Angewandte Chemie最新文献_第5页

Stereoselective Synthesis of Aminals Through Enzyme-Catalyzed Intermolecular C(sp3)-H Amidation of Azacycles 酶催化氮杂环分子间C(sp3)-H酰胺化立体选择性合成动物

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-08 DOI: 10.1002/ange.6337773

Anwita Chattopadhyay, Satyajit Roy, Rudi Fasan

{"title":"Stereoselective Synthesis of Aminals Through Enzyme-Catalyzed Intermolecular C(sp3)-H Amidation of Azacycles","authors":"Anwita Chattopadhyay, Satyajit Roy, Rudi Fasan","doi":"10.1002/ange.6337773","DOIUrl":"https://doi.org/10.1002/ange.6337773","url":null,"abstract":"<div>\u0000 \u0000 Stereogenic aminals are widespread in natural products, pharmaceuticals, and biologically active compounds, including important classes of antibiotics. Methodologies for asymmetric synthesis of aminals are therefore highly desirable, yet they remain scarce and mostly rely on C─N bond formation at functionalized carbon centers such as carbonyls. Here we report the development of a strategy for asymmetric synthesis of aminals via direct, stereoselective C(sp3)–H functionalization of cyclic amines via an enzyme-catalyzed intermolecular nitrene transfer reaction with dioxazolones. Using engineered variants of thermophilic cytochrome P450 (CYP119) from Sulfolobus solfataricus as catalysts, this approach enables the synthesis of a diverse set of indoline-based aminals in good to high yields, excellent regio- and chemoselectivity, and with enantioselectivity up to >99% ee. This methodology could be further extended to pyrrolidines, piperidines, or morpholines as well as different dioxazolone reagents, yielding a diverse range of enantioenriched aminal scaffolds. This work expands the scope of abiological intermolecular C(sp3)–H amination reactions accessible through biocatalysis and provides a convenient, new route to the synthesis of enantioenriched aminal compounds.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149100285","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}

引用次数: 0

Bottlebrush Polyolefin Sulfones as Triggerable and Degradable Pressure-Sensitive Adhesives 瓶刷聚烯烃砜作为可触发和可降解的压敏粘合剂

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-10 DOI: 10.1002/ange.7449383

Clark Vu, Isaac D. Addo, Woojung Ham, Udita Choudhury, Joshua C. Worch, John B. Matson

{"title":"Bottlebrush Polyolefin Sulfones as Triggerable and Degradable Pressure-Sensitive Adhesives","authors":"Clark Vu, Isaac D. Addo, Woojung Ham, Udita Choudhury, Joshua C. Worch, John B. Matson","doi":"10.1002/ange.7449383","DOIUrl":"https://doi.org/10.1002/ange.7449383","url":null,"abstract":"The molecular architecture (topology) of bottlebrush polymers, featuring densely grafted side chains along a polymeric backbone, leads to unique physical properties, enabling their use as functional materials including elastomers and pressure-sensitive adhesives (PSAs). Bottlebrush polymers can form additive-free PSAs due to their architecture, but most are crosslinked materials that include all-carbon backbones, have thermally unstable disulfide bonds, or do not reach the high molar masses needed for bottlebrush PSAs. Here, we applied the alternating free-radical copolymerization of sulfur dioxide (SO2) and norbornene-based macromonomers in a grafting-through approach to make bottlebrush polymers with number-average molar masses exceeding 1100 kg/mol and backbone degrees of polymerization exceeding 900. These first examples of poly(olefin sulfone) bottlebrush polymers incorporated polyacrylate, polymethacrylate, polystyrene, and poly(lactic acid) side chains, all attached to a poly(norbornene-alt-SO2) backbone. Under mild alkaline conditions, these very high molecular weight bottlebrush polymers degraded considerably within 10 min and completely within 4 h. Finally, a bottlebrush polymer synthesized using this approach behaved as a PSA with a peel strength of ∼1200 N/m, substantially higher than non-degradable PSAs in commercial tapes. In sum, this work offers a versatile approach to synthesize triggerable and degradable bottlebrush polymer adhesives enabling end-of-life disposal following their intended applications.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.7449383","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149099989","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}

