ACS Catalysis 最新文献

{"title":"Mechanistic Insights into GTP Hydrolysis by the RhoA Protein: Catalytic Impact of Glutamine Tautomerism","authors":"Jorge Pardos, Adrián García-Martínez, J. Javier Ruiz-Pernía, Iñaki Tuñón","doi":"10.1021/acscatal.5c00719","DOIUrl":"https://doi.org/10.1021/acscatal.5c00719","url":null,"abstract":"We present a systematic evaluation of different possible reaction mechanisms for GTP hydrolysis in RhoA, a member of the Ras superfamily of enzymes that uses this reaction to switch from an active to an inactive conformation. These enzymes are activated by the presence of a GTPase activating protein (or GAP) that forms an intimate complex with residues of the two proteins present in the active site. We have explored the multidimensional reactional free energy landscape in the active site of the complex formed by RhoA and p50RhoGAP. Our molecular dynamics simulations show that the activating enzyme p50RhoGAP establishes catalytically important interactions with the phosphate groups of GTP through its so-called arginine finger (Arg85) and also with the RhoA residue Gln63. This is a key residue because it not only interacts with the nucleophilic water molecule but also participates actively in the reaction mechanism. Adaptive string method simulations using hybrid quantum mechanics/molecular mechanics (QM/MM) potentials with both tight-binding and density functional Hamiltonians show that GTP hydrolysis proceeds through the formation of a metaphosphate metastable species. Mechanistic proposals differ in the proton transfer rearrangements required to form the inorganic phosphate ion. Our simulations discard a solvent-assisted mechanism and point to the participation of Gln63 in the proton transfer process by means of the side chain tautomerism from the amide to the imide form. The proton transfer required to recover the amide form of Gln63 requires the participation of the inorganic phosphate, and it is the rate-limiting step of the process, with a free energy barrier of 20.2 kcal mol^–1 at the B3LYPD3/MM level, in good agreement with the experimentally derived value. The amide–imide tautomerism could also be relevant in other enzymes, facilitating proton transfer events in complex mechanisms.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"66 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518295","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}

{"title":"One-Pot Synthesis of Valeric Biofuels via Esterification–Hydrogenolysis","authors":"Ruiqi Fang, Jie Kang, Fengliang Wang, Xin Zhao, Yingwei Li","doi":"10.1021/acscatal.5c00636","DOIUrl":"https://doi.org/10.1021/acscatal.5c00636","url":null,"abstract":"The production of valerate esters, a class of transportation biofuels (additives), usually undergoes alternate hydrogenation and acid-catalysis dehydration processes that suffer from inevitable coke deposition and undesirable side reactions. We report a one-pot esterification–hydrogenolysis reaction pathway for valeric biofuels synthesis from biomass-derived 2-furoic acid, which was proceeded over the elaborate CoPt_<i>X</i>@Co₃O₄-NC (<i>X</i> = 0.01, 0.02, 0.05, and 0.1) catalysts. The catalysts were constructed through a MOF-engaged etching-pyrolysis-replacement strategy to obtain mesoporous pocket cube nanoboxes-in-nanobox morphology and uniform CoPt_<i>X</i>@Co₃O₄ core–shell nanoparticles with Pt moieties in tunable content and size (from single-atom scale to 2.4 nm). The obtained acid-free CoPt_<i>X</i>@Co₃O₄-NC catalyst achieved an average 92.2% yield of ethyl valerate at a complete conversion of 2-furoic acid, and the reaction ran steadily in a microchannel continuous flow reactor for at least 200 h, which also inhibited the byproduct generation and coke deposition. A mechanistic study suggested that 2-furoic acid was preferably adsorbed on the oxyphilic Co₃O₄ shell for esterification initially; then the generated esters underwent sequential and exclusive hydrogenolysis steps over the CoPt core to yield valerate esters. The high industrial application prospect of this reaction pathway was additionally highlighted by producing 12 kinds of valeric biofuels from 2-furoic acid and the corresponding C₁ ∼ C₇ primary, secondary, and tertiary alcohols.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"22 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143518294","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}

