Angewandte Chemie (International ed. in English)最新文献

{"title":"Dual-Affinity Host Engineering for Highly Reversible Zinc-Iodine Batteries.","authors":"Meijia Chen, Chuang Sun, Yuxuan Zhu, Mengting Zheng, Jun Lu","doi":"10.1002/anie.5243975","DOIUrl":"10.1002/anie.5243975","url":null,"abstract":"<p><p>Aqueous zinc-iodine (Zn-I₂) batteries are promising for large-scale energy storage, yet their practical development is impeded by the coupled degradation of both electrodes, including instability Zn anode and sluggish iodine kinetics of cathode. Existing approaches typically focus on individual optimization of each electrode, limiting full cell to achieve synergistic enhancement and inevitably increases system complexity. Herein, a dual-affinity three-dimensional host is constructed by integrating one-dimensional carbon nanotubes with two-dimensional vermiculite nanosheets. The incorporation of vermiculite overcomes the intrinsically low polarity and weak adsorption capability with active material of the conventional 3D carbon frameworks. Benefiting from the densely stacked hybrid architecture with high mechanical strength, excellent electrical conductivity and dual affinity toward Zn and polyiodides, the 3D host concurrent regulate Zn deposition and iodine conversion chemistry. The zincophilic vermiculite regulate Zn²⁺ flux, lower the nucleation barrier and promote uniform deposition, while the porous structure effectively suppress polyiodide shuttling through synergistic physical confinement and chemical anchoring. Consequently, the Zn composite anode exhibits remarkable cycling stability over 3000 cycles at 20 mA cm^-2 at 60% depth-of-discharge, whereas the integrated Zn-I₂ full cell maintains 90.0% capacity retention after 2000 cycles. This work offers a route for designing durable, highly efficient Zn-I₂ batteries.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5243975"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Cobalt/Vanadium Relay Catalysis: Enantioselective Markovnikov Hydrooxygenation of Alkenes.","authors":"Pan Peng, Cong Zhou, Zongang Liu, Xuezheng Yi, Yongsheng Tao, Weipeng Zheng, Fabao Li, Qingquan Lu","doi":"10.1002/anie.1324586","DOIUrl":"10.1002/anie.1324586","url":null,"abstract":"<p><p>The direct enantioselective intermolecular Markovnikov hydrooxygenation of alkenes remains a fundamental challenge, as it requires simultaneous control over regioselectivity, stereochemistry, and reactivity. Here we report an electrochemical cobalt/vanadium relay catalytic strategy that overcomes these constraints by decoupling regio- and stereochemical control across two distinct catalytic events. A cobalt hydride selectively engages alkenes through metal-hydride hydrogen atom transfer to generate a Markovnikov alkyl radical, while a vanadium catalyst mediates a subsequent stereodetermining bimolecular homolytic substitution (S_H2) to form the C─O bond with high enantioselectivity. Electrochemical modulation of the cobalt and vanadium redox states enables efficient catalytic relay under mild conditions, suppressing overoxidation pathways and eliminating the need for stoichiometric chemical oxidants. This approach provides access to a broad range of enantioenriched alcohols and derivatives with high functional group tolerance and scalability, offering streamlined access to pharmaceutically relevant scaffolds. More broadly, the demonstrated compatibility of vanadium-catalyzed asymmetric bond formation with electrochemical control establishes a general framework for stereoselective C─O bond construction via radical intermediates.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1324586"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877095","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Drug-Derived Tetrahydropyrazines for Late-Stage α- and β-Functionalization of Piperazine-Based Pharmaceuticals.","authors":"Soichiro Mori, Cunyuan Zhao, Tenghui Wang, Yuankai Wang, Yu Nishio, Matthew D Disney, Masayuki Wasa","doi":"10.1002/anie.6711809","DOIUrl":"10.1002/anie.6711809","url":null,"abstract":"<p><p>Piperazine is one of the most prevalent saturated nitrogen heterocycles in pharmaceuticals, yet late-stage access to α- and β-substituted piperazine analogues remains challenging. Here, we report a flavin-photocatalyzed platform that converts complex piperazine-containing drugs into persistent tetrahydropyrazine intermediates that serve as versatile branch points for downstream functionalization. Under blue-light irradiation, riboflavin tetraacetate (RFTA) promotes sequential α- and β-C─H bond cleavage of N-alkyl, N-aryl, and N-heteroaryl piperazines under mild conditions and with tolerance of diverse functional groups. The resulting drug-derived tetrahydropyrazines can be isolated or directly telescoped into reactions