ACS Catalysis 最新文献

{"title":"Cooperative Ligand-Enabled Facile Synthesis of γ-C(sp3)–H Alkenylated Aliphatic Amides: A Comprehensive Protocol to Free N–H Tolerance","authors":"Suparna Dutta, Nikunj Kumar, Minhajul Islam, Wajid Ali, Puneet Gupta, Debabrata Maiti","doi":"10.1021/acscatal.4c07905","DOIUrl":"https://doi.org/10.1021/acscatal.4c07905","url":null,"abstract":"Site-selective distal C(<i>sp³</i>)–H functionalization of aliphatic amides is one of the longstanding challenges in synthetic methodology. Herein, we report a palladium-catalyzed <i>γ</i>-C(<i>sp³</i>)–H alkenylation of native aliphatic amide, exploiting a cooperative ligand approach to harness the weak coordinating ability of the amide functional group. Apart from tertiary amides, the protocol developed by us is also suitable for secondary, primary, and relatively unbiased <i>β</i>-C–H bond-containing amides, which remain unexplored till date. Theoretical calculations revealed that the combination of ligands is crucial for the reaction. Monoprotected amino acid (MPAA) ligand is essential for the concerted metalation–deprotonation (CMD) step of the C–H activation, occurring <i>via</i> a distinctive [5,6]-palladacyclic transition state. Meanwhile, the pyridone ligand plays a key role in forming the catalyst resting state, promoting <i>β</i>-hydride elimination, and facilitating product release. Both experimental and computational mechanistic studies confirm that C–H activation is the rate-limiting step in this process, providing crucial insights into the factors governing regioselective functionalization at the distant <i>γ</i>-site.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"136 3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627384","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":"CatTSunami: Accelerating Transition State Energy Calculations with Pretrained Graph Neural Networks","authors":"Brook Wander, Muhammed Shuaibi, John R. Kitchin, Zachary W. Ulissi, C. Lawrence Zitnick","doi":"10.1021/acscatal.4c04272","DOIUrl":"https://doi.org/10.1021/acscatal.4c04272","url":null,"abstract":"Direct access to transition state energies at low computational cost unlocks the possibility of accelerating catalyst discovery. We show that the top performing graph neural network potential trained on the OC20 data set, a related but different task, is able to find transition states energetically similar (within 0.1 eV) to density functional theory (DFT) 91% of the time with a 28× speedup. This speaks to the generalizability of the models, having never been explicitly trained on reactions, the machine learned potential approximates the potential energy surface well enough to be performant for this auxiliary task. We introduce the Open Catalyst 2020 Nudged Elastic Band (OC20NEB) data set, which is made of 932 DFT nudged elastic band calculations, to benchmark machine learned model performance on transition state energies. To demonstrate the efficacy of this approach, we for the first time explicitly treated a large reaction network with 61 intermediates and 174 dissociation reactions at DFT resolution (40 meV). To find low energy transition states we densely enumerate many possible NEBs. Using DFT this would have taken 52 GPU years. With ML we realized a 1500× speedup for dense enumerations, using just 12 GPU days of compute. Similar searches for complete reaction networks could become routine using the approach presented here. Finally, we constructed an ammonia synthesis activity volcano and systematically found lower energy configurations of the transition states and intermediates on six stepped unary surfaces than had previously been reported. This scalable approach offers a more complete treatment of configurational space to improve and accelerate catalyst discovery.