Pub Date : 2024-12-20DOI: 10.1038/s41929-024-01264-8
Sergio González-Granda, Corey R. J. Stephenson
A catalytic, metal-free method for generating carbanion equivalents has been developed, providing a modern alternative to classical Grignard addition reactions. This approach overcomes the traditional drawbacks associated with the use of stoichiometric amounts of metalated reagents, aligning this strategy with contemporary sustainability requirements.
{"title":"Generating alkyl carbanions for organic synthesis","authors":"Sergio González-Granda, Corey R. J. Stephenson","doi":"10.1038/s41929-024-01264-8","DOIUrl":"10.1038/s41929-024-01264-8","url":null,"abstract":"A catalytic, metal-free method for generating carbanion equivalents has been developed, providing a modern alternative to classical Grignard addition reactions. This approach overcomes the traditional drawbacks associated with the use of stoichiometric amounts of metalated reagents, aligning this strategy with contemporary sustainability requirements.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1257-1258"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858175","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}
Pub Date : 2024-12-20DOI: 10.1038/s41929-024-01241-1
Sang Gu Ji, Minho M. Kim, Man Ho Han, Junsic Cho, Yoosang Son, Young Yong Kim, Jaeyoung Jeong, Zee Hwan Kim, Keun Hwa Chae, Hyung-Suk Oh, Hyungjun Kim, Chang Hyuck Choi
Alkali metal cations (AM+) exhibit high solubility and ionic conductivity, making them optimal components in aqueous electrolytes. Despite the conventional belief that AM+ are chemically inert spectators, the strong dependence of electrocatalysis on AM+ has recently provoked debates about their unforeseen catalytic role. However, conclusive evidence is still lacking. Here we demonstrate that AM+ can couple with reaction intermediates and determine kinetics as homogeneous cocatalysts in aqueous conditions, for the alkaline oxygen reduction reaction on a carbon catalyst. In situ X-ray absorption spectroscopy reveals a change in the electronic structure of Na+ from its hydrated state on a charged electrode. In situ Raman spectroscopy further identifies that this change is due to the formation of water-unstable NaO2 as a key intermediate in OOH− production. Together with theoretical calculations, this finding enunciates the counterintuitive cocatalytic role of AM+ in aqueous environments, highlighting the exigency of refined interface design principles for better electrocatalysis. Alkali cations in electrolytes are commonly considered chemically inert species, but their role has recently been called into question. Now, using in situ spectroscopy and molecular dynamics simulations, it is shown that alkali cations couple with intermediates in the oxygen reduction reaction, acting as cocatalysts.
{"title":"Alkali metal cations act as homogeneous cocatalysts for the oxygen reduction reaction in aqueous electrolytes","authors":"Sang Gu Ji, Minho M. Kim, Man Ho Han, Junsic Cho, Yoosang Son, Young Yong Kim, Jaeyoung Jeong, Zee Hwan Kim, Keun Hwa Chae, Hyung-Suk Oh, Hyungjun Kim, Chang Hyuck Choi","doi":"10.1038/s41929-024-01241-1","DOIUrl":"10.1038/s41929-024-01241-1","url":null,"abstract":"Alkali metal cations (AM+) exhibit high solubility and ionic conductivity, making them optimal components in aqueous electrolytes. Despite the conventional belief that AM+ are chemically inert spectators, the strong dependence of electrocatalysis on AM+ has recently provoked debates about their unforeseen catalytic role. However, conclusive evidence is still lacking. Here we demonstrate that AM+ can couple with reaction intermediates and determine kinetics as homogeneous cocatalysts in aqueous conditions, for the alkaline oxygen reduction reaction on a carbon catalyst. In situ X-ray absorption spectroscopy reveals a change in the electronic structure of Na+ from its hydrated state on a charged electrode. In situ Raman spectroscopy further identifies that this change is due to the formation of water-unstable NaO2 as a key intermediate in OOH− production. Together with theoretical calculations, this finding enunciates the counterintuitive cocatalytic role of AM+ in aqueous environments, highlighting the exigency of refined interface design principles for better electrocatalysis. Alkali cations in electrolytes are commonly considered chemically inert species, but their role has recently been called into question. Now, using in situ spectroscopy and molecular dynamics simulations, it is shown that alkali cations couple with intermediates in the oxygen reduction reaction, acting as cocatalysts.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1330-1338"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858064","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}
Pub Date : 2024-12-20DOI: 10.1038/s41929-024-01273-7
Andrea Belluati, Nico Bruns
Polymer/whole-cell hybrid catalysts were created by synthesizing catalytically active polymers from the surface of Escherichia coli cells that recombinantly expressed enzymes. The surface-engineered bacteria allowed for orthogonal tandem catalysis, involving photo- or chemocatalytic steps by the polymers on the cells and biocatalytic steps by the enzymes within the cells.
