{"title":"Cooperative Activation of CO and Pyridine by an Aluminum(I) Complex Ligated with a Silylene-Borane Ligand.","authors":"Jinghuang Lv, Xiao Fang, Fanshu Cao, Zhenbo Mo","doi":"10.1002/anie.202512084","DOIUrl":"10.1002/anie.202512084","url":null,"abstract":"<p><p>Cooperative main-group systems based on alumylenes are highly attractive due to their potential for activating and transforming inert chemical bonds and small molecules. However, their development has been hindered by the scarcity of suitable supporting ligands. Herein, we report the synthesis of an amphiphilic carboranyl silylene-borane ligand (1) and demonstrate its effectiveness in stabilizing an aluminum(I) complex 2. Complex 2 has been unambiguously characterized by spectroscopic analysis, X-ray diffraction analysis, and DFT calculations, which reveals a unique structure featuring both silicon(II)→aluminum(I) and aluminum(I)→boron(III) donor-acceptor bonds. The synergistic interplay between the silylene-borane ligand and the aluminum(I) center in 2 drives its unusual reactivity toward CO and pyridine activation, facilitating cleavage of the C≡O bond and dearomatization of pyridine.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202512084"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144593705","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":"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":"<p><p>Artificial ion channels with specific organelle-targeting capabilities have been scarcely investigated. Here, we 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 (CH<sub>2</sub>) linkers in the benzyl groups. These CH<sub>2</sub> units reduce positive charge delocalization to enhance σ-hole-anion interactions, while also enabling H-atoms from both the CH<sub>2</sub> 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 IC<sub>50</sub> values ranging from 1.42 to 3.04 µM across three cancer cell lines.</p>","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}
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":"<p><p>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.</p>","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}
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":"<p><p>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.</p>","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}
{"title":"Reversible Structural Oscillation Mediates Stable Oxygen Evolution Reaction.","authors":"Qunlei Wen, Tianyang Liu, Danji Huang, Yu Lin, Zhenhong Yang, Ruoou Yang, Youwen Liu, Xiaomeng Ai, Jiakun Fang, Yafei Li, Bao Yu Xia, Shijie Cheng, Tianyou Zhai","doi":"10.1002/anie.202509915","DOIUrl":"10.1002/anie.202509915","url":null,"abstract":"<p><p>The dynamic dissolution of active species of electrocatalysts suffers severe durability issues thus limiting practical sustainable electrochemical application despite the enormous strides in the activity. An atomistic understanding of the dynamic pattern is a fundamental prerequisite for realizing prolonged stability. Herein, modeling on NiFe LDHs, multiple operando spectroscopies revealed the structural oscillation of the local [Ni-O2-Fe] unit identified a strong dependence on the alternant Fe dissolution and redeposition during the oxygen evolution reaction (OER) process, thus mediating the dynamic stability. At this point, a proof-of-concept strategy with S, Co co-doping was demonstrated to tune structural oscillation. In-situ S leaching that alleviates the lattice mismatch suppresses Fe dissolution while the electron-withdrawing Co as a deposition site promotes Fe redeposition, thus achieving the reversible oscillation of local [Ni/Co-O2-Fe] units and dynamic stability. The implementation of the modified NiFe LDH in industrial water electrolysis equipment operated steadily over 800 h (5000-h lifetime obtained by epitaxial method with 10% attenuation) with an energy consumption of 4.05 kWh Nm-3 H2 @ 4000 A m-2. The levelized cost of hydrogen of US$2.315/KgH2 overmatches the European Commission's target for the coming decade (<US$ 2.5/kgH2).</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509915"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586156","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}
Kang Wang, Yao Jiang, Hui Zhang, Shaojun Jia, Qi Wang, Peng Cui, Thamraa AlShahrani, Shengqian Ma
{"title":"Engineering the Microporous Environment of Flexible Metal-Organic Frameworks with Bifunctionality for Promoting the Separation of Ethylene from a Ternary Mixture.","authors":"Kang Wang, Yao Jiang, Hui Zhang, Shaojun Jia, Qi Wang, Peng Cui, Thamraa AlShahrani, Shengqian Ma","doi":"10.1002/anie.202508419","DOIUrl":"10.1002/anie.202508419","url":null,"abstract":"<p><p>The separation of ethylene (C<sub>2</sub>H<sub>4</sub>) from mixtures with carbon dioxide (CO<sub>2</sub>) and acetylene (C<sub>2</sub>H<sub>2</sub>) is of great industrial importance but remains a critical challenge. Here, we report that a rationally designed flexible metal-organic framework (FMOF), featuring a specifically engineered microporous environment with bifunctionality, can promote the efficient one-step separation of C<sub>2</sub>H<sub>4</sub> from a ternary mixture. Adsorption isotherms and dynamic breakthrough tests provide experimental evidence confirming the selective adsorption of CO<sub>2</sub> and C<sub>2</sub>H<sub>2</sub> over C<sub>2</sub>H<sub>4</sub> on such a FMOF, as well as its ability to separate C<sub>2</sub>H<sub>4</sub> from a CO<sub>2</sub>/C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> ternary mixture. Theoretical calculations and simulations provide critical insights into the flexible adsorption process and the separation mechanism of the FMOF. The bifunctionality incorporated in FMOF provides exceptionally strong binding of CO<sub>2</sub> and C<sub>2</sub>H<sub>2</sub> but inhibition of C<sub>2</sub>H<sub>4</sub>, which, in turn, enables high adsorption selectivity for CO<sub>2</sub>/C<sub>2</sub>H<sub>4</sub> and C<sub>2</sub>H<sub>2</sub>/C<sub>2</sub>H<sub>4</sub>. This FMOF has high potential for industrial applications in the separation of C<sub>2</sub>H<sub>4</sub> from gas mixtures.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508419"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144593706","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}
