Nature CatalysisPub Date : 2026-10-15DOI: 10.1038/s41929-026-01620-w
Anku Guha,Ranga Rohit Seemakurthi,Bárbara Polesso,Prathama Haldar,Ranit Ram,Adrián Pinilla-Sánchez,Indrajit Mondal,David Kernan,Núria López,F. Pelayo García de Arquer
{"title":"Operando resolution of CO2 electrolysis interfaces at application-relevant current density reveals water gating","authors":"Anku Guha,Ranga Rohit Seemakurthi,Bárbara Polesso,Prathama Haldar,Ranit Ram,Adrián Pinilla-Sánchez,Indrajit Mondal,David Kernan,Núria López,F. Pelayo García de Arquer","doi":"10.1038/s41929-026-01620-w","DOIUrl":"https://doi.org/10.1038/s41929-026-01620-w","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"52 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209934","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 CatalysisPub Date : 2026-10-09DOI: 10.1038/s41929-026-01618-4
Patrick Rabe,Hiroki Makita,Rebecca Southwart,Midhun George Thomas,Mihails Kazaks,Shyam Basak,Tiankun Zhou,William K. Myers,Margaret D. Doyle,Philipp S. Simon,Shusaku Hayama,J. Frederick W. Mosselmans,Alexander T. Stead,Abraham O. Oluwole,Malkit Sami,Ian Clifton,Pierre Aller,Asmit Bhowmick,Anthony Tumber,Jos J. A. G. Kamps,Karina Calvopiña,Agata Butryn,Robert Bosman,Arjun Cheema,Jordan Welsh,James D. S. Linyard,Frederick J. H. Foster,Pauline A. Lang,Mariska de Munnik,Stephen M. Keable,Medhanjali Dasgupta,In-Sik Kim,Isabel Bogacz,Kuntal Chatterjee,Kyle D. Sutherlin,Corey J. Kaminsky,Jürgen Brem,Michael A. McDonough,Christina Redfield,James R. D. Montgomery,Coral Mycroft,Anastasya Shilova,Nicholas Devenish,Frederic P. Poitevin,Sebastian Dehe,Vandana Tiwari,Humberto Sanchez,Daniel J. Rosenberg,Mark S. Hunter,Leland B. Gee,Uwe Bergmann,Roberto Alonso-Mori,Jaehyun Park,Shigeki Owada,Kensuke Tono,Danny Axford,Robin L. Owen,Daniel W. Paley,Nicholas K. Sauter,David Mittan-Moreau,Aaron S. Brewster,Carol V. Robinson,Vittal K. Yachandra,Junko Yano,Edgars Suna,Christo Z. Christov,Allen M. Orville,Jan F. Kern,Christopher J. Schofield
{"title":"Unanticipated intermediates during isopenicillin N synthase catalysis identified by time-resolved X-ray free-electron laser studies","authors":"Patrick Rabe,Hiroki Makita,Rebecca Southwart,Midhun George Thomas,Mihails Kazaks,Shyam Basak,Tiankun Zhou,William K. Myers,Margaret D. Doyle,Philipp S. Simon,Shusaku Hayama,J. Frederick W. Mosselmans,Alexander T. Stead,Abraham O. Oluwole,Malkit Sami,Ian Clifton,Pierre Aller,Asmit Bhowmick,Anthony Tumber,Jos J. A. G. Kamps,Karina Calvopiña,Agata Butryn,Robert Bosman,Arjun Cheema,Jordan Welsh,James D. S. Linyard,Frederick J. H. Foster,Pauline A. Lang,Mariska de Munnik,Stephen M. Keable,Medhanjali Dasgupta,In-Sik Kim,Isabel Bogacz,Kuntal Chatterjee,Kyle D. Sutherlin,Corey J. Kaminsky,Jürgen Brem,Michael A. McDonough,Christina Redfield,James R. D. Montgomery,Coral Mycroft,Anastasya Shilova,Nicholas Devenish,Frederic P. Poitevin,Sebastian Dehe,Vandana Tiwari,Humberto Sanchez,Daniel J. Rosenberg,Mark S. Hunter,Leland B. Gee,Uwe Bergmann,Roberto Alonso-Mori,Jaehyun Park,Shigeki Owada,Kensuke Tono,Danny Axford,Robin L. Owen,Daniel W. Paley,Nicholas K. Sauter,David Mittan-Moreau,Aaron S. Brewster,Carol V. Robinson,Vittal K. Yachandra,Junko Yano,Edgars Suna,Christo Z. Christov,Allen M. Orville,Jan F. Kern,Christopher J. Schofield","doi":"10.1038/s41929-026-01618-4","DOIUrl":"https://doi.org/10.1038/s41929-026-01618-4","url":null,"abstract":"Abstract Biosynthesis of penicillin and cephalosporin antibiotics involves the oxidation of the tripeptide δ-( l -α-aminoadipoyl)- l -cysteinyl- d -valine (ACV) to give the conformationally strained bicyclic penicillin ring system, as catalysed by the Fe(II)-dependent oxidase isopenicillin