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Site‐Selective Radical Aromatic C–H Functionalization of Alloxazine and Flavin through Ground‐State Single Electron Transfer Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Agnideep Das, Oscar Charpentier, Cheriehan Hessin, Jules Schleinitz, David Pianca, Nolwenn Le Breton, Sylvie Choua, Laurence Grimaud, Christophe Gourlaouen, Marine Desage-El Murr
Flavins and their alloxazine isomers are key chemical scaffolds for bioinspired electron transfer strategies. Their properties can be fine‐tuned by functional groups, which must be introduced at an early stage of the synthesis as their aromatic ring is inert towards post‐functionalization. We show that the introduction of a remote metal‐binding redox site on alloxazine and flavin activates their aromatic
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Corrigendum: Effects of Deuterium Isotopes on Pt(II) Complexes and Their Impact on Organic NIR Emitters Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17
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Merging High‐Pressure Syngas Metal Catalysis and Biocatalysis in Tandem One‐Pot Processes for the Synthesis of Non‐chiral and Chiral Alcohols from Alkenes in Water Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Hannah Bork, Kim E. Naße, Andreas J. Vorholt, Harald Gröger
While simultaneously proceeding reactions are among the most fascinating features of biosynthesis, this concept of tandem processes also offers high potential in the chemical industry in terms of less waste production and improved process efficiency and sustainability. Although examples of one‐pot chemoenzymatic syntheses exist, the combination of completely different reaction types is rare. In this
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A Dicopper(II)‐Based Carbonic Anhydrase Model ‐ Quantum‐Chemical Evaluation of the Mechanistic Pathway Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Peter Comba, Gunasekaran Velmurugan, Philipp Baur
The cyanobacterium Prochloron didemni, an obligate symbiont of different species of colonial ascidians, occurring in the Pacific and Indian Oceans, produces a variety of cyclic peptides. These patellamide‐type macrocycles lead to relatively stable dicopper(II) complexes that are extremely efficient carbonic anhydrase mimics, the most active model systems known so far. Importantly, it recently was shown
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Organo‐Photocatalytic Anti‐Markovnikov Hydroamidation of Alkenes with Sulfonyl Azides: A Combined Experimental and Computational Study Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Rui Fu, Mengyu Xu, Yujing Wang, Xinxin Wu, Xiaoguang Bao
The construction of C(sp3)−N bonds via direct N‐centered radical addition with olefins under benign conditions is a desirable but challenging strategy. Herein, we describe an organo‐photocatalytic approach to achieve anti‐Markovnikov alkene hydroamidation with sulfonyl azides in a highly efficient manner under transition‐metal‐free and mild conditions. A broad range of substrates, including both activated
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SilE‐R and SilE‐S ‐ DABB Proteins Catalyzing Enantiospecific Hydrolysis of Organosilyl Ethers Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Lisa M. Pick, Viviane Oehme, Julia Hartmann, Jessica Wenzlaff, Qingyun Tang, Gideon Grogan, Marion B. Ansorge-Schumacher
Silyl ethers fulfil a fundamental role in synthetic organic chemistry as protecting groups and their selective cleavage is an important factor in their application. We present here for the first time two enzymes, SilE‐R and SilE‐S, which are able to hydrolyze silyl ethers. They belong to the stress‐response A/B barrel domain (DABB) family and are able to cleave the Si‐O bond with opposite enantiopreference
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Perfluorooxosulfate Salts as SOF4‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Armir Zogu, Karim Ullah, Stefanos Spanopoulos, Ermal Ismalaj, Wim M. De Borggraeve, Joachim Demaerel
Sulfur(VI) Fluoride Exchange (SuFEx) chemistry stands as a well‐established method for swiftly constructing complex molecules in a modular fashion. An especially promising segment of this toolbox is reserved for multidimensional SuFEx hubs: three or more substituents pluggable into a singular SVI centre to make ‘beyondlinear’ clicked constructions. Sulfurimidoyl difluorides (RNSOF2) stand out as the
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Quantitative Factors Introduced in the Feasibility Analysis of Reactive Oxygen Species (ROS)‐Sensitive Triggers Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Shameer M. Kondengadan, Binghe Wang
