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Merging Organocatalysis with 1,2-Boronate Rearrangement: A Lewis Base-Catalyzed Asymmetric Multicomponent Reaction J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Hong-Cheng Shen, Varinder K. Aggarwal
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Achieving over 90% Faradaic Efficiency in Cyclohexanone Oxime Electrosynthesis Using the Cu–Mo Dual-Site Catalyst J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Runyao Zhao, Yiding Wang, Jiaju Fu, Fengtao Zhang, Linzi Wen, Yanfei Zhao, Bo Guan, Buxing Han, Zhimin Liu
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Classifieds: Jobs and Awards, Products and Services Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24
Are you looking for a (new) job? Do you know someone who deserves an award? Are you trying to find a product or service to make your work more efficient? Our partners can help.
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Bidentate Coordination Enables Anions-Regulated Solvation Structure for Advanced Aqueous Zinc Metal Batteries Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Dongdong Wang, Rui Li, Jingjing Dong, Zhongchao Bai, Nana Wang, Shi Xue Dou, Jian Yang
Rechargeable aqueous Zn metal batteries (AZMBs) are attractive for stationary energy storage due to their low cost and high safety. However, their practical application is hindered by the excessive use of zinc anodes and poor high-temperature performance, caused by severe side reactions and dendritic growth issues. Here, an electrolyte design strategy is reported based on bidentate coordination of
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An Automated Electrochemical Flow Platform to Accelerate Library Synthesis and Reaction Optimization Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Eduardo Rial-Rodríguez, Jason D. Williams, David Cantillo, Thomas Fuchß, Alena Sommer, Hans-Michael Eggenweiler, C. Oliver Kappe, Gabriele Laudadio
Automated batch and flow reactors are well-established for high throughput experimentation in both thermal chemistry and photochemistry. However, the development of automated electrochemical platforms is hindered by cell miniaturization challenges in batch and difficulties in designing effective single-pass flow systems. In order to address these issues, we have designed and implemented a new, slug-based
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Chemo-Enzymatic Depolymerization of Functionalized Low-Molecular-Weight Polyethylene Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Uwe Bornscheuer, Thomas Oiffer, Friedemann Leipold, Philipp Süss, Daniel Breite, Jan Griebel, Muhammad Khurram, Yannick Branson, Erik de Vries, Agnes Schulze, Christiane A. Helm, Ren Wei
Polyethylene (PE) is the most commonly used plastic type in the world, contributing significantly to the plastic waste crisis. Microbial degradation of PE in natural environments is unlikely due to its inert saturated carbon-carbon backbones, which are difficult to break down by enzymes, challenging the development of a biocatalytic recycling method for PE waste. Here, we demonstrated the depolymerization
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Cross-Coupling of Gaseous Alkanes with (Hetero)Aryl Bromides via Dual Nickel/Photoredox Catalysis Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Akshay M. Nair, Pol Martínez-Balart, Sergio Barbeira-Arán, Martín Fañanás-Mastral
Gaseous alkanes represent the most abundant carbon-based chemical feedstocks in our planet. However, the intrinsic inertness of their C-H bonds has rendered the use of these alkanes very difficult for purposes beyond aerobic combustion and energy intensive processes. Thus, clean and energy-efficient transformations for their use in synthetic organic chemistry are still rare. Here we report a catalytic
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Investigating Competing Inner- and Outer-Sphere Electron-Transfer Pathways in Copper Photoredox-Catalyzed Atom-Transfer Radical Additions: Closing the Cycle Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Le Nhan Pham, Angus Olding, Curtis C. Ho, Alex C. Bissember, Michelle L. Coote
This integrated computational and experimental study comprehensively examines the viability of competing inner-sphere electron transfer (ISET) and outer-sphere electron transfer (OSET) processes in [Cu(dap)2]+-mediated atom-transfer radical additions (ATRA) of olefins and CF3SO2Cl that can deliver both R–SO2Cl and R–Cl products. Five sterically- and electronically-varied representative alkenes were
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Visualizing Active Sites in Electrospun Photoactive Membranes via Fluorescence Lifetime Imaging Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Anzhela Galstyan, Fabian Terlau, Hanna M. Martin