{"title":"Manipulating the Dynamic Proton Transport in Electrocatalysis at the Nanoscale","authors":"Lei Feng, Qin Liu, Guangyuan Xu, Min Ge, Wentuan Bi, Yi Huang, Jing Zhang, Xiaoye Liu, Si Chen, Fujing Nie, Zhendong Liu, Zhang Cai, Yuan Kong, Chengwei Wang, Junling Lu, Min Zhou, Huan Yan","doi":"10.1021/acscatal.5c00266","DOIUrl":"https://doi.org/10.1021/acscatal.5c00266","url":null,"abstract":"Proton transport plays a crucial role in many hydrogen-based technologies. However, there is limited investigation on the manipulation of proton transport at the nanoscale, especially for the highly catalytic performance in electrocatalysis. Here, we encapsulated the polyoxometalate (POM, a well-known proton carrier) into the microchannel of a single-walled carbon nanotube (SWCNT) and selectively deposited the Pt clusters on the outside surface of the SWCNT, to establish a pseudo “proton shuttle” and achieve a fast proton transport and form a nanoscale “Pt–POM” kinetic coupling. With the enhanced proton transport, this proton nexus catalyst could accelerate the kinetic process of the probe reaction (hydrogen evolution reaction, HER) and outperform the counterparts. This strategy of manipulation of proton transport with the precise arrangement of functional sites is validated as a promising routine to obtain a highly catalytic performance in other proton-related electrocatalytic reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"210 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143506898","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}

{"title":"Accelerated Optimization of Compositions and Chemical Ordering for Bimetallic Alloy Catalysts Using Bayesian Learning","authors":"Xiangfu Niu, Shuwei Li, Zheyu Zhang, Haohong Duan, Rui Zhang, Jianqiu Li, Liang Zhang","doi":"10.1021/acscatal.5c00467","DOIUrl":"https://doi.org/10.1021/acscatal.5c00467","url":null,"abstract":"Alloy materials are crucial to various applications, including catalysis and energy storage, due to their superior performance, cost-efficiency, and tunable properties. However, the vast compositional space and complex chemical ordering of alloys pose significant challenges in identifying the optimal material designs. We present an active learning framework utilizing Bayesian optimization to streamline the discovery of high-performance alloy materials. Applying this framework to PtNi oxygen reduction reaction (ORR) catalysts, we successfully identified the global optimal structures featuring a Pt shell and a PtNi core. Our approach was further extended to explore different morphologies and compositions, revealing the most favorable chemical orderings for ORR. This work provides a comprehensive strategy for the accelerated design of multicomponent alloy materials and highlights the critical role of chemical ordering in optimizing the structure–performance relationship, facilitating the development of high-performance catalysts for energy applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495762","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}

{"title":"Activity Regulation of a Glutamine Amidotransferase Bienzyme Complex by Substrate-Induced Subunit Interface Expansion","authors":"Franziska Jasmin Funke,&nbsp;Sandra Schlee,&nbsp;Isabel Bento,&nbsp;Gleb Bourenkov,&nbsp;Reinhard Sterner* and Matthias Wilmanns*,&nbsp;","doi":"10.1021/acscatal.4c0743810.1021/acscatal.4c07438","DOIUrl":"https://doi.org/10.1021/acscatal.4c07438https://doi.org/10.1021/acscatal.4c07438","url":null,"abstract":"<p >Glutamine amidotransferases are multienzyme machineries in which reactive ammonia is generated by a glutaminase and then transferred through a sequestered protein tunnel to a synthase active site for incorporation into diverse metabolites. To avoid wasteful metabolite consumption, there is a requirement for synchronized catalysis, but any generally applicable mechanistic insight is still lacking. As synthase activity depends on glutamine turnover, we investigated possible mechanisms controlling glutaminase catalysis using aminodeoxychorismate synthase involved in folate biosynthesis as a model. By analyzing this system in distinct states of catalysis, we found that incubation with glutamine leads to a subunit interface expansion by one-third of its original area. These changes completely enclose the glutaminase active site for sequestered catalysis and the subsequent transport of volatile ammonia to the synthase active site. In view of similar rearrangements in other glutamine amidotransferases, our observations may provide a general mechanism for the catalysis synchronization of this multienzyme family.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 5","pages":"4359–4373 4359–4373"},"PeriodicalIF":11.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c07438","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561455","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}