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619060","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":"The Implementation and Impact of Chemical High-Throughput Experimentation at AstraZeneca","authors":"James J. Douglas, Andrew D. Campbell, David Buttar, Gary Fairley, Magnus J. Johansson, Allyson C. Mcintyre, Anthony J. Metrano, Richard S. Morales, Rachel H. Munday, Thanh V. Q. Nguyen, Samantha Staniland, Michele Tavanti, Erik Weis, Simon D. Yates, Zirong Zhang","doi":"10.1021/acscatal.4c07969","DOIUrl":"https://doi.org/10.1021/acscatal.4c07969","url":null,"abstract":"High-throughput experimentation (HTE) is a critical tool in modern pharmaceutical discovery and development. The ability to perform multiple parallel experiments in miniaturized plate-based formats has revolutionized how chemical reactions are optimized. HTE has been especially enabling for catalytic reactions, where the complexity of factors influencing the outcome makes the HTE approach especially suitable. We detail AstraZeneca’s 20-year journey with HTE, from early beginnings to a global community of HTE specialists that are critical to the delivery of our complex portfolio with reduced environmental impact. With an emphasis on catalytic reactions, we provide relevant case study examples from across discovery and development, discuss current technology, data science and workflows, and provide insights into where we see future advances in HTE.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608371","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":"Monomer Discrimination in the Enantioselective Living Coordinative Chain Transfer Polymerization of α,ω-Nonconjugated Dienes vs α-Olefins","authors":"Cole M. Burrows,&nbsp;Peter Y. Zavalij and Lawrence R. Sita*,&nbsp;","doi":"10.1021/acscatal.5c0055810.1021/acscatal.5c00558","DOIUrl":"https://doi.org/10.1021/acscatal.5c00558https://doi.org/10.1021/acscatal.5c00558","url":null,"abstract":"<p >The stereoselective living coordinative polymerization (LCP) of α-olefins and α,ω-nonconjugated dienes can be achieved using initiators derived from the homochiral, configurationally stable, monocyclopentadienyl, 7- and 9-membered-ring <i>cycloamidinate</i> group 4 metal complexes, <b>1</b>–<b>3</b>, respectively, as preinitiators in combination with borate <b>B1</b> as activating co-initiator. However, yield, molar mass (<i>M</i>_n), and degree of stereoregularity in these LCPs were found to be highly dependent upon initial monomer concentration due to decreased magnitudes for monomer complexation and site isomerization, <i>K</i>_M, and <i>K</i>_SI, respectively. The <i>enantioselective</i> living coordinative chain transfer polymerization (LCCTP) of 1,5-hexadiene using the initiator derived from <b>1</b>/<b>B1</b> and excess equivalents of ZnEt₂ as chain transfer agent (CTA) provides isotactic <i>cis</i>/<i>trans</i> poly(methylene-1,3-cyclopentane) (PMCP) in high yield. In contrast, under identical conditions, all attempts to carry out the enantioselective LCCTP of 1-hexene failed. It is proposed that this unprecedented discrimination of polymerizability between the two monomer types for LCCTP is due to stark differences in conformational freedom of the growing polyolefin chains. More specifically, in the case of the rigid-rod nature of growing PMCP, reversible chain transfer is not sterically impeded and can occur as required, whereas the unrestricted conformational flexibility of side chains in poly(1-hexene) creates a steric barrier that prohibits chain transfer to occur after just a few monomer insertions. Collectively, these results provide insights for designs of the next generation of enantiopure and configurationally stable cycloamidinate preinitiators that can potentially lead to the successful enantioselective LCCTP of both α,ω-nonconjugated dienes and α-olefins with high stereoregularity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 6","pages":"5219–5228 5219–5228"},"PeriodicalIF":11.3,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666824","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":"Monomer Discrimination in the Enantioselective Living Coordinative Chain Transfer Polymerization of α,ω-Nonconjugated Dienes vs α-Olefins","authors":"Cole M. Burrows, Peter Y. Zavalij, Lawrence R. Sita","doi":"10.1021/acscatal.5c00558","DOIUrl":"https://doi.org/10.1021/acscatal.5c00558","url":null,"abstract":"The stereoselective living coordinative polymerization (LCP) of α-olefins and α,ω-nonconjugated dienes can be achieved using initiators derived from the homochiral, configurationally stable, monocyclopentadienyl, 7- and 9-membered-ring <i>cycloamidinate</i> group 4 metal complexes, <b>1</b>–<b>3</b>, respectively, as preinitiators in combination with borate <b>B1</b> as activating co-initiator. However, yield, molar mass (<i>M</i>_n), and degree of stereoregularity in these LCPs were found to