Pub Date : 2024-09-02DOI: 10.1038/s41929-024-01221-5
Takayoshi Awakawa, Takahiro Mori, Lena Barra, Yusef Ahmed, Richiro Ushimaru, Yaojie Gao, Naruhiko Adachi, Toshiya Senda, Tohru Terada, Dean J. Tantillo, Ikuro Abe
SbzP is a unique pyridoxal-5′-phosphate-dependent enzyme, which catalyses a [3+2] annulation between the pyridinium ring of β-nicotinamide adenine dinucleotide (β-NAD) and an electron rich β,γ-unsaturated quinonoid derived from S-adenosylmethionine in natural product azaindane antibiotics biosynthesis. The SbzP-mediated annulation has been proposed to be a rare tandem C–C bond formation, but its structural basis and catalytic mechanism remain largely unknown. Here we report the β-NAD-complexed structure of PseP (SbzP homologue), identified by cryo-electron microscopy. Structure-based mutagenesis, stopped-flow analysis, thermal shift and surface plasmon resonance analysis identified the important residues for the substrate binding. Molecular dynamics simulations provided insights regarding how the enzyme orients the Cγ of the unsaturated quinonoid to β-NAD. In addition, density functional theory calculations confirmed that the proposed stepwise mechanism is more likely than a pericyclization mechanism. This study provides the structural basis of a pyridoxal-5′-phosphate-dependent enzyme that catalyses nucleophilic Cγ addition and β-NAD processing in natural product biosynthesis. Recently, the pyridoxal-5′-phosphate-dependent enzyme SbzP was reported to catalyse a [3+2]-annulation reaction yielding β-NAD-derived antibiotics. Now, cryo-electron microscopy structures of a stable homologue and computational simulations provide structural and mechanistic insights into this enzymatic reaction.
{"title":"The structural basis of pyridoxal-5′-phosphate-dependent β-NAD-alkylating enzymes","authors":"Takayoshi Awakawa, Takahiro Mori, Lena Barra, Yusef Ahmed, Richiro Ushimaru, Yaojie Gao, Naruhiko Adachi, Toshiya Senda, Tohru Terada, Dean J. Tantillo, Ikuro Abe","doi":"10.1038/s41929-024-01221-5","DOIUrl":"10.1038/s41929-024-01221-5","url":null,"abstract":"SbzP is a unique pyridoxal-5′-phosphate-dependent enzyme, which catalyses a [3+2] annulation between the pyridinium ring of β-nicotinamide adenine dinucleotide (β-NAD) and an electron rich β,γ-unsaturated quinonoid derived from S-adenosylmethionine in natural product azaindane antibiotics biosynthesis. The SbzP-mediated annulation has been proposed to be a rare tandem C–C bond formation, but its structural basis and catalytic mechanism remain largely unknown. Here we report the β-NAD-complexed structure of PseP (SbzP homologue), identified by cryo-electron microscopy. Structure-based mutagenesis, stopped-flow analysis, thermal shift and surface plasmon resonance analysis identified the important residues for the substrate binding. Molecular dynamics simulations provided insights regarding how the enzyme orients the Cγ of the unsaturated quinonoid to β-NAD. In addition, density functional theory calculations confirmed that the proposed stepwise mechanism is more likely than a pericyclization mechanism. This study provides the structural basis of a pyridoxal-5′-phosphate-dependent enzyme that catalyses nucleophilic Cγ addition and β-NAD processing in natural product biosynthesis. Recently, the pyridoxal-5′-phosphate-dependent enzyme SbzP was reported to catalyse a [3+2]-annulation reaction yielding β-NAD-derived antibiotics. Now, cryo-electron microscopy structures of a stable homologue and computational simulations provide structural and mechanistic insights into this enzymatic reaction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1099-1108"},"PeriodicalIF":42.8,"publicationDate":"2024-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01221-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142117989","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 : 2024-08-30DOI: 10.1038/s41929-024-01220-6
Subham Choudhury, Bharath Narayanan, Michael Moret, Vassily Hatzimanikatis, Ljubisa Miskovic
Generating large omics datasets has become routine for gaining insights into cellular processes, yet deciphering these datasets to determine metabolic states remains challenging. Kinetic models can help integrate omics data by explicitly linking metabolite concentrations, metabolic fluxes and enzyme levels. Nevertheless, determining the kinetic parameters that underlie cellular physiology poses notable obstacles to the widespread use of these mathematical representations of metabolism. Here we present RENAISSANCE, a generative machine learning framework for efficiently parameterizing large-scale kinetic models with dynamic properties matching experimental observations. Through seamless integration of diverse omics data and other relevant information, including extracellular medium composition, physicochemical data and expertise of domain specialists, RENAISSANCE accurately characterizes intracellular metabolic states in Escherichia coli. It also estimates missing kinetic parameters and reconciles them with sparse experimental data, substantially reducing parameter uncertainty and improving accuracy. This framework will be valuable for researchers studying metabolic variations involving changes in metabolite and enzyme levels and enzyme activity in health and biotechnology. Despite the availability of large omics datasets, determining intracellular metabolic states is challenging. Now a generative machine learning framework called RENAISSANCE has been developed to estimate missing kinetic parameters and determine time-resolved metabolic reaction rates and metabolite concentrations without requiring training data.