Reactive oxygen species (ROS) are critical for cellular signaling. Various pathophysiological conditions are also associated with elevated levels of ROS. Hence, ROS‐sensitive triggers have been extensively used for selective payload delivery. Such applications are predicated on two key functions: (1) a sufficient magnitude of concentration difference for the interested ROS between normal tissue/cells
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A Zeolitic Octahedral Metal Oxide with Ultrahigh Porosity for High‐temperature and High‐humidity Alkyne/Alkene Separation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-17 Baokai Ma, Panpan Hu, Liangcheng Zou, Qianqian Zhu, Lifeng Zhang, Satoshi Ishikawa, Wataru Ueda, Yanshuo Li, Zhenxin Zhang
Zeolitic octahedral metal oxide is a newly synthesized all‐inorganic zeolitic material and has been used for adsorption, separation, and catalysis. Herein, a new zeolitic octahedral metal oxide was synthesized and characterized. The porous framework was established through the assembly of [P2Mo13O50] clusters with PO4 linkers. Guest molecules occupied the framework, which could be removed through heat
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Selective Arylation of RNA 2′‐OH Groups via SNAr Reaction with Trialkylammonium Heterocycles Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Sayantan Chatterjee, Lu Xiao, Wenrui Zhong, Sheng Feng, Eric T. Kool
Small‐molecule reactions at the 2′‐OH groups of RNA enable useful applications for transcriptome technology and biology. To date, all reactions have involved carbonyl acylation and mechanistically related sulfonylation, limiting the types of modifications and properties that can be achieved. Here we report that electron‐deficient heteroaryl species selectively react with 2′‐OH groups of RNA in water
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Ternary Complex‐Templated Dynamic Combinatorial Chemistry for the Selection and Identification of Homo‐PROTACs Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Claudia J. Diehl, Alessandra Salerno, Alessio Ciulli
Dynamic combinatorial chemistry (DCC) leverages a reversible reaction to generate compound libraries from constituting building blocks under thermodynamic control. The position of this equilibrium can be biased by addition of a target macromolecule towards enrichment of bound ligands. While DCC has been applied to select ligands for a single target protein, its application to identifying chimeric molecules
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Ethylenedioxythiophene‐based Small Molecular Donor with Multiple Conformation Locks for Organic Solar Cells with Efficiency of 19.3% Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Qian Xie, Xiangmeng Deng, Chaowei Zhao, Jie Fang, Dongdong Xia, Yuefeng Zhang, Feng Ding, Jiali Wang, Mengdi Li, Zhou Zhang, Chengyi Xiao, Xunfan Liao, Lang Jiang, Bin Huang, Runying Dai, Weiwei Li
Ternary organic solar cells (T‐OSCs) represent an efficient strategy for enhancing the performance of OSCs. Presently, the majority of high‐performance T‐OSCs incorporates well‐established Y‐acceptors or donor polymers as the third component. In this study, a novel class of conjugated small molecules has been introduced as the third component, demonstrating exceptional photovoltaic performance in T‐OSCs
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Small Ionic Liquid‐based Molecule Drives Strong Adhesives Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Kai Liu, peiyi Wu
Nature has inspired scientists to fabricate adhesive materials for applications in many burgeoning areas. However, it is still a significant challenge to develop small‐molecule adhesives with high‐strength, low‐temperature and recyclable properties, although these merits are of great interest in various aspects. Herein, we report a series of strong adhesives based on low‐molecular‐weight molecular
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Breaking Highly Ordered PtPbBi Intermetallic with Disordered Amorphous Phase for Boosting Electrocatalytic Hydrogen Evolution and Alcohol Oxidation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Fukai Feng, Chaoqun Ma, Sumei Han, Xiao Ma, Caihong He, Huaifang Zhang, Wenbin Cao, Xiangmin Meng, Jing Xia, Lijie Zhu, Yahui Tian, Qi Wang, Qinbai Yun, Qipeng Lu
Constructing amorphous/intermetallic (A/IMC) heterophase structures by breaking the highly ordered IMC phase with disordered amorphous phase is an effective way to improve the electrocatalytic performance of noble metal‐based IMC electrocatalysts because of the optimized electronic structure and abundant heterophase boundaries as active sites. In this study, we report the synthesis of ultrathin A/IMC
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Anion‐Coordination Foldamer‐Based Polymer Network: from Molecular Spring to Elastomer Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Jiangping Qin, Yongming Wang, Tian Wang, Na Wang, Wenhua Xu, Lin Cheng, Wei Yu, Xuzhou Yan, Lingyan Gao, Bo Zheng, Biao Wu