{"title":"Identification of Sabatier Descriptors for Hydrodeoxygenation Activity and Selectivity on Supported Molybdenum Oxide Catalysts","authors":"Andrew J. Kohler, Mahmudul H. Khan, Brent H. Shanks","doi":"10.1021/acscatal.4c07504","DOIUrl":"https://doi.org/10.1021/acscatal.4c07504","url":null,"abstract":"While molybdenum oxide shows promise in deoxygenating lignin monomers to petrochemically relevant aromatics and alkenes, its current applicability is hindered by its tendency to oversaturate the aliphatic byproducts to alkanes, limiting the ability of the product stream to be directly integrated into the existing infrastructure. Previously, detailed kinetic experiments indicated that this parasitic alkane pathway can result from competitive C–O hydrogenolysis during deoxygenation rather than direct hydrogenation of alkenes. Here, we evaluate how modulating the properties of the molybdenum active site could ameliorate this pathway for short-chain (&lt;C₅) carbonyl hydrodeoxygenation (HDO) by synthesizing a library of catalysts across an array of metal oxide supports (Al₂O₃, Nb₂O₅, SiO₂, TiO₂, and ZrO₂) at incremental MoO_<i>x</i> surface densities to alter the degree of two-dimensional MoO_<i>x</i> oligomerization. The study reveals that MoO_<i>x</i> structure sensitivity for oxygen removal highly depends on the supporting metal oxide. Notably, the electronegativity of the support and the MoO_<i>x</i> structure alter the electronic density of the average Mo active site (as quantified by the terminal Mo=O bond Raman shift) in parallel, leading to a Sabatier relationship between oxygen adsorption strength and the overall rate of oxygen removal. Conversely, this combinatorial MoO_<i>x</i> structure/support effect does not apply to the selectivity between the alkane and alkene products. Instead, the support appears to be the primary driver of the competitive hydrogenolysis pathway, with the support’s point of zero charge (PZC) being an apparent Sabatier descriptor for the relative alkane selectivity, implying the bridging Mo–O-support bond as the hydrogenolysis site. Interestingly, the Sabatier optimum for the hydrogenolysis pathway is reactant dependent as a shift to stronger binding on higher PZC supports occurs for molecules with less stable intermediates like the more lignin-relevant aldehyde molecules.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495759","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}

{"title":"Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds","authors":"Wei-Dong Lu,&nbsp;Zhi-Lin Liu,&nbsp;Zi-Hao Liao,&nbsp;Zi-Yi Gao,&nbsp;Kai Chen*,&nbsp;Hao-Yue Xiang* and Hua Yang*,&nbsp;","doi":"10.1021/acscatal.4c0786910.1021/acscatal.4c07869","DOIUrl":"https://doi.org/10.1021/acscatal.4c07869https://doi.org/10.1021/acscatal.4c07869","url":null,"abstract":"<p >Transition-metal-catalyzed asymmetric allylic substitution (AAS) reaction is one of the most synthetically useful and powerful reactions for the assembly of carbon–carbon and carbon–heteroatom bonds in an asymmetric fashion. Herein, we accomplished a photoinduced, palladium-catalyzed formal AAS reaction without preinstalling the allylic structural unit, which rationally integrates photocatalytic desaturation and asymmetric allylic substitution. A series of sterically congested optically pure 2-alkyltetrahydropyridine scaffolds were facilely prepared from inexpensive and readily available piperidine derivatives with carbon-centered nucleophiles, with excellent compatibility (51 examples), high efficiency (up to 96% yield), excellent regioselectivity (only α-product), and outstanding enantioselectivities (up to 95.5:4.5 er). Comprehensive computational studies rationalized the compatibility of photoinduced radical chemistry and transition-metal-catalyzed AAS reaction and disclosed the origin of regioselectivity and enantioselectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 5","pages":"4384–4393 4384–4393"},"PeriodicalIF":11.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561469","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}

{"title":"Activity Regulation of a Glutamine Amidotransferase Bienzyme Complex by Substrate-Induced Subunit Interface Expansion","authors":"Franziska Jasmin Funke, Sandra Schlee, Isabel Bento, Gleb Bourenkov, Reinhard Sterner, Matthias Wilmanns","doi":"10.1021/acscatal.4c07438","DOIUrl":"https://doi.org/10.1021/acscatal.4c07438","url":null,"abstract":"Glutamine amidotransferases are multienzyme machineries in which reactive ammonia is generated by a glutaminase and then transferred through a sequestered protein tunnel to a synthase active site for incorporation into diverse metabolites. To avoid wasteful metabolite consumption, there is a requirement for synchronized catalysis, but any generally applicable mechanistic insight is still lacking. As synthase activity depends on glutamine turnover, we investigated possible mechanisms controlling glutaminase catalysis using aminodeoxychorismate synthase involved in folate biosynthesis as a model. By analyzing this system in distinct states of catalysis, we found that incubation with glutamine leads to a subunit interface expansion by one-third of its original area. These changes completely enclose the glutaminase active site for sequestered catalysis and the subsequent transport of volatile ammonia to the synthase active site. In view of similar rearrangements in other glutamine amidotransferases, our observations may provide a general mechanism for the catalysis synchronization of this multienzyme family.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495758","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}

