Nature Catalysis最新文献_第4页

Eliminating redox-mediated electron transfer mechanisms on a supported molecular catalyst enables CO2 conversion to ethanol 消除支撑分子催化剂上氧化还原介导的电子传递机制，实现二氧化碳到乙醇的转化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-13 DOI: 10.1038/s41929-024-01225-1

Maryam Abdinejad, Amirhossein Farzi, Robin Möller-Gulland, Fokko Mulder, Chengyu Liu, Junming Shao, Jasper Biemolt, Marc Robert, Ali Seifitokaldani, Thomas Burdyny

{"title":"Eliminating redox-mediated electron transfer mechanisms on a supported molecular catalyst enables CO2 conversion to ethanol","authors":"Maryam Abdinejad, Amirhossein Farzi, Robin Möller-Gulland, Fokko Mulder, Chengyu Liu, Junming Shao, Jasper Biemolt, Marc Robert, Ali Seifitokaldani, Thomas Burdyny","doi":"10.1038/s41929-024-01225-1","DOIUrl":"10.1038/s41929-024-01225-1","url":null,"abstract":"Molecular catalysts play a significant role in chemical transformations, utilizing changes in redox states to facilitate reactions. To date molecular electrocatalysts have efficiently produced single-carbon products from CO2 but have struggled to achieve a carbon–carbon coupling step. Conversely, copper catalysts can enable carbon–carbon coupling, but lead to broad C2+ product spectra. Here we subvert the traditional redox-mediated reaction mechanisms of organometallic compounds through a heterogeneous nickel-supported iron tetraphenylporphyrin electrocatalyst, facilitating electrochemical carbon–carbon coupling to produce ethanol. This represents a marked behavioural shift compared with carbon-supported metalloporphyrins. Extending the approach to a three-dimensional porous nickel support with adsorbed iron tetraphenylporphyrin, we attain ethanol Faradaic efficiencies of 68% ± 3.2% at −0.3 V versus a reversible hydrogen electrode (pH 7.7) with partial ethanol current densities of −21 mA cm−2. Separately we demonstrate maintained ethanol production over 60 h of operation. Further consideration of the wide parameter space of molecular catalyst and metal electrodes shows promise for additional chemistries and achievable metrics. The electrochemical reduction of CO2 on organometallic catalysts is commonly limited to two-electron products. Now, an iron tetraphenylporphyrin catalyst immobilized onto a nickel electrode is shown to achieve a Faradaic efficiency for ethanol of 68% due to the strong electronic coupling between the catalyst and the support.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142174943","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

Enantioselective Chan–Lam S-arylation of sulfenamides 磺酰胺的对映选择性 Chan-Lam S- 芳基化反应

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-09 DOI: 10.1038/s41929-024-01213-5

Qingjin Liang, Xinping Zhang, Madeline E. Rotella, Zeyu Xu, Marisa C. Kozlowski, Tiezheng Jia

{"title":"Enantioselective Chan–Lam S-arylation of sulfenamides","authors":"Qingjin Liang, Xinping Zhang, Madeline E. Rotella, Zeyu Xu, Marisa C. Kozlowski, Tiezheng Jia","doi":"10.1038/s41929-024-01213-5","DOIUrl":"10.1038/s41929-024-01213-5","url":null,"abstract":"Sulfur stereogenic molecules have a significant impact on drug development. Among them, sulfilimines are chiral molecules bearing S(IV) stereocentres, which exhibit great value in chemistry and biology but have so far been synthetically challenging to achieve. Similarly, it has also been a challenge to control the stereochemistry in Chan–Lam coupling, which has been widely used to construct C–N, C–O and C–S bonds by coupling nucleophiles with boronic acids using copper complexes. Here we report a highly chemoselective and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids to deliver an array of thermodynamically disfavoured aryl sulfilimines containing a sulfur stereocentre. A copper catalyst from a 2-pyridyl N-phenyl dihydroimidazole ligand has been designed that enables effective enantiocontrol by means of a well-defined chiral environment and high reactivity that outcompetes the background racemic transformation. A combined experimental and computational study establishes the reaction mechanism and unveils the origin of chemoselectivity and stereoselectivity. Sulfilimines are a class of chiral molecules that bear S(IV) stereocentres, which are of high value in drug discovery but difficult to synthesize. Now the authors report a chemo- and enantioselective Chan–Lam S-arylation of sulfenamides with arylboronic acids that delivers diaryl and alkyl aryl sulfilimines.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":null,"pages":null},"PeriodicalIF":42.8,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142158829","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

The structural basis of pyridoxal-5′-phosphate-dependent β-NAD-alkylating enzymes 依赖吡哆醛-5′-磷酸的β-NAD-烷基化酶的结构基础

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-09-02 DOI: 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

{"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":null,"pages":null},"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}

引用次数: 0

Generative machine learning produces kinetic models that accurately characterize intracellular metabolic states 机器学习生成的动力学模型能准确描述细胞内的代谢状态

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-08-30 DOI: 10.1038/s41929-024-01220-6

Subham Choudhury, Bharath Narayanan, Michael Moret, Vassily Hatzimanikatis, Ljubisa Miskovic

{"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":null,"pages":null},"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}

引用次数: 0

Understanding the interplay between electrocatalytic C(sp3)‒C(sp3) fragmentation and oxygenation reactions 了解电催化 C(sp3)-C(sp3)碎片化和加氧反应之间的相互作用

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-08-29 DOI: 10.1038/s41929-024-01218-0

Christine Lucky, Shengli Jiang, Chien-Rung Shih, Victor M. Zavala, Marcel Schreier

{"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":null,"pages":null},"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}

引用次数: 0

Organocatalytic acylation of remote arene C–H bonds 远端芳烃 C-H 键的有机催化酰化反应

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-08-27 DOI: 10.1038/s41929-024-01195-4

引用次数: 0

Radical control for enantioselective Csp3–Csp3 cross-coupling 对映选择性 Csp3-Csp3 交叉偶联的辐射控制

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-08-27 DOI: 10.1038/s41929-024-01208-2

Ju Byeong Chae, Annika R. Holm, Liviu M. Mirica

引用次数: 0

A structured catalyst for anion exchange membrane water electrolysis 用于阴离子交换膜电解水的结构催化剂

IF 42.8 1区化学