Angewandte Chemie International Edition最新文献_第7页

Azothiophenes as Visible-Light Photoswitches via n-π∗ Excitations. 偶氮噻吩在n-π *激发下的可见光光开关。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202517858

Tongtong Dang,Xuan-Chi Yu,Xiao Liu,Zhao-Yang Zhang,Xu Zhang,XueBo Chen,Tao Li

引用次数: 0

Microporous Metal-Containing Hydrogen-Bonded Organic Frameworks with Benchmark C2H2 Storage Density for Efficient C2H2/C2H4 and C2H2/CO2 Separations. C2H2/C2H4和C2H2/CO2高效分离的基准C2H2存储密度含金属氢键有机骨架

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202514417

Jiali Fu,Qingxue Hui,Yu-Hao Gu,Qi Ding,Haoning Xu,Biao Yang,Chengyu Huangfu,Qingqing Wang,Xin-Li Liu,Xin-Yi Wang,Youting Wu,Xingbang Hu,Shuai Yuan,Zhaoqiang Zhang

{"title":"Microporous Metal-Containing Hydrogen-Bonded Organic Frameworks with Benchmark C2H2 Storage Density for Efficient C2H2/C2H4 and C2H2/CO2 Separations.","authors":"Jiali Fu,Qingxue Hui,Yu-Hao Gu,Qi Ding,Haoning Xu,Biao Yang,Chengyu Huangfu,Qingqing Wang,Xin-Li Liu,Xin-Yi Wang,Youting Wu,Xingbang Hu,Shuai Yuan,Zhaoqiang Zhang","doi":"10.1002/anie.202514417","DOIUrl":"https://doi.org/10.1002/anie.202514417","url":null,"abstract":"Separation of C2H2 from industrially important gas pairs using energy-efficient adsorptive techniques with multifunctional porous materials remains a significant yet challenging issue. Here, we report the highly efficient separation of C2H2/CO2 and C2H2/C2H4 mixtures with isostructural metal-containing hydrogen-bonded organic frameworks (M-HOFs), which feature micropore channels decorated with high-density and uncoordinated carboxyl groups. Single-crystal X-ray diffraction analysis reveals that each free carboxyl group is capable of trapping one C2H2 molecule through hydrogen bonding. This endows the M-HOFs with excellent C2H2 capture capability, achieving a benchmark storage density of 396.0 mg cm-3, while simultaneously demonstrating remarkable selectivity over C2H4 (420-97) and CO2 (188-53). Breakthrough experiments confirm that binary gas mixtures can be efficiently separated by M-HOFs, where an impressive C2H4 productivity (137.4 mol kg-1) is realized in the separation of C2H2/C2H4 (1/99), and an outstanding separation factor (17) is achieved for C2H2/CO2 (50/50) splitting. Coupled with their superior chemical stability, these M-HOFs display tremendous potential for practical applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"91 1","pages":"e202514417"},"PeriodicalIF":16.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Heteromultivalency Enhances Resolution in Cellular Mechanical Sorting. 异多价提高细胞机械分选的分辨率。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202515324

Jialu Zhang,Yihao Huang,Shuang Wan,Guihong Lin,Qi Guan,Ximing Chen,Yanling Song

{"title":"Heteromultivalency Enhances Resolution in Cellular Mechanical Sorting.","authors":"Jialu Zhang,Yihao Huang,Shuang Wan,Guihong Lin,Qi Guan,Ximing Chen,Yanling Song","doi":"10.1002/anie.202515324","DOIUrl":"https://doi.org/10.1002/anie.202515324","url":null,"abstract":"Cells sense their microenvironment and neighboring cells by exerting finely tuned mechanical forces through receptor-ligand interactions, which shape mechanophenotypes critical to biological development, immunity, and disease. Profiling these mechanophenotypes requires ligands with variable avidities. However, conventional strategies based on discrete valency changes lack the precision for continuous modulation, limiting the resolution of subtle mechanotypic differences. Here, we introduce a bivariate strategy to construct heteromultivalent ligands that independently modulate both unit affinity and valency within a single DNA nanoscaffold. By co-assembling two aptamers with distinct binding affinities, each targeting different epitopes of the same receptor, we generate ligand architectures with tunable avidities through precise stoichiometric modulation. This strategy produces a continuous avidity spectrum, overcoming the limitations of traditional homovalent systems, which are constrained by the discrete nature of valency adjustments. These heteromultivalent ligands enhance the sensitivity of force measurements, revealing subtle mechanical differences in cells with varying epithelial cell adhesion molecule (EpCAM) expressions, and enabling efficient, sequential sorting of phenotypically similar subpopulations via simple flow rate adjustments. These findings underscore the critical importance of avidity modulation in multivalent interaction engineering and mechanical cell profiling, showcasing the advantages of molecularly assembled heteromultivalent interactions over conventional homovalent strategies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"78 1","pages":"e202515324"},"PeriodicalIF":16.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Decoding a Gut Commensal Signal: Structural and Immunological Profiling of Segatella Copri Lipopolysaccharide. 解码肠道共生信号：秋葵脂多糖的结构和免疫学分析。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202512947

