{"title":"Frontispiece: Alkali Metal Cations Impact the Selectivity of Radical-Mediated Electrochemical C─H Chlorination","authors":"","doi":"10.1002/ange.202583602","DOIUrl":"https://doi.org/10.1002/ange.202583602","url":null,"abstract":"<p>Using electrochemistry to enact organic molecule transformations offers a potential route towards greener chemical manufacturing. However, such reactions can often be complex with a multitude of factors at play. In their Communication (e202509115), Yanwei Lum et al. performed a systematic study of the impact of electrolyte cations on the selectivity of electrochemical C─H chlorination of cyclohexane. It was found that larger cations increase the propensity towards the formation of chlorine radicals, which then facilitates the formation of chlorocyclohexane through a radical non-chain mechanism.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 36","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202583602","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144927533","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":"Outside Front Cover: Highly Selective Adsorption of Para-Xylene, Ethylbenzene, and Explicit Exclusion of Ortho-Xylene from Xylene Isomers Using a Pillar-Layered MOF with Tuned Pore Channels (Angew. Chem. 39/2025)","authors":"Seonghwan Lee, Amitosh Sharma, Jae Hyeok Lee, Jaewoong Lim, Prof.Dr. Seung Kyu Min, Prof.Dr. Hyungphil Chun, Prof.Dr. Myoung Soo Lah","doi":"10.1002/ange.202518729","DOIUrl":"10.1002/ange.202518729","url":null,"abstract":"<p>Molecular sieving of xylene isomers was achieved by Myoung Soo Lah et al. in their Research Article (e202512244), using a pillar-layered MOF, Ni-HDB, incorporating DABCO pillars that block lateral diffusion and enforce transport through elliptical windows. This confined geometry enables record selectivity for PX and EB over OX via kinetic sieving, offering a new strategy for energy-efficient hydrocarbon separation.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 39","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202518729","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128773","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}
Lenard Saile, Dr. Kun Dai, Dr. Mahesh D. Pol, Thejus Pramod, Dr. Ralf Thomann, Dr. Charalampos G. Pappas
{"title":"Inside Back Cover: Chirality Makes or Breaks Chemically Driven Self-Assembly (Angew. Chem. 38/2025)","authors":"Lenard Saile, Dr. Kun Dai, Dr. Mahesh D. Pol, Thejus Pramod, Dr. Ralf Thomann, Dr. Charalampos G. Pappas","doi":"10.1002/ange.202518660","DOIUrl":"https://doi.org/10.1002/ange.202518660","url":null,"abstract":"<p>In their Research Article (e202508481), Lenard Saile and Kun Dai et al. describe a feedback mechanism that controls non-equilibrium systems. Enantiomeric aminoacyl phosphates, depicted as left and right hands drive the formation of distinct peptide assemblies. These structures, in turn, regulate the kinetics of the reaction cycle, providing control through stereochemical information rather than broad structural changes. The image was created by Ella Maru studio.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 38","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202518660","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062351","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}
Mercedes Moreno-Albarracín, Alvaro M. Rodriguez-Jimenez, Omar Nuñez, Pablo Garrido-Barros
{"title":"Outside Back Cover: Multisite Proton-Coupled Electron Transfer Facilitates Oxidative Photocatalysis in a Molecular Zr-Based Coordination Compound (Angew. Chem. 38/2025)","authors":"Mercedes Moreno-Albarracín, Alvaro M. Rodriguez-Jimenez, Omar Nuñez, Pablo Garrido-Barros","doi":"10.1002/ange.202518413","DOIUrl":"https://doi.org/10.1002/ange.202518413","url":null,"abstract":"<p>Harnessing multisite proton-coupled electron transfer (PCET) through deprotonation of a photoactive Zr coordination cage unlocks oxidative photocatalysis of strong C─H and O─H bonds. This reactivity overcomes the energetic barrier that renders electron transfer alone inaccessible. The Zr platform acts as an ambipolar mediator that unites oxidative and reductive PCET pathways, each operating through distinct mechanisms, and offers new insights for sustainable solar-to-chemical energy conversion, as reported by Pablo Garrido-Barros et al. in their Communication (e202510723).\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 38","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202518413","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145062352","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}
Xinyu Zhao, Haibin Yin, Hongfei Lin, Zijin Dai, Xin Chen, Wenlong Wu, Hongliang Li, Bo Wu, Jie Zeng