with electrophiles and nucleophiles, enabling late-stage access to cyclopropyl-, trifluoromethyl-, carbonyl-, amide-, and cyano-substituted piperazine analogues. By decoupling C─H oxidation from subsequent bond construction, this two-stage strategy enables transformations that would otherwise be incompatible with flavin-mediated oxidation. The utility of this approach is demonstrated through the rapid preparation of diverse analogues of piperazine-based pharmaceuticals and a preliminary structure-activity relationship (SAR) study of erastin, which reveals that piperazine-core substitution and stereochemistry can substantially influence cellular activity. Stern-Volmer quenching experiments, cyclic voltammetry, and characterization of intermediates formed under photoirradiation provide insight into the reaction mechanism. This work establishes drug-derived tetrahydropyrazines as practical late-stage intermediates for expanding medicinally relevant chemical space around piperazine-containing drug leads.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e6711809"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering Atomically Precise Cu₄I₄ Nanoclusters With Integrated Adsorption and Hydrogenation Functions for Efficient Photocatalytic Nitrate-to-Ammonia Conversion.","authors":"Wanting Zhang, Yuehua Li, Junjie Jin, Chunwei Dong, Xi Cao, Xingchi Li, Xuanjun Wu, Jiaqi Wang, Atta Ullah, Gaspar Ferreyra Vaggione, Rodrigo A Iglesias, Yun Chen, Emiliano Cortés, Dengsong Zhang","doi":"10.1002/anie.5529008","DOIUrl":"10.1002/anie.5529008","url":null,"abstract":"<p><p>Photocatalytic nitrate reduction to ammonia offers a sustainable route that couples environmental remediation with nitrogen resource utilization. However, this transformation suffers from sluggish kinetics and insufficient hydrogenation, leading to poor selectivity and efficiency. Herein, we report the deposition of Cu₄I₄ nanocluster onto TiO₂ (Cu₄I₄/TiO₂) that achieves efficient and selective photocatalytic nitrate reduction to ammonia under mild conditions. The active site derived from an atomically precise Cu₄I₄Py₄ (Py = pyridine) nanocluster introduces sterically accessible copper sites with intrinsically unsaturated coordination and enhanced Lewis acidity for nitrate adsorption and activation. The iodide ligands in Cu₄I₄ motif directly bonded to copper atoms are suggestive of promoting the generation of reactive hydrogen species (*H). The atomic-scale proximity of copper and iodide sites facilitates efficient *H utilization in the multistep hydrogenation toward NH₃. Consequently, Cu₄I₄/TiO₂ delivers an ammonia generation rate of 26.8 mmol·g_cat ^-1·h^-1 with good selectivity in a sacrificial-reagent-assisted photocatalytic nitrate reduction system. In situ characterizations and theoretical calculations support the plausible cooperative dual-site mechanism, which synergistically ensures the deep hydrogenation of nitrate and its intermediates to ammonia. This work establishes an atomic-level design paradigm for constructing multifunctional nanocluster catalysts that address the selectivity and efficiency challenges inherent to complex multiple proton/electron-involved reactions.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5529008"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676402/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Orchestrating Anion-π⁺ Interactions to Accelerate Metal-Free Room-Temperature Phosphorescence.","authors":"Eetu Hakkarainen, Corentin Montagne, Hao-Cheng Lin, Chen-Yu Lin, Khai-Nghi Truong, Po-Yu Chen, Anton Nechaev, Fabien B L Cougnon, Igor O Koshevoy, Toni Eskelinen, Hao-Wu Lin, Pi-Tai Chou, Andrey Belyaev","doi":"10.1002/anie.4386683","DOIUrl":"10.1002/anie.4386683","url":null,"abstract":"<p><p>Overcoming the long-standing trade-off between efficiency and radiative rate in metal-free phosphorescence remains a central challenge in molecular photophysics and is pivotal for the next-generation optoelectronic technologies. Here, we demonstrate that tuning the strength of anion-π⁺ interactions in pyridinium-based contact ion pairs (CIPs) enables exceptionally fast room-temperature phosphorescence (RTP) spanning 540 to 605 nm and, with radiative rates reaching 5.2×10⁵ s^-1, places this crystalline material among the fastest known organic phosphors. By systematically tuning electron deficiency, steric confinement, and CIP organization through mono- and dicarboxyester-functionalized pyridinium iodides, we achieved unusually short and highly polarized I^--π⁺ tunable contacts that approach 3.50 Å. Structural analysis reveals not only tightly bound, sandwich-like, and columnar-organized ion pairs but also unexpected dynamic behavior, including reversible, thermally activated anion drift in the solid state. Collectively, these solid state features engender strongly coupled iodide → π⁺ charge-transfer states with enhanced spin-orbit coupling, thereby promoting ultrafast intersystem crossing. Spectroscopic and theoretical studies identify an intensity-borrowing mechanism within the charge-transfer manifold that underlies the accelerated phosphorescence and/or thermally stimulated delayed phosphorescence. The resulting materials show promising X-ray scintillation performance. Our work establishes anion-π⁺ engineering as a general and previously underexploited strategy for achieving high-rate, metal-free phosphorescence.