Catalytic Generation of Carbanions through Carbonyl Umpolung
Angew Chem Int Ed Engl. 2021 May 15. doi: 10.1002/anie.202105469. Online ahead of print.ABSTRACTCarbonyl Umpolung is a powerful strategy in organic chemistry to construct complex molecules. Over the last years, versatile catalytic approaches for the generation of acyl anion equivalents from carbonyls have been developed, but methods to obtain alkyl carbanions from carbonyls in a catalytic fashions are still at an early stage. This Minireview summarizes recent progress in the generation of alkyl carbanions through catalytic carbonyl Umpolung. Two different catalytic approaches can be utilized to enable alkyl carbanion gener...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Shun Wang Burkhard K önig Source Type: research

Heteroaromatic Hyperbranched Polyelectrolytes: Multicomponent Polyannulation and Photodynamic Biopatterning
In this study, we reported an efficient multicomponent polyannulation for in situ generation of heteroaromatic hyperbranched polyelectrolytes by using readily accessible internal diynes and low-cost, commercially available arylnitriles, NaSbF 6 , and H 2 O/AcOH. The polymers were obtained in excellent yields (up to 99%) with extraordinary high molecular weights (Mw up to 1.011 × 10^6 ) and low polydispersity indices. The resulting polymers showed good processibility and high quantum yields with tunable emission in the solid state, making them as ideal materials for highly ordered fluorescent photopatterning. These hy...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Xiaolin Liu Minghui Xiao Ke Xue Mingzhao Li Dongming Liu Yong Wang Xinzhe Yang Yubing Hu Ryan T K Kwok Anjun Qin Chunlei Zhu Jacky W Y Lam Ben Zhong Tang Source Type: research

Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent
In this study, polymeric mechanoradicals were formed in situ under ball-milling conditions to undergo radical-radical coupling with a prefluorescent nitroxide-based reagent in order to incorporate a luminophore into the polymer main chains via a covalent bond. This method allowed the direct and conceptually simple preparation of luminescent polymeric materials from a wide range of generic polymers such as polystyrene, polymethyl methacrylate, and polyethylene. These results indicate that the present mechanoradical coupling strategy may help to transform existing commodity polymers into more valuable functional materials.PM...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Koji Kubota Naoki Toyoshima Daiyo Miura Julong Jiang Satoshi Maeda Mingoo Jin Hajime Ito Source Type: research

Stable Dye-Sensitized Solar Cells Based on Copper(II/I) Redox Mediators Bearing a Pentadentate Ligand
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202104563. Online ahead of print.ABSTRACTIn recent years, copper redox mediators have attracted growing interest in dye-sensitized solar cells (DSCs), exhibiting high photovoltage of over 1.0 V and outstanding performance under ambient lighting. However, emerging experimental evidence reveals that the ubiquitously used Lewis base additives in the electrolytes, such as 4- tert -butylpyridine (TBP), coordinate to the Cu(II) species, which restricts further enhancement of device performance and stability for these electrolytes. Here, we report for the first time the appli...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Ze Yu Hailong Rui Junyu Shen Lihua Li Hongxian Han Licheng Sun Source Type: research

DNA framework-engineered long-range electrostatic interactions for DNA hybridization reactions
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202106010. Online ahead of print.ABSTRACTLong-range electrostatic interactions beyond biomolecular interaction interfaces have not been extensively studied due to the limitation in engineering electric double layers in physiological fluids. Here we find that long-range electrostatic interactions play an essential role in kinetic modulation of DNA hybridizations. Protein and gold nanoparticles with different charges are encapsulated in tetrahedral frameworks to exert diverse electrostatic effects on site-specifically tethered single DNA strands. Using this strategy, we ...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Zhibei Qu Yi Nan Zhang Zheze Dai Yichi Zhang Yaya Hao Jianlei Shen Fei Wang Qian Li Chunhai Fan Xiaoguo Liu Source Type: research

Nocathioamides, uncovered by a Tunable Metabologenomic Approach, define a Novel Class of Chimeric Lanthipeptides
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202102571. Online ahead of print.ABSTRACTThe increasing number of available genomes, in combination with advanced genome mining techniques, unveiled a plethora of biosynthetic gene clusters (BGCs) coding for ribosomal synthesized and post-translationally modified peptides (RiPPs). The products of these BGCs often represent an enormous resource for new and bioactive compounds, but frequently, they cannot be readily isolated and remain cryptic. Here, we describe a tunable metabologenomic approach that recruits a synergism of bioinformatics in tandem with isotope- and NMR...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Hamada Saad Saefuddin Aziz Matthias Gehringer Markus Kramer Jan Straetener Anne Berscheid Heike Br ötz-Oesterhelt Harald Gross Source Type: research