Luca De Simone Carone,Giusi Barra,Roberta Cirella,Marcello Ziaco,Marcello Mercogliano,Francesca Olmeo,Emanuela Andretta,Valentina Mazziotti,Carmela Fusco,Giuliana D'Ippolito,Katarzyna Anna Duda,Freda M Farquharson,Petra Louis,Angelo Fontana,Alba Silipo,Antonio Molinaro,Fabrizio Chiodo,Flaviana Di Lorenzo

{"title":"Decoding a Gut Commensal Signal: Structural and Immunological Profiling of Segatella Copri Lipopolysaccharide.","authors":"Luca De Simone Carone,Giusi Barra,Roberta Cirella,Marcello Ziaco,Marcello Mercogliano,Francesca Olmeo,Emanuela Andretta,Valentina Mazziotti,Carmela Fusco,Giuliana D'Ippolito,Katarzyna Anna Duda,Freda M Farquharson,Petra Louis,Angelo Fontana,Alba Silipo,Antonio Molinaro,Fabrizio Chiodo,Flaviana Di Lorenzo","doi":"10.1002/anie.202512947","DOIUrl":"https://doi.org/10.1002/anie.202512947","url":null,"abstract":"The immunological effects of lipopolysaccharides (LPSs) from gut microbiota remain poorly explored, overshadowed by the longstanding view of LPS as a prototypical pro-inflammatory molecule. Herein, we report the first comprehensive chemical and immunological characterization of LPS from Segatella copri DSM 18205, a prominent member of the human oral and intestinal microbiota. This LPS features a unique chemical architecture, including a mannose- and glucose-rich oligosaccharide (OS) and a highly heterogeneous, hypo-acylated lipid A domain, as elucidated by advanced mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy. Functionally, S. copri LPS displayed attenuated TLR4 activation and weak pro-inflammatory activity. Strikingly, high-dimensional cytometry by time-of-flight (CyTOF) revealed a selective preservation of CD14+CD16+ monocytes, immune subsets typically depleted by canonical enterobacterial LPSs. These findings identify S. copri LPS as a chemically and functionally distinct microbial signature, offering new insights into host-microbiota immune crosstalk and highlighting its potential for microbiome-informed immunomodulatory strategies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"100 1","pages":"e202512947"},"PeriodicalIF":16.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Amide and Thioester Synthesis Via Oxidative Coupling of Alcohols with Amines or Thiols Using Alcohol Dehydrogenases. 醇脱氢酶催化醇与胺或硫醇氧化偶联合成酰胺和硫酯。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202515469