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e4386683"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676399/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"TADF-Active Tetrazole Luminophores for Visible-Light Functionalization of Nanoparticles and Surfaces.","authors":"Ryoga Hojo, Katrina Bergmann, Siyuan L Xie, Connor S Durfy, William L Primrose, Athan T Gogoulis, Seja A Elgadi, Mitchell J Demchuk, Thomas Kalab, Peiqi Hu, Eva M Nichols, Zachary M Hudson","doi":"10.1002/anie.9410589","DOIUrl":"10.1002/anie.9410589","url":null,"abstract":"<p><p>Thermally activated delayed fluorescence (TADF) materials have found broad use in technologies spanning displays, bioimaging, and photocatalysis. In parallel, tetrazoles have become powerful \"click\" reagents for light-activated, bioorthogonal ligations, yet remain unexplored in reagents with delayed emission lifetimes. Here we report the design and synthesis of TADF-active tetrazole luminophores with photochemical reactivity for the rapid functionalization of nanoparticles and surfaces. The combination of electron-rich phenoxazine donors with electron-deficient tetrazole acceptors yields luminophores with bright emission and tunable TADF lifetimes, governed by the 1,3-dipolar cycloaddition partner. Cycloaddition with alkene dipolarophiles affords saturated dihydropyrazoles that undergo photoinduced aerobic aromatization to generate pyrazole products exhibiting pronounced turn-on TADF behavior. Leveraging their charge-transfer character, we also demonstrate a gold surface modified with TADF luminophores, wherein we propose the first example of reversible visible light-induced surface adsorption. Furthermore, we demonstrate the surface functionalization of organic nanoparticles using TADF-active materials. This work introduces a class of functional materials that combine photochemical reactivity with TADF properties, introducing a light-driven platform for surface functionalization using TADF materials.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9410589"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676396/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852331","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modular and Stereoselective Synthesis of Cyclobutane β-Amino Alcohols.","authors":"Xinyu Yang, Tomoya Ozaki, Bo Li, Shih-Yuan Liu","doi":"10.1002/anie.1530338","DOIUrl":"10.1002/anie.1530338","url":null,"abstract":"<p><p>Cyclobutane β-amino alcohols are valuable structural motifs, yet their development has lagged behind that of five- and six-membered analogs due to limited synthetic accessibility. In this work, we report a general and modular strategy for the synthesis of diversely substituted cyclobutane β-amino alcohols. The electronic structure of 1,2-azaborines is leveraged to achieve regioselective mono- and difunctionalization at all four carbon positions. The installed functionalities are subsequently translated into cyclobutane β-amino alcohol frameworks through a tandem photoisomerization-hydrogenation-oxidation sequence. This strategy provides access to eight distinct substitution patterns with high levels of modularity and diastereoselectivity.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1530338"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676385/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852293","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iron-Photocatalyzed Alkene Chloroaminoxylation: A Platform for Orthogonally Activatable Building Blocks.","authors":"Amrita Chaudhuri, Meghana Aladahalli Shekar, Mohammad Zafar, Marianne Engeser, Gregor Schnakenburg, Ala Bunescu","doi":"10.1002/anie.5509453","DOIUrl":"10.1002/anie.5509453","url":null,"abstract":"<p><p>We report the development of an iron-photocatalyzed 1,2-chloroaminoxylation of alkenes that installs two orthogonal and independently activatable synthetic handles, a chlorine atom and an alkoxyamino group, across a diverse range of alkene substrates. The reaction is driven by iron's ability to generate chlorine radicals via photoinduced chloride-to-iron charge transfer, followed by addition across the carbon-carbon double bond and subsequent trapping by TEMPO