Rational Design of Crystallization Induced Emission Probes to Detect Amorphous Protein Aggregation in Live Cells
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202103674. Online ahead of print.ABSTRACTUnlike amyloid, amorphous protein aggregation of no defined structures has been challenging to target and detect in complex cellular milieu. Herein, we rationally designed amorphous protein aggregation sensors from aggregation induced emission probes (AIEgens). Utilizing dicyanoisophorone as a model AIEgen scaffold, we first sensitized the fluorescence of AIEgens to non-polar and viscous environment mimicking the interior of amorphous aggregated proteins. We identified a generally applicable moiety (dimethylaminophenylene) for s...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Di Shen Wenhan Jin Yulong Bai Yanan Huang Haochen Lyu Lianggang Zeng Mengdie Wang Yuqi Tang Wang Wan Xuepeng Dong Zhenming Gao Hai-Long Piao Xiaojing Liu Yu Liu Source Type: research

Kirkendall Effect Boosts Phosphorylated nZVI for Efficient Heavy Metal Wastewater Treatment
Angew Chem Int Ed Engl. 2021 May 15. doi: 10.1002/anie.202104586. Online ahead of print.ABSTRACTRemoval of non-biodegradable heavy metals has been the top priority in wastewater treatment; the development of green technologies remains a significant challenge. Here we show the phosphorylated nanoscale zero-valent iron (nZVI) is promising for heavy metals (Ni(II), Cu(II), Cr(VI), Hg(II)) removal via boosted Kirkendall effect. Phosphorylation confines tensile hoop stress on the nZVI particles and "breaks" the structurally-dense spherical nZVI to produce numerous radial nanocracks. Exemplified by Ni(II) removal, the ...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Lizhi Zhang Meiqi Li Huan Shang Hao Li Yanfeng Hong Cancan Ling Kai Wei Biao Zhou Chengliang Mao Zhihui Ai Source Type: research

Catalytic Generation of Carbanions through Carbonyl Umpolung
Angew Chem Int Ed Engl. 2021 May 15. doi: 10.1002/anie.202105469. Online ahead of print.ABSTRACTCarbonyl Umpolung is a powerful strategy in organic chemistry to construct complex molecules. Over the last years, versatile catalytic approaches for the generation of acyl anion equivalents from carbonyls have been developed, but methods to obtain alkyl carbanions from carbonyls in a catalytic fashions are still at an early stage. This Minireview summarizes recent progress in the generation of alkyl carbanions through catalytic carbonyl Umpolung. Two different catalytic approaches can be utilized to enable alkyl carbanion gener...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Shun Wang Burkhard K önig Source Type: research

Heteroaromatic Hyperbranched Polyelectrolytes: Multicomponent Polyannulation and Photodynamic Biopatterning
In this study, we reported an efficient multicomponent polyannulation for in situ generation of heteroaromatic hyperbranched polyelectrolytes by using readily accessible internal diynes and low-cost, commercially available arylnitriles, NaSbF 6 , and H 2 O/AcOH. The polymers were obtained in excellent yields (up to 99%) with extraordinary high molecular weights (Mw up to 1.011 × 10^6 ) and low polydispersity indices. The resulting polymers showed good processibility and high quantum yields with tunable emission in the solid state, making them as ideal materials for highly ordered fluorescent photopatterning. These hy...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Xiaolin Liu Minghui Xiao Ke Xue Mingzhao Li Dongming Liu Yong Wang Xinzhe Yang Yubing Hu Ryan T K Kwok Anjun Qin Chunlei Zhu Jacky W Y Lam Ben Zhong Tang Source Type: research

Introduction of a Luminophore into Generic Polymers via Mechanoradical Coupling with a Prefluorescent Reagent
In this study, polymeric mechanoradicals were formed in situ under ball-milling conditions to undergo radical-radical coupling with a prefluorescent nitroxide-based reagent in order to incorporate a luminophore into the polymer main chains via a covalent bond. This method allowed the direct and conceptually simple preparation of luminescent polymeric materials from a wide range of generic polymers such as polystyrene, polymethyl methacrylate, and polyethylene. These results indicate that the present mechanoradical coupling strategy may help to transform existing commodity polymers into more valuable functional materials.PM...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Koji Kubota Naoki Toyoshima Daiyo Miura Julong Jiang Satoshi Maeda Mingoo Jin Hajime Ito Source Type: research

Stable Dye-Sensitized Solar Cells Based on Copper(II/I) Redox Mediators Bearing a Pentadentate Ligand
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202104563. Online ahead of print.ABSTRACTIn recent years, copper redox mediators have attracted growing interest in dye-sensitized solar cells (DSCs), exhibiting high photovoltage of over 1.0 V and outstanding performance under ambient lighting. However, emerging experimental evidence reveals that the ubiquitously used Lewis base additives in the electrolytes, such as 4- tert -butylpyridine (TBP), coordinate to the Cu(II) species, which restricts further enhancement of device performance and stability for these electrolytes. Here, we report for the first time the appli...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Ze Yu Hailong Rui Junyu Shen Lihua Li Hongxian Han Licheng Sun Source Type: research