Foldamer is a scaled‐down version of coil spring, which can absorb and release energy by conformational change. Here, polymer networks with high‐density of molecular springs were developed by employing anion‐coordination‐based foldamers as the monomer. The coiling of the foldamer is controlled by oligourea ligands coordinating to chloride ions; subsequently, the folding and unfolding of foldamer conformations
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Ternary Rotational Polyanion Coupling Enables Fast Li Ion Dynamics in Tetrafluoroborate Ion Doped Antiperovskite Li2OHCl Solid Electrolyte Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Juncao Bian, Sifan Ling, Bei Deng, Haibin Lin, Ruo Zhao, Long Kong, Huimin Yuan, Jinlong Zhu, Songbai Han, Liping Wang, Ruiqin Zhang, Yusheng Zhao, Zhouguang Lu
Li‐rich antiperovskite (LiRAP) hydroxyhalides are emerging as attractive solid electrolyte (SEs) for all‐solid‐state Li metal batteries (ASSLMBs) due to their low melting point, low cost, and ease of scaling‐up. The incorporation of rotational polyanions can reduce the activation energy and thus improve the Li ion conductivity of SEs. Herein, we propose a ternary rotational polyanion coupling strategy
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Non‐Fluorinated Ethers to Mitigate Electrode Surface Reactivity in High‐Voltage NCM811‐Li Batteries Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Zhijie Wang, Xiangli Che, Danni Wang, Yanyan Wang, Xiaomei He, Ye Zhu, Biao Zhang
Lithium (Li) metal batteries (LMBs) with nickel (Ni)‐rich layered oxide cathodes exhibit twice the energy density of conventional Li‐ion batteries. However, their lifespan is limited by severe side reactions caused by high electrode reactivity. Fluorinated solvent‐based electrolytes can address this challenge, but they pose environmental and biological hazards. This work reports on the molecular engineering
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Unveiling Crucial Chemical Processing Parameters Influencing the Performance of Solution‐processed Inorganic Thermoelectric Materials Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Christine Fiedler, Mariano Calcabrini, Yu Liu, Maria Ibáñez
Production of thermoelectric materials from solution‐processed particles involves the synthesis of particles, their purification and densification into pelletized material. Chemical changes that occur during each one of these steps render them performance determining. Particularly the purification steps, bypassed in conventional solid‐state synthesis, are the cause for large discrepancies among similar
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Two‐Dimensional Conjugated Metal–Organic Frameworks with a Ring‐in‐Ring Topology and High Electrical Conductance Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Mingyu Yang, Yi Zhang, Renlong Zhu, Junjun Tan, Jinxin Liu, Wei Zhang, Meng Zhou, Zheng Meng
Electrically conducting two‐dimensional (2D) metal‐organic frameworks (MOFs) have garnered significant interest due to their remarkable structural tunability and outstanding electrical properties. However, the design and synthesis of high‐performance materials face challenges due to the limited availability of specific ligands and pore structures. In this study, we have employed a novel highly branched
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Engineering of Halide Methyltransferase BxHMT through Dynamic Cross‐correlation Network Analysis Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Chun-Yu Gao, Gui-Ying Yang, Xu-Wei Ding, Jian-He Xu, Xiaolin Cheng, Gao-Wei Zheng, QI CHEN
Halide methyltransferases (HMTs) provide an effective way to regenerate S‐adenosyl methionine (SAM) from S‐adenosyl homocysteine and reactive electrophiles such as methyl iodide (MeI) or methyl toluene sulfonate (MeOTs). Compared with MeI, the cost‐effective unnatural substrate MeOTs can be accessible directly from cheap and abundant alcohols, but shows only limited reactivity in SAM production. Herein
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Mitigating Sodium Ordering for Enhanced Solid Solution Behavior in Layered NaNiO2 Cathodes Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Krishnakanth Sada, Steven Kmiec, Arumugam Manthiram
The O‐type layered nickel oxides suffer from undesired co‐operative Jahn‐Teller distortion stemming from Ni3+ ions and undergo multiple biphasic structural transformations during the insertion/extraction of large Na+ ions, posing a significant challenge to stabilize the structural integrity. We present here a systematic investigation of the impact of substituting 5% divalent (Mg2+) or trivalent (Al3+
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Electrochemical Asymmetric Radical Functionalization of Aldehydes Enabled by a Redox Shuttle Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Daniele Mazzarella, Chun Qi, Michael Vanzella, Andrea Sartorel, Giorgio Pelosi, Luca Dell'Amico
