Jia Gao, Leyao Chen, Karin Steffen, Henrik Schweder, Birgit Schreckenberger, Shu-Ming Li, Ben Auxier, Antonis Rokas, Reinhard Fischer
{"title":"Intermolecular Carbon–Carbon Naphthalene Coupling Involves a Radical Mechanism Driven by Cytochrome P450 in Alternaria alternata","authors":"Jia Gao, Leyao Chen, Karin Steffen, Henrik Schweder, Birgit Schreckenberger, Shu-Ming Li, Ben Auxier, Antonis Rokas, Reinhard Fischer","doi":"10.1002/anie.2505284","DOIUrl":"10.1002/anie.2505284","url":null,"abstract":"<p>Dihydroxynaphthalene (DHN) derivatives are precursors of biologically important molecules, including melanin and perylenequinones (PQs). Biosynthesis of DHN-derived metabolites requires precise spatial control of radical reactions to form specific C─C or C─O─C bonds. Investigating fungal PQ biosynthesis in <i>Alternaria alternata</i>, we identified a cytochrome P450 enzyme that catalyzes a highly regio- and stereospecific C─C radical coupling reaction. Conversely, a DHN-converting P450 from <i>Berkleasmium</i> sp. utilizes a diradical mechanism yielding a C─O─C bridge. Comparing these enzymes revealed five sequence motifs that, with structural modeling, allowed the identification of a novel <i>A. alternata</i> enzyme converting 1,8-DHN to a 2-2' DHN dimer. We demonstrate that P450-dependent PQ biosynthesis in <i>A. alternata</i> is fundamentally distinct from the laccase-fasciclin-mediated pathway in <i>Cercospora beticola</i>, indicating that PQ biosynthesis evolved via distinct, lineage-specific pathways through convergent evolution. Finally, PQs contribute to microbial niche shaping on tomato fruits. Understanding these pathways provides a foundation for producing PQs for medical applications.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.2505284","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Correspondence on “Water-Derived Radical Species Initiate Six-Electron Oxidation of Cyclic Ketones in Microdroplets” Angew. Chem. Int. Ed. 2026, e1888676","authors":"Willem H. Koppenol","doi":"10.1002/anie.6377017","DOIUrl":"10.1002/anie.6377017","url":null,"abstract":"<div>\u0000 \u0000 <p>Cooks and coworkers (<i>Angewandte Chemie</i> <i>65</i> (2026), e1888676, <span>https://doi.org/10.1002/anie.1888676</span>) claim that cyclic ketones are oxidized by H<sub>2</sub>O<sup>•+</sup>. Formation of this species requires a substantial input of energy to be formed and is, even if it were to be formed, too short-lived to participate in bimolecular reactions.</p>\u0000 </div>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093362","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}
{"title":"Gold Clusters With Open-Shell Ligands: Superatom Mediated Magnetic Interaction","authors":"Katsuya Mutoh, Kosei Hayashi, Yoichi Kobayashi, Kazunobu Sato, Rika Tanaka, Daichi Kitagawa, Tatsuya Tsukuda, Takuya Nakashima","doi":"10.1002/anie.3543072","DOIUrl":"10.1002/anie.3543072","url":null,"abstract":"<p>Understanding the magnetic interactions within gold clusters that involve superatomic orbitals is critically important in advancing the development of nanoscale materials with magnetic functionality. In this study, we report on the synthesis of Ir-doped Au<sub>12</sub> (Ir@Au<sub>12</sub>) icosahedral clusters functionalized with two open-shell verdazyl radicals at opposite poles, along with an investigation into their electronic, magnetic, and photophysical properties. The photoluminescence from the Ir@Au<sub>12</sub> cluster core is drastically quenched by the introduction of verdazyl ligands. The ultrafast time-resolved absorption spectroscopy reveals the electron transfer from the Ir@Au<sub>12</sub> core in the triplet excited state to the verdazyl ligand. The EPR study discloses the hyperfine coupling with the Au and Ir nuclei, indicating the spin density of the verdazyl radical moderately delocalized over the Ir@Au<sub>12</sub> core. These results provide direct evidence of electronic interaction between the organic radicals and Ir@Au<sub>12</sub> superatomic core. Furthermore, the variable temperature EPR study suggests weak magnetic communication between the two verdazyl radical ligands mediated by the Ir@Au<sub>12</sub> superatomic core. These findings will establish superatom–organic radical hybrids as a new class of multi-spin systems and provide a design strategy for photofunctional and magnetic nanomaterials based on atomically precise metal clusters.