ligand of the Pt complex, dibenzo‐(f,h)quinoxaline Pt dipivaloylmethane, (dbx)Pt(dpm), show an ≈20% increased fraction of horizontally aligned transition dipole moments compared to (dbx)Pt(dpm) doped into a 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl, CBP, host. Alternatively, a template composed of highly ordered 3,4,9,10‐perylenetetracarboxylic dianhydride monolayers is predeposited to drive the alignment of a subsequently deposited emissive layer comprising (2,3,7,8,12,13,17,18‐octaethyl)‐21H,23H‐porphyrinplatinum(II) doped into triindolotriazine. This results in a 60% increase in horizontally aligned transition dipole moments compared to the film deposited in the absence of the template. The findings provide a systematic route for controlling molecular alignment during layer growth, and ultimately to increase the optical outcoupling in organic light‐emitting diodes.

Spotlights on our sister journals: Angew. Chem. Int. Ed. 26/2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

New Members and Foreign Associates of the National Academy of Sciences 2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Graphical Abstract: Angew. Chem. Int. Ed. 26/2019

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Cover Picture: Rhodium(I)‐Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh−C Bond by a Tethered Hydroxy Group (Angew. Chem. Int. Ed. 26/2019)

By Yoshihiro Oonishi, Shuichi Masusaki, Shunki Sakamoto, Yoshihiro Sato from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A chiral quaternary carbon center at the ring junction can be prepared by RhI‐catalyzed cyclization of enynes, as described by Y. Oonishi, Y. Sato et al. in their Communication on page 8736 ff. It was revealed that the cyclization proceeds through a novel reaction pathway. The cleavage of the Rh−C(sp2) bond of the chiral rhodacycle by an O−H bond in the tether occurs, then β‐hydride elimination from the resultant oxarhodacycle, followed by reductive elimination to give cyclic compounds with a chiral quaternary carbon center in high yields and with high ee values.

Frontispiece: Reaction Environment Modification in Covalent Organic Frameworks for Catalytic Performance Enhancement

By Qi Sun, Yongquan Tang, Briana Aguila, Sai Wang, Feng‐Shou Xiao, Praveen K. Thallapally, Abdullah M. Al‐Enizi, Ayman Nafady, Shengqian Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Covalent Organic Frameworks In their Communication on page 8670 ff., S. Ma and co‐workers show that the catalytic performance of sulfonic acid groups in covalent organic frameworks (COFs) can be greatly amplified by the introduction of polymeric solvent analogues.

Back Cover: Molecular Heterostructures of Covalent Triazine Frameworks for Enhanced Photocatalytic Hydrogen Production (Angew. Chem. Int. Ed. 26/2019)

By Wei Huang, Qing He, Yongpan Hu, Yanguang Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Molecular heterostructures can facilitate charge carrier separation and promote photocatalytic activity. In their Communication on page 8676 ff., Y. G. Li et al. report a sequential polymerization strategy to prepare heterostructured covalent triazine frameworks containing spatially separated benzothiadiazole and thiophene moieties. The resultant product exhibits remarkable photocatalytic activity in H2 production that is far superior to those of most other conjugated polymer photocatalysts.

Inside Back Cover: Electropolymerization of Molecular‐Sieving Polythiophene Membranes for H2 Separation (Angew. Chem. Int. Ed. 26/2019)

By Mengxi Zhang, Xuechun Jing, Shuang Zhao, Pengpeng Shao, Yuanyuan Zhang, Shuai Yuan, Yanshuo Li, Cheng Gu, Xiaoqi Wang, Yanchun Ye, Xiao Feng, Bo Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Electropolymerized membranes with outstanding hydrogen separation performance are described by X. Feng and co‐workers in their Communication on page 8768 ff. A strategy for softness adjustment of rigid networks (SARs) was adopted to produce flexible, stand‐alone, and molecular‐sieving membranes by electropolymerization. Remarkable H2/CO2, H2/N2, and H2/CH4 separation performances were achieved, ranking among the best observed with purely organic polymeric membranes.

Inside Cover: Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts (Angew. Chem. Int. Ed. 26/2019)

By Xing Huang, Detre Teschner, Maria Dimitrakopoulou, Alexey Fedorov, Benjamin Frank, Ralph Kraehnert, Frank Rosowski, Harry Kaiser, Stephan Schunk, Christiane Kuretschka, Robert Schlögl, Marc‐Georg Willinger, Annette Trunschke from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Atomic‐level insight about the metal–promoter interaction in Rh‐based catalysts for the conversion of syngas to ethanol is provided by X. Huang, M. G. Willinger, A. Trunschke, and co‐workers in their Communication on page 8709 ff. In the best‐performing catalyst (Mn and Fe bi‐promoted Rh on silica), the metal–promoter interaction leads to the formation of an active structure containing a bimetallic Rh–Fe alloy surrounded by MnOx species.

N‐Heterocyclic Carbene Catalyzed Radical Coupling of Aldehydes with Redox‐Active Esters

By Runjiang Song, Yonggui Robin Chi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

N‐Heterocyclic carbene (NHC) catalyzed reactions that proceed through radical pathways are summarized in this Highlight, with a particular focus on a recent contribution from Ohmiya and co‐workers on the coupling of aldehydes with alkyl radicals. Abstract N‐Heterocyclic carbene catalyzed radical reactions are challenging and underdeveloped. In a recent study, Ohmiya, Nagao and co‐workers found that aldehyde carbonyl carbon centers can be coupled with alkyl radicals under NHC catalysis. An elegant aspect of this study is the use of a redox‐active carboxylic ester that behaves as an single‐electron oxidant to convert the Breslow intermediate into a radical adduct and concurrently release an alkyl radical intermediate as a reaction partner.

Organic Imine Cages: Molecular Marriage and Applications

By Koushik Acharyya, Partha Sarathi Mukherjee from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

More than a cage: Organic imine cages (OICs) are a great success story among porous solids, and many opportunities remain to develop fascinating structures and applications. This Minireview details lesser‐known self‐sorting/self‐selection processes in OICs that may be employed in synthetic design strategies. Recent discoveries concerning implementation of OICs in applications are discussed. Abstract Imine condensation has been known to chemists for more than a century and is used extensively to synthesize large organic cages of defined shapes and sizes. Surprisingly, in the context of the synthetic methods for organic imine cages (OICs), a self‐sorting/self‐selection (molecular marriage) process has been overlooked over the years. Such processes are omnipresent in nature, from the creation of galaxies to the formation of the smallest building blocks of life (the cell). Such processes have the incredible ability to guide a system toward the formation of a specific product or products out of a collection of equally probable multiple possibilities. This Minireview sheds light on new opportunities in cage design offered by the self‐sorting/self‐selection protocol in OICs. Recent efforts to explore organic cages for various exciting new applications are discussed; for example, for detection of harmful small organic molecules, as templates for nucleation of metal nanoparticles (MNPs), and as proton‐conducting materials.

C−H Functionalization of Commodity Polymers

By Jill B. Williamson, Sally E. Lewis, Robert R. Johnson, Irene M. Manning, Frank A. Leibfarth from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Hot commodities: This Review discusses the historical significance of and contemporary advances in the C−H functionalization of commodity polymers. Exciting new directions for the field are presented, including uncovering new material properties and upcycling post‐consumer plastic waste. Abstract Synthetic manipulation of polymer substrates is one of the oldest and most reliable methods to increase the functional diversity of soft materials. Modifying the chemical structure of polymers that are already produced on a commodity scale leverages the current high‐volume and low‐cost production of commodity plastics for the discovery of modern materials. A myriad of polymer C−H functionalization methods have been developed which enable the modification of material properties on both a laboratory and industrial scale. More recently, driven by advances in C−H activation, photoredox catalysis, and radical chemistry, chemoselective approaches have emerged as a means to impart precise functionality onto commodity polymer substrates. This Review discusses the historical significance of and contemporary advances in the C−H functionalization of commodity polymers. The conceptual approach outlined herein presents exciting new directions for the field, including increasing the value of otherwise pervasive materials, uncovering entirely new material properties, and a viable path to upcycle post‐consumer plastic waste.

Consideration of Molecular Structure in the Excited State to Design New Luminogens with Aggregation‐Induced Emission

By Kenta Kokado, Kazuki Sada from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Aggregation‐induced emission (AIE) is a photoluminescence phenomenon in which a so‐called AIE luminogen (AIEgen) exhibits intense emission in the aggregated or solid state but only weak or no emission in the solution state. This Minireview investigates the crucial role that changes to the molecular structure of an AIEgen in the excited state (for example a π twist) have on the mechanism of AIE. Abstract Aggregation‐induced emission (AIE) is a photoluminescence phenomenon in which an AIE luminogen (AIEgen) exhibits intense emission in the aggregated or solid state but only weak or no emission in the solution state. Understanding the mechanism of AIE requires consideration of excited state molecular geometry (for example, a π twist). This Minireview examines the history of AIEgens with a focus on the representative AIEgen, tetraphenylethylene (TPE). The mechanisms of solution‐state quenching are reviewed and the crucial role of excited‐state molecular transformations for AIE is discussed. Finally, recent progress in understanding the relationship between excited state molecular transformations and AIE is overviewed for a range of different AIEgens.

Nickel‐Catalyzed 1,1‐Alkylboration of Electronically Unbiased Terminal Alkenes

By Yangyang Li, Hailiang Pang, Dong Wu, Zheqi Li, Wang Wang, Hong Wei, Ying Fu, Guoyin Yin from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

An unprecedented alkylboration of electronically unbiased terminal alkenes, featuring 1,1‐regioselectivity, was achieved by using a novel nickel catalyst. This reaction provides remarkable regioselectivity without the assistance of coordinating groups. Moreover, it exhibits excellent functional‐group tolerance and chemoselectivity toward monosubstituted double bonds. Abstract An unprecedented nickel‐catalyzed 1,1‐alkylboration of electronically unbiased alkenes has been developed, providing straightforward access to secondary aliphatic boronic esters from readily available materials under very mild reaction conditions. The regioselectivity of this reaction is governed by a unique pyridyl carboxamide ligated catalyst, rather than the substrates. Moreover, this transformation shows excellent chemo‐ and regio‐selectivity and remarkably good functional‐group tolerance. We also demonstrate that under balloon pressure, ethylene can also be utilized as a substrate. Additionally, competence experiments indicate that selective bond formation is favored at the α‐position of boron and preliminary mechanistic studies indicate that the key step in this three‐component reaction involves a 1,2‐nickel migration.

Porphyrin Nanocage‐Embedded Single‐Molecular Nanoparticles for Cancer Nanotheranostics

By Guocan Yu, Tian‐Yong Cen, Zhimei He, Shu‐Ping Wang, Zhantong Wang, Xin‐Wen Ying, Shijun Li, Orit Jacobson, Sheng Wang, Lei Wang, Li‐Sen Lin, Rui Tian, Zijian Zhou, Qianqian Ni, Xiaopeng Li, Xiaoyuan Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Sophisticated porphyrin nanocages, which can be utilized as a functional platform to develop single molecular nanoparticles, were synthesized. The unique topological structure of the nanocages results in their excellent performance as cancer nanotheranostics, as demonstrated through applications in PET imaging and photodynamic therapy. Abstract Single molecular nanoparticles (SMNPs) integrating imaging and therapeutic capabilities exhibit unparalleled advantages in cancer theranostics, ranging from excellent biocompatibility, high stability, prolonged blood lifetime to abundant tumor accumulation. Herein, we synthesize a sophisticated porphyrin nanocage that is further functionalized with twelve polyethylene glycol arms to prepare SMNPs (porSMNPs). The porphyrin nanocage embedded in porSMNPs can be utilized as a theranostic platform. PET imaging allows dynamic observation of the bio‐distribution of porSMNPs, confirming their excellent circulation time and preferential accumulation at the tumor site, which is attributed to the enhanced permeability and retention effect. Moreover, the cage structure significantly promotes the photosensitizing effect of porSMNs by inhibiting the π–π stacking interactions of the photosensitizers, ablating of the tumors without relapse by taking advantage of photodynamic therapy.

Electronic Communication across Porphyrin Hexabenzocoronene Isomers

By Max M. Martin, Dominik Lungerich, Philipp Haines, Frank Hampel, Norbert Jux from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Clear communication: Hexabenzocoronene was utilized as a model system for nanographenes and probed spectroscopically through peripherally attached porphyrins that served as quasi optical electrodes. Nanographenes functionalized selectively in the ortho‐, meta‐, and para‐positions showed differences in the electronic communication between the porphyrins, which is reflected by a distortion of the B‐band. Abstract Single‐molecule electronic components (SMECs) are envisioned as next‐generation building blocks in quantum circuit systems. However, challenges such as the reproducibility of the electrode attachment to the individual molecules hamper their fundamental investigation. For our purpose, we introduced quasi optoelectronic electrodes (QOEs) that allow for rapid investigations of the properties and suitability of compounds for molecular electronic devices. In particular, we probed hexa‐peri‐hexabenzocoronene (HBC) as a model system for D6h‐symmetrical nanographenes, with porphyrins as QOEs attached to the periphery. We prepared selectively bis‐porphyrin‐functionalized HBCs with ortho‐, meta‐ and para‐substitution and studied their communication properties, in correlation to the geometrical alignment and size of the system, by electrochemistry and optical spectroscopy. Further insights into structure–property relationships were gained by DFT calculations and X‐ray diffraction analysis.

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

By Si‐Wen Yuan, Hui Han, Yan‐Lin Li, Xueli Wu, Xiaoguang Bao, Zheng‐Yang Gu, Ji‐Bao Xia from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

No directing: A novel rhodium‐catalyzed three‐component reaction has been developed to synthesize amides from readily available organic azides, carbon monoxide, and (hetero)arenes, and proceeds by direct C−H functionalization via nitrene intermediates. Neither directing groups on the arenes nor additives are needed in this reaction. Abstract Amide bond formation is one of the most important reactions in organic chemistry because of the widespread presence of amides in pharmaceuticals and biologically active compounds. Existing methods for amides synthesis are reaching their inherent limits. Described herein is a novel rhodium‐catalyzed three‐component reaction to synthesize amides from organic azides, carbon monoxide, and (hetero)arenes via nitrene‐intermediates and direct C−H functionalization. Notably, the reaction proceeds in an intermolecular fashion with N2 as the only by‐product, and either directing groups nor additives are required. The computational and mechanistic studies show that the amides are formed via a key Rh‐nitrene intermediate.

A Biomimetic Coordination Nanoplatform for Controlled Encapsulation and Delivery of Drug–Gene Combinations

By Bei Liu, Feng Hu, Jingfang Zhang, Congli Wang, Lele Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Inspired by natural biomineralization, a biomimetic nanoplatform was developed for delivery of drug–gene combinations. The nanoparticles possess uniform size, ultra‐high drug loading efficiency and capacities, and precisely adjustable ratios of two therapeutic agents, thus allowing synergistic inhibition of tumor growth through a combination of gene therapy and chemotherapy. Abstract Inspired by natural biomineralization processes, a simple and universal strategy is introduced to construct a biomimetic nanoplatform for systemic codelivery of a nucleic acid therapeutic (G3139) and a chemotherapeutic drug doxorubicin (DOX). This codelivery system was synthesized through one‐pot supramolecular self‐assembly of G3139, DOX, and FeII ions through multiple coordination interactions, followed by an adapted surface mineralization with metal–organic frameworks. The resulting core–shell nanoparticles have uniform size, well‐defined nanosphere structure, robust colloidal stability, ultrahigh drug loading efficiency and capacity, and precisely adjustable ratios of two therapeutic agents. The system can efficiently accumulate in the tumor, allowing for sensitive MRI detection and synergistical inhibition of tumor growth without apparent systemic toxicity.