Aminocatalysis is a well‐established tool that enables the production of enantioenriched compounds under mild conditions. Its versatility is underscored by its seamless integration with various synthetic approaches. While the combination of aminocatalysis with metal catalysis, photochemistry, and stoichiometric oxidants has been extensively explored, its synergy with electrochemical activation remains
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Fabrication of Large‐area Multi‐stimulus Responsive Thin Films via Interfacially Confined Irreversible Katritzky Reaction Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Yuanhong Shu, Yan Luo, Hexi Wei, Lingya Peng, Jingjing Liang, Binbin zhai, Liping Ding, Yu Fang
Fabrication of large‐area thin films through irreversible reactions remains a formidable task. This study reports a breakthrough strategy for in situ synthesis of large‐area, free‐standing, robust and multi‐stimulus responsive thin films through a catalyst‐free and irreversible Katritzky reaction at a liquid–liquid interface. The as resulted films are featured with adjustable thickness of 1–3 μm and
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Alveoli‐Inspired Carbon Cathodes with Interconnected Porous Structure and Asymmetric Coordinated Vanadium Sites for Superior Li‐S Batteries Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Rui Yan, Zhenyang Zhao, Ran Zhu, Min Wu, Xu Liu, Mohsen Adeli, Bo Yin, Chong Cheng, Shuang Li
Accelerating sulfur conversion catalysis to alleviate the shuttle effect has become a novel paradigm for effective Li‐S batteries. Although nitrogen‐coordinated metal single‐atom (M‐N4) catalysts have been investigated, further optimizing its utilization rate and catalytic activities is urgently needed for practical applications. Inspired by the natural alveoli tissue with interconnected structure
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Development of an FeII Complex Exhibiting Intermolecular Proton Shifting Coupled Spin Transition Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Tianchi Ji, Shengqun Su, Shuqi Wu, Yuta Hori, Yasuteru Shigeta, Yubo Huang, Wenwei Zheng, Wenhuang Xu, Xiaopeng Zhang, Ryoji Kiyanagi, Koji Munakata, Takashi Ohhara, Takumi Nakanishi, Osamu Sato
In this study, we investigated reversible intermolecular proton shifting (IPS) coupled with spin transition (ST) in a novel FeII complex. The host FeII complex and the guest carboxylic acid anion were connected by intermolecular hydrogen bonds (IHBs). We extended the intramolecular proton transfer coupled ST phenomenon to the intermolecular system. The dynamic phenomenon was confirmed by variable‐temperature
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Regulating Sulfur Redox Kinetics by Coupling Photocatalysis for High‐Performance Photo‐Assisted Lithium‐Sulfur Batteries Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Yuhao Liu, Feng Wu, Zhengqiang Hu, Fengling Zhang, Ke Wang, Li Li, Renjie Chen
Challenges such as shuttle effect have hindered the commercialization of lithium‐sulfur batteries (LSBs), despite their potential as high‐energy‐density storage devices. To address these issues, we explore the integration of solar energy into LSBs, creating a photo‐assisted lithium‐sulfur battery (PA‐LSB). The PA‐LSB provides a novel and sustainable solution by coupling the photocatalytic effect to
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Molecular Engineering for Modulating Photocatalytic Hydrogen Evolution of Fully Conjugated 3D Covalent Organic Frameworks Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Yaqin Wang, Zelong Qiao, Han Li, Rui Zhang, Zhonghua Xiang, Dapeng Cao, Shitao Wang
Covalent organic frameworks (COFs) have recently shown great potential for photocatalytic hydrogen production. Currently almost all reports are focused on two‐dimensional (2D) COFs, while the 3D counterparts are rarely explored due to their non‐conjugated frameworks derived from the sp3 carbon based tetrahedral building blocks. Here, we rationally designed and synthesized a series of fully conjugated
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Umbrella‐Shaped Amphiphiles: Internal Alkylation of an Aromatic Micelle and Its Impact on Cavity Features Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Masaya Endo, Shinji Aoyama, Yoshitaka Tsuchido, Lorenzo Catti, Michito Yoshizawa
To develop new hybrid micelles with alkyl/polyaromatic core‐shell structures, we synthesized umbrella‐shaped amphiphiles bearing a bent anthracene dimer with a linear alkyl chain (i.e., octyl and hexadecyl groups). The amphiphiles quantitatively assemble into spherical micelles (~2‐3 nm in core diameter), possessing an alkylated cavity surrounded by a polyaromatic framework, in water. The alkylation
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Photoswitching Reagent for Super‐resolution Fluorescence Microscopy Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Ga-eun Go, Uidon Jeong, Hyunbum Park, Seokran Go, Doory Kim