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.3543072","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148715365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Graphene as a Synthetic Platform for Post-Graphene 2D Materials and Heterostructures","authors":"Jing Wen, Boxi Yin, Jun Shen, Jing Li, Shan Liu, Huaping Wang, Yong-Chao Zheng, Xu-Bing Li, Gui Yu","doi":"10.1002/anie.9317311","DOIUrl":"10.1002/anie.9317311","url":null,"abstract":"<div>\u0000 \u0000 <p>Graphene's pioneering role as the first isolated and systematically studied 2D material has fueled intense research into its synthesis and applications, while simultaneously accelerating the discovery and development of numerous other 2D materials. Recent progress in synthesizing high-quality graphene, especially through the chemical vapor deposition (CVD) method, has been particularly significant, solidifying its position as a critical platform for propelling research across the entire field of 2D materials. This review summarizes the applications of high-quality graphene single crystals and films in synthesizing and engineering other 2D materials—including conventional inorganic and emerging organic 2D materials. We focus specifically on graphene's functions as a growth substrate and epitaxial template for optimizing the preparation of post-graphene 2D materials, and on its use in constructing heterostructures that broaden application prospects and enhance device performance. We further examine current challenges and future research directions, aiming to leverage high-quality graphene to achieve facile synthesis of post-graphene 2D materials and their heterostructures with precise control over composition, orientation, and interfacial interactions. Such advances are anticipated to enable high-performance devices in next-generation electronics, optoelectronics, sensors, catalysts, spintronics, and beyond.</p>\u0000 </div>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821696","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}
Sai Chu, Jiahui Guo, Meiling Qi, Qiaozhi Li, Jiajia Zheng, Ken-ichi Otake, Wenqi Xu, Rosantha Kumara, Xi Wang, Xiuyan Qiu, Tianfei Chu, Kuo Liu, Susumu Kitagawa, Zongxian Yang, Long Chen, Ming-Shui Yao
{"title":"Space-Confined Water Isotope Transport in Conductive MOF Thin Film","authors":"Sai Chu, Jiahui Guo, Meiling Qi, Qiaozhi Li, Jiajia Zheng, Ken-ichi Otake, Wenqi Xu, Rosantha Kumara, Xi Wang, Xiuyan Qiu, Tianfei Chu, Kuo Liu, Susumu Kitagawa, Zongxian Yang, Long Chen, Ming-Shui Yao","doi":"10.1002/anie.7017206","DOIUrl":"10.1002/anie.7017206","url":null,"abstract":"<div>\u0000 \u0000 <p>The century-old challenge of isotope separation might be addressed by conductive metal–organic framework (cMOF) thin films featuring ordered nanopores, designable charge-transport pathways, and potential flexibility. However, resolving and amplifying the microscopic kinetic differences between water isotopologues within such confined spaces remains nontrivial. In this work, proton- and electron-coupled two-dimensional π-conjugated cMOF thin films (Cu<sub>1</sub>TPB<sub>0.1</sub>−<i>x</i>C) are fabricated through controllable layer-by-layer growth with oriented narrow pores and flexibility. Correlating electrical- and mass-transduced gas-sensor technologies, the subtle differences in the interactions of H<sub>2</sub>O and D<sub>2</sub>O with the framework were identified, revealing a complex multistage mass transport. Comparison of cMOFs with different pore sizes shows that this identification originates from distinct conduction mechanisms. Notably, the Cu<sub>1</sub>TPB<sub>0.1</sub>−<i>x</i>C thin film with a strong space-confined effect exhibits a complex multistage electrical response due to its unique proton–electron-coupled conduction characteristics, thereby enabling further differentiation of the transport processes of H<sub>2</sub>O and D<sub>2</sub>O on the outer surface and within the confined spaces. The oriented cMOF films therefore provide a real-time platform for resolving and amplifying subtle isotope-dependent transport dynamics in confined pores, offering mechanistic guidance for the design of porous materials with controlled water-isotopologue transport.</p>\u0000 </div>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148860979","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}