Molecular Heterostructures of Covalent Triazine Frameworks for Enhanced Photocatalytic Hydrogen Production

By Wei Huang, Qing He, Yongpan Hu, Yanguang Li from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Happily separated: Molecular heterostructures of covalent triazine frameworks were constructed by sequential polymerization to facilitate charge‐carrier separation and photocatalytic H2 evolution (see picture; TEOA=triethanolamine). The selective incorporation of electron‐withdrawing benzothiadiazole and electron‐donating thiophene moieties led to a remarkable H2 evolution rate of 6.6 mmol g−1 h−1 under visible‐light irradiation for the optimal hybrid. Abstract Conjugated polymers have emerged as promising candidates for photocatalytic H2 production owing to their structural designability and functional diversity. However, the fast recombination of photoexcited electrons and holes limits their H2 production rates. We have now designed molecular heterostructures of covalent triazine frameworks to facilitate charge‐carrier separation and promote photocatalytic H2 production. Benzothiadiazole and thiophene moieties were selectively incorporated into the covalent triazine frameworks as electron‐withdrawing and electron‐donating units, respectively, by a sequential polymerization strategy. The resulting hybrids exhibited much improved charge‐carrier‐separation efficiency as evidenced by photophysical and electrochemical characterization. An H2 evolution rate of 6.6 mmol g−1 h−1 was measured for the optimal sample under visible‐light irradiation (λ>420 nm), which is far superior to that of most reported conjugated‐polymer photocatalysts.

Size‐Independent Fast Ion Intercalation in Two‐Dimensional Titania Nanosheets for Alkali‐Metal‐Ion Batteries

By Jinlin Yang, Xu Xiao, Wenbin Gong, Liang Zhao, Guohui Li, Kun Jiang, Renzhi Ma, Mark H. Rummeli, Feng Li, Takayoshi Sasaki, Fengxia Geng from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Any old ion: By regulating the interlayer structure of titania sheets, fast ion intercalations in non‐aqueous electrolyte can be achieved not only for small lithium ions but also for large‐radius sodium and potassium ions, even with 80‐μm‐thick electrodes. Abstract Compared to lithium ions, the fast redox intercalation of large‐radius sodium or potassium ions into a solid lattice in non‐aqueous electrolytes is an elusive goal. Herein, by regulating the interlayer structure of stacked titania sheets through weakened layer‐to‐layer interactions and a robustly pillared gallery space, the two‐dimensional channel between neighboring sheets was completely open to guest intercalation, allowing fast intercalation that was practically irrespective of the carrier‐ion sizes. Regardless of employing regular Li or large‐radius Na and K ions, the material manifested zero strain‐like behavior with no significant change in both host structure and interlayer space, enabling comparable capacities for all tested ions along with excellent rate behaviors and extraordinarily long lifetimes, even with 80‐μm‐thick electrodes. The result highlights the importance of interlayer structural features for unlocking the electrochemical activity of a layered material.

A Catalase‐Like Metal‐Organic Framework Nanohybrid for O2‐Evolving Synergistic Chemoradiotherapy

By Zhimei He, Xiaolin Huang, Chen Wang, Xiangli Li, Yijing Liu, Zijian Zhou, Sheng Wang, Fuwu Zhang, Zhantong Wang, Orit Jacobson, Jun‐Jie Zhu, Guocan Yu, Yunlu Dai, Xiaoyuan Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A catalase‐like nanohybrid based on AuNPs/gold(III) porphyrinic metal‐organic frameworks is fabricated for O2 self‐supported chemoradiotherapy. Such an all‐in‐one nanohybrid holds advantages of modulating tumor hypoxia, amplifying radiation effect, regulating drug release and combining chemotherapy with radiotherapy, which will be a paradigm in O2‐elevated radiochemotherapy that offers a novel strategy in multimodal cancer therapy. Abstract Tumor hypoxia, the “Achilles’ heel” of current cancer therapies, is indispensable to drug resistance and poor therapeutic outcomes especially for radiotherapy. Here we propose an in situ catalytic oxygenation strategy in tumor using porphyrinic metal‐organic framework (MOF)‐gold nanoparticles (AuNPs) nanohybrid as a therapeutic platform to achieve O2‐evolving chemoradiotherapy. The AuNPs decorated on the surface of MOF effectively stabilize the nanocomposite and serve as radiosensitizers, whereas the MOF scaffold acts as a container to encapsulate chemotherapeutic drug doxorubicin. In vitro and in vivo studies verify that the catalase‐like nanohybrid significantly enhances the radiotherapy effect, alleviating tumor hypoxia and achieving synergistic anticancer efficacy. This hybrid nanomaterial remarkably suppresses the tumor growth with minimized systemic toxicity, opening new horizons for the next generation of theranostic nanomedicines.

Synthesis of Hypervalent Iodine(III) Reagents Containing a Transferable (Diarylmethylene)amino Group and Their Use in the Oxidative Amination of Silyl Ketene Acetals

By Kensuke Kiyokawa, Daichi Okumatsu, Satoshi Minakata from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Into hyperspace: Hypervalent iodine reagents containing a transferable nitrogen functional group derived from benzophenone imine derivatives were synthesized. These reagents can be readily prepared and stored as a bench‐stable solid. They were successfully used in the transition‐metal‐free oxidative amination of silyl ketene acetals to afford the corresponding α‐amino esters, the benzophenone imine moieties of which could be easily hydrolyzed to form primary amines. Abstract The preparation of some hypervalent iodine reagents containing a transferable amino group derived from benzophenone imine derivatives is reported. The reagents can be readily prepared and stored as a bench‐stable solid, and were successfully used in the transition‐metal‐free oxidative amination of silyl ketene acetals to afford the corresponding α‐amino esters, the benzophenone imine moieties of which could be easily hydrolyzed, thereby leading to the formation of primary amines.

Efficient Kinetic Resolution of Sulfur‐Stereogenic Sulfoximines by Exploiting CpXRhIII‐Catalyzed C−H Functionalization

By Marcus Brauns, Nicolai Cramer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Choosing sides: An efficient method to access chiral sulfoximines through a C−H functionalization based kinetic resolution is disclosed. Together, phthaloyl phenylalanine and a CpxRhIII complex participate in the selective C−H activation of just one of the two sulfoximine enantiomers and its reaction with diazo compounds to give benzothiazines. Excellent enantioselectivity values are obtained for both enantiomers, resulting in s‐values of up to >200. Abstract Chiral sulfoximines with stereogenic sulfur atoms are promising motifs in drug discovery. We report an efficient method to access chiral sulfoximines through a C−H functionalization based kinetic resolution. A rhodium(III) complex equipped with a chiral Cpx ligand selectively participates in conjunction with phthaloyl phenylalanine in the C−H activation of just one of the two sulfoximine enantiomers. The intermediate reacts with various diazo compounds, providing access to chiral 1,2‐benzothiazines with synthetically valuable substitution patterns. Both sulfoximines and 1,2‐benzothiazines were obtained in high yields and excellent enantioselectivity, with s‐values of up to 200. The utility of the method is illustrated by the synthesis of the key intermediates of two pharmacologically relevant kinase inhibitors.

A Nickel(II) Nitrite Based Molecular Perovskite Ferroelectric

By Yu‐An Xiong, Tai‐Ting Sha, Qiang Pan, Xian‐Jiang Song, Shu‐Rong Miao, Zheng‐Yin Jing, Zi‐Jie Feng, Yu‐Meng You, Ren‐Gen Xiong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Through a combination of quasi‐spherical shape, hydrogen bonding functionality, and H/F substitution, a molecular perovskite ferroelectric was successfully synthesized, [FMeTP][Ni(NO2)3] (FMeTP=N‐fluoromethyl tropine). As an unprecedented nitrite‐based molecular ferroelectric, it undergoes a ferroelectric phase transition at 400 K with an Aizu notation of 6/mmmFm, showing multiaxial characteristics. Abstract The X‐site ion in organic–inorganic hybrid ABX3 perovskites (OHPs) varies from halide ion to bridging linkers like HCOO−, N3−, NO2−, and CN−. However, no nitrite‐based OHP ferroelectrics have been reported so far. Now, based on non‐ferroelectric [(CH3)4N][Ni(NO2)3], through the combined methodologies of quasi‐spherical shape, hydrogen bonding functionality, and H/F substitution, we have successfully synthesized an OHP ferroelectric, [FMeTP][Ni(NO2)3] (FMeTP=N‐fluoromethyl tropine). As an unprecedented nitrite‐based OHP ferroelectric, the well‐designed [FMeTP][Ni(NO2)3] undergoes the ferroelectric phase transition at 400 K with an Aizu notation of 6/mmmFm, showing multiaxial ferroelectric characteristics. This work is a great step towards not only enriching the molecular ferroelectric families but also accelerating the potential practical applications.

Synergy between Plasmonic and Electrocatalytic Activation of Methanol Oxidation on Palladium–Silver Alloy Nanotubes

By Lin Huang, Jiasui Zou, Jin‐Yu Ye, Zhi‐You Zhou, Zhang Lin, Xiongwu Kang, Prashant K. Jain, Shaowei Chen from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Plasmonic excitation of a palladium‐silver alloy nanotube electrocatalyst results in the enhancement of methanol oxidation reaction. Although photothermal heating of the electrochemical interface contributes to the enhancement, the primary mechanism involves hot holes generated by plasmonic excitation. Hot holes drive a methanol oxidation pathway that is complementary to electro‐oxidation. Abstract Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel‐cell‐relevant reaction. The electrocatalyst consists of PdxAg alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible‐light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the PdxAg NTs.

Non‐Thermoresponsive Decanano‐sized Domains in Thermoresponsive Hydrogel Microspheres Revealed by Temperature‐Controlled High‐Speed Atomic Force Microscopy

By Yuichiro Nishizawa, Shusuke Matsui, Kenji Urayama, Takuma Kureha, Mitsuhiro Shibayama, Takayuki Uchihashi, Daisuke Suzuki from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Decanano: By using temperature‐controlled high‐speed AFM, non‐thermoresponsive decanano‐sized domains were found to exist in temperature‐responsive microgels. A comparison to a series of microgels, which differ with respect to cross‐linking density, size, and polymerization techniques, suggested that this heterogeneous structure is characteristic for microgels obtained from precipitation polymerization reactions. This finding will be important for correlating the structures and functions of microgels. Abstract Despite the tremendous efforts devoted to the structural analysis of hydrogel microspheres (microgels), many details of their structures remain unclear. Reported in this study is that thermoresponsive poly(N‐isopropyl acrylamide) (pNIPAm)‐based microgels exhibit not only the widely accepted core–shell structures, but also inhomogeneous decanano‐sized non‐thermoresponsive spherical domains within their dense cores, which was revealed by temperature‐controlled high‐speed atomic force microscopy (TC‐HS‐AFM). Based on a series of experiments, it is concluded that the non‐thermoresponsive domains are characteristic for pNIPAm microgels synthesized by precipitation polymerization, and plausible structures for microgels prepared by other polymerization techniques are proposed.

Cryogenic Exfoliation of Non‐layered Magnesium into Two‐Dimensional Crystals

By Chen Zhang, Yingfeng Xu, Ping Lu, Chenyang Wei, Chenxi Zhu, Heliang Yao, Fangfang Xu, Jianlin Shi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Revealing the layers: Based on the identification of the cryogenic temperature‐induced specific inactivation of basal slip in a metallic Mg lattice, which results in cleavage anisotropy in response to the external mechanical stress, non‐layered magnesium with directionless metallic bonds could be physically exfoliated into 2D crystals at cryogenic temperature. Abstract Physical exfoliation of layered precursors is one of the most prevailing techniques to prepare two‐dimensional (2D) crystals, which, however, is considered to be intrinsically inapplicable to non‐layered bulks. Now, plane cleavage differentiation is identified in metallic magnesium at cryogenic temperature (CT), and a cryogenic exfoliation strategy of non‐layered magnesium into 2D crystals is developed. The cleavage anisotropy of the Mg lattice in response to the external mechanical stress originates from the CT‐induced specific inactivation of basal slip, which results in the basal cleavage perpendicular to c axis. The exfoliated novel 2D Mg crystals exhibit remarkable localized surface plasmon resonances, holding great promise for the applications in harvesting and converting solar energy. Beyond creating a new member for the burgeoning 2D family, this study may provide a useful tool for the physical exfoliations of various non‐layered materials.

Cross‐Peaks in Simple Two‐Dimensional NMR Experiments from Chemical Exchange of Transverse Magnetisation

By Christopher A. Waudby, Tom Frenkiel, John Christodoulou from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Tales of the unexpected: Chemical‐exchange‐induced cross‐peaks can arise in even the simplest two‐dimensional NMR experiments. These peaks originate from exchange of magnetisation during chemical shift evolution and coherence transfer periods and may be useful both as a qualitative indicator of exchange in routine experiments, and for quantitative characterisation of exchange kinetics by lineshape fitting. Abstract Two‐dimensional correlation measurements such as COSY, NOESY, HMQC, and HSQC experiments are central to small‐molecule and biomolecular NMR spectroscopy, and commonly form the basis of more complex experiments designed to study chemical exchange occurring during additional mixing periods. However, exchange occurring during chemical shift evolution periods can also influence the appearance of such spectra. While this is often exploited through one‐dimensional lineshape analysis (“dynamic NMR”), the analysis of exchange across multiple chemical shift evolution periods has received less attention. Here we report that chemical exchange‐induced cross‐peaks can arise in even the simplest two‐dimensional NMR experiments. These cross‐peaks can have highly distorted phases that contain rich information about the underlying exchange process. The quantitative analysis of such peaks, from a single 2D spectrum, can provide a highly accurate characterisation of underlying exchange processes.

Atomic‐Scale Observation of the Metal–Promoter Interaction in Rh‐Based Syngas‐Upgrading Catalysts

By Xing Huang, Detre Teschner, Maria Dimitrakopoulou, Alexey Fedorov, Benjamin Frank, Ralph Kraehnert, Frank Rosowski, Harry Kaiser, Stephan Schunk, Christiane Kuretschka, Robert Schlögl, Marc‐Georg Willinger, Annette Trunschke from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Atomic insights about the metal–promoter interaction and the roles of promoters (Mn, Fe) in Rh‐based catalysts for the conversion of syngas to ethanol are provided based on a careful aberration‐corrected high‐resolution transmission electron microscopy study. Abstract The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO2 utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO2 catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided.

Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts

By Evgeniya Vorobyeva, Edvin Fako, Zupeng Chen, Sean M. Collins, Duncan Johnstone, Paul A. Midgley, Roland Hauert, Olga V. Safonova, Gianvito Vilé, Núria López, Sharon Mitchell, Javier Pérez‐Ramírez from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

An atom apart: Exploiting the versatile coordination chemistry of carbon nitride to accommodate low‐nuclearity metal species allows the properties and catalytic performance of palladium atoms, dimers, and trimers, to be interrogated. The results show that in C−C coupling and alkyne semi‐hydrogenation reactions opposite requirements give the optimal atom economy. Abstract Controlling the structure sensitivity of catalyzed reactions over metals is central to developing atom‐efficient chemical processes. Approaching the minimum ensemble size, the properties enter a non‐scalable regime in which each atom counts. Almost all trends in this ultra‐small frontier derive from surface science approaches using model systems, because of both synthetic and analytical challenges. Exploiting the unique coordination chemistry of carbon nitride, we discriminate through experiments and simulations the interplay between the geometry, electronic structure, and reactivity of palladium atoms, dimers, and trimers. Catalytic tests evidence application‐dependent requirements of the active ensemble. In the semi‐hydrogenation of alkynes, the nuclearity primarily impacts activity, whereas the selectivity and stability are affected in Suzuki coupling. This powerful approach will provide practical insights into the design of heterogeneous catalysts comprising well‐defined numbers of atoms.