N synthase (IPNS). The structures of the precursors for the sequential β-lactam and thiazolidine ring forming steps in IPNS have remained elusive. Here we studied the reaction of anaerobic IPNS:Fe(II):ACV microcrystals with O 2 using time-resolved serial femtosecond crystallography and X-ray emission spectroscopy. High-resolution structures reveal that ACV cysteinyl oxidation produces a thioaldehyde that unexpectedly does not coordinate the iron centre. The use of deuterium-labelled ACV enabled the observation of a monocyclic β-lactam with restoration of the Fe–S bond. Together with mutagenesis, spectroscopic and computational studies, the results support Fe(IV)-mediated penicillin formation involving active-site water molecules. These findings provide structural insight into IPNS catalysis, inform on the wider Fe(II) oxygenase superfamily and highlight the power of X-ray free-electron laser methods for resolving transient enzymatic intermediates.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"43 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2026-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151307","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 CatalysisPub Date : 2026-09-29DOI: 10.1038/s41929-026-01616-6
Aleksander R. Bena, Trisha Banik, Christos Giannoudis, Florian Ortis, Daniel Bím, Haralds Baunis, Gayathri H. Palissery, Bartholomäus Pieber
{"title":"Ligand design broadens NiI-catalysed C(sp2)–heteroatom couplings of aryl bromides at low catalyst loadings","authors":"Aleksander R. Bena, Trisha Banik, Christos Giannoudis, Florian Ortis, Daniel Bím, Haralds Baunis, Gayathri H. Palissery, Bartholomäus Pieber","doi":"10.1038/s41929-026-01616-6","DOIUrl":"https://doi.org/10.1038/s41929-026-01616-6","url":null,"abstract":"The formation of C(sp2)–heteroatom bonds through cross-coupling catalysis is central to the synthesis of pharmaceuticals, agrochemicals and materials. Whereas Pd0/PdII catalysis requires substrate-specific ligand optimization to balance the competing demands of oxidative addition and reductive elimination, NiI/NiIII catalysis offers a complementary strategy because the bond-forming step is intrinsically favourable. However, contemporary NiI/NiIII methodologies suffer from insufficient oxidative addition reactivity, restricting the aryl halide scope and requiring high catalyst loadings. Here we show that mechanistically guided ligand design overcomes these limitations. Together with a non-nucleophilic base additive that promotes direct visible-light generation of NiI from a bench-stable NiII precatalyst, this ligand design enables the coupling of electron-rich aryl bromides with N-, O-, S- and P-based nucleophiles at nickel loadings as low as 100 ppm. The method is compatible with sterically encumbered nucleophiles and enables gram-scale synthesis and late-stage functionalization of complex molecules.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"18 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2026-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149087650","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 CatalysisPub Date : 2026-09-21DOI: 10.1038/s41929-026-01612-w
K. Jenkinson, T. Stoops, A. De Backer, E. Arslan Irmak, A. Pedrazo-Tardajos, N. Claes, T. Altantzis, A. Sánchez-Iglesias, L. M. Liz-Marzán, S. Van Aert, B. M. Weckhuysen, S. Bals