{"title":"Generative machine learning produces kinetic models that accurately characterize intracellular metabolic states","authors":"Subham Choudhury, Bharath Narayanan, Michael Moret, Vassily Hatzimanikatis, Ljubisa Miskovic","doi":"10.1038/s41929-024-01220-6","DOIUrl":"10.1038/s41929-024-01220-6","url":null,"abstract":"Generating large omics datasets has become routine for gaining insights into cellular processes, yet deciphering these datasets to determine metabolic states remains challenging. Kinetic models can help integrate omics data by explicitly linking metabolite concentrations, metabolic fluxes and enzyme levels. Nevertheless, determining the kinetic parameters that underlie cellular physiology poses notable obstacles to the widespread use of these mathematical representations of metabolism. Here we present RENAISSANCE, a generative machine learning framework for efficiently parameterizing large-scale kinetic models with dynamic properties matching experimental observations. Through seamless integration of diverse omics data and other relevant information, including extracellular medium composition, physicochemical data and expertise of domain specialists, RENAISSANCE accurately characterizes intracellular metabolic states in Escherichia coli. It also estimates missing kinetic parameters and reconciles them with sparse experimental data, substantially reducing parameter uncertainty and improving accuracy. This framework will be valuable for researchers studying metabolic variations involving changes in metabolite and enzyme levels and enzyme activity in health and biotechnology. Despite the availability of large omics datasets, determining intracellular metabolic states is challenging. Now a generative machine learning framework called RENAISSANCE has been developed to estimate missing kinetic parameters and determine time-resolved metabolic reaction rates and metabolite concentrations without requiring training data.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 10","pages":"1086-1098"},"PeriodicalIF":42.8,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01220-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142101999","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 : 2024-08-29DOI: 10.1038/s41929-024-01218-0
Christine Lucky, Shengli Jiang, Chien-Rung Shih, Victor M. Zavala, Marcel Schreier
Achieving the selective electrocatalytic activation of C(sp3)–C(sp3) and C(sp3)−H bonds is key to enabling the electricity-driven synthesis of chemicals, the sustainable upgrading of plastics and the development of fuel cells operating on energy-dense liquid fuels. When exposed to electrodes under oxidative bias, hydrocarbons undergo both C–C bond fragmentation and oxygenation. Currently, we lack control over the bifurcation of these pathways. Here we provide insights into the complex network of alkyl transformation reactions, showing that under oxidizing potentials, adsorbed butane transforms to adsorbed CHx fragments, which can be desorbed as methane before oxidation to adsorbed CO. Identifying the branchpoint between C‒C fragmentation and oxygenation allowed us to steer selectivity by applying pulsed potentials tailored to the desorption potential of specific adsorbates and the kinetics of intermediate oxidation. Our findings provide design criteria for improved fuel cell catalysts and open the door to selective C‒C cleavage in electrosynthetic pathways. The electrochemical activation of alkanes on metal catalysts is a complex process that is not fully understood. Now an electrochemical protocol is put forward to isolate the adsorption, fragmentation and oxygenation potential-dependent steps of butane activation on a platinum electrode and derive its intricate reaction network.