DNA framework-engineered long-range electrostatic interactions for DNA hybridization reactions
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202106010. Online ahead of print.ABSTRACTLong-range electrostatic interactions beyond biomolecular interaction interfaces have not been extensively studied due to the limitation in engineering electric double layers in physiological fluids. Here we find that long-range electrostatic interactions play an essential role in kinetic modulation of DNA hybridizations. Protein and gold nanoparticles with different charges are encapsulated in tetrahedral frameworks to exert diverse electrostatic effects on site-specifically tethered single DNA strands. Using this strategy, we ...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Zhibei Qu Yi Nan Zhang Zheze Dai Yichi Zhang Yaya Hao Jianlei Shen Fei Wang Qian Li Chunhai Fan Xiaoguo Liu Source Type: research

Nocathioamides, uncovered by a Tunable Metabologenomic Approach, define a Novel Class of Chimeric Lanthipeptides
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202102571. Online ahead of print.ABSTRACTThe increasing number of available genomes, in combination with advanced genome mining techniques, unveiled a plethora of biosynthetic gene clusters (BGCs) coding for ribosomal synthesized and post-translationally modified peptides (RiPPs). The products of these BGCs often represent an enormous resource for new and bioactive compounds, but frequently, they cannot be readily isolated and remain cryptic. Here, we describe a tunable metabologenomic approach that recruits a synergism of bioinformatics in tandem with isotope- and NMR...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Hamada Saad Saefuddin Aziz Matthias Gehringer Markus Kramer Jan Straetener Anne Berscheid Heike Br ötz-Oesterhelt Harald Gross Source Type: research

Rational Design of Crystallization Induced Emission Probes to Detect Amorphous Protein Aggregation in Live Cells
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202103674. Online ahead of print.ABSTRACTUnlike amyloid, amorphous protein aggregation of no defined structures has been challenging to target and detect in complex cellular milieu. Herein, we rationally designed amorphous protein aggregation sensors from aggregation induced emission probes (AIEgens). Utilizing dicyanoisophorone as a model AIEgen scaffold, we first sensitized the fluorescence of AIEgens to non-polar and viscous environment mimicking the interior of amorphous aggregated proteins. We identified a generally applicable moiety (dimethylaminophenylene) for s...
Source: Angewandte Chemie - May 15, 2021 Category: Chemistry Authors: Di Shen Wenhan Jin Yulong Bai Yanan Huang Haochen Lyu Lianggang Zeng Mengdie Wang Yuqi Tang Wang Wan Xuepeng Dong Zhenming Gao Hai-Long Piao Xiaojing Liu Yu Liu Source Type: research

Non-invasive Regulation of Cellular Morphology Using a Photoswitchable Mechanical DNA Polymer
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202105425. Online ahead of print.ABSTRACTThe extracellular matrix, residing the cells provides a dynamic and reversible environment. Spatiotemporal cues are essential when cells are undergoing morphogenesis, repair and differentiation. Recapitulation of such an intricate system with reversible presentation of nanoscale cues can help us better understand cellular processes and can allow precise manipulation of cell function in vitro. Herein, we formulated a photoswitchable DNA mechanical nanostructure containing azobenzene moieties and dynamically regulated the spatial ...
Source: Angewandte Chemie - May 14, 2021 Category: Chemistry Authors: Soumya Sethi Kumi Hidaka Hiroshi Sugiyama Masayuki Endo Source Type: research

Merging Electron Transfer with 1,2-Metalate Rearrangement: Deoxygenative Arylation of Inert Amides with Arylboronic Esters
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202104359. Online ahead of print.ABSTRACTAmides are essentially inert carboxyl derivatives in many types of chemical transformations. In particular, deoxygenative C-C bond formation of amides to synthetically important amines is a long-standing challenge for synthetic chemists due to the inertness of the resonance-stabilized amide C=O bond. Herein, it is disclosed that by merging electron transfer induced activation with 1,2-metalate rearrangement, a wide range of inert amides react smoothly with arylboron regents, affording a series of biologically relevant diarylmeth...
Source: Angewandte Chemie - May 14, 2021 Category: Chemistry Authors: Xiaoming Wang Jiwen Jiao Source Type: research

Interfacial Microenvironment Modulation Boosting Electron Transfer between Metal Nanoparticles and MOFs for Enhanced Photocatalysis
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202104219. Online ahead of print.ABSTRACTInterfacial electron transfer between cocatalyst and photosensitizer plays a key role in heterogeneous photocatalysis, yet the underlying mechanism remains subtle and unclear. Particularly, the surfactant coated on the metal cocatalysts, greatly modulating the microenvironment of catalytic sites, is largely ignored. Herein, a series of Pt co-catalysts with modulated microenvironments, including polyvinylpyrrolidone (PVP) capped Pt nanoparticles (denoted as Pt PVP ), Pt with partially removed PVP (Pt rPVP ), and clean Pt without ...
Source: Angewandte Chemie - May 14, 2021 Category: Chemistry Authors: Mingliang Xu Dandan Li Kang Sun Long Jiao Chenfan Xie Chunmei Ding Hai-Long Jiang Source Type: research

