Angewandte Chemie (International ed. in English)最新文献_第3页

Light-Induced Fe-LMCT Catalysis for Redox-Coupled Conversion of NO_x and SO₂ Mixture. 光诱导Fe-LMCT催化氧化还原耦合转化NOx和SO2混合物。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202510456

Ruimin Chen, Jielin Wang, Taobo Huang, Chunling Zhang, Xiuping Zhu, Jieyuan Li, Fan Dong

{"title":"Light-Induced Fe-LMCT Catalysis for Redox-Coupled Conversion of NOx and SO2 Mixture.","authors":"Ruimin Chen, Jielin Wang, Taobo Huang, Chunling Zhang, Xiuping Zhu, Jieyuan Li, Fan Dong","doi":"10.1002/anie.202510456","DOIUrl":"10.1002/anie.202510456","url":null,"abstract":"The coexistent nitrogen oxides (NOx) and sulfur dioxide (SO2) in flue gas pose inherent challenges for simultaneous removal due to their disparate reactivities. Conventional sequential treatments for their simultaneous removal face major issues of catalyst deactivation and byproduct generation. Here, we develop a subtle strategy using light-induced ligand-to-metal charge transfer (LMCT) catalysis with Fe(II) ethylenediaminetetraacetic acid (EDTA-Feᴵᴵ) to achieve redox-coupled conversion of NO and SO2 mixtures. LMCT excitation in EDTA-FeII induces directional charge separation under irradiation, routing photogenerated electrons (e⁻) to Feᴵᴵ for driving selective NO-to-N2 conversion (selectivity: 99.89%), while photogenerated holes (h+) oxidize SO2 to SO4 2⁻ (selectivity: 96.34%). This spatial segregation of redox pathways suppresses N2O generation, enabling continuous operation with 90.3% NO and nearly 100% SO2 removal efficiency. Mechanism studies reveal the LMCT-enhanced charge transfer from carboxyl/amino groups to Fe centers, while in situ EPR confirms the •SO3 2⁻ radical-mediated h+ scavenging that accelerates charge separation and utilization. This work establishes Fe-LMCT catalysis as a sustainable platform for gas-phase pollutants remediation, achieving unprecedented selectivity through precise redox pathway control.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202510456"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586145","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

Stretch-Induced Structural Ordering and Orientation for Tensile Yield Behavior and Anisotropic Optical Property of Molecular Granular Materials. 拉伸诱导分子颗粒材料的拉伸屈服行为和各向异性光学性能的结构排序和取向。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202510392

Wei Liu-Fu, Shengqiu Liu, Jiadong Chen, Jia-Fu Yin, Panchao Yin

{"title":"Stretch-Induced Structural Ordering and Orientation for Tensile Yield Behavior and Anisotropic Optical Property of Molecular Granular Materials.","authors":"Wei Liu-Fu, Shengqiu Liu, Jiadong Chen, Jia-Fu Yin, Panchao Yin","doi":"10.1002/anie.202510392","DOIUrl":"10.1002/anie.202510392","url":null,"abstract":"The densely packed sub-nm particles, molecular granular materials (MGMs), represent a new class of functional materials that deliver distinct mechanical properties from polymers and conventional granular materials. However, their costly synthesis and the vague understanding of their mechanical property hinder extensive progress. Herein, the supramolecular complexation approach is developed for the feasible construction of MGMs with hierarchical structures, while in situ small angle X-ray scattering (SAXS) is applied to monitor the mechanical deformation of MGMs for microscopic understanding. Amphiphilic oligomers are assembled from the ionic attraction of 1 nm molecular clusters and further pack into ordered hexagonal phases (HEX1) driven by hydrophobic interaction. Interestingly, stretching can induce structural orientation, and thus triggering the transformation of HEX1 to another hexagonal phase (HEX2) with denser packing, accounting for the tensile yield behavior of the MGMs. The supramolecular structure endows hierarchical structure relaxation dynamics, enabling their unique viscoelasticity with a resilient rubbery plateau even at high temperatures. Their flexibility renders the capability to facilely process the MGMs into highly oriented films and coatings with anisotropic properties for potential applications in optical device fabrications.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202510392"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586158","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