{"title":"Understanding the interplay between electrocatalytic C(sp3)‒C(sp3) fragmentation and oxygenation reactions","authors":"Christine Lucky, Shengli Jiang, Chien-Rung Shih, Victor M. Zavala, Marcel Schreier","doi":"10.1038/s41929-024-01218-0","DOIUrl":"10.1038/s41929-024-01218-0","url":null,"abstract":"Achieving the selective electrocatalytic activation of C(sp3)–C(sp3) and C(sp3)−H bonds is key to enabling the electricity-driven synthesis of chemicals, the sustainable upgrading of plastics and the development of fuel cells operating on energy-dense liquid fuels. When exposed to electrodes under oxidative bias, hydrocarbons undergo both C–C bond fragmentation and oxygenation. Currently, we lack control over the bifurcation of these pathways. Here we provide insights into the complex network of alkyl transformation reactions, showing that under oxidizing potentials, adsorbed butane transforms to adsorbed CHx fragments, which can be desorbed as methane before oxidation to adsorbed CO. Identifying the branchpoint between C‒C fragmentation and oxygenation allowed us to steer selectivity by applying pulsed potentials tailored to the desorption potential of specific adsorbates and the kinetics of intermediate oxidation. Our findings provide design criteria for improved fuel cell catalysts and open the door to selective C‒C cleavage in electrosynthetic pathways. The electrochemical activation of alkanes on metal catalysts is a complex process that is not fully understood. Now an electrochemical protocol is put forward to isolate the adsorption, fragmentation and oxygenation potential-dependent steps of butane activation on a platinum electrode and derive its intricate reaction network.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 9","pages":"1021-1031"},"PeriodicalIF":42.8,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142089960","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 : 2024-08-27DOI: 10.1038/s41929-024-01195-4
Site-selective acylation of remote arene C(sp2)−H bonds is achieved through N-heterocyclic carbene organocatalysis. This catalytic transformation proceeds through a nitrogen radical-mediated pathway and enables the late-stage modification of drugs, amino acids and peptides under mild conditions.
{"title":"Organocatalytic acylation of remote arene C–H bonds","authors":"","doi":"10.1038/s41929-024-01195-4","DOIUrl":"10.1038/s41929-024-01195-4","url":null,"abstract":"Site-selective acylation of remote arene C(sp2)−H bonds is achieved through N-heterocyclic carbene organocatalysis. This catalytic transformation proceeds through a nitrogen radical-mediated pathway and enables the late-stage modification of drugs, amino acids and peptides under mild conditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"864-865"},"PeriodicalIF":42.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084591","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 : 2024-08-27DOI: 10.1038/s41929-024-01208-2
Ju Byeong Chae, Annika R. Holm, Liviu M. Mirica
The enantioselective formation of Csp3–Csp3 bonds is still a substantial challenge in the synthesis of complex molecules. Now, a photocatalytic system has been developed for the enantioselective alkylation of α-amino Csp3−H bonds that promotes the generation of two different alkyl radicals, followed by their cross-coupling at a chiral nickel centre.
{"title":"Radical control for enantioselective Csp3–Csp3 cross-coupling","authors":"Ju Byeong Chae, Annika R. Holm, Liviu M. Mirica","doi":"10.1038/s41929-024-01208-2","DOIUrl":"10.1038/s41929-024-01208-2","url":null,"abstract":"The enantioselective formation of Csp3–Csp3 bonds is still a substantial challenge in the synthesis of complex molecules. Now, a photocatalytic system has been developed for the enantioselective alkylation of α-amino Csp3−H bonds that promotes the generation of two different alkyl radicals, followed by their cross-coupling at a chiral nickel centre.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"857-859"},"PeriodicalIF":42.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084598","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 : 2024-08-27DOI: 10.1038/s41929-024-01212-6
Amani M. Ebrahim
The catalysis Gordon Research Conference is a much-anticipated biennial gathering of the community to discuss the frontiers in design and development of catalytic materials and processes. Amani Ebrahim briefly touches upon this year’s themes centred on enabling technologies for sustainable societies.