Alkyne gem‐Hydrogenation: Formation of Pianostool Ruthenium Carbene Complexes and Analysis of Their Chemical Character

By Tobias Biberger, Christopher P. Gordon, Markus Leutzsch, Sebastian Peil, Alexandre Guthertz, Christophe Copéret, Alois Fürstner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Portrayal: Less electron‐donating cyclopentadienyl (CpX) ligands lower the barrier for the perplexing gem‐hydrogenation of alkynes by [CpXRu] complexes and kinetically stabilize the resulting pianostool ruthenium carbenes. The chemical shift tensors extracted from solid state 13C NMR spectra draw a portrait of electrophilic carbenes of the Fischer‐type with a certain flavor reminiscent of Grubbs catalysts. Abstract Parahydrogen (p‐H2) induced polarization (PHIP) NMR spectroscopy showed that [CpXRu] complexes with greatly different electronic properties invariably engage propargyl alcohol derivatives into gem‐hydrogenation with formation of pianostool ruthenium carbenes; in so doing, less electron rich CpX rings lower the barriers, stabilize the resulting complexes and hence provide opportunities for harnessing genuine carbene reactivity. The chemical character of the resulting ruthenium complexes was studied by DFT‐assisted analysis of the chemical shift tensors determined by solid‐state 13C NMR spectroscopy. The combined experimental and computational data draw the portrait of a family of ruthenium carbenes that amalgamate purely electrophilic behavior with characteristics more befitting metathesis‐active Grubbs‐type catalysts.

Hydrogenative Cyclopropanation and Hydrogenative Metathesis

By Sebastian Peil, Alexandre Guthertz, Tobias Biberger, Alois Fürstner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Janus character: gem‐Hydrogenation of propargyl alcohol derivatives provides a conceptually novel entry into metal carbene complexes. Specifically, the use of [Cp*RuCl]4 as catalyst affords pianostool ruthenium carbenes that engage in either cyclopropanation or metathetic ring closure; the outcome of the reaction is largely dictated by the substitution pattern of the chosen olefinic trap. Abstract The unusual geminal hydrogenation of a propargyl alcohol derivative with [CpXRuCl] as the catalyst entails formation of pianostool ruthenium carbenes in the first place; these reactive intermediates can be intercepted with tethered alkenes to give either cyclopropanes or cyclic olefins as the result of a formal metathesis event. The course of the reaction is critically dependent on the substitution pattern of the alkene trap.

How Dihalogens Catalyze Michael Addition Reactions

By Trevor A. Hamlin, Israel Fernández, F. Matthias Bickelhaupt from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Pauli rules! The catalytic effect of dihalogen molecules on Michael addition reactions increases along the series: X2=F2

Transition‐Metal‐Free Deconstructive Lactamization of Piperidines

By Julio Romero‐Ibañez, Silvano Cruz‐Gregorio, Jacinto Sandoval‐Lira, Julio M. Hernández‐Pérez, Leticia Quintero, Fernando Sartillo‐Piscil from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Breaking down and building up: A new synthetic disconnection complementary to classical lactamization procedures is used to convert piperidines into pyrrolidinones in an unprecedented transition‐metal‐free reaction that can be conducted in one pot or in two steps. This selective oxidative ring contraction of N‐substituted piperidines should provide access to potentially bioactive compounds. Abstract One of the major challenges in organic synthesis is the activation or deconstructive functionalization of unreactive C(sp3)–C(sp3) bonds, which requires using transition or precious metal catalysts. We present here an alternative: the deconstructive lactamization of piperidines without using transition metal catalysts. To this end, we use 3‐alkoxyamino‐2‐piperidones, which were prepared from piperidines through a dual C(sp3)–H oxidation, as transitory intermediates. Experimental and theoretical studies confirm that this unprecedented lactamization occurs in a tandem manner involving an oxidative deamination of 3‐alkoxyamino‐2‐piperidones to 3‐keto‐2‐piperidones, followed by a regioselective Baeyer–Villiger oxidation to give N‐carboxyanhydride intermediates, which finally undergo a spontaneous and concerted decarboxylative intramolecular translactamization.

Gold Difluorocarbenoid Complexes: Spectroscopic and Chemical Profiling

By Alexander G. Tskhovrebov, Julia B. Lingnau, Alois Fürstner from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

(Dis)Integrate: Gold carbenoids generated by Lewis‐acid‐mediated α‐fluoride elimination from LAuCF3 are so deprived in electron density that they even retain “weakly coordinating” counteranions (triflate, triflimide); they disintegrate, however, on reaction with (E)‐ or (Z)‐stilbene to give a carbenium intermediate that accounts for the observed downstream chemistry. Abstract Gold carbenes of the general type [LAu=CR2]+ are sufficiently long‐lived for spectroscopic inspection only if the substituents compensate for the largely missing stabilization of the carbene center by the [LAu]+ fragment. π‐Donation by two fluorine substituents (R=F) is insufficient; rather, difluorocarbene complexes are so deprived in electron density that they sequester even “weakly coordinating” anions such as triflate or triflimide. This particular bonding situation translates into unmistakable carbenium ion chemistry upon reaction with stilbene as a model substrate.

Motion Control of Polymeric Nanomotors Based on Host–Guest Interactions

By Yingfeng Tu, Fei Peng, Josje M. Heuvelmans, Shuwen Liu, Roeland J. M. Nolte, Daniela A. Wilson from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Azobenzene is introduced to facilitate the binding of β‐cyclodextrins with high steric hindrance to nanomotors. This results in lowering diffusion of hydrogen peroxide and decreased motion. Upon light irradiation, formed cis‐azobenzene leads to the detachment of β‐cyclodextrins due to their inability to form complexes with the cis‐isomer. As a result, the speed of the nanomotors increases accordingly. Abstract Controlling the motion of artificial self‐propelled micro‐ and nanomotors independent of the fuel concentration is still a great challenge. Here we describe the first report of speed manipulation of supramolecular nanomotors via blue light‐responsive valves, which can regulate the access of hydrogen peroxide fuel into the motors. Light‐sensitive polymeric nanomotors are built up via the self‐assembly of functional block copolymers, followed by bowl‐shaped stomatocyte formation and incorporation of platinum nanoparticles. Subsequent addition of β‐cyclodextrin (β‐CD) leads to the formation of inclusion complexes with the trans‐isomers of the azobenzene derivatives grafted from the surfaces of the stomatocytes. β‐CDs attachment decreases the diffusion rate of hydrogen peroxide into the cavities of the motors because of partly blocking of the openings of the stomatocyte. This results in a lowering of the speed of the nanomotors. Upon blue light irradiation, the trans‐azobenzene moieties isomerize to the cis‐form, which lead to the detachment of the β‐CDs due to their inability to form complexes with the cis‐isomer. As a result, the speed of the nanomotors increases accordingly. Such a conformational change provides us with the unique possibility to control the speed of the supramolecular nanomotor via light‐responsive host–guest complexation. We envision that such artificial responsive nano‐systems with controlled motion could have potential applications in drug delivery.

Excitation Wavelength Dependent Fluorescence of an ESIPT Triazole Derivative for Amine Sensing and Anti‐Counterfeiting Applications

By Yujian Zhang, Heyi Yang, Huili Ma, Gaofeng Bian, Qiguang Zang, Jingwei Sun, Cheng Zhang, Zhongfu An, Wai‐Yeung Wong from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Molecular sleuth: Excitation wavelength dependent fluorescence behavior was achieved in an excited state intramolecular proton transfer (ESIPT) active chromophore by manipulating the relaxation pathways of the excited states. Moreover, the optical applications of this material, including in amine sensing and anti‐counterfeiting, have been demonstrated. Abstract Excitation wavelength dependent (Ex‐De) emission materials have potential applications in anti‐counterfeiting labels and bioimaging. Nevertheless, few purely organic chromophores are used in these areas. In this study, multiple excited states were incorporated into a molecule that was excited state intramolecular proton transfer (ESIPT) active, with the goal of manipulating the relaxation pathways of the excited states. The triazole derivative exhibits Ex‐De photoluminescence (PL), and the maximum PL wavelength is located at 526 nm and 593 nm under a series of excitation wavelengths. Spectral identification indicates that the excimer and ESIPT processes are responsible for the green (526 nm) and orange (593 nm) fluorescence, respectively. Importantly, the quick response code and test strip prepared with this triazole derivative can be used for anti‐counterfeiting and food spoilage detection applications, respectively. This research opens the door for developing novel Ex‐De materials for anti‐counterfeiting purposes.

Catechol Oxidase versus Tyrosinase Classification Revisited by Site‐Directed Mutagenesis Studies

By Sarah M. Prexler, Martin Frassek, Bruno M. Moerschbacher, Mareike E. Dirks‐Hofmeister from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Site‐directed mutagenesis of phylogenetically diverse dandelion polyphenol oxidases (PPOs) disagrees with the crystal‐structure‐based hypothesis that plant PPOs are exclusively diphenolases (catechol oxidases, COs). Plant PPOs of phylogenetic group 2 are COs, whereas plant PPOs of phylogenetic group 1 additionally show monophenolase activity and, therefore, are actually tyrosinases (TYRs). Abstract Catechol oxidases (COs) and tyrosinases (TYRs) are both polyphenol oxidases (PPOs) that catalyze the oxidation of ortho‐diphenols to the corresponding quinones. By the official classification, only TYRs can also catalyze the hydroxylation of monophenols to ortho‐diphenols. Researchers have been trying to find the molecular reason for the mono‐/diphenolase specificity for decades. However, the hypotheses for the lack of monophenolase activity of plant COs are only based on crystal structures so far. To test these hypotheses, we performed site‐directed mutagenesis studies and phylogenetic analyses with dandelion PPOs offering high phylogenetic diversity, the results of which refute the structure‐based hypotheses. While plant PPOs of phylogenetic group 2 solely exhibit diphenolase activity, plant PPOs of phylogenetic group 1 unexpectedly also show monophenolase activity. This finding sheds new light upon the molecular basis for mono‐/diphenol substrate specificity and challenges the current practice of generally naming plant PPOs as COs.

A 1,3,2‐Diazaphospholene‐Catalyzed Reductive Claisen Rearrangement

By John H. Reed, Pavel A. Donets, Solène Miaskiewicz, Nicolai Cramer from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A DAP hand at rearrangement: 1,3,2‐Diazaphospholenes (DAPs) are efficient catalysts for ambient‐temperature reductive Claisen rearrangements. This method tolerates a wide variety of functional groups and is enantiospecific for substrates with existing stereogenic centers. The diastereoselectivity can be controlled by the choice of solvent and DAP catalyst. Abstract 1,3,2‐Diazaphospholenes (DAPs) are an emerging class of organic hydrides. In this work, we exploited them as efficient catalysts for very mild reductive Claisen rearrangements. The method is tolerant towards a wide variety of functional groups and operates at ambient temperature. Besides being enantiospecific for substrates with existing stereogenic centers, the diastereoselectivity can be switched by varying solvents and DAP catalysts. The reaction kinetics show direct rearrangements of O‐bound phospholene enolates and provide a proof‐of‐principle for catalytic enantioselective reactions.

How Many Phosphoric Acid Units Are Required to Ensure Uniform Occlusion of Sterically Stabilized Nanoparticles within Calcite?

By Marcel Douverne, Yin Ning, Aikaterini Tatani, Fiona C. Meldrum, Steven P. Armes from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Judicious design of polymeric nanoparticles comprising tunable anionic phosphate units made it possible to determine the number of anionic units required to achieve uniform occlusion of sterically stabilized nanoparticles within calcite crystals. This study provides insight into the synthesis of novel hybrid nanocomposites. Abstract Polymerization‐induced self‐assembly (PISA) mediated by reversible addition–fragmentation chain transfer (RAFT) polymerization offers a platform technology for the efficient and versatile synthesis of well‐defined sterically stabilized block copolymer nanoparticles. Herein we synthesize a series of such nanoparticles with tunable anionic charge density within the stabilizer chains, which are prepared via statistical copolymerization of anionic 2‐(phosphonooxy)ethyl methacrylate (P) with non‐ionic glycerol monomethacrylate (G). Systematic variation of the P/G molar ratio enables elucidation of the minimum number of phosphate groups per copolymer chain required to promote nanoparticle occlusion within a model inorganic crystal (calcite). Moreover, the extent of nanoparticle occlusion correlates strongly with the phosphate content of the steric stabilizer chains. This study is the first to examine the effect of systemically varying the anionic charge density of nanoparticles on their occlusion efficiency and sheds new light on maximizing the loading of guest nanoparticles within calcite host crystals.

Plasmonic Nanocavities Enable Self‐Induced Electrostatic Catalysis

By Clàudia Climent, Javier Galego, Francisco J. Garcia‐Vidal, Johannes Feist from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Self‐control: Introducing a molecule into a plasmonic nanocavity allows self‐induced electrostatic catalysis to emerge. This approach is also exploited to modify the spin‐crossover transition temperature of metal complexes, the prime example of molecular switches, paving the way towards single‐molecule chemical control. Abstract The potential of strong interactions between light and matter remains to be further explored within a chemical context. Towards this end herein we study the electromagnetic interaction between molecules and plasmonic nanocavities. By means of electronic structure calculations, we show that self‐induced catalysis emerges without any external stimuli through the interaction of the molecular permanent and fluctuating dipole moments with the plasmonic cavity modes. We also exploit this scheme to modify the transition temperature T1/2 of spin‐crossover complexes as an example of how strong light–matter interactions can ultimately be used to control a materials responses.

Oxygen Evolution Electrocatalysis of a Single MOF‐Derived Composite Nanoparticle on the Tip of a Nanoelectrode

By Harshitha Barike Aiyappa, Patrick Wilde, Thomas Quast, Justus Masa, Corina Andronescu, Yen‐Ting Chen, Martin Muhler, Roland A. Fischer, Wolfgang Schuhmann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Electrocatalysis at the tip: A unique “particle on a stick” approach is employed to extract the intrinsic catalytic activity of a single particle of a ZIF‐67‐derived Co/N‐doped carbon nanocomposite under industrially relevant OER conditions. TEM analyses of the nanoassembly offers insight into structural transformations within the nanoparticle during pyrolytic activation and after electrocatalytic activity measurement at extremely high oxygen evolution rates. Abstract Determination of the intrinsic electrocatalytic activity of nanomaterials by means of macroelectrode techniques is compromised by ensemble and film effects. Here, a unique “particle on a stick” approach is used to grow a single metal–organic framework (MOF; ZIF‐67) nanoparticle on a nanoelectrode surface which is pyrolyzed to generate a cobalt/nitrogen‐doped carbon (CoN/C) composite nanoparticle that exhibits very high catalytic activity towards the oxygen evolution reaction (OER) with a current density of up to 230 mA cm−2 at 1.77 V (vs. RHE), and a high turnover frequency (TOF) of 29.7 s−1 at 540 mV overpotential. Identical location transmission electron microscopy (IL‐TEM) analysis substantiates the “self‐sacrificial” template nature of the MOF, while post‐electrocatalysis studies reveal agglomeration of Co centers within the CoN/C composite during the OER. “Single‐entity” electrochemical analysis allows for deriving the intrinsic electrocatalytic activity and furnishes insight into the transient behavior of the electrocatalyst under reaction conditions.

Hydrodifluoromethylation of Alkenes with Difluoroacetic Acid

By Claudio F. Meyer, Sandrine M. Hell, Antonio Misale, Andrés A. Trabanco, Véronique Gouverneur from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Terminal alkenes undergo net hydrodifluoromethylation in the presence of an excess of difluoroacetic acid and phenyliodine(III) diacetate in tetrahydrofuran under visible‐light irradiation (λ=450 nm). This highly practical procedure telescopes access to biorelevant building blocks that would require multiple synthetic steps applying deoxyfluorination chemistry. Abstract A facile method for the regioselective hydrodifluoromethylation of alkenes is reported using difluoroacetic acid and phenyliodine(III) diacetate in tetrahydrofuran under visible‐light activation. This metal‐free approach stands out as it uses inexpensive reagents, does not require a photocatalyst, and displays broad functional group tolerance. The procedure is also operationally simple and scalable, and provides access in one step to high‐value building blocks for application in medicinal chemistry.