Interest in antibacterial nanomaterials has surged in recent years, driven by the rise in antibiotic resistance among microbes. However, their practical application remains limited because many crucial properties have yet to be thoroughly investigated. In this study, we have developed novel nanofibrous membranes based on hydrophilic polyacrylonitrile (PAN) or hydrophobic polycaprolactone (PCL) with
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Rational Construction of Cyanide-Functionalized D-A-π-D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Liecheng Guo, Lele Gong, Yuting Yang, Zhecheng Huang, Xing Liu, Feng Luo
Sacrificial-agent-free overall photosynthesis of H2O2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide-functionalized
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Harnessing 4f Electron Itinerancy for Integrated Dual-Band Redox Systems Boosts Lithium-Oxygen Batteries Electrocatalysis Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Mengyao Huang, Lina Song, Nan Wang, Yaning Fu, Rongchang Ren, Zhongjun Li, Youcai Lu, Jijing Xu, Qing-chao Liu
In-depth comprehension and manipulation of band occupation at metal centers are crucial for facilitating effective adsorption and electron transfer in lithium-oxygen battery (LOB) reactions. Rare earth elements play a unique role in band hybridization due to their deep orbitals and strong localization of 4f electrons. Herein, we anchor single Ce atoms onto CoO, constructing a highly active and stable
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Development of DuoMYC: a synthetic cell penetrant miniprotein that efficiently inhibits the oncogenic transcription factor MYC Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Brecht D. Ellenbroek, Jan Pascal Kahler, Damiano Arella, Cherina Lin, Willem Jespers, Eliane Ann-Katrin Züger, Micha Drukker, Sebastian J. Pomplun
The master regulator transcription factor MYC is implicated in numerous human cancers, and its targeting is a long-standing challenge in drug development. MYC is a typical ‘undruggable’ target, with no binding pockets on its DNA binding domain and extensive intrinsically disordered regions. Rather than trying to target MYC directly with classical modalities, here we engineer synthetic miniproteins
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An Expedient Route to Bio-based Polyacrylate Alternatives with Inherent Degradation Capabilities by Organic Catalysis for Polymerization of Muconate Esters Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Daniel Taton, Thomas Dardé, Emilie Diomar, Schultze Xavier
The quest for polymers that would be at the same time bio-based and degradable after usage, in addition to offering chemical post-modification options, remains a daunting challenge in contemporary polymer science. Despite advances in polymer chemistry, attempts at controlling the chain-growth polymerization of muconate esters remain unexplored. Here we show that dialkyl muconates can be rapidly polymerized
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Thermally-stable single-site Pd on CeO2 catalyst for selective amination of phenols to aromatic amines without external hydrogen Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Yaqin Wang, Bingfeng Chen, Lina Li, Xuelei Mei, Yucheng Gu, Haihong Wu, Mingyuan He, Buxing Han
Developing a new route to produce aromatic amines as key chemicals from renewable phenols is a benign alternative to current fossil-based routes like nitroaromatic hydrogenation, but is challenging because of the high dissociation energy of the Ar-OH bond and difficulty in controlling side reactions. Herein, an aerosolizing-pyrolysis strategy was developed to prepare high-density single-site cationic
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Orderly Coating of Bilayer Polymer to Tailor Microenvironment for Efficient C-N Coupling Toward Highly Selective Urea Electrosynthesis Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-24 Zhichao Wang, Mengfan Wang, Qiyang Cheng, Yanzheng He, Sisi Liu, Jie Liu, Xiaolei Yuan, Yunfei Huan, Tao Qian, Chenglin Yan
Electrosynthesis of urea from co-reduction of carbon dioxide and nitrate is a promising alternative to the industrial process. However, the overwhelming existence of proton and nitrate as well as the insufficient supply of CO2 at the reaction interface usually result in complex product distributions from individual nitrate reduction or hydrogen evolution, instead of C-N coupling. In this work, we systematically
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Molecular Photoswitching Unlocks Glucose Oxidase for Synergistically Reinforcing Fenton Reactions for Antitumor Chemodynamic Therapy Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Zhiyuan Tian, Zicheng Wang, Weier Bao, Baerlike Wujieti, Ming Liu, Xiaojuan Li, Zhecheng Ma, Wei Cui
