Nature Catalysis最新文献_第2页

An unsung hero in electrochemistry

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01265-7

Yang-Fan Xu, Xiangfeng Chen, Xiangdong Yao

引用次数: 0

Merging photoredox with metalloenzymatic catalysis for enantioselective decarboxylative C(sp3)‒N3 and C(sp3)‒SCN bond formation

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01257-7

Jinyan Rui, Xinpeng Mu, Jordi Soler, Jared C. Paris, Yisong Guo, Marc Garcia-Borràs, Xiongyi Huang

{"title":"Merging photoredox with metalloenzymatic catalysis for enantioselective decarboxylative C(sp3)‒N3 and C(sp3)‒SCN bond formation","authors":"Jinyan Rui, Xinpeng Mu, Jordi Soler, Jared C. Paris, Yisong Guo, Marc Garcia-Borràs, Xiongyi Huang","doi":"10.1038/s41929-024-01257-7","DOIUrl":"10.1038/s41929-024-01257-7","url":null,"abstract":"The scope of nature’s catalytic abilities has been expanded by recent advancements in biocatalysis to include synthetic transformations with no biological equivalent. However, these newly introduced catalytic functions represent only a small fraction of reactions utilized in synthetic catalysis. Here we present a biocatalytic platform that combines photoredox and metalloenzymatic catalysis for enantioselective radical transformations. Under green light irradiation, the eosin Y photocatalyst enables 4-hydroxyphenylpyruvate dioxygenases to catalyse enantioselective decarboxylative azidation and thiocyanation of N-hydroxyphthalimide esters. The final optimized variant obtained through directed evolution can afford diverse chiral organic azide and thiocyanate compounds with up to 77% yield, 385 total turnovers and 94% enantiomeric excess. Mechanistic studies show that the eosin Y catalyst mediates the generation of both C(sp3) radical and Fe(III)‒N3/Fe(III)‒NCS intermediate, leading to efficient enantioselective C‒N3 and C‒SCN bond formation in the enzyme active site. These findings establish an adaptable biocatalytic platform for introducing abiological metallophotoredox catalysis into biology. Decarboxylative azidation is a valuable transformation in organic chemistry, but a biocatalytic equivalent remained elusive. Now merging photoredox with metalloenzymatic catalysis enables the enantioselective decarboxylative radical azidation and thiocyanation of N-hydroxyphthalimide esters.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1394-1403"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858194","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}

引用次数: 0

Earth-abundant electrocatalysts for acidic oxygen evolution 用于酸性氧进化的地球富集电催化剂

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-17 DOI: 10.1038/s41929-024-01266-6

Rendian Wan, Tenghui Yuan, Liuchen Wang, Bing Li, Meilin Liu, Bote Zhao

{"title":"Earth-abundant electrocatalysts for acidic oxygen evolution","authors":"Rendian Wan, Tenghui Yuan, Liuchen Wang, Bing Li, Meilin Liu, Bote Zhao","doi":"10.1038/s41929-024-01266-6","DOIUrl":"10.1038/s41929-024-01266-6","url":null,"abstract":"Proton-exchange membrane water electrolysis is a promising technology for green hydrogen production, but its widespread commercialization is hindered by the high cost and scarcity of precious-metal-based catalysts for the oxygen evolution reaction (OER). Recent progress has been made in developing low-cost, earth-abundant electrocatalysts for the acidic OER, but little is known about degradation pathways. This makes the design of active and robust catalysts challenging. Here we review recent advances in the design of earth-abundant catalysts for the acidic OER, examining the degradation mechanisms from the device level to the catalyst electronic structure level, and highlighting the relevant characterization techniques. We discuss the thermodynamic and kinetic stability of the catalysts and present a quantitative comparative analysis of electrochemical data to evaluate different materials and design strategies for catalysts. We also examine the performance of the catalysts in proton-exchange membrane water electrolysers and conclude with a discussion of the key scientific challenges and future perspectives in the field. Proton-exchange membrane water electrolysers often rely on scarce iridium or ruthenium catalysts at the anode, as many low-cost, earth-abundant catalysts cannot withstand the harsh operational conditions. This Review discusses the state of the art in earth-abundant water oxidation catalysts and examines their degradation mechanisms at multiple levels.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1288-1304"},"PeriodicalIF":42.8,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832610","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}