An All‐Inorganic Colloidal Nanocrystal Flexible Polarizer

By Simin Zhang, Wenxiong Shi, Timothy D. Siegler, Xiaoqing Gao, Feng Ge, Brian A. Korgel, Yan He, Shuzhou Li, Xun Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A strong likeness: Inorganic sub‐1 nm nanowires (NWs) are similar to linear polymers from a dimension viewpoint. By using sub‐1 nm GdOOH nanowires as building blocks, thin films with anisotropic, transparent, flexible and stable (ATFS) features showing great potential for optical applications were fabricated. Abstract Inorganic single crystals with anisotropic structures usually suffer from high brittleness and stiffness. Flexible polymers are used to replace inorganic crystals, but the hot‐stretching‐induced orientation process is tedious, and oriented molecular chains tend to revert to random coils during aging. To overcome these obstacles and using the similarities between sub‐1 nm nanowires (NWs) and linear polymers, we successfully fabricated anisotropic, transparent, flexible, and stable (ATFS) NW films with great potential for optical applications through a wet‐spinning method. The NW films show birefringence, and their birefractive index is higher than that of many polymers. They also showed polarized absorption of UV light and anisotropic scattering of visible light. The integrated films composed of NWs and quantum dots showed good fluorescence polarization. The tedious synthesis of quantum rods and fabrication of oriented polymer films can thus be avoided.

Photoenzymatic Catalysis Enables Radical‐Mediated Ketone Reduction in Ene‐Reductases

By Braddock A. Sandoval, Sarah I. Kurtoic, Megan M. Chung, Kyle F. Biegasiewicz, Todd K. Hyster from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Flavin misbehavin′: Merging photocatalysis with biocatalysis leads to new chemical reactivity for flavin‐dependent ene‐reductases. Mechanistic studies support a mechanism in which enantioenriched alcohols are produced by hydrogen‐atom transfer from flavin to the ketyl radical. Abstract Flavin‐dependent ene‐reductases (EREDs) are known to stereoselectively reduce activated alkenes, but are inactive toward carbonyls. Demonstrated here is that in the presence of photoredox catalysts, these enzymes will reduce aromatic ketones. Mechanistic experiments suggest this reaction proceeds through ketyl radical formation, a reaction pathway that is distinct from the native hydride‐transfer mechanism. Furthermore, this reactivity is accessible without modification of either the enzyme or cofactors, allowing both native and non‐natural mechanisms to occur simultaneously. Based on control experiments, we hypothesize that binding to the enzyme active site attenuates the reduction potential of the substrate, enabling single‐electron reduction. This reactivity highlights opportunities to access new catalytic manifolds by merging photoredox catalysis with biocatalysis.

The Glycosylation Mechanisms of 6,3‐Uronic Acid Lactones

By Hidde Elferink, Rens A. Mensink, Wilke W. A. Castelijns, Oscar Jansen, Jeroen P. J. Bruekers, Jonathan Martens, Jos Oomens, Anouk M. Rijs, Thomas J. Boltje from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A β‐selective mannosylation donor, based on C‐4 acetyl mannuronic acid 6,3‐lactone donors, was developed and its glycosylation mechanism was elucidated using an integrated approach combining infrared ion spectroscopy with quantum‐chemical calculations and variable‐temperature NMR spectroscopy. Abstract Uronic acids are important constituents of polysaccharides found on the cell membranes of different organisms. To prepare uronic‐acid‐containing oligosaccharides, uronic acid 6,3‐lactones can be employed as they display a fixed conformation and a unique reactivity and stereoselectivity. Herein, we report a highly β‐selective and efficient mannosyl donor based on C‐4 acetyl mannuronic acid 6,3‐lactone donors. The mechanism of glycosylation is established using a combination of techniques, including infrared ion spectroscopy combined with quantum‐chemical calculations and variable‐temperature nuclear magnetic resonance (VT NMR) spectroscopy. The role of these intermediates in glycosylation is assayed by varying the activation protocol and acceptor nucleophilicity. The observed trends are analogous to the well‐studied 4,6‐benzylidene glycosides and may be used to guide the development of next‐generation stereoselective glycosyl donors.

Chemical Bonding in Polarised Push–Pull Ethylenes

By Hikaru Yanai, Takumi Suzuki, Florian Kleemiss, Haruhiko Fukaya, Yasuo Dobashi, Lorraine A. Malaspina, Simon Grabowsky, Takashi Matsumoto from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Twist and shout: 1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. In both compounds, the bonding properties of the central C−C bonds were analysed using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). Abstract 1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). In the twisted compound, a dominant contribution of the charge‐separated resonance structure was revealed. On the contrary, the nearly planar compound still showed π‐bonding character, however, with a considerable contribution of the charge‐separated resonance structure.

Rapid Detection of Exosomal MicroRNAs Using Virus‐Mimicking Fusogenic Vesicles

By Xihui Gao, Sha Li, Fei Ding, Hongjia Fan, Leilei Shi, Lijuan Zhu, Jing Li, Jing Feng, Xinyuan Zhu, Chuan Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A virus‐mimicking fusogenic vesicle (Vir‐FV) is developed for the rapid in situ detection of exosomal miRNAs. Vir‐FVs can target the sialic acid receptors on exosomes, inducing efficient fusion between Vir‐FVs and exosomes. Molecular beacons encapsulated in Vir‐FVs can specifically detect target exosomal miRNAs, providing a promising strategy for cancer diagnosis and treatment monitoring. Abstract Exosomal microRNAs (miRNAs) are important biomarkers for clinical diagnosis and disease treatment monitoring. However, most approaches for exosomal miRNA detection are time‐consuming, laborious, and expensive. Herein, we report a virus‐mimicking fusogenic vesicle (Vir‐FV) that enables rapid, efficient, and high‐throughput detection of exosomal miRNAs within 2 h. Fusogenic proteins on Vir‐FVs can specifically target the sialic‐acid‐containing receptors on exosomes, inducing efficient fusion of Vir‐FVs and exosomes. Upon vesicle content mixing, the molecular beacons encapsulated in Vir‐FVs specifically hybridize with the target miRNAs in the exosomes, generating fluorescence. Combined with flow cytometry, the Vir‐FVs can not only detect exosomal miRNAs but also distinguish tumor exosomes from normal exosomes by sensing the tumor‐related miRNAs, paving the way towards the rapid and efficient detection of exosomal miRNAs for diagnosis and prognosis prediction of diseases.

Cobalt‐Catalyzed Enantioselective Hydroboration/Cyclization of 1,7‐Enynes: Asymmetric Synthesis of Chiral Quinolinones Containing Quaternary Stereogenic Centers

By Caizhi Wu, Jiayu Liao, Shaozhong Ge from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Give me a ring: A highly enantioselective cobalt‐catalyzed hydroboration/cyclization of 1,7‐enynes with pinacolborane (HBpin) using a catalyst generated from Co(acac)2 and (S,S)‐Ph‐BPE was developed. This method provides a general approach to access a series of chiral quinoline derivatives containing quaternary stereocenters. Abstract An asymmetric cobalt‐catalyzed hydroboration/cyclization of 1,7‐enynes to synthesize chiral six‐membered N‐heterocyclic compounds was developed. A variety of aniline‐tethered 1,7‐enynes react with pinacolborane to afford the corresponding chiral boryl‐functionalized quinoline derivatives in high yields with high enantioselectivity. This cobalt‐catalyzed asymmetric cyclization of 1,7‐enyens provides a general approach to access a series of chiral quinoline derivatives containing quaternary stereocenters.

Transformation of a [4+6] Salicylbisimine Cage to Chemically Robust Amide Cages

By Avinash S. Bhat, Sven M. Elbert, Wen‐Shan Zhang, Frank Rominger, Michael Dieckmann, Rasmus R. Schröder, Michael Mastalerz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Stay in shape: A large shape‐persistent [4+6] amide cage has been synthesized in 21 % yield by transforming an imine cage in just two steps, using a twelvefold Pinnick oxidation as the key step. The amide cage is chemically robust in both acidic and basic media over a large pH range from −1 to 14.5. This chemical robustness allowed post‐functionalization under harsh conditions, such as a twelvefold bromination or nitration. Abstract In recent years, interest in shape‐persistent organic cage compounds has steadily increased, not least because dynamic covalent bond formation enables such structures to be made in high to excellent yields. One often used type of dynamic bond formation is the generation of an imine bond from an aldehyde and an amine. Although the reversibility of the imine bond formation is advantageous for high yields, it is disadvantageous for the chemical stability of the compounds. Amide bonds are, in contrast to imine bonds much more robust. Shape‐persistent amide cages have so far been made by irreversible amide bond formations in multiple steps, very often accompanied by low yields. Here, we present an approach to shape‐persistent amide cages by exploiting a high‐yielding reversible cage formation in the first step, and a Pinnick oxidation as a key step to access the amide cages in just three steps. These chemically robust amide cages can be further transformed by bromination or nitration to allow post‐functionalization in high yields. The impact of the substituents on the gas sorption behavior was also investigated.

A Yolk–Shell Structured Silicon Anode with Superior Conductivity and High Tap Density for Full Lithium‐Ion Batteries

By Lei Zhang, Chengrui Wang, Yuhai Dou, Ningyan Cheng, Dandan Cui, Yi Du, Porun Liu, Mohammad Al‐Mamun, Shanqing Zhang, Huijun Zhao from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Improving the conductivity and tap density of yolk–shell‐structured Si/C anodes for lithium‐ion batteries is possible by introducing Fe2O3 nanoparticles (NPs) embedded in carbon nanotube (CNT) networks into the void space between the Si yolks and the outer double shell. A full cell can achieve a high reversible capacity of 260 mAh g−1 after 300 cycles. Abstract The poor cycling stability resulting from the large volume expansion caused by lithiation is a critical issue for Si‐based anodes. Herein, we report for the first time of a new yolk–shell structured high tap density composite made of a carbon‐coated rigid SiO2 outer shell to confine multiple Si NPs (yolks) and carbon nanotubes (CNTs) with embedded Fe2O3 nanoparticles (NPs). The high tap density achieved and superior conductivity can be attributed to the efficiently utilised inner void containing multiple Si yolks, Fe2O3 NPs, and CNTs Li+ storage materials, and the bridged spaces between the inner Si yolks and outer shell through a conductive CNTs “highway”. Half cells can achieve a high area capacity of 3.6 mAh cm−2 and 95 % reversible capacity retention after 450 cycles. The full cell constructed using a Li‐rich Li2V2O5 cathode can achieve a high reversible capacity of 260 mAh g−1 after 300 cycles.

Reaction Environment Modification in Covalent Organic Frameworks for Catalytic Performance Enhancement

By Qi Sun, Yongquan Tang, Briana Aguila, Sai Wang, Feng‐Shou Xiao, Praveen K. Thallapally, Abdullah M. Al‐Enizi, Ayman Nafady, Shengqian Ma from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Creating a solvation environment: The catalytic performance of sulfonic acid groups in covalent organic frameworks (COFs) can be greatly amplified by the introduction of polymeric solvent analogues, which create desired solvation environments through hydrogen‐bonding interactions. Improved activity and selectivity was demonstrated by the COF‐catalyzed dehydration of fructose to produce 5‐hydroxymethylfurfural. Abstract Herein, we show how the spatial environment in the functional pores of covalent organic frameworks (COFs) can be manipulated in order to exert control in catalysis. The underlying mechanism of this strategy relies on the placement of linear polymers in the pore channels that are anchored with catalytic species, analogous to outer‐sphere residue cooperativity within the active sites of enzymes. This approach benefits from the flexibility and enriched concentration of the functional moieties on the linear polymers, enabling the desired reaction environment in close proximity to the active sites, thereby impacting the reaction outcomes. Specifically, in the representative dehydration of fructose to produce 5‐hydroxymethylfurfural, dramatic activity and selectivity improvements have been achieved for the active center of sulfonic acid groups in COFs after encapsulation of polymeric solvent analogues 1‐methyl‐2‐pyrrolidinone and ionic liquid.

Oxygen Evolution Reaction at Carbon Edge Sites: Investigation of Activity Evolution and Structure–Function Relationships with Polycyclic Aromatic Hydrocarbons

By Yangming Lin, Qing Lu, Feihong Song, Linhui Yu, Anna K. Mechler, Robert Schlögl, Saskia Heumann from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

The active roles of the armchair and zigzag edge sites of carbon materials in the electrochemical oxygen evolution reaction (OER) have been investigated by using polycyclic aromatic hydrocarbons with designated configurations as active edge probes. Zigzag motifs play a more positive role in the OER. The underlying structure–function relationships could be further established by extending the exposed zigzag units. Abstract The abundance of available surface chemical information and edge structures of carbon materials have attracted tremendous interest in catalysis. For the oxygen evolution reaction (OER), the edge effects of carbon materials have rarely been studied in detail because of the complexity of various coexisting edge configurations and the controversy between carbon corrosion and carbon catalysis. Herein, the exact roles of common carbon active edge sites in the OER were interrogated using polycyclic aromatic hydrocarbons (PAHs) with designated configurations (zigzag and armchair) as model probe molecules, with a focus on structure–function relationships. Zigzag configurations of PAHs showed high activity for the OER while also showing a good stability at a reasonable potential. They show a TOF value of 0.276 s−1 in 0.1 m KOH. The catalytic activity of carbon edge sites was further effectively regulated by extending the π conjugation structure at a molecular level.

Rhodium(I)‐Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh−C Bond by a Tethered Hydroxy Group

By Yoshihiro Oonishi, Shuichi Masusaki, Shunki Sakamoto, Yoshihiro Sato from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Rhodium(I)‐catalyzed enantioselective intramolecular cyclization of enynes with a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh−C(sp2) bond in the rhodacyclopentene intermediate was intramolecularly cleaved by σ‐bond metathesis of a tethered O−H bond in the substrate. Abstract Rhodium(I)‐catalyzed enantioselective intramolecular cyclization of enynes having a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh−C(sp2) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by σ‐bond metathesis of a tethered O−H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ees even when the starting materials having a racemic secondary alcohol moiety were used in this reaction.

High‐Resolution Photoelectron Imaging of IrB3−: Observation of a π‐Aromatic B3+ Ring Coordinated to a Transition Metal

By Joseph Czekner, Ling Fung Cheung, G. Stephen Kocheril, Maksim Kulichenko, Alexander I. Boldyrev, Lai‐Sheng Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Two at a minimum: High‐resolution photoelectron imaging and ab initio calculations (see picture) identified two isomers of IrB3− that compete for the global minimum in the anion. Bonding analysis revealed that an η2‐B3 isomer is stabilized by covalent interactions, whereas an η3‐B3 isomer is more ionic with the negative charge transferred to Ir to form a (B3)+Ir− complex. Abstract In a high‐resolution photoelectron imaging and theoretical study of the IrB3− cluster, two isomers were observed experimentally with electron affinities (EAs) of 1.3147(8) and 1.937(4) eV. Quantum calculations revealed two nearly degenerate isomers competing for the global minimum, both with a B3 ring coordinated with the Ir atom. The isomer with the higher EA consists of a B3 ring with a bridge‐bonded Ir atom (Cs , 2A′), and the second isomer features a tetrahedral structure (C3v , 2A1). The neutral tetrahedral structure was predicted to be considerably more stable than all other isomers. Chemical bonding analysis showed that the neutral C3v isomer involves significant covalent Ir−B bonding and weak ionic bonding with charge transfer from B3 to Ir, and can be viewed as an Ir–(η3‐B3+) complex. This study provides the first example of a boron‐to‐metal charge‐transfer complex and evidence of a π‐aromatic B3+ ring coordinated to a transition metal.

Copper‐Catalyzed N−F Bond Activation for Uniform Intramolecular C−H Amination Yielding Pyrrolidines and Piperidines

By Daniel Bafaluy, José María Muñoz‐Molina, Ignacio Funes‐Ardoiz, Sebastian Herold, Adiran J. de Aguirre, Hongwei Zhang, Feliu Maseras, Tomás R. Belderrain, Pedro J. Pérez, Kilian Muñiz from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Two for one: A copper‐based catalytic protocol involving N−F activation serves in the synthesis of both pyrrolidines and the more challenging piperidines. The catalytic cycle is based on a copper(I/II) redox cycle. Abstract The dual function of the N−F bond as an effective oxidant and subsequent nitrogen source in intramolecular aliphatic C−H functionalization reactions is explored. Copper catalysis is demonstrated to exercise full regio‐ and chemoselectivity control, which opens new synthetic avenues to nitrogenated heterocycles with predictable ring sizes. For the first time, a uniform catalysis manifold has been identified for the construction of both pyrrolidine and piperidine cores. The individual steps of this new copper oxidation catalysis were elucidated by control experiments and computational studies, clarifying the singularity of the N−F function and characterizing the catalytic cycle to be based on a copper(I/II) manifold.