We have developed a new type of nanoparticles with potent antitumor activity photoactivatable via the combination of molecular photoswitching of spiropyran (SP) and enzymatic reaction of glucose oxidase (GOx). As two key processes involved therein, Fe(III)-to-Fe(II) photoreduction in Fe(III) metal-organic frameworks (MOFs) brings about the release of free Fe2+/Fe3+ while the photoswitching of SP to
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Controlling the Redox Chemistry of Cobalt Radiopharmaceuticals Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Wilson Lin, Dariusz Śmiłowicz, M. Andrey Joaqui-Joaqui, Abhijit Bera, Zhuoran Zhong, Eduardo Aluicio-Sarduy, Jason C. Mixdorf, Todd E. Barnhart, Jonathan W. Engle, Eszter Boros
The elementally matched 55Co (t1/2 = 17.53 h, Iβ+ = 77%)/58mCo (t1/2 = 9.10 h, IC= 100%) radioisotope pair is of interest for development of paired diagnostic/therapeutic radiopharmaceuticals. Due to the accessibility of the Co2+/3+ redox couple, the redox state can be readily modulated. Here, we show that macroscopic and radiochemical redox reactions can be closely monitored and controlled using spectroscopic
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p-Block Metal Based Single-Atom Catalysts Surpass Transition-Metal Counterparts in Photocatalytic H2O2 Production Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Haijiao Lu, Hanqing Yin, Jeffrey Harmer, Mu Xiao, Jiakang You, Peng Chen, Tongen Lin, Aijun Du, Zhiliang Wang, Lianzhou Wang
Growing interest in p-block metal single-atom catalysts (PM-SACs) is driven by their low toxicity, economic viability, and transition metal-like catalytic properties. However, selection criteria for p-block single-atom species and catalytic mechanisms of PM-SACs remain unclear. This study explores the catalytic abilities of PM-SACs and their transition metal counterparts (TM-SACs) based on polymetric
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Synergize Strong and Reactive Metal-Support Interactions to Construct Sub-2 nm Metal Phosphide Cluster for Enhanced Selective Hydrogenation Activities Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Zemin Chen, Xinyu Li, Guangyue Xu, Tianci Xiao, Dechen Wang, Chufei Wang, Kaihang Zhang, Jiong Li, Yang Pan, Yan Qiao, Ying Zhang
Strong metal-support interactions (SMSI) are crucial for stabilizing sub-2 nm metal sites, e.g. single atom (M1) or cluster (Mn). However, further optimizing sub-2 nm sites to break the activity–stability trade-off due to excessive interactions remains significant challenges. Accordingly, for the first time, we propose synergizing SMSI with reactive metal-support interactions (RMSI). Comprehensive
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Nanohoops Favour Light-Induced Energy Transfer over Charge Separation in Porphyrin/[10]CPP/Fullerene Rotaxanes Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Fabian Schwer, Simon Zank, Markus Freiberger, Fabian M. Steudel, Niklas Geue, Lei Ye, Perdita E. Barran, Thomas Drewello, Dirk Guldi, Max von Delius
[2]Rotaxanes offer unique opportunities for studying and modulating charge separation and energy transfer, because the mechanical bond allows the robust, yet spatially dynamic tethering of photoactive groups. In this work, we synthesized [2]rotaxane triads comprising a central (aza)[10]CPP⊃C60 bis-adduct complex and two zinc porphyrin stoppers to address how the movable nanohoop affects light-induced
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Intermolecular 1,2-Aminoboration of Alkynes and the Critical Role of Electron-Rich Alkynes Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Simon Dotzauer, Arumugam Jayaraman, David Reinhart, Holger Braunschweig
The intramolecular 1,2-aminoboration of alkynes by aminoboranes is rare and invariably requires a catalyst to proceed, while the intermolecular aminoboration of alkynes is yet entirely unknown. Through an exploration of the significance of electronics in alkynes for activating the B–N σ-bond of aminoboranes, we demonstrate in this work the first intermolecular 1,2-aminoboration of alkynes. These reactions
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Electronic Response and Charge Inversion at Polarized Gold Electrode Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Linnéa Andersson, Michiel Sprik, Juerg Hutter, Chao Zhang
We have studied polarized Au(100) and Au(111) electrodes immersed in electrolyte solution by implementing finite-field methods in density functional theory-based molecular dynamics simulations. This allows us to directly compute the Helmholtz capacitance of electric double layer by including both electronic and ionic degrees of freedom, and the results turn out to be in excellent agreement with experiments