{"title":"Operando single-atom tracking in individual Pt nanoparticles detects the coexistence of Langmuir and Taylor active sites","authors":"K. Jenkinson, T. Stoops, A. De Backer, E. Arslan Irmak, A. Pedrazo-Tardajos, N. Claes, T. Altantzis, A. Sánchez-Iglesias, L. M. Liz-Marzán, S. Van Aert, B. M. Weckhuysen, S. Bals","doi":"10.1038/s41929-026-01612-w","DOIUrl":"https://doi.org/10.1038/s41929-026-01612-w","url":null,"abstract":"The development of next-generation catalysts strongly depends on structure–composition–performance relationships, yet the underlying fundamental concepts, even for textbook processes such as the platinum-catalysed oxidation of carbon monoxide, are based on assumptions due to the limitations of analytical techniques. Despite extensive studies, key aspects of this exemplary reaction remain unresolved, and identifying active sites in nanoparticle-based catalysts under actual reaction conditions remains a central challenge. Here, using quantitative atomic-resolution three-dimensional operando transmission electron microscopy, we track atom-level structural transformations in individual Pt nanoparticles during a series of activation/deactivation/reactivation cycles. We thereby establish an experimental link between the abundance of coordinatively unsaturated surface atoms and catalytic performance. Our results indicate that Taylor- and Langmuir-like active sites coexist and interchange within the same realistic catalyst. More broadly, this approach enables quantitative tracking of facets and undercoordinated atoms in catalytic nanoparticles, opening opportunities to experimentally investigate the role of active sites in catalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"4 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2026-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010478","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 CatalysisPub Date : 2026-09-15DOI: 10.1038/s41929-026-01600-0
Shih-Chieh Kao, Kang-Jie Bian, Jess C. Tang, Shijin Yu, Yongchen Wang, Ying Chen, Xiaowei Chen, Julian G. West
{"title":"Anti-Markovnikov alkene hydroalkylation via iron photocatalysis","authors":"Shih-Chieh Kao, Kang-Jie Bian, Jess C. Tang, Shijin Yu, Yongchen Wang, Ying Chen, Xiaowei Chen, Julian G. West","doi":"10.1038/s41929-026-01600-0","DOIUrl":"10.1038/s41929-026-01600-0","url":null,"abstract":"Hydroalkylation provides a direct approach to C(sp3)–C(sp3) bond formation from abundant alkenes, yet general methods for linear-selective hydroalkylation remain limited, particularly for simple alkyl groups such as methyl and ethyl. Here we introduce traceless radical polarity reversal, in which a removable electron-withdrawing group promotes radical alkene addition and is subsequently deleted in situ under the reaction conditions. Using a visible-light-promoted iron-and-thiol dual-catalytic system, this strategy enables hydroalkylation reactions that were previously difficult to access, including hydromethylation, hydroethylation and hydrocyclobutylation, with high linear selectivity from simple malonic acids. The method also provides direct access to gem-monofluoroalkyl and gem-difluoroalkyl motifs from fluorinated malonic acids and enables efficient synthesis of bioactive targets, including a GPR119 agonist. Preliminary mechanistic studies support a dual-catalytic radical pathway involving visible-light-induced homolysis and hydrogen-atom transfer processes. Hydroalkylation, the addition of a C–H across an alkene bond, is an ideal method for making C(sp3)–C(sp3) bonds; however, linear selectivity is challenging. Here the authors report on achieving this with malonic acids as the alkyl donor reagents using iron photocatalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 9","pages":"976-988"},"PeriodicalIF":48.3,"publicationDate":"2026-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-026-01600-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149010525","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}