Nature chemistryPub Date : 2025-10-23DOI: 10.1038/s41557-025-01976-9
Judy I Wu
{"title":"The human story of benzene.","authors":"Judy I Wu","doi":"10.1038/s41557-025-01976-9","DOIUrl":"https://doi.org/10.1038/s41557-025-01976-9","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145355595","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}
Nature chemistryPub Date : 2025-10-21DOI: 10.1038/s41557-025-01958-x
Yanan Du,Anyarat Thanapipatsiri,Jesús J Blancas Cortez,Xavier E Salas-Solá,Chi-Yun Lin,Amie K Boal,Carsten Krebs,J Martin Bollinger,Kenichi Yokoyama
{"title":"Azetidine amino acid biosynthesis by non-haem iron-dependent enzymes.","authors":"Yanan Du,Anyarat Thanapipatsiri,Jesús J Blancas Cortez,Xavier E Salas-Solá,Chi-Yun Lin,Amie K Boal,Carsten Krebs,J Martin Bollinger,Kenichi Yokoyama","doi":"10.1038/s41557-025-01958-x","DOIUrl":"https://doi.org/10.1038/s41557-025-01958-x","url":null,"abstract":"Azetidine, a four-membered aza-cycle, is a crucial structure in many bioactive compounds and drugs. However, their biosynthesis is frequently enigmatic. Here we report the mechanism of azetidine amino acid (polyoximic acid) biosynthesis in the polyoxin antifungal pathway. Genetic, enzymological and structural experiments revealed that PolF is a member of haem-oxygenase-like dimetal oxidase and/or oxygenase (HDO) superfamily, and this enzyme alone is sufficient for the transformation of L-isoleucine (L-Ile) and L-valine to their azetidine derivatives via a 3,4-desaturated intermediate. Mechanistic studies of PolF suggested that a μ-peroxo-Fe(III)2 intermediate is directly responsible for the unactivated C-H bond cleavage, and the post-H-abstraction reactions, including the C-N bond formation, probably proceed through radical mechanisms. We also found that PolE, a member of the DUF6421 family, is an Fe and pterin-dependent oxidase that catalyses the desaturation of L-Ile, assisting PolF by increasing the flux of L-Ile desaturation. The results provide important insights into azetidine biosynthesis and the catalytic mechanisms of HDO enzymes in general.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"92 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145338717","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":"Copper-catalysed asymmetric cross-coupling reactions tolerant of highly reactive radicals.","authors":"Li-Wen Fan,Jun-Bin Tang,Li-Lei Wang,Zeng Gao,Ji-Ren Liu,Yu-Shuai Zhang,Dai-Lei Yuan,Li Qin,Yu Tian,Zhi-Chao Chen,Fu Liu,Jin-Min Xiang,Pei-Jie Huang,Wei-Long Liu,Chen-Yu Xiao,Cheng Luan,Zhong-Liang Li,Xin Hong,Zhe Dong,Qiang-Shuai Gu,Xin-Yuan Liu","doi":"10.1038/s41557-025-01970-1","DOIUrl":"https://doi.org/10.1038/s41557-025-01970-1","url":null,"abstract":"Achieving high enantioselectivity in asymmetric catalysis, especially with very reactive species such as radicals, often comes at the expense of generality. Radicals with exceptionally high reactivity are typically unsuitable for existing asymmetric methodologies. Here we present a general catalytic approach to asymmetric radical cross-coupling that combines copper-catalysed enantioselective stereocentre resolution or formation with copper-mediated, chirality-transferring radical substitution. This sequential strategy enables the efficient coupling of over 50 distinct carbon-, nitrogen-, oxygen-, sulfur- and phosphorus-centred radicals, including highly reactive methyl, tert-butoxyl and phenyl radicals, yielding structurally diverse C-, P- and S-chiral compounds with outstanding enantioselectivity. Our method thus provides a unified platform for the synthesis of carbon, phosphorus and sulfur stereocentres, with important implications for the preparation of chiral molecules relevant to medicinal chemistry and related disciplines. Furthermore, this sequential stereodiscrimination and chirality transfer strategy offers a promising blueprint for the development of highly enantioselective methodologies applicable to other classes of highly reactive species beyond radicals.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"15 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145331964","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}