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Catalytic Edges in One-Dimensional Covalent Organic Frameworks for the Oxygen Reduction Reaction Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Yumeng Chang, Chao Lin, Haifeng Wang, Xiaotong Wu, Luyao Zou, Jixin Shi, Qi Xiao, Qing Xu, Xiaopeng Li, Wei Luo
Metal-free covalent organic frameworks (COFs) are employed in oxygen reduction reactions (ORR) because of their diverse structural units and controllable catalytic sites, and the edge sites have high catalytic activity than the basal sites. However, it is still challenge to modulate the edge sites in COFs, because the extended frameworks in two- or three-dimensional topologies resulted in limited edge
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Solid-Liquid-Gas Three-Phase Indirect Electrolysis Enabled by Affinity Auxiliary Imparted Covalent Organic Frameworks Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Yi-Rong Wang, Ming Yue, Gang Liu, Jia-Li Zhang, Qi Li, Jing-Wen Shi, Jia-Yong Weng, Run-Han Li, Yifa Chen, Shun-Li Li, Ya-Qian Lan
The design of efficient heterogenous redox mediators with favorable affinity to substrate and electrolyte are much desired yet still challenging for the development of indirect electrolysis system. Herein, for the first time, we have developed a solid-liquid-gas three-phase indirect electrolysis system based on a covalent organic framework (Dha-COF-Cu) as heterogenous redox mediator for S-S coupling
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Ion-Pairing Chromonic Liquid Crystals via Alternately Stacked Assembly of Amphiphilic Charged π-Electronic Systems Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Yuto Maruyama, Koji Harano, Hayato Kanai, Yasuhiro Ishida, Hiroki Tanaka, Shinya Sugiura, Hiromitsu Maeda
In this study, a new assembly strategy for lyotropic chromonic liquid crystals (LCLCs) is proposed using iπ–iπ interactions, mainly comprising electrostatic and dispersion forces, between charged π-electronic systems to form stacking structures supported by the hydration of triethylene glycol (TEG) units. Meso-TEG-aryl-substituted porphyrin AuIII complex, an amphiphilic π-electronic cation, showed
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Atmosphere Induces Tunable Oxygen Vacancies to Stabilize Single-Atom Copper in Ceria for Robust Electrocatalytic CO2 Reduction to CH4 Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Fang Huang, Xiangyu Chen, Huanhuan Sun, Qingduo Zeng, Junjie Ma, Dong Wei, Jinliang Zhu, Zhengjun Chen, Taoyuan Liang, Xucai Yin, Xijun Liu, Jing Xu, Huibing He
Electrochemical carbon dioxide reduction (ECO2RR) shows great potential to create high-value carbon-based chemicals, while designing advanced catalysts at the atomic level remains challenging. The ECO2RR performance is largely dependent on the catalyst microelectronic structure that can be effectively modulated through surface defect engineering. Here, we provide an atmosphere-assisted low-temperature
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Room-Temperature Single-Molecule Infrared Imaging and Spectroscopy through Bond-Selective Fluorescence Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Haomin Wang, Philip A. Kocheril, Ziguang Yang, Dongkwan Lee, Noor Naji, Jiajun Du, Li-En Lin, Lu Wei
Infrared (IR) spectroscopy stands as a workhorse for exploring bond vibrations, offering a wealth of chemical insights across diverse frontiers. With increasing focus on the regime of single molecules, obtaining IR-sensitive information from individual molecules at room temperature would provide essential information about unknown molecular properties. Here, we leverage bond-selective fluorescence
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Hollow Hydrogels for Excellent Aerial Water Collection and Autonomous Release Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Lidong Zhang, Shumin Liang, Marieh Al Handawi, Tao Chen, Panče Naumov
Air moisture is a valuable and omnipresent resource of fresh water. However, traditional water collectors come with an enduring problem of the water-release step, which requires special devices and additional energy to remove the water from the adsorbent, such as heat, sunlight, or both. Herein, we report the first composite conical hollow hydrogel to harvest water from aerial humidity. This hollow
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Constructing Unsaturated Ru Atom Arrays Confined in Mn Oxides to Boost Neutral Water Reduction Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Qi Hu, Jianyong Cao, Shuai Qi, Na Meng, Jingwen Zhao, Tianchi Huang, Jiao You, Taiyu Liang, Chunyan Shang, Jiaying Yu, Hengpan Yang, Chuanxin He