引用次数: 0

Paramagnetic d-Block Metal Organic Cages as MRI or Chemical Shift Probes 顺磁性d块金属有机笼作为MRI或化学位移探针

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-22 DOI: 10.1002/ange.1137232

Aruni Dissanayake, Jaclyn J. Raymond, Priya Ranjan Sahoo, Janet R. Morrow

引用次数: 0

A Review of Electrochemical–Biological Coupling Systems for CO2 Valorization: Catalytic Fundamentals, System Integration, and Industrial Outlook 电化学-生物耦合系统对CO2增值的综述：催化原理、系统集成和工业展望

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-11 DOI: 10.1002/ange.9183730

Xuefeng Shi, Chang Li, Feng Guo, Yufan Jing, Yafei Guo, Hongliang Li, Meng Qiao, Xianzhu Huang, Xi Chen, Chuanwen Zhao, Wenming Zhang, Xing Zhang, Jie Zeng

{"title":"A Review of Electrochemical–Biological Coupling Systems for CO2 Valorization: Catalytic Fundamentals, System Integration, and Industrial Outlook","authors":"Xuefeng Shi, Chang Li, Feng Guo, Yufan Jing, Yafei Guo, Hongliang Li, Meng Qiao, Xianzhu Huang, Xi Chen, Chuanwen Zhao, Wenming Zhang, Xing Zhang, Jie Zeng","doi":"10.1002/ange.9183730","DOIUrl":"https://doi.org/10.1002/ange.9183730","url":null,"abstract":"<div>\u0000 \u0000 To support dual-carbon goals and address the limitations of conventional CO2 valorization technologies, this review summarizes recent advances in electrochemical–biological coupling systems for high-value CO2 utilization, with emphasis on catalytic fundamentals, system integration, and industrial prospects. We discuss catalyst and reactor design for CO2 electroreduction to C1/C2 liquid platform molecules, particularly formate, acetate, and methanol, and their subsequent biological conversion. The review further examines metabolic and engineering strategies by which microbial cell factories assimilate electro-generated substrates to produce high-value compounds, including amino acids, organic acids, polysaccharides, and polyhydroxybutyrate (PHB). Key bottlenecks in electrocatalyst stability, gas diffusion electrodes, reactor operation, carbonate accumulation, cathode flooding, metabolic compatibility, flux matching, and system-level coupling are analyzed. We also highlight the roles of artificial intelligence, multiscale modeling, smart control, techno-economic analysis, and life-cycle assessment in accelerating scale-up and industrial translation. Overall, electrochemical–biological coupling provides a “capture-convert-valorize” route that integrates renewable-electricity-driven electrocatalysis with biomanufacturing, enabling CO2 conversion into multicarbon, value-added products and offering a promising platform for sustainable carbon recycling and carbon-negative manufacturing.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149100118","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}

引用次数: 0

Synergizing Schottky/S-Scheme Dual-Junction With Cu/Pb Dual-Site in a 0D/3D Cu@CsPbBr3/g-C3N4 Heterojunction for Efficient CO2-to-C2H4 Photoreduction 0D/3D Cu@CsPbBr3/g-C3N4异质结中Cu/Pb双位协同Schottky/S-Scheme双结的CO2-to-C2H4光还原效率

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-07-08 DOI: 10.1002/ange.4202059

Zexiang Wang, Feng Xiang, Haixia Wang, Mingyue Zheng, Yuxia Wang, Ying Wang, Ruizhi Li, Xian Zhao, Weiliu Fan