Nature chemistryPub Date : 2025-10-17DOI: 10.1038/s41557-025-01981-y
Souvik Ghosh, Mathieu G Baltussen, Anna C Knox, Rianne Haije, Quentin Duez, Anastasia T Tsitsimeli, Man Him Chak, Jonathon E Beves, Wilhelm T S Huck
{"title":"A recursive enzymatic competition network capable of multitask molecular information processing.","authors":"Souvik Ghosh, Mathieu G Baltussen, Anna C Knox, Rianne Haije, Quentin Duez, Anastasia T Tsitsimeli, Man Him Chak, Jonathon E Beves, Wilhelm T S Huck","doi":"10.1038/s41557-025-01981-y","DOIUrl":"https://doi.org/10.1038/s41557-025-01981-y","url":null,"abstract":"<p><p>Living cells understand their environment by combining, integrating and interpreting chemical and physical stimuli. Despite considerable advances in the design of enzymatic reaction networks that mimic hallmarks of living systems, these approaches lack the complexity to fully capture biological information processing. Here we introduce a scalable approach to design complex enzymatic reaction networks capable of reservoir computation based on recursive competition of substrates. This protease-based network can perform a broad range of classification tasks based on peptide and physicochemical inputs and can simultaneously perform an extensive set of discrete and continuous information processing tasks. The enzymatic reservoir can act as a temperature sensor from 25 °C to 55 °C with 1.3 °C accuracy, and performs decision-making, activation and tuning tasks common to neurological systems. We show a possible route to temporal information processing and a direct interface with optical systems by demonstrating the extension of the network to incorporate sensitivity to light pulses. Our results show a class of competition-based molecular systems capable of increasingly powerful information-processing tasks.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145313389","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}
Nature chemistryPub Date : 2025-10-16DOI: 10.1038/s41557-025-01972-z
Benjamin A Baker, Grace G D Han
{"title":"Light-driven direct air capture of CO<sub>2</sub>.","authors":"Benjamin A Baker, Grace G D Han","doi":"10.1038/s41557-025-01972-z","DOIUrl":"https://doi.org/10.1038/s41557-025-01972-z","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145308350","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}
Nature chemistryPub Date : 2025-10-15DOI: 10.1038/s41557-025-01992-9
{"title":"Making isolable halosilylium Lewis superacids by protonation.","authors":"","doi":"10.1038/s41557-025-01992-9","DOIUrl":"https://doi.org/10.1038/s41557-025-01992-9","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145302036","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}
Nature chemistryPub Date : 2025-10-15DOI: 10.1038/s41557-025-01991-w
Ricardo Martínez-Hincapié, Janis Timoshenko, Timon Wagner, Eduardo Ortega, Jody Druce, Mariana C O Monteiro, Martina Rüscher, Joonbaek Jang, Elif Öykü Alagöz, Samuele Lasagna, Leon Jacobse, Arno Bergmann, Beatriz Roldan Cuenya, Sebastian Z Oener
{"title":"Author Correction: Interfacial solvation pre-organizes the transition state of the oxygen evolution reaction.","authors":"Ricardo Martínez-Hincapié, Janis Timoshenko, Timon Wagner, Eduardo Ortega, Jody Druce, Mariana C O Monteiro, Martina Rüscher, Joonbaek Jang, Elif Öykü Alagöz, Samuele Lasagna, Leon Jacobse, Arno Bergmann, Beatriz Roldan Cuenya, Sebastian Z Oener","doi":"10.1038/s41557-025-01991-w","DOIUrl":"10.1038/s41557-025-01991-w","url":null,"abstract":"","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145302021","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}