Samuel J Paravizzini, Linda M Haugaard-Kedström, Craig A Hutton, John A Karas
{"title":"Backbone Protecting Groups for Enhanced Peptide and Protein Synthesis.","authors":"Samuel J Paravizzini, Linda M Haugaard-Kedström, Craig A Hutton, John A Karas","doi":"10.1002/anie.202509939","DOIUrl":"10.1002/anie.202509939","url":null,"abstract":"<p><p>Solid-phase peptide synthesis has become an indispensable technique for the routine preparation of linear peptides of up to approximately 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 macrocyclization, 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 analyzed, and a commentary on future directions is provided.</p>","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}
Joost J B V D Tol, Magda M J Dekker, Ádám Müller, Puck Springintveld, E W Meijer, Ghislaine Vantomme
{"title":"Macromolecule-Driven Supramolecular Polymerization Induced by Crowding Effects.","authors":"Joost J B V D Tol, Magda M J Dekker, Ádám Müller, Puck Springintveld, E W Meijer, Ghislaine Vantomme","doi":"10.1002/anie.202512216","DOIUrl":"10.1002/anie.202512216","url":null,"abstract":"<p><p>Macromolecular crowding plays a crucial role in biological systems by regulating dynamic processes, yet its effects in fully synthetic environments remain largely unexplored. Here, we systematically investigate how excluded volume effects influence supramolecular polymerizations in organic media. We employ various discotic supramolecular monomers that assemble sequentially into polymers and kinetically-controlled higher-order aggregates (HOAs) only in the presence of macromolecular crowders. The phase diagram of the supramolecular assemblies reveals a strong dependence on the macromolecule concentration, size, and polarity, which can be tuned to control polymerization. Remarkably, at high crowder concentrations, large condensed and aligned assemblies were observed in dried samples, suggesting a transition to phase-separated states. By testing different monomers, macromolecules, and solvents, we establish the general applicability and versatility of macromolecular crowding in guiding supramolecular polymerization. This work provides fundamental insights into assembly processes in crowded environments and opens new avenues for applying macromolecular crowding beyond aqueous systems.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202512216"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586147","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}
Julia Diecker, Benedikt Hermanns, Jennifer Rüschenbaum, René Rasche, Wolfgang Dörner, Alexander Schröder, Daniel Kümmel, Henning D Mootz
{"title":"Structural Basis for a Scaffolding Role of the COM Domain in Nonribosomal Peptide Synthetases.","authors":"Julia Diecker, Benedikt Hermanns, Jennifer Rüschenbaum, René Rasche, Wolfgang Dörner, Alexander Schröder, Daniel Kümmel, Henning D Mootz","doi":"10.1002/anie.202506621","DOIUrl":"10.1002/anie.202506621","url":null,"abstract":"<p><p>Nonribosomal peptide synthetases (NRPSs) are multi-domain enzymes that catalyze the biosynthesis of therapeutically relevant natural products. Efficient peptide synthesis relies on intricate domain interactions, whose underlying principles remain poorly understood. The communication-mediating (COM) domains facilitate interactions between separate NRPS subunits. For unknown reasons, COM domains co-occur with epimerization (E) domains, are partially embedded within the adjacent condensation (C) domains and can also be found as internal cis-COM domains. These features set COM domains apart from other docking domains. We present the first crystal structure of a cis-COM domain within an E-COM-C domain arrangement from modules 4 and 5 of bacitracin synthetase 3 (BacC). The structure reveals a compactly folded COM domain sandwiched between E and C domains, suggesting a role of the COM domain in orienting these domains for efficient peptidyl carrier protein (PCP) shuttling. Through mutational analyses, dipeptide formation assays, and proximity-dependent photo-crosslinking experiments, we investigated both cis- and trans-COM domains and provide evidence supporting a principal role of COM domains as scaffolds of NRPS architecture. Their function as docking domains may be a secondary consequence of their division into separate donor and acceptor parts.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506621"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144593751","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":"Establishing 3d-4d Orbital Hybridization for Efficient Photothermal Catalytic CO2 Hydrogenation.","authors":"Yisi Yang, Fengliang Wang, Wenyuan Lyu, Dawang Tang, Datong Chen, Xin Zhao, Ruiqi Fang, Yingwei Li","doi":"10.1002/anie.202509855","DOIUrl":"10.1002/anie.202509855","url":null,"abstract":"<p><p>Photothermal catalytic CO2 conversion offers a promising way to address the energy and environmental issues, however, the development of self-supporting catalyst with high activity and selectivity remains a great challenge. Here, we report the decoration of PdCo alloy on self-supporting carbon cloth with N-doped carbon arrays (PdCo-NC/CC) for efficient photothermal catalytic methanation. In situ spectra and density function theoretical (DFT) calculations demonstrate that the 3d-4d hybridization between Co and Pd enables an increase in the energy level of the dz2-5σ and dyz-2π* states in the CO/PdCo alloy, thus enhancing the binding strength of the *CO intermediate and accelerating the CO hydrogenation. Specifically, the self-supporting substrate provides highly dispersed metal sites for CO2 methanation while serves as a photo-to-heat converter to improve the temperature of reaction system. As a result, PdCo-NC/CC exhibits unprecedent photothermal performance toward CO2 methanation, delivering a CH4 generation rate as high as 15.23 mol gmetal-1 h-1 and a selectivity of 100% in batch reaction under the irradiation of Xenon lamp without any external thermal source. Moreover, the continuous flow photothermal reaction can be smoothly proceeded over 100 h, demonstrating the high stability of PdCo-NC/CC in CO2 hydrogenation.</p>","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202509855"},"PeriodicalIF":0.0,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144586142","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}