The Current Status of MOF and COF Applications
Angew Chem Int Ed Engl. 2021 May 14. doi: 10.1002/anie.202106259. Online ahead of print.ABSTRACTThe amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine-tuning of metal-organic framework (MOF) and covalent organic framework (COF) properties beyo...
Source: Angewandte Chemie - May 14, 2021 Category: Chemistry Authors: Ralph Freund Orysia Zaremba Giel Arnauts Rob Ameloot Grigorii Skorupskii Mircea Dinc ă Anastasiya Bavykina Jorge Gascon Aleksander Ejsmont Joanna Go ściańska Markus Kalmutzki Ulrich L ächelt Evelyn Ploetz Christian Diercks Stefan Wuttke Source Type: research

The First High-Temperature Supramolecular Radical Ferroics
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202105744. Online ahead of print.ABSTRACTSince the discovery of TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) in 1973, organic radical ferroics attracted widespread interest among the scientific community. However, the relatively low Curie temperature of 287 K and melting point of 311 K severely hinder its application potential. Despite extensive interest, high-temperature radical ferroics have not been found to date. Here, taking advantage of chemical design theory and supramolecular radical chemistry, we successfully designed two high-temperature organic supramolecula...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Yibao Li Chao-Ran Huang Ye Du Hang Peng Yu-Ling Zeng Jun-Chao Liu Yongfa Xie Ren-Gen Xiong Source Type: research

Carboxylate Ligands-Promoted Superior Electrocatalytic Performance for Oxygen Evolution Reaction and Their Mechanisms
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104148. Online ahead of print.ABSTRACTMetal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very efficient for oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in situ transformed metal (oxy)hydroxides during OER is often overlooked. Here we detailedly reveal the extraordinary role and mechanism of surface adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER electrocatalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), syn...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Cheng-Fei Li Jia-Wei Zhao Ling-Jie Xie Jin-Qi Wu Qian Ren Yu Wang Gao-Ren Li Source Type: research

All-inorganic quantum dot LEDs based on phase-stabilized α-CsPbI3 perovskite
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104812. Online ahead of print.ABSTRACTThe all-inorganic nature of CsPbI 3 perovskites offers an avenue to enhance stability in perovskite devices. Concerted research efforts have led to improved stability of the black phase in CsPbI 3 films; however, these strategies - including strain and doping - are based on organic-ligand-capped perovskites, which prevent perovskites from forming the close-packed QD solids necessary to achieve high charge transport and thermal transport. Here we develop an inorganic ligand exchange that leads to CsPbI 3 QD films that unite super...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Ya-Kun Wang Fanglong Yuan Yitong Dong Jiao-Yang Li Andrew Johnston Bin Chen Makhsud I Saidaminov Chun Zhou Xiaopeng Zheng Yi Hou Koen Bertens Hinako Ebe Dongxin Ma Zhengtao Deng Shuai Yuan Rui Chen Laxmi Kishore Sagar Jiakai Liu James Fan Peicheng Li Xiya Source Type: research

Mechanosynthesis of Higher-Order Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202101248. Online ahead of print.ABSTRACTThe ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research. To date, numerous examples of multicomponent crystals comprising organic molecules have been reported. However, the crystal engineering of cocrystals comprising both organic and inorganic chemical units is still poorly understood and mostly unexplored. Here, we report a new diverse set of higher-order cocrystals (HOCs) based on the structurally versatile - yet largely unexplored - phosph(V/V)azane ...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Zi Xuan Ng Davin Tan Wei Liang Teo Felix Le ón Xiaoyan Shi Ying Sim Yongxin Li Rakesh Ganguly Yanli Zhao Sharmarke Mohamed Felipe Garcia Source Type: research

Leakage-Proof Electrolyte Chemistry for High Performance Lithium-Sulfur Battery
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202103209. Online ahead of print.ABSTRACTIt is well known that electrolyte leakage is a severe safety concern in commercially available lithium batteries, especially for pouch cell applications. With highly volatile 1,2-dimethoxyethane as solvent, the leakage related hazards are more pronounced and serious for promising lithium-sulfur batteries, which feature high energy density exceeding 500 Wh kg -1 . To address this concern, a leakage-proof electrolyte is delicately designed through tuning the electrolyte chemistry to achieve high performance lithium-sulfur batterie...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Jiangwei Ju Shanmu Dong Yanyan Cui Yanfeng Zhang Ben Tang Feng Jiang Zili Cui Huanrui Zhang Xiaofan Du Tao Lu Lang Huang Guanglei Cui Liquan Chen Source Type: research

H2O-Built Proton Transfer Bridge Pronouncedly Enhances Continuous Methane Oxidation to Methanol over Cu-BEA Zeolite
Angew Chem Int Ed Engl. 2021 May 13. doi: 10.1002/anie.202105167. Online ahead of print.ABSTRACTDirect oxidation of methane to methanol (DMTM) constitutes a big challenge in C 1 chemistry. Herein, we present a continuous N 2 O-DMTM investigation by simultaneously introducing 10 vol% H 2 O into the reaction system over Cu-BEA zeolites. Combining a D 2 O isotopic tracer technique and ab initio molecular dynamics (AIMD) simulation, we for the first time demonstrate that the H 2 O molecules can participate in the reaction through a proton transfer route, wherein the H 2 O molecules can build a high-speed proton transfer bridge...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Ruinian Xu Ning Liu Chengna Dai Yan Li Jie Zhang Bin Wu Gangqiang Yu Biaohua Chen Source Type: research