Transition‐Metal‐Free Cross‐Coupling of Benzothiophenes and Styrenes in a Stereoselective Synthesis of Substituted (E,Z)‐1,3‐Dienes

By Mindaugas Šiaučiulis, Nanna Ahlsten, Alexander P. Pulis, David J. Procter from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Double couple, no trouble: A transition‐metal‐free stereoselective one pot synthesis of (E,Z)‐1,3‐dienes proceeds through an interrupted Pummerer reaction/ligand‐coupling sequence. Readily accessible yet underexplored benzothiophene S‐oxides couple with styrene partners, and the addition of an organometallic reagent triggers controlled dismantling of the benzothiophene scaffold by selective ligand coupling in rarely exploited sulfurane intermediates. Abstract A transition metal‐free one‐pot stereoselective approach to substituted (E,Z)‐1,3‐dienes was developed by using an interrupted Pummerer reaction/ligand‐coupling strategy. Readily available benzothiophene S‐oxides, which can be conveniently prepared by oxidation of the parent benzothiophenes, undergo Pummerer coupling with styrenes. Reaction of the resultant sulfonium salts with alkyllithium/magnesium reagents generates underexploited hypervalent sulfurane intermediates that undergo selective ligand coupling, resulting in dismantling of the benzothiophene motif and the formation of decorated (E,Z)‐1,3‐dienes.

Electropolymerization of Molecular‐Sieving Polythiophene Membranes for H2 Separation

By Mengxi Zhang, Xuechun Jing, Shuang Zhao, Pengpeng Shao, Yuanyuan Zhang, Shuai Yuan, Yanshuo Li, Cheng Gu, Xiaoqi Wang, Yanchun Ye, Xiao Feng, Bo Wang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A soft touch: Softness adjustment of rigid networks is reported to produce flexible, stand‐alone, and molecular‐sieving membranes by electropolymerization. Outstanding H2/CO2, H2/N2, and H2/CH4 separation performances have been achieved, ranking among the best of the state‐of‐the‐art pure organic polymeric membranes for H2 separation and purification. Abstract Membrane technologies that do not rely on heat for industrial gas separation would lower global energy cost. While polymeric, inorganic, and mixed‐matrix separation membranes have been rapidly developed, the bottleneck is balancing the processability, selectivity, and permeability. Reported here is a softness adjustment of rigid networks (SARs) strategy to produce flexible, stand‐alone, and molecular‐sieving membranes by electropolymerization. Here, 14 membranes were rationally designed and synthesized and their gas separation ability and mechanical performance were studied. The separation performance of the membranes for H2/CO2, H2/N2, and H2/CH4 can exceed the Robeson upper bound, among which, H2/CO2 separation selectivity reaches 50 with 626 Barrer of H2 permeability. The long‐term and chemical stability tests demonstrate their potential for industrial applications. This simple, scalable, and cost‐effective strategy holds promise for the design other polymers for key energy‐intensive separations.

Asymmetric Synthesis of Chiral 1,4‐Enynes through Organocatalytic Alkenylation of Propargyl Alcohols with Trialkenylboroxines

By Jian‐Fei Bai, Kento Yasumoto, Taichi Kano, Keiji Maruoka from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

An organocatalytic alkenylation of propargyl alcohols with trialkenylboroxines was developed that enables the synthesis of chiral 1,4‐enynes with high enantioselectivity. A highly acidic chiral N‐triflyl phosphoramide, which has two distant Lewis basic oxygen atoms, was identified as an effective catalyst in terms of both reactivity and selectivity. Abstract A highly enantioselective synthesis of 1,4‐enynes is described that proceeds through an organocatalytic reaction between propargyl alcohols and trialkenylboroxines. Our strategy relies on acid‐mediated generation of the carbocationic intermediate from propargyl alcohols followed by enantioselective alkenylation with trialkenylboroxines. A range of chiral 1,4‐enynes were obtained in moderate to good yields with high levels of enantioselectivity. Use of a highly acidic chiral N‐triflyl phosphoramide catalyst, which has two distant Lewis basic oxygen atoms, was found to be crucial for both high reactivity and selectivity in the present reaction.

Mechanochromism, Twisted/Folded Structure Determination, and Derivatization of (N‐Phenylfluorenylidene)acridane

By Yutaka Matsuo, Ya Wang, Hiroshi Ueno, Takafumi Nakagawa, Hiroshi Okada from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Color control: (N‐Phenylfluorenylidene)acridane compounds with electron‐withdrawing and ‐donating substituents at the para position of the phenyl group were synthesized and the X‐ray crystal structures of both the folded and twisted conformers of the nitro derivative determined. Not only do the compounds show various chromic properties, carrier transport properties are also evident. Abstract (N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO2‐C6H4‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors.

Catalytic Asymmetric (4+3) Cyclizations of In Situ Generated ortho‐Quinone Methides with 2‐Indolylmethanols

By Meng Sun, Chun Ma, Si‐Jia Zhou, Sai‐Fan Lou, Jian Xiao, Yinchun Jiao, Feng Shi from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

The first catalytic asymmetric (4+3) cyclization of in situ generated ortho‐quinone methides with 2‐indolylmethanols was developed, and was used to construct seven‐membered heterocycles in high yields and excellent enantioselectivity. This approach represents the first catalytic asymmetric (4+3) cyclization of o‐hydroxybenzyl alcohols, and also enabled the unprecedented catalytic asymmetric (4+3) cyclization of 2‐indolylmethanols. Abstract The first catalytic asymmetric (4+3) cyclization of in situ generated ortho‐quinone methides with 2‐indolylmethanols has been established, which constructed seven‐membered heterocycles in high yields (up to 95 %) and excellent enantioselectivity (up to 98 %). This approach not only represents the first catalytic asymmetric (4+3) cyclization of o‐hydroxybenzyl alcohols, but also enabled an unprecedented catalytic asymmetric (4+3) cyclization of 2‐indolylmethanols. In addition, a scarcely reported catalytic asymmetric (4+3) cyclization of para‐quinone methide derivatives was accomplished.

A Two‐Dimensional Iron(II) Coordination Polymer with Synergetic Spin‐Crossover and Luminescent Properties

By Jing‐Yuan Ge, Zhongyan Chen, Li Zhang, Xiao Liang, Jian Su, Mohamedally Kurmoo, Jing‐Lin Zuo from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A square‐grid layered FeII coordination polymer based on a luminophore connector TPPE was studied. This framework not only features a solvent‐dependent structure and spin crossover (SCO) behavior, but also exhibits a switch between spin transition and fluorescence for the guest‐free species. Theoretical calculation reveals an energy‐transfer mechanism. Abstract A composite material, {[Fe(L)(TPPE)0.5]⋅3 CH3OH}n, has been constructed by integrating the spin‐crossover (SCO) subunit FeII{diethyl(E,E)‐2,2′‐[1,2‐phenyl‐bis(iminomethylidyne)]bis(3‐oxobutanoate)‐(2‐)‐N,N′,O3,O3′} and the highly luminescent connector 1,1,2,2‐tetrakis(4‐(pyridin‐4‐yl)phenyl)‐ethene. Its structure contains four staggered 4×4 layers and intercalated methanol. The packing is dominated by considerable H‐bonds either between adjacent layers and between layers and guests. A crystal‐structure transformation was detected upon removal of the guest molecules. The SCO transition of the solvated crystals is centered at ca. 215 K with a non‐symmetrical hysteresis of 25 K wide, and the desolvated [Fe(L)(TPPE)0.5]n exhibits gradual SCO without hysteresis. Intriguingly, the intensity of the fluorescence at 460 nm for the latter is maximized at the SCO transition. The energy transfer between luminescent and SCO entities is achievable as confirmed by theoretical calculations.

Boosting Solid‐State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution

By Parvin Adeli, J. David Bazak, Kern Ho Park, Ivan Kochetkov, Ashfia Huq, Gillian R. Goward, Linda F. Nazar from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

At the limit of the solid solution regime: Li5.5PS4.5Cl1.5 exhibits a high Li+ ion conductivity of 9.4 mS cm−1 at 298 K with an activation energy of 0.29 eV, and a high Li+ diffusion coefficient of 1.01×10−11 m2 s−1 determined by NMR transport measurements, suggesting its excellent prospect as a solid Li‐ion electrolyte. Abstract Developing high‐performance all‐solid‐state batteries is contingent on finding solid electrolyte materials with high ionic conductivity and ductility. Here we report new halide‐rich solid solution phases in the argyrodite Li6PS5Cl family, Li6−xPS5−xCl1+x, and combine electrochemical impedance spectroscopy, neutron diffraction, and 7Li NMR MAS and PFG spectroscopy to show that increasing the Cl−/S2− ratio has a systematic, and remarkable impact on Li‐ion diffusivity in the lattice. The phase at the limit of the solid solution regime, Li5.5PS4.5Cl1.5, exhibits a cold‐pressed conductivity of 9.4±0.1 mS cm−1 at 298 K (and 12.0±0.2 mS cm−1 on sintering)—almost four‐fold greater than Li6PS5Cl under identical processing conditions and comparable to metastable superionic Li7P3S11. Weakened interactions between the mobile Li‐ions and surrounding framework anions incurred by substitution of divalent S2− for monovalent Cl− play a major role in enhancing Li+‐ion diffusivity, along with increased site disorder and a higher lithium vacancy population.

Synthesis, Properties, and Application of Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−

By Mark Niemann, Beate Neumann, Hans‐Georg Stammler, Berthold Hoge from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Gallium chemistry: The new weakly coordinating anion [Ga(C2F5)4]− is accessible in the form of various salts, including a hydronium dication, by the reaction of [GaCl3(dmap)] (dmap=4‐dimethylaminopyridine) with LiC2F5. Thermolysis of [(O2H5)2(OH2)2][Ga(C2F5)4]2 yields a dihydrate of a tris(pentafluoroethyl)gallane, [Ga(C2F5)3(OH2)2]. [Li(dec)2][Ga(C2F5)4] (dec=diethyl carbonate) was investigated for its application in lithium‐ion batteries. Abstract Weakly coordinating anions (WCAs) are important for academic reasons as well as for technical applications. Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−, a new WCA, is accessible by treatment of [GaCl3(dmap)] (dmap=4‐dimethylaminopyridine) with LiC2F5. The anion [Ga(C2F5)4]− proved to be reluctant towards deterioration by aqueous hydrochloric acid or lithium hydroxide. Various salts of [Ga(C2F5)4]− were synthesized with cations such as [PPh4]+, [CPh3]+, [(O2H5)2(OH2)2]2+, and [Li(dec)2]+ (dec=diethyl carbonate). Thermolysis of [(O2H5)2(OH2)2][Ga(C2F5)4]2 gives rise to a dihydrate of tris(pentafluoroethyl)gallane, [Ga(C2F5)3(OH2)2]. All products were characterized by NMR and IR spectroscopy, mass spectrometry, X‐ray diffraction, and elemental analysis. Furthermore, an outlook for the application of [Li(dec)2][Ga(C2F5)4] as a conducting salt in lithium‐ion batteries is presented.

Aqueous Platinum(II)‐Cage‐Based Light‐Harvesting System for Photocatalytic Cross‐Coupling Hydrogen Evolution Reaction

By Zeyuan Zhang, Zhengqing Zhao, Yali Hou, Heng Wang, Xiaopeng Li, Gang He, Mingming Zhang from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Harvest lights: An aqueous light‐harvesting system, based on a platinum(II) cage and eosin Y, demonstrates efficient energy transfer. The system showed improved photocatalytic activity in a cross‐coupling hydrogen evolution reaction compared with the reaction employing just eosin Y alone. Abstract Photosynthesis is a process wherein the chromophores in plants and bacteria absorb light and convert it into chemical energy. To mimic this process, an emissive poly(ethylene glycol)‐decorated tetragonal prismatic platinum(II) cage was prepared and used as the donor molecule to construct a light‐harvesting system in water. Eosin Y was chosen as the acceptor because of its good spectral overlap with that of the metallacage, which is essential for the preparation of light‐harvesting systems. Such a combination showed enhanced catalytic activity in catalyzing the cross‐coupling hydrogen evolution reaction, as compared with eosin Y alone. This study offers a pathway for using the output energy from the light‐harvesting system to mimic the whole photosynthetic process.

Xiao‐Feng Wu

By from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

“My favorite motto is be good, be happy, be motivated. My biggest motivation is to overcome challenges …” Find out more about Xiao‐Feng Wu in his Author Profile.

A High‐Throughput Mass Spectrometric Enzyme Activity Assay Enabling the Discovery of Cytochrome P450 Biocatalysts

By Tristan de Rond, Jian Gao, Amin Zargar, Markus de Raad, Jack Cunha, Trent R. Northen, Jay D. Keasling from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Easy as pecan pie: A high‐throughput enzyme assay was developed, based on a combination of click chemistry, fluorous affinity purification, and nanostructure‐initiator mass spectrometry. The utility of the technique, called PECAN, was demonstrated by screening a library of cytochrome P450s for activity on valencene. Abstract Assaying for enzymatic activity is a persistent bottleneck in biocatalyst and drug development. Existing high‐throughput assays for enzyme activity tend to be applicable only to a narrow range of biochemical transformations, whereas universal enzyme characterization methods usually require chromatography to determine substrate turnover, greatly diminishing throughput. We present an enzyme activity assay that allows the high‐throughput mass‐spectrometric detection of enzyme activity in complex matrices without the need for a chromatographic step. This technology, which we call probing enzymes with click‐assisted NIMS (PECAN), can detect the activity of medically and biocatalytically significant cytochrome P450s in cell lysate, microsomes, and bacteria. Using this approach, a cytochrome P450BM3 mutant library was successfully screened for the ability to catalyze the oxidation of the sesquiterpene valencene.

Quantum‐Confined‐Superfluidics‐Enabled Moisture Actuation Based on Unilaterally Structured Graphene Oxide Papers

By Yong‐Lai Zhang, Yu‐Qing Liu, Dong‐Dong Han, Jia‐Nan Ma, Dan Wang, Xian‐Bin Li, Hong‐Bo Sun from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Inspired from the natural “quantum‐tunneling‐fluidics‐effect,” moisture actuation of a solo graphene oxide (GO) paper enabled by quantum‐confined superfluidics is achieved by introducing unilateral nanofolding. Featuring a state‐of‐the‐art ultrafast response, large deformation degree, and complex and predictable deformation, the smart GO films are used for a creeping centipede and a smart leaf that can catch a living ladybug. Abstract The strong interaction between graphene oxides (GO) and water molecules has trigged enormous research interest in developing GO‐based separation films, sensors, and actuators. However, sophisticated control over the ultrafast water transmission among the GO sheets and the consequent deformation of the entire GO film is still challenging. Inspired from the natural “quantum‐tunneling‐fluidics‐effect,” here quantum‐confined‐superfluidics‐enabled moisture actuation of GO paper by introducing periodic gratings unilaterally is reported. The folded GO nanosheets that act as quantum‐confined‐superfluidics channels can significantly promote water adsorption, enabling controllable and sensitive moisture actuation. Water‐adsorption‐induced expansion along and against the normal direction of a GO paper is investigated both theoretically and experimentally. Featuring state‐of‐the‐art of ultrafast response (1.24 cm−1 s−1), large deformation degree, and complex and predictable deformation, the smart GO papers are used for biomimetic mini‐robots including a creeping centipede and a smart leaf that can catch a living ladybug. The reported method is simple and universal for 2D materials, revealing great potential for developing graphene‐based smart robots.