引用次数: 0

Parahydrogen-enhanced magnetic resonance identification of intermediates in [Fe]-hydrogenase catalysis

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-13 DOI: 10.1038/s41929-024-01262-w

Lukas Kaltschnee, Andrey N. Pravdivtsev, Manuel Gehl, Gangfeng Huang, Georgi L. Stoychev, Christoph Riplinger, Maximilian Keitel, Frank Neese, Jan-Bernd Hövener, Alexander A. Auer, Christian Griesinger, Seigo Shima, Stefan Glöggler

{"title":"Parahydrogen-enhanced magnetic resonance identification of intermediates in [Fe]-hydrogenase catalysis","authors":"Lukas Kaltschnee, Andrey N. Pravdivtsev, Manuel Gehl, Gangfeng Huang, Georgi L. Stoychev, Christoph Riplinger, Maximilian Keitel, Frank Neese, Jan-Bernd Hövener, Alexander A. Auer, Christian Griesinger, Seigo Shima, Stefan Glöggler","doi":"10.1038/s41929-024-01262-w","DOIUrl":"10.1038/s41929-024-01262-w","url":null,"abstract":"Hydrogenases are widespread metalloenzymes used for the activation and production of molecular hydrogen. Understanding the catalytic mechanism of hydrogenases can help to establish industrial (bio)catalytic hydrogen production and conversion. Here we show the observation of so-far undetectable intermediates of [Fe]-hydrogenase in its catalytic cycle. We observed these intermediates by applying a signal-enhancing NMR technique based on parahydrogen. Molecular hydrogen occurs as orthohydrogen or parahydrogen, depending on its nuclear spin state. We found that catalytic conversion of parahydrogen by the [Fe]-hydrogenase leads to notably enhanced NMR signals (parahydrogen-induced polarization, PHIP). The observed signals encode information about how the [Fe]-hydrogenase binds hydrogen during catalysis. Our data support models of the catalytic mechanism that involve the formation of a hydride at the iron centre. Moreover, PHIP enabled studying the binding kinetics. This work demonstrates the hitherto unexploited power of PHIP to study catalytic mechanisms of hydrogenases. The catalytic mechanism of [Fe]-hydrogenases is not well understood. Now a signal-enhanced nuclear magnetic resonance method based on parahydrogen is introduced to study [Fe]-hydrogenase under turnover conditions in situ, revealing intermediates of the catalytic cycle.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1417-1429"},"PeriodicalIF":42.8,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01262-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815516","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}

引用次数: 0

Engineering living cells with polymers for recyclable photoenzymatic catalysis

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-11 DOI: 10.1038/s41929-024-01259-5

Jian Ning, Zhiyong Sun, René Hübner, Henrik Karring, Morten Frendø Ebbesen, Mathias Dimde, Changzhu Wu