Chemical Identification of Catalytically Active Sites on Oxygen-doped Carbon Nanosheet to Decipher the High Activity for Electro-synthesis Hydrogen Peroxide
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104480. Online ahead of print.ABSTRACTElectrochemical production of hydrogen peroxide through two-electron (2e- ) oxygen reduction reaction (ORR) is an on-site and clean route. Oxygen-doped carbon materials with high ORR activity and H2O2 selectivity have been considered as the promising catalysts, however, there is still a lack of direct experimental evidence to identify true active sites at complex carbon surface. Herein, we proposed a chemical titration strategy to decipher the oxygen-doped carbon nanosheet (OCNS900 ) catalyst for 2e- ORR. The OCNS900 exhibits ou...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Shanyong Chen Tao Luo Kejun Chen Yiyang Lin Junwei Fu Kang Liu Chao Cai Qiyou Wang Huangjingwei Li Xiaojing Li Junhua Hu Hongmei Li Mingshan Zhu Min Liu Source Type: research

Mechanistic study of carbon dioxide hydrogenation over Pd/ZnO-based catalysts: the role of palladium-zinc alloy in selective methanol synthesis
Angew Chem Int Ed Engl. 2021 May 13. doi: 10.1002/anie.202103087. Online ahead of print.ABSTRACTPd/ZnO catalysts show good activity and high selectivity to methanol during catalytic CO 2 hydrogenation. The palladium-zinc alloy phase has been usually considered as the active phase, though mechanistic studies under operando conditions have not been conducted to verify this. Here, we report a detailed mechanistic study under realistic conditions of methanol synthesis, using in situ and operando X-ray absorption spectroscopy, X-ray powder diffraction and time-resolved isotope labeling experiments coupled with FTIR spectroscopy...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Maxim Zabilskiy Vitaly L Sushkevich Mark A Newton Frank Krumeich Maarten Nachtegaal Jeroen A van Bokhoven Source Type: research

Ultra long-lived triplet excited state in water at room temperature: Insights on the molecular design of tridecafullerenes
We report the finding of an ultra long-lived triplet with a mean lifetime of 93 ms in aqueous phase at room temperature, measured for a globular tridecafullerene with a highly compact glycodendrimeric structure. A series of three tridecafullerenes bearing different glycodendrons and spacers to the C 60 units have been synthesized and characterized. UV/Vis spectra and DLS experiments prove their aggregation in water. Steady state and time-resolved fluorescence experiments suggest a different degree of inner solvation of the multifullerenes depending on their molecular design. Efficient quenching of the triplet states by O 2...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Javier Ramos-Soriano Alfonso P érez-Sánchez Sergio Ram írez-Barroso Beatriz M Illescas Khalid Azmani Antonio Rodr íguez-Fortea Josep M Poblet Cormac Hally Santi Nonell David Garc ía-Fresnadillo Javier Rojo Nazario Mart ín Source Type: research

The First High-Temperature Supramolecular Radical Ferroics
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202105744. Online ahead of print.ABSTRACTSince the discovery of TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) in 1973, organic radical ferroics attracted widespread interest among the scientific community. However, the relatively low Curie temperature of 287 K and melting point of 311 K severely hinder its application potential. Despite extensive interest, high-temperature radical ferroics have not been found to date. Here, taking advantage of chemical design theory and supramolecular radical chemistry, we successfully designed two high-temperature organic supramolecula...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Yibao Li Chao-Ran Huang Ye Du Hang Peng Yu-Ling Zeng Jun-Chao Liu Yongfa Xie Ren-Gen Xiong Source Type: research

Carboxylate Ligands-Promoted Superior Electrocatalytic Performance for Oxygen Evolution Reaction and Their Mechanisms
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104148. Online ahead of print.ABSTRACTMetal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very efficient for oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in situ transformed metal (oxy)hydroxides during OER is often overlooked. Here we detailedly reveal the extraordinary role and mechanism of surface adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER electrocatalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), syn...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Cheng-Fei Li Jia-Wei Zhao Ling-Jie Xie Jin-Qi Wu Qian Ren Yu Wang Gao-Ren Li Source Type: research

All-inorganic quantum dot LEDs based on phase-stabilized α-CsPbI3 perovskite
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104812. Online ahead of print.ABSTRACTThe all-inorganic nature of CsPbI 3 perovskites offers an avenue to enhance stability in perovskite devices. Concerted research efforts have led to improved stability of the black phase in CsPbI 3 films; however, these strategies - including strain and doping - are based on organic-ligand-capped perovskites, which prevent perovskites from forming the close-packed QD solids necessary to achieve high charge transport and thermal transport. Here we develop an inorganic ligand exchange that leads to CsPbI 3 QD films that unite super...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Ya-Kun Wang Fanglong Yuan Yitong Dong Jiao-Yang Li Andrew Johnston Bin Chen Makhsud I Saidaminov Chun Zhou Xiaopeng Zheng Yi Hou Koen Bertens Hinako Ebe Dongxin Ma Zhengtao Deng Shuai Yuan Rui Chen Laxmi Kishore Sagar Jiakai Liu James Fan Peicheng Li Xiya Source Type: research