Nature chemistryPub Date : 2025-10-15DOI: 10.1038/s41557-025-01968-9
Johannes Schmoll, Mihajlo Novakovic, Frédéric H-T Allain
{"title":"Water-detected NMR allows dynamic observations of repeat-expansion RNA condensates.","authors":"Johannes Schmoll, Mihajlo Novakovic, Frédéric H-T Allain","doi":"10.1038/s41557-025-01968-9","DOIUrl":"https://doi.org/10.1038/s41557-025-01968-9","url":null,"abstract":"<p><p>RNA condensation is implicated in the formation of neurotoxic RNA foci in cells affected by genomic expansions of trinucleotide or hexanucleotide repeats. However, the biophysical properties of repeat-expansion RNA condensates are poorly understood. Using CAG repeat-expansion RNA as a model system, we show that these RNA condensates cannot be observed with conventional nuclear magnetic resonance techniques. Therefore, we developed a nuclear magnetic resonance approach, based on water-detected semi-solid magnetization transfer, to detect and characterize RNA condensates in vitro. Our method, termed condensate detection by semi-solid magnetization transfer (CONDENSE-MT), is broadly applicable, highly sensitive and does not require direct observation of the biomolecules of interest. Using CONDENSE-MT, we could obtain dynamic information about RNA condensates, such as the relative amount and the tumbling rate of condensed RNA, the proton-solvent exchange kinetics and the amount of water molecules transiently bound in the condensate. We find that phase separation dramatically decreases molecular tumbling and is driven by heterotypic interactions between RNA and Mg<sup>2+</sup>. We further show that increasing CAG repeats decreases condensate hydration.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145302013","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}
Nature chemistryPub Date : 2025-10-14DOI: 10.1038/s41557-025-01943-4
Iñigo J Vitórica-Yrezábal, Craig A McAnally, Matthew P Snelgrove, Mark R Warren, Adrian H Hill, Stephen P Thompson, Martin Quinn, Sam Mottley, Stephen Mottley, Ashleigh J Fletcher, Lee Brammer
{"title":"Selective CO<sub>2</sub> uptake mimics dissolution in highly fluorinated non-porous crystalline materials.","authors":"Iñigo J Vitórica-Yrezábal, Craig A McAnally, Matthew P Snelgrove, Mark R Warren, Adrian H Hill, Stephen P Thompson, Martin Quinn, Sam Mottley, Stephen Mottley, Ashleigh J Fletcher, Lee Brammer","doi":"10.1038/s41557-025-01943-4","DOIUrl":"https://doi.org/10.1038/s41557-025-01943-4","url":null,"abstract":"<p><p>Separation of CO<sub>2</sub> from gas mixtures is important in applications such as CH<sub>4</sub> gas purification and blue hydrogen production. Here we report selective CO<sub>2</sub> uptake by a family of flexible silver coordination polymers (AgCPs) that are ostensibly non-porous but exhibit latent porosity to CO<sub>2</sub> above a gate pressure, through a mechanism akin to dissolution in fluoroalkanes. The CO<sub>2</sub> sorption properties are rationally modified by changing the perfluoroalkyl chain length of the constituent perfluorocarboxylate ligands. The AgCPs do not take up CH<sub>4</sub> owing to failure of the dissolution mechanism, consistent with alkane-perfluoroalkane immiscibility. In situ single-crystal and powder X-ray diffraction enable direct visualization of the CO<sub>2</sub> molecule binding domains. These techniques also reveal associated structural changes in the AgCPs and confirm the gating mechanism of CO<sub>2</sub> uptake. The combination of perfluoroalkylcarboxylate ligands with the flexible silver(I) coordination sphere generates highly fluorinated but mobile regions of the crystals that play an integral role in the selective uptake of CO<sub>2</sub> over CH<sub>4</sub>.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145293006","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}