{"title":"Polymer-decorated bacteria for cascade catalysis","authors":"Andrea Belluati, Nico Bruns","doi":"10.1038/s41929-024-01273-7","DOIUrl":"10.1038/s41929-024-01273-7","url":null,"abstract":"Polymer/whole-cell hybrid catalysts were created by synthesizing catalytically active polymers from the surface of Escherichia coli cells that recombinantly expressed enzymes. The surface-engineered bacteria allowed for orthogonal tandem catalysis, involving photo- or chemocatalytic steps by the polymers on the cells and biocatalytic steps by the enzymes within the cells.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1261-1263"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858074","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}
Pub Date : 2024-12-20DOI: 10.1038/s41929-024-01252-y
Methane has been notoriously difficult to activate for useful chemistry. Now, a tandem catalyst system comprising an iron-modified zeolite and an enzyme is developed for the partial oxidation of methane to formaldehyde under ambient conditions using hydrogen peroxide as the oxidizing agent. This approach achieves high selectivity and conversion to formaldehyde.
{"title":"Methanotrophic catalysis for methane oxidation to formaldehyde","authors":"","doi":"10.1038/s41929-024-01252-y","DOIUrl":"10.1038/s41929-024-01252-y","url":null,"abstract":"Methane has been notoriously difficult to activate for useful chemistry. Now, a tandem catalyst system comprising an iron-modified zeolite and an enzyme is developed for the partial oxidation of methane to formaldehyde under ambient conditions using hydrogen peroxide as the oxidizing agent. This approach achieves high selectivity and conversion to formaldehyde.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1270-1271"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858120","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}
Pub Date : 2024-12-20DOI: 10.1038/s41929-024-01265-7
Yang-Fan Xu, Xiangfeng Chen, Xiangdong Yao
Recent findings on electrocatalysis promoted by alkali metal ions (AM+) have challenged the prevailing consensus that AM+ are chemically inert spectators. Now, theoretical and experimental evidence of an AM+-coupled reaction intermediate contribute to confirming the catalytic role of AM+ in electrochemical processes.
{"title":"An unsung hero in electrochemistry","authors":"Yang-Fan Xu, Xiangfeng Chen, Xiangdong Yao","doi":"10.1038/s41929-024-01265-7","DOIUrl":"10.1038/s41929-024-01265-7","url":null,"abstract":"Recent findings on electrocatalysis promoted by alkali metal ions (AM+) have challenged the prevailing consensus that AM+ are chemically inert spectators. Now, theoretical and experimental evidence of an AM+-coupled reaction intermediate contribute to confirming the catalytic role of AM+ in electrochemical processes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1259-1260"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858174","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}
Pub Date : 2024-12-20DOI: 10.1038/s41929-024-01257-7
Jinyan Rui, Xinpeng Mu, Jordi Soler, Jared C. Paris, Yisong Guo, Marc Garcia-Borràs, Xiongyi Huang
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.
{"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}
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.
质子交换膜水电解法是一种前景广阔的绿色制氢技术，但其广泛的商业化应用却因成本高昂和用于氧进化反应（OER）的贵金属催化剂稀缺而受到阻碍。最近，在开发用于酸性 OER 的低成本、多土电催化剂方面取得了进展，但人们对降解途径知之甚少。这使得活性和稳健催化剂的设计面临挑战。在此，我们回顾了设计用于酸性 OER 的富土催化剂的最新进展，考察了从器件级到催化剂电子结构级的降解机制，并重点介绍了相关表征技术。我们讨论了催化剂的热力学和动力学稳定性，并对电化学数据进行了定量比较分析，以评估催化剂的不同材料和设计策略。我们还考察了催化剂在质子交换膜水电解槽中的性能，最后讨论了该领域的主要科学挑战和未来展望。
{"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}
Pub Date : 2024-12-13DOI: 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
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.
{"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}
Pub Date : 2024-12-11DOI: 10.1038/s41929-024-01259-5
Jian Ning, Zhiyong Sun, René Hübner, Henrik Karring, Morten Frendø Ebbesen, Mathias Dimde, Changzhu Wu
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.
{"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}
Pub Date : 2024-12-04DOI: 10.1038/s41929-024-01251-z
Daniel J. Lundberg, Jimin Kim, Yu-Ming Tu, Cody L. Ritt, Michael S. Strano
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.
由于现有的甲烷氧化途径依赖于高温或高压，人为甲烷排放，特别是来自扩散和稀释源的甲烷排放，对氧化和增值构成了重大挑战。本文报道了醇氧化酶与铁修饰的ZSM-5 （Fe-ZSM-5）沸石催化剂的催化偶联，创建了一个串联的甲烷氧化系统，该系统在室温和常压下部分氧化甲烷。甲烷在Fe-ZSM-5上反应生成甲醇，然后在酶下氧化为甲醛和过氧化氢。后者随后与Fe-ZSM-5反应并在催化偶对中氧化甲烷。我们表明，在室温下，甲烷对甲醛的选择性可以超过90%。生成的甲醛迅速融入到生长的尿素聚合物中，材料生长速度超过5.0 mg gcat - 1 h - 1，与许多甲烷化生物的生长速度相当或超过。这项工作提出了一种可持续的甲烷氧化途径，在环境条件下由空气中的氧气驱动，产生高价值聚合物并使甲烷排放流增值。
{"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}
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