Copper(II)-Photocatalyzed Radical Anellation of Nitroalkanes with Alkenes or Alkynes for the Synthesis of Isoxazolines and Isoxazoles. 铜（II）光催化硝基烷烃与烯或炔的自由基交联合成异恶唑啉和异恶唑。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202509658

Sunaina Sardana, Aryaman Pattanaik, Julia Rehbein, Oliver Reiser

引用次数: 0

Dual-Function Tetrabenzylphosphonium Groups as Mitochondria-Targeting Artificial Anion Channels. 双功能四苯并磷基团作为线粒体靶向的人工阴离子通道。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202511936

Fei Gou, Xinlei Huangfu, Qiuting Wang, Zihong Yang, Xiyu Yuan, Wenju Chang, Jie Shen, Wen-Xiong Zhang, Huaqiang Zeng

{"title":"Dual-Function Tetrabenzylphosphonium Groups as Mitochondria-Targeting Artificial Anion Channels.","authors":"Fei Gou, Xinlei Huangfu, Qiuting Wang, Zihong Yang, Xiyu Yuan, Wenju Chang, Jie Shen, Wen-Xiong Zhang, Huaqiang Zeng","doi":"10.1002/anie.202511936","DOIUrl":"10.1002/anie.202511936","url":null,"abstract":"Artificial ion channels with specific organelle-targeting capabilities have been scarcely investigated. Here, w e report the first-in-class mitochondria-targeting anion channels derived from a structurally simple tetrabenzylphosphonium framework, in stark contrast to its phenyl-based counterpart, which lacks anion transport activity. Structural and computational analyses underscore the critical role of the methylene (CH2) linkers in the benzyl groups. These CH2 units reduce positive charge delocalization to enhance σ-hole-anion interactions, while also enabling H-atoms from both the CH2 linkers and aromatic rings to cooperatively form multiple C-H···anion H-bonds. In further conjunction with the rigid benzene rings, they help create sufficient spatial voids to accommodate anion translocation, collectively facilitating and energizing the anion transport process. Among the series studied, those bearing methyl and tert-butyl substituents exhibit the highest transport activity via a channel mechanism, with a conductance value as high as 26.5 ± 0.8 pS. Furthermore, leveraging the cationic nature of the quaternary phosphonium center, this family of anion channels readily achieves targeted mitochondrial localization, demonstrating potent anticancer activity, with IC50 values ranging from 1.42 to 3.04 μM across three cancer cell lines .","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511936"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586139","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

Rational Design of CDK12/13 and BRD4 Molecular Glue Degraders. CDK12/13和BRD4分子胶降解剂的合理设计。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202508427

Nathanael Schiander Gray, Zhe Zhuang, Woong Sub Byun, Zuzanna Kozicka, Katherine Donovan, Brendan Dwyer, Abby Thornhill, Hannah Jones, Zixuan Jiang, Xijun Zhu, Eric Fischer, Nicolas Thomä

{"title":"Rational Design of CDK12/13 and BRD4 Molecular Glue Degraders.","authors":"Nathanael Schiander Gray, Zhe Zhuang, Woong Sub Byun, Zuzanna Kozicka, Katherine Donovan, Brendan Dwyer, Abby Thornhill, Hannah Jones, Zixuan Jiang, Xijun Zhu, Eric Fischer, Nicolas Thomä","doi":"10.1002/anie.202508427","DOIUrl":"10.1002/anie.202508427","url":null,"abstract":"Targeted protein degradation (TPD) is an emerging therapeutic approach for the selective elimination of disease-related proteins. While molecular glue degraders exhibit drug-like properties, their discovery has traditionally been serendipitous and often requires post-hoc rationalization. In this study, we demonstrate the rational, mechanism-guided design of molecular glue degraders using gluing moieties. Building on established principles, by appending a chemical gluing moiety to several small molecule inhibitors, we successfully transformed them into degraders, obviating the need for a specific E3 ubiquitin ligase recruiter. Specifically, we found that incorporating a hydrophobic aromatic ring or a double bond into a cyclin-dependent kinase 12 and 13 (CDK12/13) dual inhibitor enabled the recruitment of DNA damage-binding protein 1 (DDB1), thereby transforming a high-molecular-weight bivalent CDK12 degrader into a potent monovalent CDK12/13 molecular glue degrader. We also showcase that attaching a cysteine-reactive warhead to a bromodomain-containing protein 4 (BRD4) inhibitor converts it into a degrader by recruiting the DDB1 and CUL4 associated factor 16 (DCAF16) E3 ligase.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508427"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586155","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