Recently, Ru single atoms supported on carbon nanomaterials have demonstrated ultrahigh activity for acid hydrogen evolution reaction (HER), however their neutral HER activity remains low due to the sluggish kinetics for both the water dissociation step to generate H* intermediates and subsequent H* recombination in neutral electrolytes. Here, we synthesize ordered low-coordinated Ru atom arrays confined
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Small-Molecule Mixed Ionic-Electronic Conductors for Efficient N-Type Electrochemical Transistors: Structure-Function Correlations Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Yongjoon Cho, Lin Gao, Yao Yao, Jaehyun Kim, Dayong Zhang, Giacomo Forti, Isaiah Daniel Duplessis, Yuyang Wang, Robert M. Pankow, Xudong Ji, Jonathan Rivnay, Tobin J. Marks, Antonio Facchetti
The fundamental challenge in electron-transporting organic mixed ionic-electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6-type/U-shaped non-fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol
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A Green and Efficient Electrocatalytic Route for the Highly-Selective Oxidation of C–H Bonds in Aromatics over 1D Co3O4-Based Nanoarrays Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Zhaohui Yin, Zirui Gao, Lan Luo, Xiaohui Zhang, Wenxiang Hou, Wenjing Dai, Shuheng Tian, Xuetao Qin, Maolin Wang, Mi Peng, Kaihua Li, Songbo Wang, Lei Zhang, Hong Wang, Jianxin Li, Qingjun Zhu, Bowen Cheng, Zhen Yin, Ding Ma
Electrocatalytic oxidation of C-H bonds in hydrocarbons represents an efficient and sustainable strategy for the synthesis of value-added chemicals. Herein, a highly selective and continuous-flow electrochemical oxidation process of toluene to various oxygenated products (benzyl alcohol, benzaldehyde, and benzyl acetate) is developed with the electrocatalytic membrane electrodes (ECMEs). The selectivity
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Enantioselective Synthesis of α-Aryl Ketones by a Cobalt-Catalyzed Semipinacol Rearrangement Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-23 Panagiotis G. Kalomenopoulos, Balakumar Emayavaramban, Craig Paterson Johnston
A highly enantioselective cobalt-catalyzed semipinacol rearrangement of symmetric α,α-diarylallylic alcohols is disclosed. A chiral cobalt-salen catalyst generates a highly electrophilic carbocation surrogate following hydrogen atom transfer and radical–polar crossover steps. This methodology provides access to enantioenriched α-aryl ketones through invertive displacement of a cobalt(IV) complex during
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Tailoring the Properties of Chemically Recyclable Polyethylene-Like Multiblock Polymers by Modulating the Branch Structure Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-22 Yucheng Zhao, Emma Rettner, Megan Battson, Zhitao hu, Joel Miscall, Nicholas Rorrer, Garret Miyake
Developing plastics that fill the need of polyolefins yet are more easily recyclable is a critical need to address the plastic waste crisis. However, most efforts in this vein have focused on high-density polyethylene (PE), while many different types of PE exist. To create broadly sustainable PE with modular properties, we present the synthesis, characterization, and demonstration of materials applications
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Quantum Spin Exchange Interactions Trigger O p Band Broadening for Enhanced Aqueous Zinc-Ion Battery Performance Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Shiyu Wang, Shuyun Yao, Feike Zhang, Kang Ji, Yingjie Ji, Jingxian Li, Weijie Fu, Yuanming Liu, Jinghua Yang, Ruilong Liu, Jiangzhou Xie, Zhiyu Yang, Yi-Ming Yan
The pressing demand for large-scale energy storage solutions has propelled the development of advanced battery technologies, among which zinc-ion batteries (ZIBs) are prominent due to their resource abundance, high capacity, and safety in aqueous environments. However, the use of manganese oxide cathodes in ZIBs is challenged by their poor electrical conductivity and structural stability, stemming
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Visualizing Triplet Energy Transfer in Organic Near-Infrared Phosphorescent Host-Guest Materials Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Zihao Deng, Fan-Cheng Kong, Ziqi Deng, Jiaming Zhou, Shengyi Yang, Shan He, Jianyu Zhang, Yunfei Zuo, Jin Wang, Xinmeng Chen, Ryan T. K. Kwok, Guocheng Jia, Philip C. Y. Chow, David Lee Phillips, Parvej Alam, Jacky W. Y. Lam, Ben Zhong Tang
Limited by the energy gap law, purely organic materials with efficient near-infrared room temperature phosphorescence are rare and difficult to achieve. Additionally, the exciton transition process among different emitting species in host-guest phosphorescent materials remains elusive, presenting a significant academic challenge. Herein, using a modular nonbonding orbital-π bridge-nonbonding orbital