Single‐molecule localization microscopy (SMLM) has revolutionized optical microscopy by exceeding the diffraction limit and revealing previously unattainable nanoscale details of cellular structures and molecular dynamics. This super‐resolution imaging capability relies on fluorophore photoswitching, which is crucial for optimizing the imaging conditions and accurately determining the fluorophore positions
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Expedient Access to 18F‐Fluoroheteroarenes via Deaminative Radiofluorination of Aniline‐Derived Pyridinium Salts Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Joseph Ford, Sebastiano Ortalli, Zijun Chen, Jeroen Sap, Matthew Tredwell, Veronique Gouverneur
Herein, we disclose that pyridinium salts derived from abundant (hetero)anilines represent a novel precursor class for nucleophilic aromatic substitution reactions with [18F]fluoride. The value of this new 18F‐fluorodeamination is demonstrated with the synthesis of over 30 structurally diverse and complex heteroaryl 18F‐fluorides, several derived from scaffolds that were yet to be labelled with fluorine‐18
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N‐(sulfonio)sulfilimine reagents: Non‐oxidizing Sources of Electrophilic Nitrogen Atom for Skeletal Editing Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Tobias Heilmann, Juan M Lopez-Soria, Johannes Ulbrich, Johannes Kircher, Zhen Li, Brigitte Worbs, Christopher Golz, Ricardo A Mata, Manuel Alcarazo
The one‐pot synthesis of λ4‐dibenzothiophen‐5‐imino‐N‐dibenzothiophenium triflate (1) in multigram scale is reported. This compound reacts with Rh2(esp)2 (esp = α,α,α′,α′‐tetramethyl‐1,3‐benzenedipropionic acid) generating a Rh‐coordinated sulfonitrene species, which is able to transfer the electrophilic nitrene moiety to olefins. When indenes are used as substrates, isoquinolines are obtained in good
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Indocyanine Green‐based Nanoprobe for In Vivo Detection of Cellular Senescence Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-16 Andrew G Baker, Muhamad Hartono, Hui-Ling Ou, Andrea Bistrović Popov, Emma L Brown, James Joseph, Monika Golinska, Estela González-Gualda, David Marcias, Jianfeng Ge, Mary Denholm, Samir Morsli, Chandan Sanghera, Thomas R Else, Heather F Greer, Aude Vernet, Sarah E Bohndiek, Ljiljana Fruk, Daniel Muñoz-Espín
There is an urgent need to improve conventional cancer‐treatments by preventing detrimental side effects, cancer recurrence and metastases. Recent studies have shown that presence of senescent cells in tissues treated with chemo‐ or radiotherapy can be used to predict the effectiveness of cancer treatment. However, although the accumulation of senescent cells is one of the hallmarks of cancer, surprisingly
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Back Cover: PAM‐Engineered Toehold Switches as Input‐Responsive Activators of CRISPR‐Cas12a for Sensing Applications (Angew. Chem. Int. Ed. 17/2024) Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Neda Bagheri, Alejandro Chamorro, Andrea Idili, Alessandro Porchetta
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Graphical Abstract: Angew. Chem. Int. Ed. 17/2024 Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15
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Tuning Electron Delocalization of Redox‐Active Porous Aromatic Framework for Low‐Temperature Aqueous Zn–K Hybrid Batteries with Air Self‐Chargeability Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Junhao Wang, Xupeng Zhang, Zhaoli Liu, Jie Yu, Heng-Guo Wang, Xing-Long Wu, Fengchao Cui, Guangshan Zhu
Air self‐charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self‐charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low‐temperature
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Molecular Symmetry and Art: Visualizing the Near‐Symmetry of Molecules in Piet Mondrian’s De Stijl Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Christopher J. Kingsbury, Mathias O. Senge
Symmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost – investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vectors or coordinates, is informative, though far from engaging
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Ruthenium(II)‐Catalyzed Late‐Stage Incorporation of N‐Aryl Triazoles and Tetrazoles with Sulfonium Salts via C–H Activation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Hendrik Simon, Agnese Zangarelli, Tristan Bauch, Lutz Ackermann
The late‐stage functionalization of active pharmaceutical ingredients is a key challenge in medicinal chemistry. Furthermore, N‐aryl triazoles and tetrazoles are important structural motifs with the potential to boost the activity of diverse drug molecules. Using easily accessible dibenzothiophenium salts for the ruthenium‐catalyzed C–H arylation, these scaffolds were introduced into a variety of bioactive