{"title":"Outside Back Cover: The Importance of Si─ONa─Al Moieties in Fe/ZSM-5 Zeolite Catalysts for Selective Oxidation of Methane to Acetic Acid (Angew. Chem. 40/2025)","authors":"Xinyu Zhao, Haibin Yin, Hongfei Lin, Zijin Dai, Xin Chen, Wenlong Wu, Hongliang Li, Bo Wu, Jie Zeng","doi":"10.1002/ange.202518999","DOIUrl":"https://doi.org/10.1002/ange.202518999","url":null,"abstract":"<p>The image highlights electron transfer from Si─ONa─Al moieties to iron active sites in the Fe/ZSM-5-0.25Na driving selective C─C coupling between methane and CO, efficiently steering the reaction toward acetic acid formation. In their Research Article (e202511056), Jie Zeng, Bo Wu et al. demonstrate a strategy to bypass traditional Brønsted acid dependency, employing metal-electronic modulation to enhance catalytic efficiency, and to establishes an innovative pathway for methane conversion.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202518999","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145171913","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}
Eduard Madirov, Clara Catros, Niko Hildebrandt, Chloé Grazon
{"title":"Inside Back Cover: Inter-Nanoparticle FRET for Biosensing: Photophysics Versus Size (Angew. Chem. 39/2025)","authors":"Eduard Madirov, Clara Catros, Niko Hildebrandt, Chloé Grazon","doi":"10.1002/ange.202518732","DOIUrl":"10.1002/ange.202518732","url":null,"abstract":"<p>FRET between luminescent nanoparticles is a compromise between outstanding photophysical properties and large sizes. In their Review Article (e202510801) Niko Hildebrandt, Chloé Grazon et al. discuss the influence of nanoparticle type, architecture, surface chemistry, and optical properties on FRET and the pros and cons of inter-nanoparticle FRET for bioanalytical applications.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 39","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202518732","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128774","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}
Zheng Cui, Li-Yan Hao, Yi-Fan Yuan, Xiao-Peng Xuan, Guo-Xin Jin
{"title":"Stereoselective Self-Assembly of a Topologically Chiral [6]Catenane with 18 Crossings","authors":"Zheng Cui, Li-Yan Hao, Yi-Fan Yuan, Xiao-Peng Xuan, Guo-Xin Jin","doi":"10.1002/ange.202515400","DOIUrl":"https://doi.org/10.1002/ange.202515400","url":null,"abstract":"<p>Mechanically interlocked molecules (MIMs) exhibit unique properties and functions arising from their structural entanglement, features of which are absent in their individual components. However, synthesizing topologically complex architectures, particularly those with topological chirality, remains a significant challenge due to the lack of general methods for controlled entanglement. Herein, we report the stereoselective synthesis of a 24-metal-center topologically chiral [6]catenane featuring 18 crossings (<span></span><math></math> link), representing one of the most intricate MIMs constructed to date. This complex architecture was achieved in high yield (71%) via one-step coordination-driven self-assembly of 12 chiral semirigid bidentate ligands and 12 conjugated binuclear half-sandwich organometallic clips. Critically, chirality transfer from enantiopure ligands enabled exclusive formation of topological enantiomer pairs (<b>Rh-1</b><i>S</i>/<b>Rh-1</b><i>R</i>), each containing four topologically chiral stereogenic units—three cyclic [3]catenane components and one closed three-link chain component. The self-assembly is synergistically directed by integrated noncovalent interactions (sevenfold π–π stacking, hydrogen bonding, and solvophobic effects), as unambiguously confirmed by single-crystal X-ray diffraction and nuclear magnetic resonance spectroscopy. This design strategy, incorporating tailored noncovalent interaction sites in building blocks, provides a viable approach for synthesizing other structurally complex topologically chiral MIMs.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230631","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":"Correction to “Highly Selective Electrocatalytic 1,4-NADH Regeneration Based on Host–Guest Recognition Mediated by Cucurbit[8]Uril on NiO”","authors":"","doi":"10.1002/ange.202508948","DOIUrl":"10.1002/ange.202508948","url":null,"abstract":"<p>H. Ning, Y. Wu, C. Liu, Z. Zhao, Z. Li, J. Dai, P. Zhang, F. Li, L. Sun, F. Li, <i>Angew. Chem. Int. Ed</i>. <b>2025</b>, <i>64</i>, e202503018,</p><p>In this Research Article, the mass spectrum of NAD<sup>+</sup>@CB[8] supramolecule with <i>m/z</i> = 993.46 was collected in negative ion mode rather than in positive ion mode, as mistakenly mentioned in the article. The spectrum is shown in Figure S14 and corresponds to the doubly charged species of [NAD<sup>+</sup>@CB[8]–4H–2e]<sup>2</sup>.</p><p>In the Supporting Information, Figures S6 and S7 were incorrect. The corrected Figures S6 and S7 are shown below:</p><p>The conclusions of this article are not affected by these errors. The authors sincerely apologize for any inconvenience caused.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 39","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202508948","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145128775","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}