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Selective Cross-Metathesis Versus Ring-Closing Metathesis of Terpenes, Taking the Path Less Travelled Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Keren Iudanov, Noy Bracha Nechmad, Albert Poater, N. Gabriel Lemcoff
A diiodo ruthenium olefin metathesis pre-catalyst was employed to achieve remarkably selective cross-metathesis reactions of prenylated 1,6-dienes, effectively overcoming the entropically favored intramolecular ring-closing metathesis. This reaction was investigated using Density Functional Theory (DFT) computations and fine-tuned through the application of a Design of Experiments (DoE) approach. The
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As Aggregation-Induced Emission Meets with Noncovalent Conformational Locks: Subtly Regulating NIR-II Molecules for Multimodal Imaging-Navigated Synergistic Therapies Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Jiangao Li, Niu Niu, Deliang Wang, Jun Zhu, Xue Li, Qiyu Kong, Ben Zhong Tang, Dong Wang
Phototheranostics is growing into a sparking frontier in disease treatment. Developing single molecular species synchronously featured by powerful absorption capacity, superior second near-infrared (NIR-II) fluorescence and prominent photothermal conversion ability is highly desirable for phototheranostics, yet remains formidably challenging. In this work, we propose a molecular design philosophy that
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Disilicon-Mediated Carbon Monoxide Activation: From a 1,2,3-Trisila- to 1,3-Disilacyclopentadienes with Hypercoordinate λ4Si-λ3C Double Bonds Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Matthias Driess, Shenglai Yao, Markus Stefan Budde, Yun Xiong, Xing Yang, Lili Zhao
The facile reaction of the SiPh2-bridged bis-silylene (LSi:)2SiPh2 (L = PhC(NBut)2) with diphenylacetylene affords the unprecedented 1,2,3-trisilacyclopentadiene (LSi)2(PhC)2SiPh2 1 with a hypercoordinate λ4Si-λ3Si double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert N2O to form the bicyclic oxygenation product 2 through O-atom insertion in the Si=Si and Si-Si bonds
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LiLnGeS4 (Ln = La–Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS” Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Qian-Qian Liu, Xin Liu, Mei-Ze Li, Rui-Xi Wang, Bingxuan Li, Li-Ming Wu, Ling Chen
AgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical material. However, AGS has a narrow band gap (Eg = 2.58 eV) and a low laser-induced damage threshold (LIDT), primarily attributed to its mobile liquid-like Ag+ constituent and the unstable Ag–S chemical bond. Herein, we propose a “band reformation of AGS” strategy, which leads to the success syntheses of four lanthanide sulfides
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Solution-processing induced H-aggregate of Perylene-Diimide Zwitterion Exhibiting Compact Molecular Stacking toward Efficient Cathode Modification in Organic Solar Cells Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Zhi-Guo Zhang, Zhe Li, Yanhe Xiang, Jiayu Li, Luxin Feng, Ming Zhang, Shouke Yan, Bowei Xu
High-performance organic cathode interlayers (CILs) play a crucial role in the advance of organic solar cells (OSCs). However, organic CILs have exhibited inferior performances to their inorganic counterparts over a long time, due to the inherent shortcoming of poor charge transporting capability. Here, we designed and synthesized a perylene-diimide (PDI) zwitterion PDI-B as high-performance organic
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Metal-N Coordination in Lithium-Sulfur Batteries: Inhibiting Catalyst Passivation Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Xin Ao, Yang Kong, Shangquan Zhao, Zhongxin Chen, Yong Li, Xingyu Liao, Bingbing Tian
Lithium-sulfur (Li-S) batteries exhibit great potential as the next-generation energy storage techniques. Application of catalyst is widely adopted to accelerate the redox kinetics of polysulfide conversion reactions and improve battery performance. Although significant attention has been devoted to seeking new catalysts, the problem of catalyst passivation remains underexplored. Herein, we find that
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Recent Advances of Organic Cocrystals in Emerging Cutting-Edge Properties and Applications Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Xin Wang, Zongrui Wang, Xiang Wang, Fangyuan Kang, Qianfeng Gu, Qichun Zhang
Organic cocrystals, representing one type of new functional materials, have gathered significant interest in various engineering areas. Owing to their diverse stacking modes, rich intermolecular interactions and abundant functional components, the physicochemical properties of organic cocrystals can be tailored to meet different requirements and exhibit novel characteristics. The past few years have