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Unveiling the Pivotal Role of dx2‐y2 Electronic States in Nickel‐based Hydroxide Electrocatalysts for Methanol Oxidation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Junhua Li, Chao Wu, Zhen Wang, Haoyan Meng, Qi Zhang, Ying Tang, Anqi Zou, Yiming Zhang, Haoyin Zhong, Shibo Xi, Junmin Xue, Xiaopeng Wang, Jiagang Wu
The anodic methanol oxidation reaction (MOR) plays a crucial role in coupling with the cathodic hydrogen evolution reaction (HER) and enables the sustainable production of the high‐valued formate. Nickel‐based hydroxide (Ni(OH)2) as MOR electrocatalyst has attracted enormous attention. However, the key factor determining the intrinsic catalytic activity remains unknown, which significantly hinders
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An n‐Type Open‐Shell Conjugated Polymer with High‐Spin Ground‐State and High Intrinsic Electrical Conductivity Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Houji Cai, Haoran Tang, Tianzuo Wang, Chenhui Xu, Juxuan Xie, Muyi Fu, Xi Luo, Zhengwei Hu, Yi Zhang, Yunfeng Deng, Guangwu Li, Chunchen Liu, Fei Huang, Yong Cao
Open‐shell conjugated polymers with a high intrinsic conductivity and high‐spin ground state hold considerable promise for applications in organic electronics and spintronics. Herein, two novel acceptor‐acceptor (A‐A) conjugated polymers based on a highly electron‐deficient quinoidal benzodifurandione unit have been developed, namely DPP‐BFDO‐Th and DPP‐BFDO. The incorporation of the quinoidal moiety
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Palladium‐Catalyzed Inward Isomerization Hydroaminocarbonylation of Alkenes Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Xian-Jin Zou, Zhao-Xing Jin, Hui-Yi Yang, Fei Wu, Zhi-Hui Ren, Zheng-Hui Guan
In contrast to the kinetically favored outward isomerization‐hydrocarbonylation of alkenes, the disfavored inward isomerization‐hydrocarbonylation of alkenes remains an important challenge. Herein, we have developed a novel and effective palladium‐catalyzed inward isomerization‐hydroaminocarbonylation of unactivated alkenes and aniline hydrochlorides for the formation of synthetically valuable α‐aryl
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An Expedient Radical Approach for the Decarboxylative Synthesis of Stereodefined All‐Carbon Tetrasubstituted Olefins Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Qian Zeng, Nirwan Yamini, Jordi Benet-Buchholz, Arjan Willem Kleij
We report a user‐friendly approach for the decarboxylative formation of stereodefined and complex tri‐ and tetra‐substituted olefins from vinyl cyclic carbonates and amines as radical precursors. The protocol relies on easy photo‐initiated α‐amino‐radical formation followed by addition onto the double bond of the substrate resulting in a sequence involving carbonate ring‐opening, double bond relay
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Halogen‐Atom Transfer Enabled Catalytic Enantioselective Coupling to Chiral Trifluoromethylated Alkynes via Dual Nickel and Photocatalysis Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Shanya Lu, Zihao Hu, Dong Wang, Tao XU
With halogen‐atom transfer as an effective tool, a novel catalytic enantioselective protocol to generate chiral trifluoromethylated alkynes has been established by a cooperative photoredox and nickel catalysis system, providing a straightforward and modular route to access this type of product in good yields and enantioselectivities. The halogen‐atom transfer process is essential for the reaction and
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One‐pot Synthesis of High‐capacity Sulfur Cathodes via In‐situ Polymerization of a Porous Imine‐based Polymer Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Guiping Li, Ye Liu, Thorsten Schultz, Moritz Exner, Ruslan Muydinov, Hui Wang, Kerstin Scheurell, Jieyang Huang, Norbert Koch, Paulina Szymoniak, Nicola Pinna, Philipp Adelhlem, Michael Janus Bojdys
Lithium‐ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur‐based cathodes, offering a high theoretical capacity of 1675 mAh g–1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state‐of‐the‐art sulfur‐based electrodes do not reach the theoretical
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Unprecedented POSS‐linked 3D Covalent Organic Frameworks with scu or sqc Topology Regulated by Porphyrin Center for Photocatalytic CO2 Reduction Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Ying Gao, Senzhi Li, Lei Gong, Jing Li, Dongdong Qi, Liu Naifang, Yongzhong Bian, Jianzhuang Jiang
The synthesis and characterization of porphyrin center regulated three‐dimensional covalent organic frameworks with 2‐fold interpenetrated scu or sqc topology have been investigated. These COFs exhibit unique structural features and properties, making them promising candidates for photocatalytic applications in CO2 reduction and artemisinin synthesis. The porphyrin center serves as an anchor for metal