{"title":"Synergizing Schottky/S-Scheme Dual-Junction With Cu/Pb Dual-Site in a 0D/3D Cu@CsPbBr3/g-C3N4 Heterojunction for Efficient CO2-to-C2H4 Photoreduction","authors":"Zexiang Wang, Feng Xiang, Haixia Wang, Mingyue Zheng, Yuxia Wang, Ying Wang, Ruizhi Li, Xian Zhao, Weiliu Fan","doi":"10.1002/ange.4202059","DOIUrl":"https://doi.org/10.1002/ange.4202059","url":null,"abstract":"<div>\u0000 \u0000 The CO2 photoreduction to multi-carbon products, particularly C2H4, remains challenging due to inefficient charge separation, high C−C coupling barriers, and limited mass transport. Herein, we designed a mixed-dimensional heterostructure integrating S-scheme and Schottky junctions, with Cu-decorated CsPbBr3 nanocrystals anchored on three-dimensionally ordered macroporous g-C3N4 (Cu@CPB/3DOM-CN). In situ x-ray photoelectron spectroscopy and femtosecond transient absorption spectroscopy demonstrate dual internal electric fields driving rectified spatial carrier separation with strong redox capability. Strong metal–support interaction induces charge redistribution, generating polarized Cu/Pb dual sites that lower the energy barrier for *CO hydrogenation to *CHO. In situ diffuse reflectance infrared Fourier transform spectroscopy combined with density functional theory calculations provides direct evidence that dual sites promote asymmetric *CO−*CHO coupling. The 3DOM framework functions as a nanoreactor, enhancing the local enrichment of CO2 and key intermediates to promote coupling kinetics. The optimized catalyst exhibits distinct selectivity across varying CO2 concentrations, achieving 52.4% C2H4 selectivity (26.37 µmol g−1 h−1) in pure CO2, which increases to 77.6% and 65.1% under 5% and 0.04% CO2 (balanced with Ar), respectively, highlighting its remarkable adaptability to diverse application scenarios. This work establishes a triple synergy of directional charge transport, active-site polarization, and reactant enrichment for efficient and selective CO2-to-C2H4 conversion.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149099560","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}

引用次数: 0

Inside Front Cover: Multi-Level Asymmetric Mesoporous Nanochannels for Photothermal-Regulated Dopamine Sensing 内页封面：光热调节多巴胺感应的多层次不对称介孔纳米通道

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-20 DOI: 10.1002/ange.2026-m1308073600

Abuduheiremu Awati, Xin Zhang, Yeqing Xu, Hui Zeng, Jie Zeng, Chengmin Hu, Runhao Zhang, Yuanbo Song, Huannuo Tao, Lei Xie, Yanjun He, Dazhang Zhu, Mingxian Liu, Kang Liang, Lei Jiang, Biao Kong

引用次数: 0

Molecularly Templated Buried Interfaces for Inverted Perovskite Solar Cells 倒置钙钛矿太阳能电池的分子模板埋设界面

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-07 DOI: 10.1002/ange.6932848

Songyang Yuan, Quanrun Qiu, Huaiman Cao, Chengda Ge, Yiting Jiang, Gengyang Su, Lingyi Ke, Gengxin Du, Guangruixing Zou, Hui Liu, Guanhua Ren, Jing Wang, Nan Zhang, Yidan An, Qingduan Li, Ze Yu, Tao Jia, Yue-Peng Cai, Shengjian Liu, Hin-Lap Yip

{"title":"Molecularly Templated Buried Interfaces for Inverted Perovskite Solar Cells","authors":"Songyang Yuan, Quanrun Qiu, Huaiman Cao, Chengda Ge, Yiting Jiang, Gengyang Su, Lingyi Ke, Gengxin Du, Guangruixing Zou, Hui Liu, Guanhua Ren, Jing Wang, Nan Zhang, Yidan An, Qingduan Li, Ze Yu, Tao Jia, Yue-Peng Cai, Shengjian Liu, Hin-Lap Yip","doi":"10.1002/ange.6932848","DOIUrl":"https://doi.org/10.1002/ange.6932848","url":null,"abstract":"The buried interface between self-assembled monolayers (SAMs) and perovskite absorbers critically governs charge extraction and stability in inverted perovskite solar cells, yet remains structurally mismatched and poorly controlled. Here, we report a buried-interface engineering strategy inspired by non‑covalent molecular templating, enabled by complementary triphenylamine-based molecular building blocks. A triphenylamine-based ammonium salt, 2-(4-(diphenylamino)phenyl)ethanammonium iodide (TPANI), is introduced into the perovskite precursor, while a structurally matched triphenylamine-based bisphosphonic acid SAM deposited on ITO serves as the hole-selective layer. Non-covalent interactions at the buried interface induce molecular templating and interfacial organization of TPANI, strengthening SAM/perovskite adhesion and reducing intergranular groove depth at the buried side of the perovskite film. The resulting monolithically integrated interface suppresses buried interfacial defects, improves energy-level alignment, and facilitates hole extraction. Consequently, inverted devices achieve a power conversion efficiency of 26.58% with an exceptionally high fill factor of 86.72%, together with markedly enhanced operational stability. These results demonstrate that non‑covalent molecular templating provides an effective and general strategy for engineering buried interfaces in perovskite photovoltaics.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.6932848","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149099753","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}