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Nucleophilic Fluoride Anion Delivery from Triazacyclononane-Supported Molecular Ca–F Complexes Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Omar Apolinar, Job J. C. Struijs, Debotra Sarkar, Véronique Gouverneur, Simon Aldridge
The major source of fluoride, namely calcium difluoride (CaF2), is derived from the mineral fluorspar. Recent advances in the activation of CaF2 via mechanochemical methods have inspired investigation of the fundamental properties of Ca–F bonds in molecular complexes. However, the paucity of well-defined molecular Ca–F-containing complexes undermines systematic understanding of the factors governing
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Single-Component High-Resolution Dual-Tone EUV Photoresists Based on Precision Self-Immolative Polymers Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Jie Cen, Wen Liu, Jie Xu, Xiuxia Wang, Jialin Zhang, Jin Zhang, Zhengyu Deng, Chenggang Zhou, Jinming Hu, Shiyong Liu
Electron beam (EB) and extreme ultraviolet (EUV) lithography are advanced techniques capable of achieving sub-10 nm resolutions, critical for fabricating next-generation nanostructures and semiconductor devices. However, developing EUV photoresists that meet all demands for resolution, line edge roughness (LER), and sensitivity (RLS) remains a significant challenge. Herein, we introduce high-performance
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Antimony Component Schottky Nanoheterojunctions as Ultrasound-Heightened Pyroptosis Initiators for Sonocatalytic Immunotherapy Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Jihu Nie, Nailin Yang, Shumin Sun, Li Wang, Zifan Pei, Jie Wu, Qiao Yu, Zhihui Han, Youdong Chen, Liang Cheng
Sonocatalytic therapy (SCT) holds promise due to its exceptional penetration depth; however, the rapid recombination of electron-hole (e−-h+) pairs and the complex tumor microenvironment (TME) impede its broader application. Herein, we discovered that antimony (Sb)-based nanomaterials induced pyroptosis in cancer cells. Therefore, a Schottky heterojunction containing a Sb component (Sb2Se3@Pt) was
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Concise and Modular Chemoenzymatic Total Synthesis of Bisbenzylisoquinoline Alkaloids Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Xiaoguang Lei, Jin Wang, Jianxiong Zhao, Zhenyang Yu, Siyuan Wang, Fusheng Guo, Jun Yang, Lei Gao
The bisbenzylisoquinoline alkaloids (bisBIAs) have attracted tremendous attention from the synthetic community due to their diverse and intriguing biological activities. Herein, we report the convergent and modular chemoenzymatic syntheses of eight bisBIAs bearing various substitutes and linkages in 5-7 steps. The gram-scale synthesis of various well-designed enantiopure benzylisoquinoline monomers
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Non-fused Star-shape Giant Trimer Electron Acceptors for Organic Solar Cells with Efficiency over 19% Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Wen Zhou, Jiabin Liu, Jiaping Xie, Shiyong You, Jiawei Deng, Fan Yu, Sang Yong Jeong, Han Young Woo, Feiyan Wu, Lie Chen
Organic solar cells (OSCs) based on giant molecular acceptors (GMAs) have attracted extensive attention due to their excellent power conversion efficiency (PCE) and operation stability. However, the large conjugated plane of GMAs poses great challenges in regulating the solubility, over-size aggregation and yield, which in turn further constrains their development in commercial products. Herein, we
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Flavin-Catalyzed, Photochemical Conversion of Dehydroalanine into 4,5-Dihydroxynorvaline Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Tim Langschwager, Golo Storch
The chemical synthesis of unnatural amino acids (UAA) is a key strategy for preparing designed peptides, including pharmaceutically active compounds. Alterations of existing amino acid residues such as dehydroalanine (Dha) are particularly important since selected positions can be addressed without the necessity of a complete de novo synthesis. The intriguing UAA 4,5-dihydroxynorvaline (Dnv) is found
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Pentagon-Rich Caged Carbon Catalyst for the Oxygen Reduction Reaction in Acidic Electrolytes Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Guoping Chen, Miho Isegawa, Taro Koide, Yasuo Yoshida, Koji Harano, kenji Hayashida, Shusaku Fujita, Kotaro Takeyasu, Katsuhiko Ariga, Junji Nakamura