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Detergent Chemistry Modulates the Transgression of Planetary Boundaries including Antimicrobial Resistance and Drug Discovery Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Marc Seewald, Lena Nielinger, Katharina Alker, Jan-Simon Behnke, Virginia Wycisk, Leonhard Hagen Urner
Detergent chemistry enables applications in the world today while harming safe operating spaces that humanity needs for survival. Aim of this review is to support a holistic thought process in the design of detergent chemistry. We harness the planetary boundary concept as a framework for literature survey to identify progresses and knowledge gaps in context with detergent chemistry and five planetary
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Divalent Titanium via Reductive N‐C Coupling of a TiIV Nitrido with π‐Acids. Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Mrinal Bhunia, Christian Sandoval-Pauker, Dominik Fehn, Lauren Grant, Shuruthi Senthil, Michael Gau, Andrew Ozarowski, Jurek Krzystek, Joshua Telser, Balazs Pinter, Karsten Meyer, Daniel J. Mindiola
The nitrido‐ate complex [(PN)2Ti(N){μ2‐K(OEt2)}]2 (1) reductively couples CO and isocyanides in the presence of DME or cryptand, to form rare, five‐coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E = O, L = Kryptofix222, (2); E = NAd, L = 3 DME, (3); E = NtBu, L = 3 DME, (4); E = NAd, L = Kryptofix222, (5)). Oxidation of 2‐5 with [Fc][OTf] afforded an isostructural TiIII
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Unified Approach to Deamination and Deoxygenation Through Isonitrile Hydrodecyanation: A Combined Experimental and Computational Investigation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Ziqi Jiao, Kyle T. Jaunich, Thomas Tao, Olivia Gottschall, Maxwell M. Hughes, Aneta Turlik, Alexander Schuppe
Herein, we describe a general hydrodefunctionalization protocol of alcohols and amines through a common isonitrile intermediate. To cleave the relatively inert C–NC bond, we leveraged dual hydrogen atom transfer (HAT) and photoredox catalysis to generate a nucleophilic boryl radical, which readily forms an imidoyl radical intermediate from the isonitrile. Rapid β‐scission then accomplishes defunctionalization
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Construct Phenylethanoid Glycosides Harnessing Biosynthetic Networks, Protein Engineering and One‐Pot Multienzyme Cascades Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Mingju Yao, Haotian Wang, Zilong Wang, Chenglin Song, Xiaolin Sa, Wei Du, Min Ye, Xue Qiao
Phenylethanoid glycosides (PhGs) exhibit a multitude of structural variations linked to diverse pharmacological activities. Assembling various PhGs via multienzyme cascades represents a concise strategy over traditional synthetic methods. However, the challenge lies in identifying a comprehensive set of catalytic enzymes. This study explores biosynthetic PhG reconstruction from natural precursors,
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3D Printing of Aqueous Two‐Phase Systems with Linear and Bottlebrush Polyelectrolytes Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Zichen Jin, Hong-Gyu Seong, Satyam Srivastava, Alex McGlasson, Todd Emrick, Murugappan Muthukumar, Thomas P Russell
We formed core‐shell‐like polyelectrolyte complexes (PECs) from an anionic bottlebrush polymer with poly (acrylic acid) side chains with a cationic linear poly (allylamine hydrochloride). By varying the pH, the number of side chains of the polyanionic BB polymers (Nbb), the charge density of the polyelectrolytes, and the salt concentration, the phase separation behavior and salt resistance of the complexes
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Achieving Near‐Unity Red Light Photoluminescence in Antimony Halide Crystals via Polyhedron Regulation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-15 Jin-Feng Liao, Zhipeng Zhang, Lei Zhou, Zikang Tang, Guichuan Xing
Exploration of efficient red emitting antimony hybrid halide with large Stokes shift and zero self‐absorption is highly desirable due to its enormous potential for applications in solid light emitting, and active optical waveguides. However, it is still challenging and rarely reported. Herein, a series of (TMS)2SbCl5 (TMS = triphenylsulfonium cation) crystals have been prepared with diverse [SbCl5]2‐
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Similarities and Differences in Benzene Reduction with Ca, Sr, Yb and Sm: Strong Evidence for Tetra‐Anionic Benzene Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-13 Sandeep Kumar Thakur, Nil Roig, Roger Monreal-Corona, Jens Langer, Mercedes Alonso, Sjoerd Harder