{"title":"Engineering living cells with polymers for recyclable photoenzymatic catalysis","authors":"Jian Ning, Zhiyong Sun, René Hübner, Henrik Karring, Morten Frendø Ebbesen, Mathias Dimde, Changzhu Wu","doi":"10.1038/s41929-024-01259-5","DOIUrl":"10.1038/s41929-024-01259-5","url":null,"abstract":"Engineering cell membranes for catalysis is challenging due to their inherent complexity. Here we introduce a polymeric strategy to overcome these challenges by chemically modifying cell membranes with catalytic polymers, enabling robust, recyclable and photoenzymatic catalysis. Through a one-step in situ atom transfer radical polymerization on living Escherichia coli cells, polymers are generated to protect the cells from environmental stressors while facilitating chemoenzymatic synthesis by integrating catalytic polymers with intracellular enzymes. As a proof of concept, a photoenzymatic cascade with an anthraquinone-based polymer and benzaldehyde lyase is demonstrated, converting benzyl alcohol into benzoin and achieving bioconversion yields that are 15 times higher than controls. Additionally, cells serve as large biological scaffolds for polymers, enabling recycling of macromolecular catalysts. A recyclable chemoenzymatic system incorporating an organometallic polymer with intracellular enzymes is also presented. Our versatile, straightforward approach offers a technology platform for engineering cell membranes for cascade synthesis, with broad implications for synthetic chemistry, polymer chemistry and biotechnology. Compatibility issues often limit chemoenzymatic systems. Now it is shown that the proximity between catalytic polymers grafted from the membrane of microorganisms and intracellular heterologous enzymes enhances the reaction rates of a photoenzymatic system, while the coating increases the stability.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1404-1416"},"PeriodicalIF":42.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804820","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}

引用次数: 0

Concerted methane fixation at ambient temperature and pressure mediated by an alcohol oxidase and Fe-ZSM-5 catalytic couple

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-04 DOI: 10.1038/s41929-024-01251-z

Daniel J. Lundberg, Jimin Kim, Yu-Ming Tu, Cody L. Ritt, Michael S. Strano

{"title":"Concerted methane fixation at ambient temperature and pressure mediated by an alcohol oxidase and Fe-ZSM-5 catalytic couple","authors":"Daniel J. Lundberg, Jimin Kim, Yu-Ming Tu, Cody L. Ritt, Michael S. Strano","doi":"10.1038/s41929-024-01251-z","DOIUrl":"10.1038/s41929-024-01251-z","url":null,"abstract":"Anthropogenic methane emissions, particularly from diffuse and dilute sources, pose a significant challenge for oxidation and valorization as existing methane oxidation routes rely on high temperatures or pressures. Here we report the catalytic coupling of alcohol oxidase with the iron-modified ZSM-5 (Fe-ZSM-5) zeolite catalyst, creating a tandem methanotrophic system that partially oxidizes methane at ambient temperatures and pressures. Methane reacts at Fe-ZSM-5 to produce methanol, which is then oxidized at the enzyme to formaldehyde and hydrogen peroxide. The latter subsequently reacts back at Fe-ZSM-5 and oxidizes methane in a catalytic couple. We show that methane-to-formaldehyde selectivity can exceed 90% at room temperature. The generated formaldehyde was rapidly incorporated into a growing urea polymer, with a material growth rate exceeding 5.0 mg gcat−1 h−1, which matches or exceeds the growth rates of many methanotrophic organisms. This work presents a sustainable route for methane oxidation, driven by oxygen in the air under ambient conditions, producing high-value polymers and valorizing methane emission streams. The development of catalytic systems for sequestering anthropogenic methane emissions from the atmosphere could potentially reduce global warming. Now, coupling the enzyme alcohol oxidase with an inorganic zeolite generates formaldehyde from methane under ambient conditions with 90% selectivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1359-1371"},"PeriodicalIF":42.8,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763638","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}

引用次数: 0

Computational methods for asymmetric catalysis

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-03 DOI: 10.1038/s41929-024-01258-6