Samuel J. Andrzejewski, Anika J. Friedman, Kathryn Mains, Annette Thompson, Nathaniel L. Hamel, Banumathi Sankaran, Peter H. Zwart, Michael R. Shirts, Jerome M. Fox
{"title":"Protein–Protein Complex Stability Controls Substrate Scope in a β-Ketoacyl-ACP Reductase Specific for Medium Chains","authors":"Samuel J. Andrzejewski, Anika J. Friedman, Kathryn Mains, Annette Thompson, Nathaniel L. Hamel, Banumathi Sankaran, Peter H. Zwart, Michael R. Shirts, Jerome M. Fox","doi":"10.1002/ange.202508316","DOIUrl":"https://doi.org/10.1002/ange.202508316","url":null,"abstract":"<p>Assembly-line enzymes carry out multistep synthesis of important metabolites by using acyl carrier proteins (ACPs) to shuttle intermediates along defined sequences of active sites. Despite longstanding interest in reprogramming these systems for metabolic engineering and biosynthetic chemistry, the mechanisms underlying their reaction order remain poorly understood and difficult to control. Here we describe a β-ketoacyl-ACP reductase from <i>Pseudomonas putida</i> (<i>Pp</i>FabG4) with an unusual selectivity for medium chains and use it to explore the molecular basis of substrate specificity in enzymes that pull intermediates from fatty acid synthesis, a common route to specialized products. X-ray crystallography shows no obvious barriers to short-chain binding. Molecular simulations and supporting mutational analyses indicate that substrate preference arises instead from a weak enzyme–ACP interaction that is stabilized by medium acyl chains but not by short chains. Indeed, mutations that strengthen this interaction for <i>Pp</i>FabG4 or weaken it for <i>Ec</i>FabG, an <i>Escherichia coli</i> β-ketoacyl-ACP reductase with a broad substrate specificity, can enhance or reduce activity on short-chain substrates by over 100-fold. Our findings show how the stability of enzyme-ACP interactions can control substrate scope in promiscuous enzymes and guide the exchange of intermediates between (and within) assembly-line systems.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 40","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145171912","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}
Yixue Xu, Fan Qiu, Prof. Yubin Fu, Shun-Feng Li, Xing Su, Prof. Kunquan Hong, Mei-Mei Zhang, Prof. Xin Zhao, Prof. Yuqiao Wang, Prof. Shun-Qi Xu
{"title":"Solvent-Driven Precise Control of Stacking Configurations in Covalent Organic Frameworks for High-Efficiency Photocatalysis","authors":"Yixue Xu, Fan Qiu, Prof. Yubin Fu, Shun-Feng Li, Xing Su, Prof. Kunquan Hong, Mei-Mei Zhang, Prof. Xin Zhao, Prof. Yuqiao Wang, Prof. Shun-Qi Xu","doi":"10.1002/ange.202512603","DOIUrl":"https://doi.org/10.1002/ange.202512603","url":null,"abstract":"<p>Two-dimensional covalent organic frameworks (2D COFs) have emerged as promising photocatalysts due to their high surface areas and precisely tunable physicochemical properties. However, it remains a significant challenge to precisely control over interlayer stacking configurations in 2D COFs, which critically influence charge carrier transport and consequently determine catalytic efficiency. In this study, we demonstrate a solvent-driven strategy to precisely regulate the interlayer stacking configurations of metal-incorporated 2D COFs, successfully achieving both AA eclipsed (COF-TD-AA) and ABC staggered (COF-TD-ABC) configurations. Notably, by modulating the coordination interactions between solvent 1-butanol and Zn<sup>2+</sup> (within the COFs), the interactions between the Zn<sup>2+</sup> and nitrogen atoms (from imine bonds, pyridine, and triazine units) can be precisely tuned, which leads to the formation of AA or ABC stacked 2D COFs. Interestingly, the ABC-stacked COF-TD-ABC exhibited an extended light absorption and superior charge migration/separation efficiency than those of COF-TD-AA. As a result, when coupled with Pt co-catalysts, COF-TD-ABC achieved a high hydrogen evolution rate up to 10.92 mmol g<sup>−1</sup> h<sup>−1</sup>, representing a ∼3.5-fold enhancement over COF-TD-AA (3.12 mmol g<sup>−1</sup> h<sup>−1</sup>). This work provides a fundamental insight into the stacking-dependent structure-property relationships in COFs, paving the way for the rational design of high-performance COF-based photocatalysts.</p>","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 41","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230887","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}