Matteo Damian,Vasilis Tseliou,Patrick Peters,Tanja Knaus,Francesco G Mutti

{"title":"Amide and Thioester Synthesis Via Oxidative Coupling of Alcohols with Amines or Thiols Using Alcohol Dehydrogenases.","authors":"Matteo Damian,Vasilis Tseliou,Patrick Peters,Tanja Knaus,Francesco G Mutti","doi":"10.1002/anie.202515469","DOIUrl":"https://doi.org/10.1002/anie.202515469","url":null,"abstract":"Amide and thioester moieties are prevalent in pharmaceuticals, natural products, and functional materials, but their chemical synthesis suffers from poor atom economy and ungreen conditions, while biocatalytic methods require ATP-dependent enzymes, activated intermediates, or show limited scope and activity. Here, we report the oxidative coupling of alcohols with ammonia or amines catalyzed by alcohol dehydrogenases (ADHs) via hemiaminal intermediates to form primary and secondary amides at pH 9.5-10.5. Pf-ADH preferably converted linear aliphatic or arylaliphatic alcohols (up to 90% conversion), while Pp-ADH and Aa-ADH preferably converted branched or aromatic alcohols (up to 99% conversion). Preparative-scale synthesis of an N-methyl amide gave >99% conversion and 87% isolated yield. The method was extended to thioacid and thioester formation via hemithioacetal intermediates using hydrogen sulfide or thiols at pH 7. Pf-ADH favored linear aliphatic alcohols (up to 93% conversion), Pp-ADH branched alcohols (up to 82% conversion), and Aa-ADH aromatic alcohols (up to 98% conversion). A KPi/MTBE biphasic system enabled the reaction with poorly soluble long-chain thiols. Structure-guided engineering of Aa-ADH led to the Y151A and L186A variants with expanded activity toward longer-chain amines or thiols. This work highlights how enzyme promiscuity with protein engineering can enable new-to-nature synthetic pathways for the production of valuable compounds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"20 1","pages":"e202515469"},"PeriodicalIF":16.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

One-Step Phosphine-Oxide Post-Modification of Multi-Resonance Emitters for Efficient, Narrowband, Quenching-Resistant OLEDs. 用于高效、窄带、抗淬灭oled的多共振发射器一步膦氧化物后修饰。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202518065

Lixiao Guo,Weibo Cui,Yexuan Pu,Linjie Li,Yuhan Sun,Pingping Zheng,Chenglong Li,Yue Wang

{"title":"One-Step Phosphine-Oxide Post-Modification of Multi-Resonance Emitters for Efficient, Narrowband, Quenching-Resistant OLEDs.","authors":"Lixiao Guo,Weibo Cui,Yexuan Pu,Linjie Li,Yuhan Sun,Pingping Zheng,Chenglong Li,Yue Wang","doi":"10.1002/anie.202518065","DOIUrl":"https://doi.org/10.1002/anie.202518065","url":null,"abstract":"Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials featuring high efficiency and narrowband emission are crucial for wide color-gamut organic light-emitting diodes (OLEDs), but they often suffer from complex synthesis and limited structural diversity. In this study, we report a one-step, metal-free phosphine-oxide (P═O) post-modification strategy to construct the first B/N/P═O fused MR-TADF emitters, PO-BCzBN and PO-tFBN. This strategy introduces a covalent P═O lock, enhancing the rigidity of the π-conjugation plane to maintain narrowband emission while simultaneously suppressing aggregation-caused quenching (ACQ) through the steric hindrance introduced by the trigonal pyramidal geometry of sp3-hybridized P atom. PO-BCzBN and PO-tFBN show photoluminescence emission peaks at 466 and 493 nm with narrow full widths at half maximum (FWHMs) of 21 and 23 nm in solution, near-unity photoluminescence quantum yields of 98% and 99%, rapid reverse intersystem crossing rates of 2.0 × 104 and 2.1 × 104 s-1, and suppressed concentration quenching in films. Sensitizer-free OLEDs based on PO-BCzBN and PO-tFBN achieve maximum external quantum efficiencies of 21.6%-34.2% (electroluminescence emission peaks, λELs, = 472-476 nm, FWHMs = 24-28 nm) and 28.3%-35.8% (λELs = 496-500 nm, FWHMs = 26-27 nm) across a broad doping range (1-20 wt%), respectively, demonstrating superior resistance to spectral broadening and ACQ.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"9 1","pages":"e202518065"},"PeriodicalIF":16.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145189306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering Artificial Mitochondria with Self-Amplifying Proton Generation for Autonomous Energy Supply and Metabolic Coupling in Artificial Cells. 具有自扩增质子产生的工程人工线粒体在人工细胞中的自主能量供应和代谢耦合。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-30 DOI: 10.1002/anie.202514980

Fangqin Fu,Xuemei Hu,Shijia Tao,Yu Gao,Daniel Crespy,Katharina Landfester,Xiangzhao Mao,Shuai Jiang