Sharon Pinus, Jérôme Genzling, Mihai Burai-Patrascu, Nicolas Moitessier

{"title":"Computational methods for asymmetric catalysis","authors":"Sharon Pinus, Jérôme Genzling, Mihai Burai-Patrascu, Nicolas Moitessier","doi":"10.1038/s41929-024-01258-6","DOIUrl":"10.1038/s41929-024-01258-6","url":null,"abstract":"Impressive progress in computational asymmetric catalysis has been made in the past twenty years owing to advancements in algorithm and method development for predicting catalyst enantioselectivity. These methods/algorithms describe reactions that can be categorized into two groups: reactions where the mechanism (or transition state for the enantioselective step) is known and used to determine catalyst stereoselectivity by modelling the diastereomeric transition states and reactions where knowledge of the mechanism is not required and leveraging experimental data to establish correlations between reaction descriptors and enantioselectivity is imperative. Although these methods have reached a suitable level of proficiency for the prediction of enantioselectivity, this field remains largely unexplored/underused by experimental chemists. In this Review we aim to shed light on the models, methods and applications used in asymmetric synthesis, with accessible language suitable for experimental chemists. Our hope is that these methods will ultimately be adopted by synthetic chemists for the design of new catalysts. The capability and importance of computational methods in organic chemistry is steadily increasing. This Review provides an overview of computational methods for the design of asymmetric catalysts, with the aim of avoiding specialist computational language to make the field more accessible to experimental chemists.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1272-1287"},"PeriodicalIF":42.8,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142760500","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}

引用次数: 0

Enantioconvergent copper-catalysed difluoromethylation of alkyl halides 铜催化烷基卤的对映体二氟甲基化反应

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-11-25 DOI: 10.1038/s41929-024-01253-x

Decai Ding, Lingfeng Yin, Andrew T. Poore, Yeu-Shiuan Ho, Yu-Ho Cheng, Chi-Tien Hsieh, Stephen C. Yachuw, Rachael M. Knieser, Jeanette A. Krause, Shiliang Tian, Mu-Jeng Cheng, Wei Liu

{"title":"Enantioconvergent copper-catalysed difluoromethylation of alkyl halides","authors":"Decai Ding, Lingfeng Yin, Andrew T. Poore, Yeu-Shiuan Ho, Yu-Ho Cheng, Chi-Tien Hsieh, Stephen C. Yachuw, Rachael M. Knieser, Jeanette A. Krause, Shiliang Tian, Mu-Jeng Cheng, Wei Liu","doi":"10.1038/s41929-024-01253-x","DOIUrl":"10.1038/s41929-024-01253-x","url":null,"abstract":"Stereochemically controlled hydrogen bond donors play essential roles in the pharmaceutical industry. Consequently, organic molecules that bear difluoromethyl (CF2H) groups at chiral centres are emerging as pivotal components in pharmaceuticals owing to their distinct hydrogen-bonding property. However, a general approach for introducing CF2H groups in an enantioselective manner has remained elusive. Here we show that enantioconvergent difluoromethylation of racemic alkyl electrophiles, through alkyl radical intermediates, represents a strategy for constructing CF2H-containing stereocentres. This strategy is enabled by using copper catalysts bound with a chiral diamine ligand bearing electron-deficient phenyl groups, and a nucleophilic CF2H-zinc reagent. This method allows the high-yield conversion of a diverse range of alkyl halides into their alkyl-CF2H analogues with excellent enantioselectivity. Mechanistic studies reveal a route involving asymmetric difluoromethylation of alkyl radicals and crucial non-covalent interactions in the enantiodetermining steps. This copper-catalysed difluoromethylation process opens an avenue for the efficient preparation of CF2H-containing pharmaceuticals. Despite the importance of difluoromethyl (CF2H)-bearing centres for pharmaceuticals, there is currently no general strategy for the stereoselective introduction of a CF2H group at chiral centres. Here the authors describe an enantioconvergent difluoromethylation method for racemic alkyl halides to construct such stereocentres.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1372-1381"},"PeriodicalIF":42.8,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142697111","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}

引用次数: 0

Seeking selectivity in alkene couplings 寻求烯烃耦合的选择性

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-11-21 DOI: 10.1038/s41929-024-01242-0

Patricia Brizuela, M. Teresa Quirós

引用次数: 0

Face to phase 面对面

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-11-21 DOI: 10.1038/s41929-024-01268-4

Davide Esposito

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