{"title":"Porous Solid Electrolyte Reactors for Function-Oriented Off-Electrode Electrosynthesis","authors":"Xiu Lin, Leonhard Tannesia, Li An, Zhichuan J. Xu","doi":"10.1002/anie.5622879","DOIUrl":"10.1002/anie.5622879","url":null,"abstract":"<div>\u0000 \u0000 <p>Electrosynthesis offers an attractive route to sustainable chemical manufacturing when coupled with renewable electricity. As electrosynthesis capability advances towards high-purity products, the traditional proximity of reaction products to the electrode surface, where the reaction happens, increasingly becomes a limiting factor. In addition, the formation and transport of reactive species are confined in the same chamber, resulting in electrolyte contamination of the product. Porous solid electrolyte (PSE) reactors address this spatial constraint by introducing an additional ion-conductive middle layer between the cathode and anode, enabling a versatile off-electrode space for product formation and transportation. Here, we frame PSE reactors as function-oriented platforms for off-electrode electrosynthesis, in which the PSE middle layer serves as a functional reaction space that enables ionic recombination, reaction-environment regulation, and improved management of reactive intermediates. By linking the underlying ionic-species transport mechanisms and reactor design principles, we establish a structure-transport-function framework for understanding how PSE reactors extend electrosynthesis beyond the electrode surface confinement and guide the rational design of scalable electrosynthesis reactors as on-site chemical manufacturing platforms.</p>\u0000 </div>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852292","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}
{"title":"Catalytic Anionic Substituents Effects as Selectivity Mediators in Photocatalytic Hydrogen Atom Transfers","authors":"Gaétan Archer, Maurice Médebielle, Jérémy Merad","doi":"10.1002/anie.9361104","DOIUrl":"10.1002/anie.9361104","url":null,"abstract":"<div>\u0000 \u0000 <p>Photo-induced hydrogen atom transfer (HAT) catalysis has become a powerful platform for the direct and selective functionalization of ubiquitous C─H bonds. Traditionally, the outcome of these transformations is dictated by the interplay between C─H bond dissociation energies and polar effects, enabling predictable yet inherently substrate-controlled selectivity. Recently, a fundamentally new strategy has emerged that relies on the catalytic and reversible modulation of substrate electronics to transiently enhance the reactivity of targeted C─H bonds. Notably, catalytic full or partial deprotonation of oxygen- and nitrogen-containing functional groups has proven remarkably effective in selectively activating adjacent C─H bonds toward HAT, a phenomenon known as the anionic substituent effect. Rather than relying solely on the intrinsic properties of a substrate, this concept allows chemists to reprogram C─H bond reactivity in situ, unlocking previously inaccessible levels of selectivity in the direct functionalization of abundant functional groups under mild photocatalytic conditions. In this minireview, we discuss the mechanistic principles underpinning catalytic anionic substituent effects (CASE), the diverse strategies developed to generate them, and their impact on photocatalytic HAT-mediated C–H functionalization. By highlighting recent advances and emerging opportunities, we illustrate how transient electronic activation is reshaping the design of selective C–H functionalization reactions.</p>\u0000 </div>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993787","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}
Sai Chu, Jiahui Guo, Meiling Qi, Qiaozhi Li, Jiajia Zheng, Ken-Ichi Otake, Wenqi Xu, Rosantha Kumara, Xi Wang, Xiuyan Qiu, Tianfei Chu, Kuo Liu, Susumu Kitagawa, Zongxian Yang, Long Chen, Ming-Shui Yao
{"title":"Outside Back Cover: Space-Confined Water Isotope Transport in Conductive MOF Thin Film (Angew. Chem. Int. Ed. 46/2026)","authors":"Sai Chu, Jiahui Guo, Meiling Qi, Qiaozhi Li, Jiajia Zheng, Ken-Ichi Otake, Wenqi Xu, Rosantha Kumara, Xi Wang, Xiuyan Qiu, Tianfei Chu, Kuo Liu, Susumu Kitagawa, Zongxian Yang, Long Chen, Ming-Shui Yao","doi":"10.1002/anie.2026-m0210095800","DOIUrl":"10.1002/anie.2026-m0210095800","url":null,"abstract":"<p>In the Research Article e7017206, Long Chen, Ming-Shui Yao, and co-workers report the real-time differentiation of H<sub>2</sub>O and D<sub>2</sub>O transport within confined spaces using oriented π-conjugated conductive metal–organic framework thin films. Proton-electron-coupled conduction converts surface hydration, confined redistribution, and guest-framework reorganization into multistage electrical signatures that reveal asymmetric isotope-displacement behaviour.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"65 46","pages":""},"PeriodicalIF":17.6,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.2026-m0210095800","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149087476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}