Mechanosynthesis of Higher-Order Cocrystals: Tuning Order, Functionality and Size in Cocrystal Design
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202101248. Online ahead of print.ABSTRACTThe ability to rationally design and predictably construct crystalline solids has been the hallmark of crystal engineering research. To date, numerous examples of multicomponent crystals comprising organic molecules have been reported. However, the crystal engineering of cocrystals comprising both organic and inorganic chemical units is still poorly understood and mostly unexplored. Here, we report a new diverse set of higher-order cocrystals (HOCs) based on the structurally versatile - yet largely unexplored - phosph(V/V)azane ...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Zi Xuan Ng Davin Tan Wei Liang Teo Felix Le ón Xiaoyan Shi Ying Sim Yongxin Li Rakesh Ganguly Yanli Zhao Sharmarke Mohamed Felipe Garcia Source Type: research

Leakage-Proof Electrolyte Chemistry for High Performance Lithium-Sulfur Battery
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202103209. Online ahead of print.ABSTRACTIt is well known that electrolyte leakage is a severe safety concern in commercially available lithium batteries, especially for pouch cell applications. With highly volatile 1,2-dimethoxyethane as solvent, the leakage related hazards are more pronounced and serious for promising lithium-sulfur batteries, which feature high energy density exceeding 500 Wh kg -1 . To address this concern, a leakage-proof electrolyte is delicately designed through tuning the electrolyte chemistry to achieve high performance lithium-sulfur batterie...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Jiangwei Ju Shanmu Dong Yanyan Cui Yanfeng Zhang Ben Tang Feng Jiang Zili Cui Huanrui Zhang Xiaofan Du Tao Lu Lang Huang Guanglei Cui Liquan Chen Source Type: research

H2O-Built Proton Transfer Bridge Pronouncedly Enhances Continuous Methane Oxidation to Methanol over Cu-BEA Zeolite
Angew Chem Int Ed Engl. 2021 May 13. doi: 10.1002/anie.202105167. Online ahead of print.ABSTRACTDirect oxidation of methane to methanol (DMTM) constitutes a big challenge in C 1 chemistry. Herein, we present a continuous N 2 O-DMTM investigation by simultaneously introducing 10 vol% H 2 O into the reaction system over Cu-BEA zeolites. Combining a D 2 O isotopic tracer technique and ab initio molecular dynamics (AIMD) simulation, we for the first time demonstrate that the H 2 O molecules can participate in the reaction through a proton transfer route, wherein the H 2 O molecules can build a high-speed proton transfer bridge...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Ruinian Xu Ning Liu Chengna Dai Yan Li Jie Zhang Bin Wu Gangqiang Yu Biaohua Chen Source Type: research

Chemical Identification of Catalytically Active Sites on Oxygen-doped Carbon Nanosheet to Decipher the High Activity for Electro-synthesis Hydrogen Peroxide
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104480. Online ahead of print.ABSTRACTElectrochemical production of hydrogen peroxide through two-electron (2e- ) oxygen reduction reaction (ORR) is an on-site and clean route. Oxygen-doped carbon materials with high ORR activity and H2O2 selectivity have been considered as the promising catalysts, however, there is still a lack of direct experimental evidence to identify true active sites at complex carbon surface. Herein, we proposed a chemical titration strategy to decipher the oxygen-doped carbon nanosheet (OCNS900 ) catalyst for 2e- ORR. The OCNS900 exhibits ou...
Source: Angewandte Chemie - May 13, 2021 Category: Chemistry Authors: Shanyong Chen Tao Luo Kejun Chen Yiyang Lin Junwei Fu Kang Liu Chao Cai Qiyou Wang Huangjingwei Li Xiaojing Li Junhua Hu Hongmei Li Mingshan Zhu Min Liu Source Type: research

Reply to Comment on "Highly Selective Removal of Perfluorinated Contaminants by Adsorption on All-Silica Zeolite Beta"
Angew Chem Int Ed Engl. 2021 May 11. doi: 10.1002/anie.202105139. Online ahead of print.NO ABSTRACTPMID:33977615 | DOI:10.1002/anie.202105139 (Source: Angewandte Chemie)
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Jannick Vercammen Dirk De Vos Source Type: research

Comments on "Highly Selective Removal of Perfluorinated Contaminants by Adsorption on All-Silica Zeolite Beta"
Angew Chem Int Ed Engl. 2021 May 11. doi: 10.1002/anie.202100231. Online ahead of print.NO ABSTRACTPMID:33977621 | DOI:10.1002/anie.202100231 (Source: Angewandte Chemie)
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Frank-Dieter Kopinke Source Type: research