{"title":"Engineering Artificial Mitochondria with Self-Amplifying Proton Generation for Autonomous Energy Supply and Metabolic Coupling in Artificial Cells.","authors":"Fangqin Fu,Xuemei Hu,Shijia Tao,Yu Gao,Daniel Crespy,Katharina Landfester,Xiangzhao Mao,Shuai Jiang","doi":"10.1002/anie.202514980","DOIUrl":"https://doi.org/10.1002/anie.202514980","url":null,"abstract":"A continuous and autonomous energy supply is essential for sustaining life-like biochemical processes in artificial cells. Although considerable efforts have been devoted to engineering artificial organelles that emulate mitochondrial energy conversion, the generation of a robust transmembrane proton gradient-essential for driving efficient ATP production-remains a major challenge. Here, we present a mitochondria-mimicking ATP nano-generator constructed through quantitative co-compartmentalization of glucose oxidase and catalase within silica nanocapsules. Enzymes are encapsulated in situ during the formation of core-shell nanocapsules, enabling precise loading, effective protection, and creation of a confined nanoscale reaction chamber that fosters catalytic synergy. Within this microenvironment, catalase rapidly decomposes H2O2 to generate O2, which is in turn utilized by glucose oxidase-thus establishing a self-reinforcing enzymatic cascade that amplifies proton production. After coating the enzyme-loaded nanocapsules with an ATPase-integrated liposome bilayer to construct the artificial mitochondrion, the resulting proton gradient across the membrane efficiently drives ATP synthase rotation, enabling high-yield ATP production. When integrated into giant unilamellar vesicles (GUVs) as synthetic cell models, this system supports autonomous nicotinamide adenine dinucleotide (NADH) biosynthesis and glucose-powered oxidative phosphorylation, mimicking key metabolic features of living mitochondria. This work establishes an effective and versatile platform for engineering energy-autonomous artificial living systems, advancing the state of the art of bottom-up synthetic biology.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":"e202514980"},"PeriodicalIF":16.6,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H2 and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal-Metal Interactions. H2和乙醇气氛下Cu在双金属Cu- y /Beta沸石上的演化：揭示双原子金属-金属相互作用的作用。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-29 DOI: 10.1002/anie.202514920

Junyan Zhang,Stephen C Purdy,Mingze Zheng,Meijun Li,Nohor River Samad,James W Harris,Kinga A Unocic,Evan C Wegener,Shan Jiang,Wenbo Li,Jeffrey T Miller,Felipe Polo-Garzon,Dongxia Liu,Theodore R Krause,Zili Wu,Andrew D Sutton,Pengfei Xie,Yanran Cui,Sheng Dai,Brandon C Bukowski,Zhenglong Li

{"title":"Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H2 and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal-Metal Interactions.","authors":"Junyan Zhang,Stephen C Purdy,Mingze Zheng,Meijun Li,Nohor River Samad,James W Harris,Kinga A Unocic,Evan C Wegener,Shan Jiang,Wenbo Li,Jeffrey T Miller,Felipe Polo-Garzon,Dongxia Liu,Theodore R Krause,Zili Wu,Andrew D Sutton,Pengfei Xie,Yanran Cui,Sheng Dai,Brandon C Bukowski,Zhenglong Li","doi":"10.1002/anie.202514920","DOIUrl":"https://doi.org/10.1002/anie.202514920","url":null,"abstract":"Understanding the dynamic evolution of Cu species under varying environmental conditions is critical for addressing challenges related to the activity and the stability of copper-based catalysts in thermo-, photo-, and electrocatalysis. However, metal-metal interactions between dual single atoms and their effects on Cu evolution after exposure to different environmental molecules remain underexplored. Herein, we synthesized bimetallic Cu-Y/Beta catalysts with dual single-atom Cu and Y sites and monometallic Cu-Beta catalysts with isolated Cu sites in dealuminated Beta zeolites. By varying Cu and Y compositions, diatomic interactions were studied under H2 and ethanol atmospheres. With 6 wt% Y loading, approximately 0.4 wt% of Cu species in Cu-Y/Beta remained partially oxidized as Cu(I) after reduction in pure H2 at 350 °C, in contrast to the full transition to metallic Cu observed in Cu-Beta. Combining X-ray absorption spectroscopy with kinetic studies revealed that metallic Cu became the predominant species after reduction with H2 as Cu loading increased from 0.4 to 1.7 wt%, quadrupling the initial ethanol dehydrogenation rate and demonstrating the dominant role of Cu(0) sites. Scanning transmission electron microscopy and density functional theory simulations indicated spatial proximity between dual single-atom Cu and Y sites and elucidated Cu speciation controlled by diatomic interactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"96 1","pages":"e202514920"},"PeriodicalIF":16.6,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrogen Affinity in Intermetallic Electrides as a Key Indicator of Catalytic Performance in Ammonia Synthesis. 金属间电子的亲氢性是氨合成催化性能的关键指标。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-29 DOI: 10.1002/anie.202516474