Inverse sandwich complexes of Yb and Sm stabilized by a bulky b‐diketiminate (BDI) ligand have been prepared: (BDI)Ln(h6,h6‐C6H6)Ln(BDI); Ln = lanthanide. Coordinated benzene ligands can be neutral, di‐anionic or, often controversially discussed, even tetra‐anionic. The formal charge on benzene is correlated to assignment of the metal oxidation state which generally poses a problem. Herein, we take
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Multidimensional electrochemistry decodes the operando mechanism of hydrogen oxidation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-13 Kaicong Yang, Hualong Ma, Renjie Ren, Li Xiao, Wenyong Jiang, Yu Xie, Gongwei Wang, Juntao Lu, Lin Zhuang
Being an efficient approach to the utilization of hydrogen energy, the hydrogen oxidation reaction (HOR) is of particular significance in the current carbon‐neutrality time. Yet the mechanistic picture of the HOR is still blurred, mostly because the elemental steps of this reaction are rapid and highly entangled, especially when deviating from the thermodynamic equilibrium state. Here we report a strategy
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Revealing the Influence of Electron Migration Inside Polymer Electrolyte on Li+ Transport and Interphase Reconfiguration for Li Metal Batteries Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-13 Yingmin Jin, Ruifan Lin, Yumeng Li, Xuebai Zhang, Siping Tan, Yong Shuai, Yueping Xiong
The development of highly producible and interfacial compatible in‐situ polymerized electrolytes for solid‐state lithium metal batteries (SSLMBs) have been plagued by insufficient transport kinetics and uncontrollable dendrite propagation. Herein, we seek to explore a rationally designed nanofiber architecture to balance all the criteria of SSLMBs, in which La0.6Sr0.4CoO3‐δ (LSC) enriched with high
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Self‐Inclusion Complexation of Electron‐Accepting Guest into Electron‐Donating Cyclic Host by Photoexcitation Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-13 Keisuke Wada, Yuuya Nagata, Luxia Cui, Toshikazu Ono, Shigehisa Akine, Shunsuke Ohtani, Kenichi Kato, Shixin Fa, Tomoki Ogoshi
Self‐inclusion complexes consisting of host–guest conjugates are one of the unique supramolecular structures because they form in‐state and out‐state depending on the external stimuli. Despite many reports of the stimuli‐responsive self‐inclusion complex formation, study of the structural relaxation from out‐state to in‐state by photoexcitation has been unexplored. Herein, we report that an electron‐donating
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Cooperative Photoredox and Cobalt‐catalyzed Acceptorless Dehydrogenative Functionalization of Cyclopropylamides towards Allylic N,O‐Acyl‐acetal Derivatives Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-13 Haohao Huang, Xinjun Luan, Zhijun Zuo
We disclose herein a novel photoredox and cobalt co‐catalyzed ring‐opening/acceptorless dehydrogenative functionalization of mono‐donor cyclopropanes, which providing a sustainable and atom‐economic approach to rapidly assemble a wide range of allylic N,O‐acyl‐acetal derivatives. The optimized conditions accommodate assorted cycloalkylamides and primary, secondary and tertiary alcohols, with applications
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A Dielectric MXene‐Induced Self‐Built Electric Field in Polymer Electrolyte Triggering Fast Lithium‐Ion Transport and High‐Voltage Cycling Stability Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-13 Baolin Zhang, Yufeng Su, Yangyang Chen, Shengguang Qi, Mianrui Li, Wenwu Zou, Guoxing Jiang, Weifeng Zhang, Yuqing Gao, Chenhui Pan, Huiyu Song, Zhiming Cui, Chuanfang Zhang, Zhenxing Liang, Li Du
Quasi‐solid polymer electrolyte (QPE) lithium (Li)‐metal battery holds significant promise in the application of high‐energy‐density batteries, yet it suffers from low ionic conductivity and poor oxidation stability. Herein, a novel self‐built electric field (SBEF) strategy is proposed to enhance Li+ transportation and accelerate the degradation dynamics of carbon‐fluorine bond cleavage in LiTFSI by
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A Stapled Peptide Inhibitor Targeting the Binding Interface of N6‐Adenosine‐Methyltransferase Subunits METTL3 and METTL14 for Cancer Therapy Angew. Chem. Int. Ed. (IF 16.6) Pub Date : 2024-04-12 Zenghui Li, Yuqing Feng, Hong Han, Xingyue Jiang, Weiyu Chen, Xuezhen Ma, Yang Mei, Dan Yuan, Dingxiao Zhang, Junfeng Shi
METTL3, a primary methyltransferase catalyzing RNA N6‐methyladenosine (m6A) modification, has been identified as an oncogene in several cancer types and thus nominated as a potentially effective target for therapeutic inhibition, although current options using this strategy are limited. In this study, we targeted protein‐protein interactions at the METTL3‐METTL14 binding interface to inhibit complex