Energy‐Tailorable Spin‐Selective Multifunctional Metasurfaces with Full Fourier Components

By Wenwei Liu, Zhancheng Li, Zhi Li, Hua Cheng, Chengchun Tang, Junjie Li, Shuqi Chen, Jianguo Tian from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Multifunctional metasurfaces are designed based on full Fourier components, which do not suffer from intrinsic noise and complex optimizations, compared with intensity‐/phase‐only manipulation of optical diffractive fields. Such multifunctional metasurfaces could be used to integrate many different functions such as generation and focusing of vortex beams with accurate predesigned intensity of each channel, and the spin‐selective behavior also shows potential in information photonics. Abstract Compact integrated multifunctional metasurface that can deal with concurrent tasks represent one of the most profound research fields in modern optics. Such integration is expected to have a striking impact on minimized optical systems in applications such as optical communication and computation. However, arbitrary multifunctional spin‐selective design with precise energy configuration in each channel is still a challenge, and suffers from intrinsic noise and complex designs. Here, a design principle is proposed to realize energy tailorable multifunctional metasurfaces, in which the functionalities can be arbitrarily designed if the channels have no or weak interference in k‐space. A design strategy is demostrated here with high‐efficiency dielectric nanopillars that can modulate full Fourier components of the optical field. The spin‐selective behavior of the dielectric metasurfaces is also investigated, which originates from the group effect introduced by numerous nanopillar arrays. This approach provides straightforward rules to control the functionality channels in the integrated metasurfaces, and paves the way for efficient concurrent optical communication.

Strong Electrochemiluminescence Emission from Oxidized Multiwalled Carbon Nanotubes

By Ruina Wang, Haishan Wu, Rui Chen, Yuwu Chi from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Thu 18 Jul 16:00: LMB Seminar Series - Francis Crick Lecture - Innovation by Evolution: Bringing New Chemistry to Life

From All Talks (aka the CURE list). Published on Jun 13, 2019.

LMB Seminar Series - Francis Crick Lecture - Innovation by Evolution: Bringing New Chemistry to Life

Not satisfied with nature’s vast catalyst repertoire, we want to create new protein catalysts and expand the space of genetically encoded enzyme functions. I will describe how we can use the most powerful biological design process, evolution, to optimize existing enzymes and invent new ones, thereby circumventing our profound ignorance of how sequence encodes function. Using mechanistic understanding and mimicking nature’s evolutionary processes, we can generate whole new enzyme families that catalyze synthetically important reactions not known in biology. Recent successes include selective carbene insertion to form C-Si and C-B bonds, and alkyne cyclopropanation to make highly strained carbocycles, all in living cells. Extending the capabilities and uncovering the mechanisms of these new enzymes derived from natural iron-heme proteins provides a basis for discovering new biocatalysts for increasingly challenging reactions. These new capabilities increase the scope of molecules and materials we can build using synthetic biology and move us closer to a sustainable world where chemical synthesis can be fully programmed in DNA .

Add to your calendar or Include in your list

Artificial Control of Cell Signaling Using a Photocleavable Cobalt(III)–Nitrosyl Complex

By Sangwon Shin, Jisu Choe, Youngchan Park, Donghyun Jeong, Hyunjoon Song, Youngmin You, Daeha Seo, Jaeheung Cho from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

See things in a new light: A cobalt(III)–nitrosyl complex has been designed and synthesized for the study of NO‐dependent cell signaling. Photolysis of this complex releases NO with high spatiotemporal control, both intracellularly and extracellularly, allowing the study of the cell signaling pathways activated by endogenously and exogenously produced NO, respectively. Abstract Cells use gaseous molecules such as nitric oxide (NO) to transmit both intracellular and intercellular signals. In principle, the endogenous small molecules regulate physiological changes, but it is unclear how randomly diffusive molecules trigger and discriminate signaling programs. Herein, it is shown that gasotransmitters use time‐dependent dynamics to discriminate the endogenous and exogenous inputs. For a real‐time stimulation of cell signaling, we synthesized a photo‐cleavable metal–nitrosyl complex, [CoIII(MDAP)(NO)(CH3CN)]2+ (MDAP=N,N′‐dimethyl‐2,11‐diaza[3,3](2,6)pyridinophane), which can stably deliver and selectively release NO with fine temporal resolution in the cytosol, and used this to study the extracellular signal‐regulated kinases (ERKs), revealing how cells use both exogenous and endogenous NO to disentangle cellular responses. This technique can be to understand how diverse cellular signaling networks are dynamically interconnected and also to control drug delivery systems.

Indeno[1,2‐b]fluorene‐Based [2,2]Cyclophanes with 4n/4n and 4n/[4n+2] π Electrons: Syntheses, Structural Analyses, and Excitonic Coupling Properties

By Chi‐Shin Wang, Yu‐Chen Wei, Kai‐Hsin Chang, Pi‐Tai Chou, Yao‐Ting Wu from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Hindsight is 20/20: anti‐[2.2](5,11)Indeno[1,2‐b]fluorenophane, which contains a rare 20/20 π‐electron system with a large overlapping π orbital and a short π–π distance, has a unique structure. This compound exhibits remarkable transannular interactions, resulting in photophysical and electrochemical properties, as well as photodynamics. The transition from the monomeric excited state to the redshifted H‐type dimeric state was observed for the first time. Abstract Indeno[1,2‐b]fluorene‐based [2,2]cyclophanes with 4n/4n and 4n/[4n+2] π‐electron systems were prepared, and their structures were identified by X‐ray crystallography. With short π–π distances around 3.0 Å, [2.2](5,11)indeno[1,2‐b]fluorenophane and its precursor [2.2](5,11)indeno[1,2‐b]fluorene‐6,12‐dionophane exhibit remarkable transannular interactions, leading to their unusual electrochemical and photophysical properties. With the aid of femtosecond transient absorption spectroscopy, the transition from the monomeric excited state to the redshifted H‐type dimeric state was first observed, correlating to the calculated excitonic energy splitting and the steady‐state absorption spectra induced by charge‐transfer‐mediated superexchange interaction.

Hydrogen by Deuterium Substitution in an Aldehyde Tunes the Regioselectivity by a Nonheme Manganese(III)–Peroxo Complex

By Prasenjit Barman, Fabián G. Cantú Reinhard, Umesh Kumar Bagha, Devesh Kumar, Chivukula V. Sastri, Sam P. de Visser from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Regioselective hydrogen‐atom abstraction: A combined experimental and computational study gives evidence of electrophilic reactivity of a side‐on manganese(III)–peroxo complex. Furthermore, isotopic substitution of the substrate changes the regioselectivity of the reaction and the product distributions. Abstract Mononuclear nonheme MnIII‐peroxo complexes are important intermediates in biology, and take part in oxygen activation by photosystem II. Herein, we present work on two isomeric biomimetic side‐on MnIII‐peroxo intermediates with bispidine ligand system and reactivity patterns with aldehydes. The complexes are characterized with UV/Vis and mass spectrometric techniques and reaction rates with cyclohexane carboxaldehyde (CCA) are measured. The reaction gives an unusual regioselectivity switch from aliphatic to aldehyde hydrogen atom abstraction upon deuteration of the substrate, leading to the corresponding carboxylic acid product for the latter, while the former gives a deformylation reaction. Mechanistic details are established from kinetic isotope effect studies and density functional theory calculations. Thus, replacement of C−H by C−D raises the hydrogen atom abstraction barriers and enables a regioselectivity switch to a competitive pathway that is slightly higher in energy.

A General and Air‐tolerant Strategy to Conjugated Polymers within Seconds under Palladium(I) Dimer Catalysis

By Guillaume Magnin, Jamie Clifton, Franziska Schoenebeck from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

A single method that allows access to a variety of different conjugated polymers within seconds at room temperature was developed. Key to this privileged reactivity is an air‐ and moisture stable dinuclear PdI catalyst. The method is operationally simple, robust and tolerant to air. Abstract While current M0/MII based polymerization strategies largely focus on fine‐tuning the catalyst, reagents and conditions for each and every monomer, this report discloses a single method that allows access to a variety of different conjugated polymers within seconds at room temperature. Key to this privileged reactivity is an air‐ and moisture stable dinuclear PdI catalyst. The method is operationally simple, robust and tolerant to air.

Confinement Effects in Zeolite‐Confined Noble Metals

By Si‐Ming Wu, Xiao‐Yu Yang, Christoph Janiak from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

The beauty of zeolite‐confined noble metals lies in their unique confinement effects on a molecular scale, and thus enables spatially confined catalysis akin to enzyme catalysis. This Minireview summarizes synthesis strategies and targeted catalysis applications for multifunctional zeolite‐confined noble metal catalysts. Abstract Confinement of noble nanometals in a zeolite matrix is a promising way to special types of catalysts that show significant advantages in size control, site adjustment, and nano‐architecture design. The beauty of zeolite‐confined noble metals lies in their unique confinement effects on a molecular scale, and thus enables spatially confined catalysis akin to enzyme catalysis. In this Minireview, the confined synthesis strategies of zeolite‐confined noble metals will be briefly discussed, showing the processes, advantages, features, and mechanisms. The confined catalysis carried on zeolite‐confined noble metals will be summarized, and great emphasis will be paid to the confinement effects involving size, encapsulation, recognition, and synergy. Great progress of atomic sites in the size effect, supercage stabilization in the encapsulation effect, site adsorption in the recognition effect, and cascade reaction in the synergy effect are highlighted. This Minireview is concluded with challenges and opportunities in terms of the synthesis of zeolite‐confined noble metals and their applications to design multifunctional catalysts with high catalytic activity, selectivity, and stability.

Propargylsilanes as Reagents for Synergistic Gold(I)‐Catalyzed Propargylation of Carbonyl Compounds: Isolation and Characterization of σ‐Gold(I) Allenyl Intermediates

By Sergio Fernández, Jairo González, Javier Santamaría, Alfredo Ballesteros from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Golden capture: A σ‐gold allenyl intermediate was isolated and characterized during the study of a novel gold‐catalyzed propargylation reaction. Propargylsilanes serve as very effective reagents for the propargylation reaction of carbonyl compounds. The reaction can be directed toward formation of either homopropargyl silyl ethers or the in situ synthesis of 2‐silyl‐4,5‐dihydrofurans. TBS=tert‐butyldimethylsilyl, TMS=trimethylsilyl. Abstract Reported herein is the isolation and characterization, for the first time, of a σ‐gold allenyl complex as an intermediate in gold catalysis. This intermediate was captured during the study of a novel gold(I)‐catalyzed propargylation of carbonyl compounds with propargylsilanes. Notably, the gold‐catalyzed propargylation reaction, which proceeds with aldehydes and ketones, can be driven to the formation of either homopropargyl silyl ethers or the in situ synthesis of corresponding 2‐silyl‐4,5‐dihydrofurans.

Trapping of a Highly Bent and Reduced Form of 2‐Phosphaethynolate in a Mixed‐Valence Diuranium–Triamidoamine Complex

By Rosie Magnall, Gábor Balázs, Erli Lu, Floriana Tuna, Ashley J. Wooles, Manfred Scheer, Stephen T. Liddle from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 13, 2019.

Carbene‐like P‐C‐O: An unprecedented highly reduced form of 2‐phosphaethynolate is trapped in a mixed‐valence diuranium(III/IV) complex that is best formulated as a uranium‐stabilised OCP2−. radical dianion. It imparts some carbene character to the P‐C‐O linkage as evidenced by its highly bent geometry and a weak U−C donor–acceptor interaction. Abstract The chemistry of 2‐phosphaethynolate is burgeoning, but there remains much to learn about this ligand, for example its reduction chemistry is scarce as this promotes P‐C‐O fragmentations or couplings. Here, we report that reduction of [U(TrenTIPS)(OCP)] (TrenTIPS=N(CH2CH2NSiPri3)3) with KC8/2,2,2‐cryptand gives [{U(TrenTIPS)}2{μ‐η2(OP):η2(CP)‐OCP}][K(2,2,2‐cryptand)]. The coordination mode of this trapped 2‐phosphaethynolate is unique, and derives from an unprecedented highly reduced and highly bent form of this ligand with the most acute P‐C‐O angle in any complex to date (P‐C‐O ∡ ≈127°). The characterisation data support a mixed‐valence diuranium(III/IV) formulation, where backbonding from uranium gives a highly reduced form of the P‐C‐O unit that is perhaps best described as a uranium‐stabilised OCP2−. radical dianion. Quantum chemical calculations reveal that this gives unprecedented carbene character to the P‐C‐O unit, which engages in a weak donor–acceptor interaction with one of the uranium ions.

Highly Efficient and Stable Solar Cells Based on Crystalline Oriented 2D/3D Hybrid Perovskite

By Tong Zhou, Hongtao Lai, Tingting Liu, Di Lu, Xiangjian Wan, Xiaodan Zhang, Yongsheng Liu, Yongsheng Chen from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

2‐Thiophenemethylammonium spacer cations are successfully embedded into formamidinium iodide (FAI)‐ and methylammonium iodide (MAI)‐based 3D perovskites, and these cations can induce the crystalline growth and orientation of the obtained 2D/3D hybrid perovskite. A champion efficiency of 21.49% is demonstrated for a 2D/3D perovskite device, which is combined with a dramatically improved stability in comparison with that of the control device. Abstract Highly efficient and stable 2D/3D hybrid perovskite solar cells using 2‐thiophenemethylammonium (ThMA) as the spacer cation are successfully demonstrated. It is found that the incorporation of ThMA spacer cation into 3D perovskite, which forms a 2D/3D hybrid structure, can effectively induce the crystalline growth and orientation, passivate the trap states, and hinder the ion motion, resulting in improved carrier lifetime and reduced recombination losses. The optimized device exhibits a power conversion efficiency (PCE) of 21.49%, combined with a high VOC of 1.16 V and a notable fill factor (FF) of 81%. More importantly, an encapsulated 2D/3D hybrid perovskite device sustains ≈99% of its initial PCE after 1680 h in the ambient atmosphere, whereas the control 3D perovskite device drops to ≈80% of the original performance. Importantly, the device stability under continuous light soaking (100 mW cm−2) is enhanced significantly for 2D/3D perovskite device in comparison with that of the control device. These results reveal excellent photovoltaic properties and intrinsic stabilities of the 2D/3D hybrid perovskites using ThMA as the spacer cation.

Diffusion–Freezing‐Induced Microphase Separation for Constructing Large‐Area Multiscale Structures on Hydrogel Surfaces

By Wenwei Lei, Shuanhu Qi, Qinfeng Rong, Jin Huang, Yichao Xu, Ruochen Fang, Kesong Liu, Lei Jiang, Mingjie Liu from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

A smart gel surface with multiscale structure is constructed by controlling the swelling and diffusion between the gel and the substrate interface. The hydrogel surface can transport a variety of liquids through the open capillary system on its surface; these properties can also be applied to the functionalization of hydrogel surfaces and the anti‐dehydration of hydrogels. Abstract Hydrogels with multiscale structured surface have attracted significant attention for their valuable applications in diverse areas. However, current strategies for the design and fabrication of structured hydrogel surfaces, which suffer from complicated manufacturing processes and specific material modeling, are not efficient to produce structured hydrogel surfaces in large area, and therefore restrict their practical applications. To address this problem, a general and reliable method is reported, which relies on the interplay between polymer chain diffusion and the subsequent freezing‐induced gelation and microphase separation processes. The basic idea is systematically analyzed and further exploited to manufacture gel surfaces with gradient structures and patterns through the introduction of temperature gradient and shape control of the contact area. Moreover, the formed micro/nanostructured surfaces are exemplified to work as capillary systems and thus can uplift the liquid spontaneously indicating the potential application for anti‐dehydration. It is believed that the proposed facile and large‐area fabrication method can inspire the design of materials with various functionalized surfaces.