derivatives. This operationally simple protocol exhibits broad functional group tolerance, exquisite chemo- and regioselectivity and efficiently converts a wide range of C═C bonds, such as styrene derivatives, unactivated alkenes, and Michael acceptors, into synthetically valuable chlorooxygenated scaffolds. The resulting products can be engaged with various nucleophiles through distinct modes of reactivity: the TEMPO-derived alkoxyamino moiety undergoes photoredox activation, while the C-Cl bond participates in nucleophilic substitution. This dual-reactivity platform enables a programmable incorporation of two different nucleophiles under complementary activation conditions, providing streamlined access to structurally diverse architectures. Comprehensive mechanistic studies, integrating reaction kinetics, UV-vis spectroscopy, high-resolution mass spectrometry (HRMS), x-ray crystallographic characterization of key catalytic intermediates, cyclic voltammetry (CV), and chronoamperometry, elucidate the underlying reaction pathway and reveal key features of the iron catalytic cycle.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5509453"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676390/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cascaded Energy Transfer in Supramolecular Assemblies Enables Amplified and Photoswitchable Circularly Polarized Luminescence.","authors":"Yanshan Sheng, Xin Wang, Minzan Zuo, Xiao-Yu Hu","doi":"10.1002/anie.1803367","DOIUrl":"10.1002/anie.1803367","url":null,"abstract":"<p><p>Photoresponsive circularly polarized luminescence (CPL) materials are promising for optical information processing and anti-counterfeiting. However, integrating high luminescence dissymmetry factor (g_lum) with high-contrast reversible switching within a single system remains a significant challenge. In this study, we present a supramolecular CPL nanoplatform that combines hierarchical chirality amplification with light-gated cascaded Förster resonance energy transfer (FRET). Selective host-guest recognition between a TPE-functionalized chiral pillar[5]arene (TPEP5) and a polymeric guest forms emissive supramolecular polymers with amplified chirality. Confined co-assembly with the achiral relay dye 4,7-di(2-thienyl)-benzo[2,1,3]thiadiazole (DBT) enables efficient FRET from TPEP5 to DBT, accompanied by concomitant chirality transfer, generating red-shifted CPL with enhanced |g_lum| values of 10^- ². Eventually, diarylethene (DAE) is incorporated as a final photoresponsive \"gatekeeper\": UV irradiation induces DAE ring closure, activating FRET pathway and quenching CPL; subsequent visible-light irradiation reverses the process, fully restoring emission and CPL activity. This orthogonal design preserves the structural integrity of the chiral scaffold over repeated switching cycles, achieving robust, fatigue-resistant, and architecture-preserving CPL on/off control. Therefore, our strategy provides a generalizable blueprint for intelligent chiral photonic materials with built-in security functionality.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1803367"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lysine Oxidation by LOXL2 in Single Strands Versus Triple Helices: Implications for Collagen-Related Diseases.","authors":"Laura M Poller, Tomas Fiala, Helma Wennemers","doi":"10.1002/anie.1329257","DOIUrl":"10.1002/anie.1329257","url":null,"abstract":"<p><p>Collagen cross-linking is essential for the structural integrity of the extracellular matrix. In several pathological conditions, the triple-helical core of collagen is disrupted, and proline-rich single strands occur. Lysyl oxidases (LOXs), enzymes that initiate cross-linking by catalyzing the oxidative deamination of lysine to allysine residues, are upregulated in disease. Surprisingly little is known about the selectivity of LOXs. LOX-initiated cross-linking is believed to occur exclusively in the unstructured terminal domains of collagen, the telopeptides. But is this really the case? Herein, we show, with a combination of tailored chemical probes, enzymatic assays, CD and NMR spectroscopic analyses, that LOXL2 oxidizes Lys in proline-rich single strands but not in triple helices. A comparison of Lys-containing collagen model peptides (CMPs) with Lys-containing telopeptides revealed comparable or higher oxidation rates in proline-rich segments. The data suggest that LOXL2-initiated cross-linking occurs in pathologically disrupted triple-helical domains, offering insights into aberrant extracellular matrix stiffening.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1329257"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676411/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852318","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}