Benchmark C2H2/CO2 Separation in an Ultramicroporous Metal-Organic Framework via Copper(I)-Alkynyl Chemistry
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202102810. Online ahead of print.ABSTRACTSeparation of acetylene from carbon dioxide remains a daunting challenge because of their very similar molecular sizes and physical properties. We herein report the first example of using copper(I)-alkynyl chemistry within an ultramicroporous MOF (CuI@UiO-66-(COOH)2) to achieve ultrahigh C2H2/CO2 separation selectivity. The anchored Cu(I) ions on the pore surfaces can specifically and strongly interact with C2H2 molecule through copper(I)-alkynyl π-complexation and thus rapidly adsorb large amount of C2H2 at low-pressure regi...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Banglin Chen Ling Zhang Ke Jiang Lifeng Yang Libo Li Enlai Hu Ling Yang Kai Shao Huabin Xing Yu Yang Yuanjing Cui Bin Li Guodong Qian Source Type: research

Synthesis of fluorinated aminoalkylboronic acids from amphoteric α-boryl aldehydes
We present evidence for the involvement of chair-like motifs, favored over the acyclic forms by up to 1.7 ± 0.1 kcal mol -1 in water and held together by an amine-boronate hydrogen bond. Fluorinated β-aminoalkylboronic acids are stable over a wide pH range and are characterized by a p K a of 3.4, which is the lowest of any alkylboronic acid.PMID:33977627 | DOI:10.1002/anie.202104133 (Source: Angewandte Chemie)
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Harjeet S Soor Diego B Diaz Katherine I Burton Andrei K Yudin Source Type: research

High-Spin Imido Cobalt Complexes with Imidyl Radical Character
We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L 2 ) - , (L = N(Dipp)SiMe 3 ), Dipp = 2,6-diisopropylphenyl) bearing very long Co-N Aryl bonds of around 1.75 Å. Their electronic structure was interrogated using a variety of physical and spectroscopic methods such as EPR or X-Ray absorption spectroscopy which leads to their description as highly unusual imidyl cobalt complexes. Computational analysis corroborate these findings and further reveal that the high-spin state is responsible for the imidyl character. Exchange of the Dipp-substituent on the imide by the smaller mesityl fu...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Alexander Reckziegel Manjinder Kour Beatrice Batistella Stefan Mebs Katrin Beuthert Robert Berger Gunnar Werncke Source Type: research

Syntheses of Cyclic Anhydrides via Ligand-Enabled C-H Carbonylation of Simple Aliphatic Acids
Angew Chem Int Ed Engl. 2021 May 11. doi: 10.1002/anie.202104645. Online ahead of print.ABSTRACTThe development of C(sp 3 )-H functionalizations of free carboxylic acids has provided a wide range of C-C and C-Y (Y = heteroatom) bond-forming reactions that both complement and expand upon what can be achieved through conventional methods. Additionally, C-H functionalizations have lent themselves to the one-step preparation of a number of valuable, synthetic motifs, that are often difficult to prepare through conventional methods. Herein, we report a β- or γ-C(sp 3 )-H carbonylation of free carboxylic acids using M...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Jin-Quan Yu Zhe Zhuang Alastair Neale Herron Source Type: research

Healable and Rearrangeable Networks of Liquid Crystal Elastomers Enabled by Diselenide Bonds
Angew Chem Int Ed Engl. 2021 May 11. doi: 10.1002/anie.202105278. Online ahead of print.ABSTRACTBased on liquid crystal elastomer (LCE) materials, hierarchically structured soft actuators could meet some requirements for "human-friendly" working mode and execute complex tasks with intelligent adaptation to environmental changes. However, few researchers have paid much attention to the preparation methods of multicomponent/hierarchical LCE actuators. In this communication, we demonstrate the successful integration of an exchangeable diselenide chain extender for the preparation of dynamic LCEs, which could be repr...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Ling Chen Hari Bisoyi Yinliang Huang Shuai Huang Meng Wang Hong Yang Quan Li Source Type: research

Electronic State Manipulation of Surface Titanium Activates Dephosphorylation over TiO2 Near Room Temperature
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104397. Online ahead of print.ABSTRACTDephosphorylation that removes a phosphate group from substrates is an important reaction for not only living organisms but also environmental protection. Although CeO2 has been shown to catalyze this reaction, as one of the rare earth elements, cerium is low in natural abundance and has a narrow global distribution (> 90% of these reserves are located within six countries). It is thus imperative to find another element/material with high worldwide abundance that can also efficiently extract the phosphate out of agricultural ...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Quan Wang Xianfeng Yi Yu-Cheng Chen Yao Xiao Anmin Zheng Jian Lin Chen Yung-Kang Peng Source Type: research

Synthesis of Boron-imidazolate Framework nanosheet with Dimer Cu units for CO2 Electroreduction to Ethylene
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202106004. Online ahead of print.ABSTRACTFundamental understanding of the dependence between the structure and composition on the electrochemical CO 2 reduction reaction (CO 2 RR) would guide the rational design of highly efficient and selective electrocatalysts. A major impediment to the deep reduction CO 2 to multi-carbon products is the complexity of carbon-carbon bond coupling. The chemically well-defined catalysts with atomically dispersed dual-metal sites are required for these C-C coupling involved processes. Here, we developed a catalyst (BIF-102NSs) that featu...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Ping Shao Wei Zhou Qin-Long Hong Luocai Yi Lirong Zheng Wenjing Wang Hai-Xia Zhang Huabin Zhang Jian Zhang Source Type: research