ZIF‐67‐Derived 3D Hollow Mesoporous Crystalline Co3O4 Wrapped by 2D g‐C3N4 Nanosheets for Photocatalytic Removal of Nitric Oxide

By Dongni Liu, Dongyun Chen, Najun Li, Qingfeng Xu, Hua Li, Jinghui He, Jianmei Lu from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Zeolitic Imidazolate Framework‐67 (ZIF‐67)‐derived 3D hollow mesoporous crystalline Co3O4 wrapped by 2D graphitic carbon nitride (g‐C3N4) nanosheets are prepared for removal of low concentrations (600 ppb) of nitric oxide (NO). The hollow mesoporous structure facilitates the irradiation of visible light and the circulation and adsorption of NO, thereby increasing catalytic efficiency of the composite catalyst. Abstract ZIF‐67‐derived 3D hollow mesoporous crystalline Co3O4 wrapped by 2D graphitic carbon nitride (g‐C3N4) nanosheets are prepared by low temperature annealing, and are used for the photocatalytic oxidation of nitric oxide (NO) at a concentration of 600 ppb. The p–n heterojunction between Co3O4 and g‐C3N4 forms a spatial conductive network frame and results in a broad visible light response range. The hollow mesoporous structure of Co3O4 contributes to the circulation and adsorption of NO, and the large specific surface area exposes abundant active sites for the reaction of active species. A maximum NO degradation efficiency of 57% is achieved by adjusting the mass of the Co3O4 precursor. Cycling tests and X‐ray diffraction indicate the high stability and recyclability of the composite, making it promising in environmental purification applications.

Vacuum‐Drying Processed Micrometer‐Thick Stable CsPbBr3 Perovskite Films with Efficient Blue‐To‐Green Photoconversion

By Yongming Yin, Muhammad Umair Ali, Ming Liu, Jingsheng Miao, Wenxiang Peng, Dongze Li, Shujhih Chen, Chiayu Lee, Hong Meng from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Micrometer‐thick stable CsPbBr3 perovskite films are obtained through a facile vacuum drying process. Green emission with a brightness as high as 200 cd m−2 is achieved from blue light with a back luminance of 1000 cd m−2, which decays by only ≈2% when the films are tested after 18 days of exposure to ambient environment. Abstract Metal halide perovskite materials have attracted great attention owing to their fascinating optoelectronic characteristics and low cost fabrication via facile solution processing. One of the potential applications of these materials is to employ them as color‐conversion layers (CCLs) for visible blue light to achieve full‐color displays. However, obtaining thick perovskite films to realize complete color conversion is a key challenge. Here, the fabrication of micrometer‐level thick CsPbBr3 perovskite films is presented through a facile vacuum drying approach. An efficient green photoconversion is realized in a 3.8 µm thick film from blue light @ 463 nm. For a back luminance of 1000 cd m−2, the brightness of the resulting green emission can reach as high as 200 cd m−2. Furthermore, only ≈2% of decay in brightness is observed when the films are tested after 18 days of exposure to ambient environment. In addition, a potential design is also proposed for full‐color displays with perovskite materials incorporated as CCLs.

NIR‐Triggered Photothermal Responsive Coatings with Remote and Localized Tunable Underwater Oil Adhesion

By Bin Shang, Min Chen, Limin Wu from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

A novel photothermal responsive coating (PTRC) with tunable underwater oil adhesion is prepared via mixing thermal responsive poly (styrene‐co‐n‐isopropylacrylamide) colloidal spheres and Fe3O4 nanoparticles with commercial polysiloxane latex. The as‐obtained coating exhibits superior near‐infrared (NIR) radiation‐induced photothermal responsiveness and outstanding thermal responsive wettability, which easily allows remotely and locally controlling the adhesion of oil droplets on the coating surfaces. Abstract Tunable underwater oil adhesion is a critical issue in interfacial science and industrial applications. Although much progress has been made to date, development of novel smart coating materials that can selectively change the wetting property at different areas is considerably scarce. Here, a simple strategy is proposed to fabricate photothermal responsive coatings, which can change the oil adhesion behavior from low‐adhesive rolling state to high‐adhesive pinning state for a variety of oily liquids in a remote, local, and reversible manner. Owing to this unique controllability, the adhesion and no‐adhesion of oil droplets on the coated surfaces can be easily manipulated by remote and local near‐infrared radiation.

Hybrid Cu0 and Cux+ as Atomic Interfaces Promote High‐Selectivity Conversion of CO2 to C2H5OH at Low Potential

By Xiaowan Bai, Qiang Li, Li Shi, Xianghong Niu, Chongyi Ling, Jinlan Wang from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Electrochemical conversion of CO2 into liquid fuels is a popular yet very challenging topic. The copper cluster supported on graphitic carbon nitride as potential CO2 reduction catalyst shows hybrid Cu0 and Cux+ as atomic interface, and high selectivity for ethanol. Abstract The mixing of charge states of metal copper catalysts may lead to a much improved reactivity and selectivity toward multicarbon products for CO2 reduction. Here, an electrocatalyst model composed of copper clusters supported on graphitic carbon nitride (g‐C3N4) is proposed; the connecting Cu atoms with g‐C3N4 can be oxidized to Cux + due to substantial charge transfer from Cu to N atoms, while others stay as Cu0. It is revealed that CO2 can be captured and reduced into *CO on the Cut0 site, owing to its zero oxidation state. More importantly, C–C coupling reaction of two *CHO species on the Cut0–Cubx+ atomic interface can occur with a rather low kinetic barrier of 0.57 eV, leading to the formation of the final C2 product, namely, C2H5OH. During the whole process, the limiting potential is just 0.68 V. These findings may open a new avenue for CO2 reduction into high‐value fuels and chemicals.

Tetrahedral Framework Nucleic Acids Promote Corneal Epithelial Wound Healing in Vitro and in Vivo

By Nanxin Liu, Xiaolin Zhang, Ni Li, Mi Zhou, Tianxu Zhang, Songhang Li, Xiaoxiao Cai, Ping Ji, Yunfeng Lin from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Tetrahedral framework nucleic acids (tFNAs) can accelerate the proliferation and migration of human corneal epithelial cells, which are important processes of corneal epithelial wound healing. In vivo experiments show that tFNAs can also promote the wound healing of rabbit corneal alkali burn. Thus, the tFNA is a promising nanomaterial to promote corneal epithelial wound healing in the future. Abstract Poor post‐traumatic wound healing can affect the normal function of damaged tissues and organs. For example, poor healing of corneal epithelial injuries may lead to permanent visual impairment. It is of great importance to find a therapeutic way to promote wound closure. Tetrahedral framework nucleic acids (tFNAs) are new promising nanomaterials, which can affect the biological behavior of cells. In the experiment, corneal wound healing is used as an example to explore the effect of tFNAs on wound healing. Results show that the proliferation and migration of human corneal epithelial cells are enhanced by exposure to tFNAs in vitro, possibly relevant to the activation of P38 and ERK1/2 signaling pathway. An animal model of corneal alkali burn is established to further identify the facilitation effect of tFNAs on corneal wound healing in vivo. Clinical evaluations and histological analyses show that tFNAs can improve the corneal transparency and accelerate the re‐epithelialization of wounds. Both in vitro and in vivo experiments show that tFNAs can play a positive role in corneal epithelial wound healing.

Controlling DNA Tug‐of‐War in a Dual Nanopore Device

By Xu Liu, Yuning Zhang, Roland Nagel, Walter Reisner, William B. Dunbar from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

A dual nanopore approach for reducing and directly controlling the speed of DNA through the nanopore is reported. Constant competing voltages at the dual pores lead to a “tug‐of‐war,” whereby opposing forces are applied to regions of the molecules threading through the pores. These forces exert both conformational and speed control over the cocaptured molecule, removing folds and reducing the translocation rate. Abstract Methods for reducing and directly controlling the speed of DNA through a nanopore are needed to enhance sensing performance for direct strand sequencing and detection/mapping of sequence‐specific features. A method is created for reducing and controlling the speed of DNA that uses two independently controllable nanopores operated with an active control logic. The pores are positioned sufficiently close to permit cocapture of a single DNA by both pores. Once cocapture occurs, control logic turns on constant competing voltages at the pores leading to a “tug‐of‐war” whereby opposing forces are applied to regions of the molecules threading through the pores. These forces exert both conformational and speed control over the cocaptured molecule, removing folds and reducing the translocation rate. When the voltages are tuned so that the electrophoretic force applied to both pores comes into balance, the life time of the tug‐of‐war state is limited purely by diffusive sliding of the DNA between the pores. A tug‐of‐war state is produced on 76.8% of molecules that are captured with a maximum two‐order of magnitude increase in average pore translocation time relative to the average time for single‐pore translocation. Moreover, the translocation slow‐down is quantified as a function of voltage tuning and it is shown that the slow‐down is well described by a first passage analysis for a 1D subdiffusive process. The ionic current of each nanopore provides an independent sensor that synchronously measures a different region of the same molecule, enabling sequential detection of physical labels, such as monostreptavidin tags. With advances in devices and control logic, future dual‐pore applications include genome mapping and enzyme‐free sequencing.

Highly Uniform and Low Hysteresis Piezoresistive Pressure Sensors Based on Chemical Grafting of Polypyrrole on Elastomer Template with Uniform Pore Size

By Jinwon Oh, Jin‐Oh Kim, Yunjoo Kim, Han Byul Choi, Jun Chang Yang, Serin Lee, Mikhail Pyatykh, Jung Kim, Joo Yong Sim, Steve Park from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Piezoresistive sensors with high uniformity and low hysteresis are fabricated via chemically grafting a conductive polymer on the surface of an elastomer template with uniform pore size and arrangement. Finite element analysis confirms the importance of pore size uniformity in sensor uniformity. Abstract Sensor‐to‐sensor variability and high hysteresis of composite‐based piezoresistive pressure sensors are two critical issues that need to be solved to enable their practical applicability. In this work, a piezoresistive pressure sensor composed of an elastomer template with uniformly sized and arranged pores, and a chemically grafted conductive polymer film on the surface of the pores is presented. Compared to sensors composed of randomly sized pores, which had a coefficient of variation (CV) in relative resistance change of 69.65%, our sensors exhibit much higher uniformity with a CV of 2.43%. This result is corroborated with finite element simulation, which confirms that with increasing pore size variability, the variability in sensor characteristics also increases. Furthermore, our devices exhibit negligible hysteresis (degree of hysteresis: 2%), owing to the strong chemical bonding between the conductive polymer and the elastomer template, which prevents their relative sliding and displacement, and the porosity of the elastomer that enhances elastic behavior. Such features of the sensor render it highly feasible for various practical applications in the near future.

Self‐Assembly of Biocompatible FeSe Hollow Nanostructures and 2D CuFeSe Nanosheets with One‐ and Two‐Photon Luminescence Properties

By Yang Deng, Dianqi Li, Xingming Ning, Dongxu Zhang, Shouting Zhang, Zhen Zhang, Duoliang Shan, Zhenyu Wang, Dingbin Liu, Xiang Mao, Xiaoquan Lu from Wiley: Small: Table of Contents. Published on Jun 13, 2019.

Ultrasmall hollow FeSe nanospheres and two‐dimensional CuFeSe nanosheets are successfully synthesized via self‐assembled and doping behaviors, respectively. Fluorescence spectra show both of these nanomaterials exhibit unique two‐photon luminescence and optical stability. Fluorescence imaging experiments confirm the excellent biocompatibility of nanomaterials. This work provides a new strategy for the future development of nanocomposites with unique optical properties. Abstract Transition metal chalcogenides are investigated for catalyst, intermediary agency, and particular optical properties because of their distinguished electron‐vacancy‐transfer (EVT) process toward different applications. In this work, one convenient approach for making pure‐phased FeSe nanocrystals (NCs) and doped CuFeSe nanosheets (NSs) through a wet chemistry method in mixed solvents is illustrated. The surface modification of each product is realized by using a peptide molecule glutathione (GSH), in which the thiol group (−SH) is ascribed to be the in situ reducer and bonding agency between the crystalline surface and surfactant in whole constructing processes. Due to the functional groups in biological GSH, highly aggregated NCs are rebuilt in the form of an FeSe hollow structure through amino and carboxyl cross‐linking functions through a spontaneous assembly procedure. Owing to the coupling procedure of Cu and Fe in the growth process, it generates enhanced EVT. Additionally, it shows the emission spectra of λEM‐PL = 436 nm (FeSe) and 452 nm (CuFeSe) while λEX‐PL = 356 nm, it also conveys two‐photon phenomenon while λEX‐PL = 720 nm. Moreover, it also shows strong off‐resonant luminescence due to two‐photon absorption, which should be valuable for biological applications.

Reducing the Barrier Energy of Self‐Reconstruction for Anchored Cobalt Nanoparticles as Highly Active Oxygen Evolution Electrocatalyst

By Myeongjin Kim, Byeongyong Lee, Hyun Ju, Seung Woo Lee, Jooheon Kim from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

Boosting self‐reconstruction of oxy‐hydroxide intermediates from transition metal is crucial for improving OER catalytic activity. This study suggests a new strategy for the effective utilization of a pyrochlore oxide support, which can facilitate the formation of transition metal–oxy‐hydroxide intermediates by efficient electron transport. Abstract It is crucial for leaping forward renewable energy technology to develop highly active oxygen evolution reaction (OER) catalysts with fast OER kinetics, and the novel design of high‐performance catalysts may come down to unveiling the origin of high catalytic behavior. Herein, a new class of heterogeneous OER electrocatalyst (metallic Co nanoparticles anchored on yttrium ruthenate pyrochlore oxide) is provided for securing fast OER kinetics. In situ X‐ray absorption spectroscopy (in situ XAS) reveals that fast OER kinetics can be achieved by the harmonious catalytic synergy of a pyrochlore oxide support to Co nanoparticles. By the facile oxidation of yttrium (A‐site) and ruthenium (B‐site) cations, the pyrochlore oxide support helps to expel the electrons generated from the catalytic behavior of Co to the inner layers of the support, facilitating the electrostatic adsorption of OH− ions and reducing the barrier energy for the formation of CoOOH intermediates. This work affords the rational design of transition metal nanoparticles anchored on pyrochlore oxide heterogeneous catalysts and the fundamental insight of catalytic origin associated with self‐reconstruction of OER electrocatalysts.

Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability

By Qi Yang, Funian Mo, Zhuoxin Liu, Longtao Ma, Xinliang Li, Daliang Fang, Shimou Chen, Suojiang Zhang, Chunyi Zhi from Wiley: Advanced Materials: Table of Contents. Published on Jun 13, 2019.

The activation of C‐coordinated Fe, as quantified by the decreased atomic ratio of Fe(III)/Fe(II), encourages the increase of capacity contribution at the voltage platform of about 1.5 V. This activation extremely weakened the FeC bond to activate C‐coordinated Fe (active sites), and thus generates a 10 000‐cycle lifespan and a superior rate capability (8 A g‐1, ≈97 C). Abstract Prussian blue analogue (PBA)‐type metal hexacyanoferrates are considered as significant cathodes for zinc batteries (ZBs). However, these PBA‐type cathodes, such as cyanogroup iron hexacyanoferrate (FeHCF), suffer from ephemeral lifespan (≤1000 cycles), and inferior rate capability (1 A g−1). This is because the redox active sites of multivalent iron (Fe(III/II)) can only be very limited activated and thus utilized. This is attributed to the spatial resistance caused by the compact cooperation interaction between Fe and the surrounded cyanogroup, and the inferior conductivity. Here, it is found that high‐voltage scanning can effectively activate the C‐coordinated Fe in FeHCF cathode in ZBs. Thanks to this activation, the Zn–FeHCF hybrid‐ion battery achieves a record‐breaking cycling performance of 5000 (82% capacity retention) and 10 000 cycles (73% capacity retention), respectively, together with a superior rate capability of maintaining 53.2% capacity at superhigh current density of 8 A g−1 (≈97 C). The reversible distortion and recovery of the crystalline structure caused by the (de)insertion of zinc and lithium ions is revealed. It is believed that this work represents a substantial advance on PBA electrode materials and may essentially promote application of PBA materials.

Wed 20 Nov 14:15: Title to be confirmed

From All Talks (aka the CURE list). Published on Jun 13, 2019.