引用次数: 0

Inside Back Cover: Synergizing Schottky/S-Scheme Dual-Junction With Cu/Pb Dual-Site in a 0D/3D Cu@CsPbBr3/G-C3N4 Heterojunction for Efficient CO2-to-C2H4 Photoreduction 内页后盖：在0D/3D Cu@CsPbBr3/G-C3N4异质结中协同Schottky/S-Scheme双结与Cu/Pb双位点用于co2到c2h4的高效光还原

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-09-21 DOI: 10.1002/ange.2026-m1709013400

Zexiang Wang, Feng Xiang, Haixia Wang, Mingyue Zheng, Yuxia Wang, Ying Wang, Ruizhi Li, Xian Zhao, Weiliu Fan

引用次数: 0

Programming Transition-Metal Reactivity With Dicationic Tetrylene Z-Type Ligands 用指示四烯z型配体编程过渡金属反应性

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-09-04 DOI: 10.1002/ange.2703109

Didier Bourissou

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Zn─F Diatomic Sites Promote Electrochemical C─N Coupling for the Synthesis of Amino Acids Zn─F双原子位促进氨基酸合成中的电化学C─N偶联

Angewandte Chemie Pub Date : 2026-10-05 Epub Date: 2026-08-19 DOI: 10.1002/ange.1293701

Jidong Yu, Rui-Ting Gao, Limin Wu, Lei Wang

{"title":"Zn─F Diatomic Sites Promote Electrochemical C─N Coupling for the Synthesis of Amino Acids","authors":"Jidong Yu, Rui-Ting Gao, Limin Wu, Lei Wang","doi":"10.1002/ange.1293701","DOIUrl":"https://doi.org/10.1002/ange.1293701","url":null,"abstract":"<div>\u0000 \u0000 While electrocatalytic C─N coupling offers a promising route for amino acid synthesis, its efficiency is limited by complex reaction pathways and competitive adsorption of reactants and intermediates on single-site catalysts. Herein, we report a catalyst with F and Zn diatomic sites on MnO2-x that enables the efficient synthesis of various amino acids from keto acids and nitrate through electrocatalytic C─N coupling in neutral electrolytes. For alanine synthesis, this catalyst exhibits a high Faradaic efficiency (FE) of 76.25% and a production rate of 543.02 µmol cm−2 h−1 across a broad potential window from –0.3 to –1.3 VRHE, while maintaining stable operation for over 300 h. In a membrane electrode assembly reactor, the catalyst sustains stable alanine production for 200 h with an average FE of 70.86%, enabling the practical isolation of 44.72 g of alanine. In situ spectroscopic and theoretical calculations demonstrate a tandem catalytic cascade, in which nitrate reduction proceeds to NH2OH on MnO2-x, NH2OH then spontaneously condenses with keto acids adsorbed on Zn sites to form C═N oxime intermediates, and these oximes migrate to F sites for hydrogenation to amino acids. This work offers insights into diatomic-site design for amino acid electrosynthesis and promotes the sustainable production of high-value organonitrogen compounds.\u0000 </div>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"138 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149100252","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}

引用次数: 0