Multisite Proton-Coupled Electron Transfer Facilitates Oxidative Photocatalysis in a Molecular Zr-Based Coordination Compound. 多位点质子耦合电子转移促进zr基分子配位化合物的氧化光催化。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202510723

Mercedes Moreno-Albarracín, Alvaro M Rodriguez-Jimenez, Omar Nuñez, Pablo Garrido-Barros

{"title":"Multisite Proton-Coupled Electron Transfer Facilitates Oxidative Photocatalysis in a Molecular Zr-Based Coordination Compound.","authors":"Mercedes Moreno-Albarracín, Alvaro M Rodriguez-Jimenez, Omar Nuñez, Pablo Garrido-Barros","doi":"10.1002/anie.202510723","DOIUrl":"10.1002/anie.202510723","url":null,"abstract":"The development of mediators that harness visible light to drive proton-coupled electron transfer (PCET) offers a promising pathway to achieving challenging redox transformations in a more sustainable manner and with enhanced thermochemical efficiency. However, designing photocatalytic systems based on earth-abundant metals while gaining precise control over their excited-state reactivity remains a significant challenge. Here, deprotonation of the hydroxy ligands in the Zr3(O)(OH)3 nodes of a photoactive coordination cage is shown to unlock the photocatalytic oxidation of strong O-H and C-H bonds (70-100 kcal·mol-1). Mechanistic investigations reveal that this oxidative process proceeds via a multisite PCET pathway involving ground-state, pre-association followed by a static quenching mechanism. This contrasts with the dynamic quenching mechanism governing the reductive PCET previously reported for the same system. Collectively, these findings establish an unprecedent ambipolar PCET mechanism with a new class of photocatalytic mediators based on an earth abundant metal.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202510723"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144593748","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

Cooperative Activation of CO and Pyridine by an Aluminum(I) Complex Ligated with a Silylene-Borane Ligand. 硅硼烷配体连接铝(I)配合物对CO和吡啶的协同活化。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202512084

Jinghuang Lv, Xiao Fang, Fanshu Cao, Zhenbo Mo

引用次数: 0

Backbone Protecting Groups for Enhanced Peptide and Protein Synthesis. 增强肽和蛋白质合成的主链保护基团。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202509939

Samuel L Paravizzini, Linda M Haugaard-Kedström, Craig A Hutton, John Andrew Karas

{"title":"Backbone Protecting Groups for Enhanced Peptide and Protein Synthesis.","authors":"Samuel L Paravizzini, Linda M Haugaard-Kedström, Craig A Hutton, John Andrew Karas","doi":"10.1002/anie.202509939","DOIUrl":"10.1002/anie.202509939","url":null,"abstract":"Solid-phase peptide synthesis has become an indispensable technique for the routine preparation of linear peptides of up to ~40 amino acids in length. However, the solid-phase approach is still hampered by chain insolubility and aggregation, which reduces synthetic yields. Moreover, many of the deletion impurities that can form are often chromatographically inseparable from the target sequence, which diminishes final product purity. The use of backbone N-protecting groups can ameliorate this synthetic inefficiency by increasing peptide chain solubility and suppressing aggregation. Backbone protection is also useful for promoting peptide macrocyclisation, suppressing common side reactions in peptide chemistry and improving solution-phase handling. Commercially available precursors containing benzyl-based groups and pseudoprolines have found widespread use, in academic laboratories and industry. A range of other strategies have also been investigated, in a bid to increase the utility of backbone protecting groups, and to develop more efficient methods for their introduction and removal. This review provides a comprehensive account of the state of the art, and includes detailed synthetic methods relating to the use of backbone protection, and its application to \"difficult\" peptides and proteins of biological significance. The strengths and weaknesses of each approach are analysed, and a commentary on future directions is provided.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509939"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586134","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

Enzyme-Assisted Confined Synthesis of Metal Nanoparticles in Covalent Organic Frameworks for Efficient Enzyme-Metal Cascade Catalysis. 酶辅助金属纳米颗粒在共价有机框架中的限制性合成用于高效酶-金属级联催化。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202509105