Title to be confirmed

Abstract not available

Add to your calendar or Include in your list

[ASAP] Record High-Proximity-Induced Anomalous Hall Effect in (BixSb1–x)2Te3 Thin Film Grown on CrGeTe3 Substrate

By Xiong Yao†, Bin Gao‡, Myung-Geun Han?, Deepti Jain§, Jisoo Moon§, Jae Wook Kim§, Yimei Zhu?, Sang-Wook Cheong†, and Seongshik Oh*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01495

[ASAP] Directional Ostwald Ripening for Producing Aligned Arrays of Nanowires

By Hye Jin Lee†, U Jeong Yang†, Kyeong Nam Kim‡, Soojin Park§, Kye Hyoung Kil?, Jun Soo Kim?, Alec M. Wodtke?, Won Jun Choi*?, Myung Hwa Kim*?, and Jeong Min Baik*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00684

[ASAP] Self-Limiting Growth of Two-Dimensional Palladium between Graphene Oxide Layers

By Yang Su†‡, Eric Prestat§, Chengyi Hu†‡, Vinod Kumar Puthiyapura†‡, Mehdi Neek-Amal*??, Hui Xiao†‡, Kun Huang†‡, Vasyl G. Kravets#, Sarah J. Haigh§, Christopher Hardacre‡, Francois M. Peeters?, and Rahul R. Nair*†‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01733

[ASAP] Chemically Tuning Quantized Acoustic Phonons in 2D Layered MoO3 Nanoribbons

By Bryan W. Reed†, Daniel R. Williams‡, Bryan P. Moser‡, and Kristie J. Koski*‡ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01068

[ASAP] Impact of the Shadowing Effect on the Crystal Structure of Patterned Self-Catalyzed GaAs Nanowires

By Philipp Schroth†‡§, Mahmoud Al Humaidi†, Ludwig Feigl§, Julian Jakob*‡§, Ali Al Hassan†, Arman Davtyan†, Hanno Ku¨pers?, Abbes Tahraoui?, Lutz Geelhaar?, Ullrich Pietsch†, and Tilo Baumbach‡§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b00380

[ASAP] Quantum Interference in a Single Perovskite Nanocrystal

By Yan Lv†, Chunyang Yin†, Chunfeng Zhang†, William W. Yu‡, Xiaoyong Wang*†, Yu Zhang*‡, and Min Xiao*†§ from Nano Letters: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01237

[ASAP] Efficient Coupling of an Ensemble of Nitrogen Vacancy Center to the Mode of a High-Q, Si3N4 Photonic Crystal Cavity

By Konstantin G. Fehler†?, Anna P. Ovvyan‡?, Nico Gruhler§, Wolfram H. P. Pernice‡, and Alexander Kubanek*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01668

[ASAP] Tip-Induced Control of Charge and Molecular Bonding of Oxygen Atoms on the Rutile TiO2 (110) Surface with Atomic Force Microscopy

By Yuuki Adachi†, Huan Fei Wen†, Quanzhen Zhang†, Masato Miyazaki†, Yasuhiro Sugawara†, Hongqian Sang‡§, Ja´n Brndiar?, Lev Kantorovich‡, Ivan S?tich??, and Yan Jun Li*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01792

[ASAP] Controlled Co-delivery of Growth Factors through Layer-by-Layer Assembly of Core–Shell Nanofibers for Improving Bone Regeneration

By Gu Cheng†, Chengcheng Yin†, Hu Tu‡, Shan Jiang§, Qun Wang?, Xue Zhou?, Xin Xing†, Congyong Xie†, Xiaowen Shi‡, Yuming Du‡, Hongbing Deng*‡, and Zubing Li*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.8b06032

[ASAP] Inhibiting Grain Pulverization and Sulfur Dissolution of Bismuth Sulfide by Ionic Liquid Enhanced Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate) for High-Performance Zinc-Ion Batteries

By Yuwei Zhao†?, Longtao Ma†?, Yongbin Zhu‡, Peng Qin‡, Hongfei Li†, Funian Mo†, Donghong Wang†, Guojin Liang†, Qi Yang†, Weishu Liu*‡, and Chunyi Zhi*†§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02986

[ASAP] Metal-Ion Modulated Structural Transformation of Amyloid-Like Dipeptide Supramolecular Self-Assembly

By Wei Ji†?, Chengqian Yuan‡?, Shai Zilberzwige-Tal†, Ruirui Xing‡, Priyadarshi Chakraborty†, Kai Tao†, Sharon Gilead†, Xuehai Yan*‡, and Ehud Gazit*†§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03444

[ASAP] Postdeposition UV-Ozone Treatment: An Enabling Technique to Enhance the Direct Adhesion of Gold Thin Films to Oxidized Silicon

By Hai Le-The*†, Roald M. Tiggelaar‡, Erwin Berenschot§, Albert van den Berg†, Niels Tas§, and Jan C. T. Eijkel*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b01403

[ASAP] Lightweight, Superelastic Yet Thermoconductive Boron Nitride Nanocomposite Aerogel for Thermal Energy Regulation

By Jiemin Wang†, Dan Liu*†, Quanxiang Li†, Cheng Chen†, Zhiqiang Chen†, Pingan Song‡, Jian Hao§, Yinwei Li§, Sobhan Fakhrhoseini†, Minoo Naebe†, Xungai Wang†, and Weiwei Lei*† from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02182

[ASAP] Iron-Sequestering Nanocompartments as Multiplexed Electron Microscopy Gene Reporters

By Felix Sigmund†‡§¶, Susanne Pettinger†‡§¶, Massimo Kube?¶, Fabian Schneider?, Martina Schifferer?#, Steffen Schneider??, Maria V. Efremova†‡§^, Jesu´s Pujol-Marti´&, Michaela Aichler?, Axel Walch?, Thomas Misgeld?#, Hendrik Dietz?, and Gil G. Westmeyer*†‡§ from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b03140

[ASAP] Photoluminescence Activation of Organic Dyes via Optically Trapped Quantum Dots

By He´ctor Rodri´guez-Rodri´guez†‡, Mari´a Acebro´n†, Francisco J. Iborra§, J. Ricardo Arias-Gonzalez*†?, and Beatriz H. Jua´rez*†‡? from ACS Nano: Latest Articles (ACS Publications). Published on Jun 13, 2019.

TOC Graphic

ACS Nano
DOI: 10.1021/acsnano.9b02835

Non‐Innocent Methylene Linker in Bridged Lewis Pair Initiators

By Michael Weger, Raphael K. Grötsch, Maximilian G. Knaus, Marco M. Giuman, David C. Mayer, Philipp J. Altmann, Estelle Mossou, Birger Dittrich, Alexander Pöthig, Bernhard Rieger from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 12, 2019.

Changing paths: The deprotonation of α‐acidic Michael‐type monomers, a formerly unwanted side reaction, is shown, in a combined study using diffraction techniques (X‐ray and neutron) as well as experimental and theoretical investigations, to be the initiation step of polymerization using Al−P‐bridged Lewis pairs. The polymerization occurs with high turnover frequencies, enables copolymerization, and yields polymers with narrow polydispersities. Abstract Deprotonation usually occurs as an unwanted side reaction in the Lewis pair polymerization of Michael acceptors, for which the conjugated addition of the Lewis base to the acid‐activated monomer is the commonly accepted initiation mechanism. This has also been reported for B−P‐based bridged Lewis pairs (BLPs) that form macrocyclic addition products. We now show that the formerly unwanted deprotonation is the likely initiation pathway in the case of Al−P‐based BLPs. In a detailed study of a series of Al−P‐based BLPs, using a combination of single‐crystal diffraction experiments (X‐ray and neutron) and mechanistic investigations (experimental and computational), an active role of the methylene bridge was revealed, acting as a base towards the α‐acidic monomers. Additionally, the polymerization studies proved a living behavior combined with significantly high activities, narrow molecular mass distributions, and the possibility of copolymerization.

Continuous‐Flow Electrochemical Generator of Hypervalent Iodine Reagents: Synthetic Applications

By Mohamed Elsherbini, Bethan Winterson, Haifa Alharbi, Ana A. Folgueiras‐Amador, Célina Génot, Thomas Wirth from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 12, 2019.

A fast and efficient electrochemical method for the generation of unstable iodine(III) reagents is reported. They can be either used directly in oxidative transformations or be converted into stable hypervalent iodine reagents. Abstract An efficient and reliable electrochemical generator of hypervalent iodine reagents has been developed. In the anodic oxidation of iodoarenes to hypervalent iodine reagents under flow conditions, the use of electricity replaces hazardous and costly chemical oxidants. Unstable hypervalent iodine reagents can be prepared easily and coupled with different substrates to achieve oxidative transformations in high yields. The unstable, electrochemically generated reagents can also easily be transformed into classic bench‐stable hypervalent iodine reagents through ligand exchange. The combination of electrochemical and flow‐chemistry advantages largely improves the ecological footprint of the overall process compared to conventional approaches.

Structural Studies Reveal Enantiospecific Recognition of a DNA G‐Quadruplex by a Ruthenium Polypyridyl Complex

By Kane McQuaid, Holly Abell, Sarah P. Gurung, David R. Allan, Graeme Winter, Thomas Sorensen, David J. Cardin, John A. Brazier, Christine J. Cardin, James P. Hall from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 12, 2019.

One Way or Another: Enantiospecificity was observed in the binding of the ruthenium polypyridyl complex Λ/Δ‐[Ru(TAP)2(11‐CN‐dppz)]2+ to the G‐quadruplex‐forming sequence d(TAGGGTTA). Crystallographic studies yielded the first crystal structure of a ruthenium‐bound G‐quadruplex and reveal that the quadruplex adopts an antiparallel topology in the presence of the Λ isomer, but retains its parallel conformation with the Δ isomer. Abstract By using X‐ray crystallography, we show that the complexes Λ/Δ‐[Ru(TAP)2(11‐CN‐dppz)]2+ (TAP=1,4,5,8‐tetraazaphenanthrene, dppz=dipyridophenazine) bind DNA G‐quadruplex in an enantiospecific manner that parallels the specificity of these complexes with duplex DNA. The Λ complex crystallises with the normally parallel stranded d(TAGGGTTA) tetraplex to give the first such antiparallel strand assembly in which syn‐guanosine is adjacent to the complex at the 5′ end of the quadruplex core. SRCD measurements confirm that the same conformational switch occurs in solution. The Δ enantiomer, by contrast, is present in the structure but stacked at the ends of the assembly. In addition, we report the structure of Λ‐[Ru(phen)2(11‐CN‐dppz)]2+ bound to d(TCGGCGCCGA), a duplex‐forming sequence, and use both structural models to provide insight into the motif‐specific luminescence response of the isostructural phen analogue enantiomers.

The Emergence of Carbon Isotope Exchange

By Karen Hinsinger, Grégory Pieters from Wiley: Angewandte Chemie International Edition: Table of Contents. Published on Jun 12, 2019.

Significant progress in C−C bond activation with transition metals has recently enabled the development of several carbon isotope exchange reactions. These methods are based on C−C bond decarboxylative carboxylation reactions in the presence of selected transition metals and labelled carbon monoxide or carbon dioxide.

Mon 11 Nov 18:00: The Maths of Whole Universes

From All Talks (aka the CURE list). Published on Jun 12, 2019.

The Maths of Whole Universes

Abstract not available

Add to your calendar or Include in your list

Wed 27 Nov 16:00: The lectin pathway of complement: The Swiss army knife of innate immunity

From All Talks (aka the CURE list). Published on Jun 12, 2019.

The lectin pathway of complement: The Swiss army knife of innate immunity

Abstract not available

Add to your calendar or Include in your list

High Energy Capacitors Based on All Metal‐Organic Frameworks Derivatives and Solar‐Charging Station Application

By Xijun Wei, Wanping Hu, Huarong Peng, Yuli Xiong, Peng Xiao, Yunhuai Zhang, Guozhong Cao from Wiley: Small: Table of Contents. Published on Jun 12, 2019.

This work successfully adds two novel materials to the family of metal‐organic frameworks (MOFs) derivatives. A high energy density device of 46 Wh kg−1 at 690 W kg−1 is assembled on the basis of NiO/Co3O4 microcubes and Fe2O3 microleaves and a solar‐charging power station is fabricated using solar cells and MOFs derivatives. Abstract High energy and efficient solar charging stations using electrochemical capacitors (ECs) are a promising portable power source for the future. In this work, two kinds of metal‐organic framework (MOF) derivatives, NiO/Co3O4 microcubes and Fe2O3 microleaves, are prepared via thermal treatment and assembled into electrochemical capacitors, which deliver a relatively high specific energy density of 46 Wh kg−1 at 690 W kg−1. In addition, a solar‐charging power system consisting of the electrochemical capacitors and monocrystalline silicon plates is fabricated and a motor fan or 25 LEDs for 5 and 30 min, respectively, is powered. This work not only adds two novel materials to the growing categories of MOF‐derived advanced materials, but also successfully achieves an efficient solar‐ECs system for the first time based on all MOF derivatives, which has a certain reference for developing efficient solar‐charge systems.

Synergistic Effects of Novel Superparamagnetic/Upconversion HA Material and Ti/Magnet Implant on Biological Performance and Long‐Term In Vivo Tracking

By Xiyu Li, Qin Zou, Yi Man, Wei Li from Wiley: Small: Table of Contents. Published on Jun 12, 2019.

The two‐step doping of Yb/Ho and Fe ions endows the hydroxyapatite (HA) material (HYH‐Fe) with both superparamagnetism and upconversion fluorescence. The HYH‐Fe material can effectively promote osteogenesis and osteointegration under the synergistic effect of a Ti/magnet implant, and provides long‐term and distinct in vivo tracking characteristics of microcomputed tomography (micro‐CT) imaging and laser scanning confocal microscope (LSCM) fluorescent imaging. Abstract To solve the clinical challenges presented by the long‐term tracking of implanted hydroxyapatite (HA) bone repair material and to investigate the synergistic effects of superparamagnetic HA and a static magnetic field (SMF) on the promotion of osteogenesis, herein a new type of superparamagnetic/upconversion‐generating HA material (HYH‐Fe) is developed via a two‐step doping method, as well as a specially‐designed titanium implant with a built‐in magnet to provide a local static magnetic field in vivo. The results show that the prepared HYH‐Fe material maintains the crystal structure of HA and exhibits good cytocompatibility. The combined use of the superparamagnetic HYH‐Fe material and SMF can effectively and synergistically promote osteogenesis/osteointegration surrounding the Ti implants. In addition, the HYH‐Fe material exhibits distinct advantages in terms of both long‐term fluorescence tracking and microcomputed tomography (micro‐CT) tracking. The new material and tracking strategy in this study provide scientific feasibility and will have important clinical value for long‐term tracking and evaluation of implanted materials and the bone repair effect.

[ASAP] Synthesis, Simulation, and Self-Assembly of a Model Amphiphile To Push the Limits of Block Polymer Nanopatterning

By Leonel Barreda†, Zhengyuan Shen†‡s, Qile P. Chen†‡§, Timothy P. Lodge*†§, J. Ilja Siepmann*†‡§, and Marc A. Hillmyer*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 12, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01248

[ASAP] Microscopic Imaging of the Stress Tensor in Diamond Using in Situ Quantum Sensors

By D. A. Broadway†§, B. C. Johnson†§, M. S. J. Barson‡, S. E. Lillie†§, N. Dontschuk†§, D. J. McCloskey†, A. Tsai†, T. Teraji¶, D. A. Simpson†, A. Stacey§#, J. C. McCallum†, J. E. Bradby?, M. W. Doherty‡, L. C. L. Hollenberg*†§, and J.-P. Tetienne*† from Nano Letters: Latest Articles (ACS Publications). Published on Jun 12, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01402

[ASAP] Observation of Intersubband Polaritons in a Single Nanoantenna Using Nano-FTIR Spectroscopy

By Chih-Feng Wang†‡, Terefe G. Habteyes†, Ting Shan Luk§?, John F. Klem?, Igal Brener§?, Hou-Tong Chen‡, and Oleg Mitrofanov*§? from Nano Letters: Latest Articles (ACS Publications). Published on Jun 12, 2019.

TOC Graphic

Nano Letters
DOI: 10.1021/acs.nanolett.9b01623