The interaction between electron spin and oxygen molecules in non-platinum catalysts, particularly carbon catalysts, significantly influences the catalytic performance of the oxygen reduction reaction (ORR). A promising approach to developing high-performance catalysts involves introducing five-membered ring structures with spin electrons into graphitic carbons. In this study, we present the successful
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Dynamic Asymmetric Diamination of Allylic Alcohols through Borrowing Hydrogen Catalysis: Diastereo-divergent Synthesis of Tetrahydrobenzodiazepines Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-21 Yufeng Liu, Peng Ji, Gongfeng Zou, Yongbing Liu, Bin-Miao Yang, Yu Zhao
We present herein an unprecedented, catalytic enantioconvergent diamination of racemic allylic alcohols with the construction of two C-N bonds and 1,3-nonadjacent stereocenters. This iridium/chiral phosphoric acid cooperative catalytic system operates through an atom-economical borrowing hydrogen amination/aza-Michael cascade, and converts readily available phenylenediamines and racemic allylic alcohols
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Harnessing the Unconventional Cubic Phase in 2D LaNiO3 Perovskite for Highly Efficient Urea Oxidation Angew. Chem. Int. Ed. (IF 16.1) Pub Date : 2024-09-20 Zhiao Wu, Miao Fan, Huiyu Jiang, Jiao Dai, Kaisi Liu, Rong Hu, Shutong Qin, Weilin Xu, Yonggang Yao, Jun Wan
Phase engineering is a critical strategy in electrocatalysis, as it allows for the modulation of electronic, geometric, and chemical properties to directly influence the catalytic performance. Despite its potential, phase engineering remains particularly challenging in thermodynamically stable perovskites, especially in a 2D structure constraint. Herein, we report phase engineering in 2D LaNiO3 perovskite
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A Wurster-Type Covalent Organic Framework with Internal Electron Transfer-Enhanced Catalytic Capacity for Tumor Therapy J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Yang Liu, Huan Zhao, Shihuai Wang, Rui Niu, Shuai Bi, Wang-Kang Han, Yinghui Wang, Shuyan Song, Hongjie Zhang, Yanli Zhao
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Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Reiji Yoshina, Junichiro Hirano, Emiko Nishimoto, Yuki Sakamoto, Keita Tajima, Shunsuke Minabe, Muhammet Uyanik, Kazuaki Ishihara, Tomoyuki Ikai, Eiji Yashima, Takuya Omine, Fumitaka Ishiwari, Akinori Saeki, Jinseok Kim, Juwon Oh, Dongho Kim, Guanting Liu, Takuma Yasuda, Hiroshi Shinokubo, Norihito Fukui
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Reserving Electrons in Cofactor Decorated Coordination Capsules for Biomimetic Electrosynthesis of α-Hydroxy/amino Esters J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Huali Wang, Yu Zhang, Guanfeng Ji, Jianwei Wei, Liang Zhao, Cheng He, Chunying Duan
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Tuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Leon Euringer, Marco Holzapfel, Ivo Krummenacher, Michael Franz, Sabine Richert, Holger Braunschweig, Christoph Lambert
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Giant Thermosalient Effect in a Molecular Single Crystal: Dynamic Transformations and Mechanistic Insights J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Mohammad Afsar Uddin, Raúl Martín, Sergio Gámez-Valenzuela, Marcelo Echeverri, M. Carmen Ruiz Delgado, Enrique Gutiérrez Puebla, Angeles Monge, Berta Gómez-Lor
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Probing the Origins of the Disorder-to-Order Transition of a Modified Cholesterol in Ternary Lipid Bilayers J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Ayan Majumder, Yuanqing Gu, Yi-Chen Chen, Xingda An, Björn M. Reinhard, John E. Straub
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Free Charge Carrier Generation by Visible-Light-Absorbing Organic Spacers in Ruddlesden–Popper Layered Perovskites J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Simon Nussbaum, Demetra Tsokkou, Aaron T. Frei, Dennis Friedrich, Jacques-E. Moser, Natalie Banerji, Jun-Ho Yum, Kevin Sivula
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Endowing 1T′-ReS2 Nanosheets with Sonopiezoelectric Property by Theoretical-Guided Vacancy-Manipulated Peierls Distortion for Tumor Ferroptosis Therapy J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Kexing Li, Shuangshuang Wang, Chunmei Chen, Lili Xia, Hui Huang, Wei Feng, Xinyue Dai, Yu Chen
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Surface Catalytic Repair for the Efficient Regeneration of Spent Layered Oxide Cathodes J. Am. Chem. Soc. (IF 14.4) Pub Date : 2024-09-24 Nengzhan Zheng, Haocheng Ji, Junxiong Wang, Mengtian Zhang, Linlin Wei, Ruyu Shi, Kai Jia, Xinru Wu, Xiao Xiao, Zhaofeng Zhuang, Bo Li, Hui-Ming Cheng, Guangmin Zhou