{"title":"Reshaping catalysis beyond the conventional","authors":"Amani M. Ebrahim","doi":"10.1038/s41929-024-01212-6","DOIUrl":"10.1038/s41929-024-01212-6","url":null,"abstract":"The catalysis Gordon Research Conference is a much-anticipated biennial gathering of the community to discuss the frontiers in design and development of catalytic materials and processes. Amani Ebrahim briefly touches upon this year’s themes centred on enabling technologies for sustainable societies.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"860-861"},"PeriodicalIF":42.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084605","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 : 2024-08-27DOI: 10.1038/s41929-024-01210-8
A heterogeneous nucleation strategy is used to synthesize a NiFe oxygen evolution reaction catalyst for anion exchange membrane water electrolysis. The resulting catalyst has high electrochemical activity and achieves a stable performance for over 21 months owing to a dense interlayer, which anchors the catalytic layer to the metal substrate.
{"title":"A structured catalyst for anion exchange membrane water electrolysis","authors":"","doi":"10.1038/s41929-024-01210-8","DOIUrl":"10.1038/s41929-024-01210-8","url":null,"abstract":"A heterogeneous nucleation strategy is used to synthesize a NiFe oxygen evolution reaction catalyst for anion exchange membrane water electrolysis. The resulting catalyst has high electrochemical activity and achieves a stable performance for over 21 months owing to a dense interlayer, which anchors the catalytic layer to the metal substrate.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"866-867"},"PeriodicalIF":42.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084629","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 : 2024-08-27DOI: 10.1038/s41929-024-01196-3
Sneha Nayak, Laura K. G. Ackerman-Biegasiewicz
Nickel photoredox catalysis is often limited to electron-deficient and neutral arenes. Arylthianthrenium salts can now be used as redox-active reagents to afford general reactivity with electron-rich arenes.
{"title":"Harnessing electron-rich arenes in nickel photoredox catalysis","authors":"Sneha Nayak, Laura K. G. Ackerman-Biegasiewicz","doi":"10.1038/s41929-024-01196-3","DOIUrl":"10.1038/s41929-024-01196-3","url":null,"abstract":"Nickel photoredox catalysis is often limited to electron-deficient and neutral arenes. Arylthianthrenium salts can now be used as redox-active reagents to afford general reactivity with electron-rich arenes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"855-856"},"PeriodicalIF":42.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084630","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 : 2024-08-27DOI: 10.1038/s41929-024-01201-9
Using electron- and X-ray-based characterization techniques, three paracrystalline structural motifs are shown to form at the surface of amorphized iridium oxide catalysts upon use for water electrolysis in acidic conditions. An iridium oxide catalyst containing only these paracrystalline structural motifs achieves enhanced performance, making more efficient use of its limited iridium content.
利用基于电子和 X 射线的表征技术，在酸性条件下用于水电解时，非晶态氧化铱催化剂表面会形成三种副晶结构图案。仅含有这些副晶结构图案的氧化铱催化剂性能得到了提高，使其有限的铱含量得到了更有效的利用。
{"title":"Identifying restructured motifs on iridium oxide catalyst surfaces for water electrolysis","authors":"","doi":"10.1038/s41929-024-01201-9","DOIUrl":"10.1038/s41929-024-01201-9","url":null,"abstract":"Using electron- and X-ray-based characterization techniques, three paracrystalline structural motifs are shown to form at the surface of amorphized iridium oxide catalysts upon use for water electrolysis in acidic conditions. An iridium oxide catalyst containing only these paracrystalline structural motifs achieves enhanced performance, making more efficient use of its limited iridium content.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"862-863"},"PeriodicalIF":42.8,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142084600","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 : 2024-08-19DOI: 10.1038/s41929-024-01205-5
Ibrahim Khalil, Marco Giulio Rigamonti, Kwinten Janssens, Aram Bugaev, Daniel Arenas Esteban, Sven Robijns, Thibaut Donckels, Mostafa Torka Beydokhti, Sara Bals, Dirk De Vos, Michiel Dusselier
Searching for sustainable polymers requires access to biomass-based monomers. In that sense, glucose-derived cis,cis-muconic acid stands as a high-potential intermediate. However, to unlock its potential, an isomerization to the value-added trans,trans-isomer, trans,trans-muconic acid, is required. Here we develop atomically dispersed low-loaded Ru on beta zeolite catalysts that produce trans,trans-muconate in ethanol with total conversion (to equilibrium) and a selectivity of >95%. We reach very high turnovers per Ru and productivity rates of 427 mM h−1 (~85 g l−1 h−1), surpassing the bio-based cis,cis-muconic acid production rates by an order of magnitude. By coupling isomerization to Diels–Alder cycloaddition, terephthalate intermediates are produced in around 90% yields, circumventing the isomer equilibrium. Isomerization is promoted by Ru hydride species where the hydrides are generated from the alcohol solvent, as evidenced by Fourier transform infrared spectroscopy. Beyond isomerization, the Ru–zeolite and its hydride-forming capacity could be of use as a heterogeneous catalyst for other hydride chemistries, demonstrated by a successful hydride transfer hydrogenation. Muconic acid is an important bio-based chemical; however its applications are limited by the lack of efficient methods to access its trans,trans-isomer. Here the authors address this problem with a catalyst based on single Ru atoms dispersed on zeolite BEA that is capable of unlocking hydride chemistries.