Fangkun Sun,Jiang Li,Yijia Liu,Yutong Gong,Peilan Shi,Masaaki Kitano,Hideo Hosono,Jiazhen Wu

{"title":"Hydrogen Affinity in Intermetallic Electrides as a Key Indicator of Catalytic Performance in Ammonia Synthesis.","authors":"Fangkun Sun,Jiang Li,Yijia Liu,Yutong Gong,Peilan Shi,Masaaki Kitano,Hideo Hosono,Jiazhen Wu","doi":"10.1002/anie.202516474","DOIUrl":"https://doi.org/10.1002/anie.202516474","url":null,"abstract":"Electrides have emerged as promising catalysts or catalyst supports for efficient ammonia synthesis under mild conditions. ATmSi compounds (A = rare earth/alkaline earth, Tm = transition metal) with a tetragonal CeFeSi-type structure represent a class of intermetallic electrides, where lattice atoms serve as active sites, offering significant potential for catalytic applications. However, with over 25 ATmSi compounds, their catalytic performance variations and optimization strategies remain poorly understood. In this study, we systematically investigated the structure-activity relationship of ATmSi compounds, focusing on their anionic electron properties and hydrogen storage capabilities. Analysis of lattice parameters revealed the A-A interlayer distance as a descriptor of anionic electron concentration, with the non-electride CaRuSi exhibiting a notable reduction in this distance due to minimal anionic electrons. The catalytic activities in ARuSi, ACoSi, and AFeSi systems all increase with the expansion of A-A interlayer spacing. Furthermore, hydrogen storage properties, where anionic electrons are replaced by hydride ions, were evaluated. It is critical for N2 hydrogenation. The hydrogen affinity, gauged by the desorption temperature, proved pivotal in determining catalytic efficiency, with optimal performance requiring balanced hydrogen binding strength. These findings provide critical insights for designing advanced catalysts for ammonia synthesis and potentially other hydrogenation reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"31 1","pages":"e202516474"},"PeriodicalIF":16.6,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Time-Dependent Divergent Synthesis via Photochemical Rearrangement. 光化学重排的时变发散合成。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-09-29 DOI: 10.1002/anie.202516222

Shu-Ya Wen,Yuchen Zhang,Jun-Jie Chen,Xiao-Song Xue,Huan-Ming Huang

{"title":"Time-Dependent Divergent Synthesis via Photochemical Rearrangement.","authors":"Shu-Ya Wen,Yuchen Zhang,Jun-Jie Chen,Xiao-Song Xue,Huan-Ming Huang","doi":"10.1002/anie.202516222","DOIUrl":"https://doi.org/10.1002/anie.202516222","url":null,"abstract":"Divergent synthesis is a powerful and economical approach in synthetic chemistry and materials science. However, achieving precise control over divergent reactions using only reaction time as a variable is still rare. Herein, we show a time-dependent photochemical rearrangement driven by energy transfer catalysis under visible light. Remarkably, by simply adjusting the reaction time, we can selectively synthesize two distinct types of fluorinated strained rings using the same photocatalyst. Mechanistic experiments and computational studies reveal that this photochemical rearrangement follows a kinetically controlled pathway, involving a sequence of steps: diradical formation, 1,4-aryl migration, and 1,3-diradical formation. Interestingly, when the reaction time is extended, the newly formed difluoromethyl cyclopropanes can reversibly revert to the starting materials. This indicates that the final product is not simply kinetically or thermodynamically favored in the ground state potential energy surface. Instead, the excited state introduces additional complexity to the situation, as the starting materials are then fully converted into 1,1-difluorocyclopropanes through an excited-state thermodynamic control pathway-defined as the product distribution being governed by the relative thermodynamic stabilities of intermediates on the excited-state potential energy surface (PES), in contrast to conventional ground-state thermodynamic control, which relies on singlet ground-state PES stabilities under thermal conditions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"10 1","pages":"e202516222"},"PeriodicalIF":16.6,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145182739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0