Qin Wang, Chunyan Xing, Mengchu Feng, Yuying Yang, Dianshen Pang, Xiao Feng, Yuanyuan Zhang, Bo Wang

{"title":"Enzyme-Assisted Confined Synthesis of Metal Nanoparticles in Covalent Organic Frameworks for Efficient Enzyme-Metal Cascade Catalysis.","authors":"Qin Wang, Chunyan Xing, Mengchu Feng, Yuying Yang, Dianshen Pang, Xiao Feng, Yuanyuan Zhang, Bo Wang","doi":"10.1002/anie.202509105","DOIUrl":"10.1002/anie.202509105","url":null,"abstract":"The integration of enzymatic and metal catalysis in cascade reactions offers a highly efficient approach for producing high-value chemicals, such as chiral pharmaceuticals. However, overcoming the inherent incompatibility between metal and enzyme catalysts and optimizing their stability and activity to achieve effective synergy, remains a significant challenge. Here, we present an enzyme-assisted, confined synthesis of metal nanoparticles (MNPs) within the nanochannels of covalent organic frameworks (COFs), to construct efficient enzyme-metal hybrid catalysts for cascade reactions. The COF nanochannels stabilize the enzyme during MNP formation and the catalytic process, and synergize with the enzyme to regulate the size, dispersion, and electronic state of the MNPs through surface amino acid residues, realizing the co-encapsulation and dual-optimization of both components. Using Candida antarctica lipase B (CALB) and Pd nanoparticles as a model system, Pd/CALB@COF exhibits an 8.2-fold higher yield in the kinetic resolution (KR) of racemic 1-phenylethylamine (1-PEA), and a 2.7-fold enhancement in racemization conversion, compared to counterparts without COF. Their synergy in dynamic kinetic resolution (DKR) delivers ~91% yield, >98% enantiomeric excess (e.e.) value, and recyclability, with applicability to various chiral amines. This strategy has been validated across different metal-enzyme systems, establishing a versatile platform for designing efficient enzyme-metal cascade systems.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509105"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586141","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

Ligand-to-Metal Charge Transfer of Ag(II) CF2X Carboxylates: Quantum Yield and Electrophotocatalytic Arene Fluoroalkylation Tuned by X. Ag(II) CF2X羧酸酯的配体-金属电荷转移：量子产率和X调谐的电光催化芳烃氟烷基化。

Angewandte Chemie (International ed. in English) Pub Date : 2025-07-08 DOI: 10.1002/anie.202511642

Brandon M Campbell, Jesse B Gordon, Elaine Reichert Raguram, Kristopher G Reynolds, Meghan G Sullivan, Daniel G Nocera

{"title":"Ligand-to-Metal Charge Transfer of Ag(II) CF2X Carboxylates: Quantum Yield and Electrophotocatalytic Arene Fluoroalkylation Tuned by X.","authors":"Brandon M Campbell, Jesse B Gordon, Elaine Reichert Raguram, Kristopher G Reynolds, Meghan G Sullivan, Daniel G Nocera","doi":"10.1002/anie.202511642","DOIUrl":"10.1002/anie.202511642","url":null,"abstract":"Incorporation of CF2X groups beyond CF3 into arene scaffolds is underdeveloped despite these groups' utility as halogen-bond donors and as precursors to bioisosteres. Herein, we report the synthesis, characterization, and comparative photochemistry of a suite of [Ag(II)(bpy)2O2CCF2X]+ and Ag(II)(bpy)(O2CCF2X)2 (bpy = 2,2´-bipyridine, X = F, CF3, Cl, Br, H, CH3) carboxylate complexes. We find a dramatic effect of the X substituent on the efficiency of generating CF2X radicals by ligand-to-metal charge transfer (LMCT), with Ag(II) photoreduction rates varying by over an order of magnitude and quantum yields spanning over 20%. We provide insight into how electronic and structural perturbations of the Ag(II)-O2CCF2X core are manifested in the LMCT quantum efficiency. With this information in hand, Ag(II)-mediated electrophotocatalytic CF2X functionalization is carried out on a range of (hetero)arenes. This work expands the nascent field of Ag(II)-based photocatalysis by allowing for (hetero)aryl-CF2X functionalization directly from unactivated fluoroalkyl carboxylate precursors.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202511642"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586144","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