{"title":"Tuning Vacancy in Metal Oxide Support to Enhance Activity and Durability of Pt Catalysts for the Methanol Oxidation Reaction","authors":"Ahmed M. Jasim,&nbsp;Gan Xu,&nbsp;Matthias J. Young and Yangchuan Xing*,&nbsp;","doi":"10.1021/acscatal.5c0025910.1021/acscatal.5c00259","DOIUrl":"https://doi.org/10.1021/acscatal.5c00259https://doi.org/10.1021/acscatal.5c00259","url":null,"abstract":"<p >Coupling Pt with metal oxides has been shown to be an effective approach for catalyst durability enhancement in the methanol oxidation reaction (MOR). Here, we report tuning valence in niobium oxide (NbO_x) as a support by tin oxide (SnO₂) as a promoter to mediate the Pt electrocatalysis in MOR. The catalyst was designed to consist of Pt supported on SnO₂-modified NbO_x coated on carbon black (Pt-TNb/C), which shows significantly enhanced electrochemical durability and activity in MOR that are better than the catalyst without SnO₂ modification (Pt-Nb/C) and those reported in the literature. Electron diffraction pair distribution function analysis showed an increase in the Nb–Nb bond length after SnO₂ incorporation, from 3.80 to 3.84 Å, indicative of a tuning effect. X-ray photoelectron spectroscopy further confirmed valence mediation in the Pt-TNb/C catalyst, as evidenced by the positive binding energy peak shifts of 0.49 and 0.66 eV in Nb 3d_5/2 and Nb 3d_3/2, respectively, as compared to those of the Pt-Nb/C catalyst. The Pt-Nb/C catalyst has MOR peak currents of 2.71 A/mg-Pt at the beginning and 1.94 A/mg-Pt at the end of 1000 cycles in 1.0 M methanol in 0.5 M H₂SO₄ electrolyte, corresponding to a 28.41% activity loss. However, the Pt-TNb/C catalyst with SnO₂ tuning has a much smaller loss at only 3.77%, with MOR peak currents of 3.45 A/mg of Pt at the beginning and 3.32 A/mg of Pt at the end under the same test conditions. The high durability and activity of the new catalyst are attributed to the effect of valence tuning of the niobium oxide, in addition to a bifunctional effect from tin oxide.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 5","pages":"4350–4358 4350–4358"},"PeriodicalIF":11.3,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561511","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}

{"title":"Tuning Vacancy in Metal Oxide Support to Enhance Activity and Durability of Pt Catalysts for the Methanol Oxidation Reaction","authors":"Ahmed M. Jasim, Gan Xu, Matthias J. Young, Yangchuan Xing","doi":"10.1021/acscatal.5c00259","DOIUrl":"https://doi.org/10.1021/acscatal.5c00259","url":null,"abstract":"Coupling Pt with metal oxides has been shown to be an effective approach for catalyst durability enhancement in the methanol oxidation reaction (MOR). Here, we report tuning valence in niobium oxide (NbO_x) as a support by tin oxide (SnO₂) as a promoter to mediate the Pt electrocatalysis in MOR. The catalyst was designed to consist of Pt supported on SnO₂-modified NbO_x coated on carbon black (Pt-TNb/C), which shows significantly enhanced electrochemical durability and activity in MOR that are better than the catalyst without SnO₂ modification (Pt-Nb/C) and those reported in the literature. Electron diffraction pair distribution function analysis showed an increase in the Nb–Nb bond length after SnO₂ incorporation, from 3.80 to 3.84 Å, indicative of a tuning effect. X-ray photoelectron spectroscopy further confirmed valence mediation in the Pt-TNb/C catalyst, as evidenced by the positive binding energy peak shifts of 0.49 and 0.66 eV in Nb 3d_5/2 and Nb 3d_3/2, respectively, as compared to those of the Pt-Nb/C catalyst. The Pt-Nb/C catalyst has MOR peak currents of 2.71 A/mg-Pt at the beginning and 1.94 A/mg-Pt at the end of 1000 cycles in 1.0 M methanol in 0.5 M H₂SO₄ electrolyte, corresponding to a 28.41% activity loss. However, the Pt-TNb/C catalyst with SnO₂ tuning has a much smaller loss at only 3.77%, with MOR peak currents of 3.45 A/mg of Pt at the beginning and 3.32 A/mg of Pt at the end under the same test conditions. The high durability and activity of the new catalyst are attributed to the effect of valence tuning of the niobium oxide, in addition to a bifunctional effect from tin oxide.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"53 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495760","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}