Enantioselective Total Synthesis and Structural Revision of Dysiherbol A
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202105733. Online ahead of print.ABSTRACTA 12-step total synthesis of the natural product dysiherbol A, a strongly anti-inflammatory and anti-tumor avarane meroterpene isolated from the marine sponge Dysidea sp., was elaborated. As key steps, the synthesis features an enantioselective Cu-catalyzed 1,4-addition/enolate-trapping opening move, an Au-catalyzed double cyclization to build up the tetracyclic core-carbon skeleton, and a late installation of the C5-bridgehead methyl group via proton-induced cyclopropane opening associated with spontaneous cyclic ether formatio...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Julian Baars Isabelle Grimm Dirk Blunk J örg-Martin Neudörfl Hans-G ünther Schmalz Source Type: research

Chemical Characterization of a Volatile Dubnium Compound, DbOCl3
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202102808. Online ahead of print.ABSTRACTThe formation and the chemical characterization of single atoms of dubnium (Db, element 105), in the form of its volatile oxychloride, was investigated using the on-line gas phase chromatography technique, in the temperature range 350-600 °C. Under the exactly same chemical conditions, comparative studies with the lighter homologs of group-5 in the Periodic Table clearly indicate the volatility sequence being NbOCl3> TaOCl3 ≥ DbOCl3. From the obtained experimental results, thermochemical data for DbOCl3 were derived. T...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Nadine Mariel Chiera Tetsuya K Sato Robert Eichler Tomohiro Tomitsuka Masato Asai Sadia Adachi Rugard Dressler Kentaro Hirose Hiroki Inoue Yuta Ito Ayuna Kashihara Hiroyuki Makii Katsuhisa Nishio Minoru Sakama Kaori Shirai Hayato Suzuki Katsuyuki Tokoi Ka Source Type: research

Pharma-molecule transport across bacterial membranes; detection and quantification approaches by electrochemistry and bioanalytical methods
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202101055. Online ahead of print.ABSTRACTAntibiotic resistance is a significant challenge encountered by healthcare systems on a global scale. Knowledge about membrane transport of antibiotics and other Antibiotic resistance is a significant challenge encountered by healthcare systems on a global scale. Knowledge about membrane transport of antibiotics and other pharmacologically relevant molecules in bacteria is crucial towards understanding and overcoming antibiotic resistance, as drug resistance often depends on drug transport. This comprehensive literature review d...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Alon Golubchik Luma Clarindo Lopes Vikram Singh Sabine Kuss Source Type: research

Enhanced Electrochemical Performance of Aprotic Li-CO2 Batteries with a Ruthenium-Complex-Based Mobile Catalyst
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202105892. Online ahead of print.ABSTRACTLi-CO 2 batteries are regarded as next-generation high-energy-density electrochemical devices, with great importance in the understanding of Li-air batteries and promising potential for application in the aviation industry. However, the greatest challenge arises from the formation of the discharge product, Li 2 CO 3 , which would accumulate and deactivate heterogenous catalysts to cause huge polarization. Herein, Ru(bpy) 3 Cl 2 was employed as a solution-phase catalyst for Li-CO 2 batteries and proved to be the most effective on...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Zhen Zhang Wen-Long Bai Zhi-Peng Cai Jin-Huan Cheng Hua-Yi Kuang Bo-Xu Dong Yu-Bo Wang Kai-Xue Wang Jie-Sheng Chen Source Type: research

FRET-Integrated Polymer Brushes for Spatially-Resolved Sensing of Changes in Polymer Conformation
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202104204. Online ahead of print.ABSTRACTPolymer brush surfaces that alter their physical properties in response to chemical stimuli have the capacity to be used as new surface-based sensing materials. For such surfaces, detecting the polymer conformation is key to their sensing capabilities. Herein, we report on FRET-integrated ultrathin (
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Quinn Alexander Besford Huaisong Yong Holger Merlitz Andrew J Christofferson Jens-Uwe Sommer Petra Uhlmann Andreas Fery Source Type: research

DNA-based microparticle tension sensors ( µTS) for measuring cell mechanics in non-planar geometries and for high-throughput quantification
Angew Chem Int Ed Engl. 2021 May 12. doi: 10.1002/anie.202102206. Online ahead of print.ABSTRACTMechanotransduction, the interplay between physical and chemical signaling, plays vital roles in many biological processes ranging from cell differentiation to metastasis. The state-of-the-art techniques to quantify cell forces employ deformable polymer films or molecular probes tethered to glass substrates. These types of flat substrates limit applications in investigating mechanotransduction on non-planar geometries where physiological activities such as phagocytosis and immunological synapse formation mostly occur. A second c...
Source: Angewandte Chemie - May 12, 2021 Category: Chemistry Authors: Yuesong Hu Victor Pui-Yan Ma Rong Ma Wenchun Chen Yuxin Duan Roxanne Glazier Brian Petrich Renhao Li Khalid Salaita Source Type: research