寻找可持续聚合物需要获得基于生物质的单体。从这个意义上说，葡萄糖衍生的顺式、顺式粘多酸是一种极具潜力的中间体。然而，要释放其潜力，需要将其异构化为高附加值的反式、反式异构体--反式、反式粘多酸。在此，我们开发了原子分散低负载 Ru 的β沸石催化剂，可在乙醇中生产反式、反式粘多酸，总转化率（达到平衡）和选择性高达 95%。我们的单位 Ru 转化率非常高，生产率达到 427 mM h-1（约 85 g l-1 h-1），比生物基顺式、顺式粘多酸生产率高出一个数量级。通过将异构化与 Diels-Alder 环加成耦合，对苯二甲酸盐中间体的产量约为 90%，避开了异构体平衡。傅立叶变换红外光谱证明，Ru 氢化物可促进异构化，而氢化物是从醇溶剂中生成的。除了异构化，Ru 沸石及其氢化物形成能力还可用作其他氢化物化学的异质催化剂，氢化物转移加氢反应的成功就证明了这一点。
{"title":"Atomically dispersed ruthenium hydride on beta zeolite as catalysts for the isomerization of muconates","authors":"Ibrahim Khalil, Marco Giulio Rigamonti, Kwinten Janssens, Aram Bugaev, Daniel Arenas Esteban, Sven Robijns, Thibaut Donckels, Mostafa Torka Beydokhti, Sara Bals, Dirk De Vos, Michiel Dusselier","doi":"10.1038/s41929-024-01205-5","DOIUrl":"10.1038/s41929-024-01205-5","url":null,"abstract":"Searching for sustainable polymers requires access to biomass-based monomers. In that sense, glucose-derived cis,cis-muconic acid stands as a high-potential intermediate. However, to unlock its potential, an isomerization to the value-added trans,trans-isomer, trans,trans-muconic acid, is required. Here we develop atomically dispersed low-loaded Ru on beta zeolite catalysts that produce trans,trans-muconate in ethanol with total conversion (to equilibrium) and a selectivity of >95%. We reach very high turnovers per Ru and productivity rates of 427 mM h−1 (~85 g l−1 h−1), surpassing the bio-based cis,cis-muconic acid production rates by an order of magnitude. By coupling isomerization to Diels–Alder cycloaddition, terephthalate intermediates are produced in around 90% yields, circumventing the isomer equilibrium. Isomerization is promoted by Ru hydride species where the hydrides are generated from the alcohol solvent, as evidenced by Fourier transform infrared spectroscopy. Beyond isomerization, the Ru–zeolite and its hydride-forming capacity could be of use as a heterogeneous catalyst for other hydride chemistries, demonstrated by a successful hydride transfer hydrogenation. Muconic acid is an important bio-based chemical; however its applications are limited by the lack of efficient methods to access its trans,trans-isomer. Here the authors address this problem with a catalyst based on single Ru atoms dispersed on zeolite BEA that is capable of unlocking hydride chemistries.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 8","pages":"921-933"},"PeriodicalIF":42.8,"publicationDate":"2024-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142007382","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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