be highly dependent upon initial monomer concentration due to decreased magnitudes for monomer complexation and site isomerization, <i>K</i>_M, and <i>K</i>_SI, respectively. The <i>enantioselective</i> living coordinative chain transfer polymerization (LCCTP) of 1,5-hexadiene using the initiator derived from <b>1</b>/<b>B1</b> and excess equivalents of ZnEt₂ as chain transfer agent (CTA) provides isotactic <i>cis</i>/<i>trans</i> poly(methylene-1,3-cyclopentane) (PMCP) in high yield. In contrast, under identical conditions, all attempts to carry out the enantioselective LCCTP of 1-hexene failed. It is proposed that this unprecedented discrimination of polymerizability between the two monomer types for LCCTP is due to stark differences in conformational freedom of the growing polyolefin chains. More specifically, in the case of the rigid-rod nature of growing PMCP, reversible chain transfer is not sterically impeded and can occur as required, whereas the unrestricted conformational flexibility of side chains in poly(1-hexene) creates a steric barrier that prohibits chain transfer to occur after just a few monomer insertions. Collectively, these results provide insights for designs of the next generation of enantiopure and configurationally stable cycloamidinate preinitiators that can potentially lead to the successful enantioselective LCCTP of both α,ω-nonconjugated dienes and α-olefins with high stereoregularity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608372","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":"Engineering of Conserved Sequence Motif 1 Residues in Halohydrin Dehalogenase HheC Simultaneously Enhances Activity, Stability, and Enantioselectivity","authors":"Sophie Staar, Miquel Estévez-Gay, Felix Kaspar, Sílvia Osuna, Anett Schallmey","doi":"10.1021/acscatal.5c00819","DOIUrl":"https://doi.org/10.1021/acscatal.5c00819","url":null,"abstract":"Halohydrin dehalogenases (HHDHs) are powerful enzymes for the asymmetric diversification of oxyfunctionalized synthons. They feature two characteristic sequence motifs that distinguish them from homologous short-chain dehydrogenases and reductases. Sequence motif 1, carrying a conserved threonine, glycine, and a central aromatic residue, lines the nucleophile binding pocket of HHDHs. It could therefore impact nucleophile binding and presumably also the activity of the enzymes. However, experimental evidence supporting this theory is largely missing. Herein, we systematically studied the mutability of the three conserved motif 1 residues as well as their resulting impact on enzyme activity, stability, and selectivity in two model HHDHs: HheC from <i>Agrobacterium radiobacter</i> AD1 and HheG from <i>Ilumatobacter coccineus</i>. In both HheC and HheG, the conserved threonine and glycine tolerated mutations to only structurally similar amino acids. In contrast, the central aromatic (i.e., phenylalanine or tyrosine) residue of motif 1 demonstrated much higher variability in HheC. Remarkably, some of these variants featured drastically altered activity, stability, and selectivity characteristics. For instance, variant HheC F12Y displayed up to 5-fold increased specific activity in various epoxide ring opening and dehalogenation reactions as well as enhanced enantioselectivity (e.g., an <i>E</i>-value of 74 in the azidolysis of epichlorohydrin compared to <i>E</i> = 22 for HheC wild type) while also exhibiting a 10 K higher apparent melting temperature. QM and MD simulations support the experimentally observed activity increase of HheC F12Y and reveal alterations in the hydrogen bonding network within the active site. As such, our results demonstrate that multiple enzyme properties of HHDHs can be altered through the targeted mutagenesis of conserved motif 1 residues. In addition, this work illustrates that motif 1 plays vital roles beyond nucleophile binding by impacting the solubility and stability properties. These insights advance our understanding of HHDH active sites and will facilitate their future engineering.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"32 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608374","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":"Rh-Catalyzed Enantioselective Synthesis of Acyclic Quaternary Carbons via Carbene Insertion","authors":"Kun He, Weikun Zeng, Yingcheng Wang, Zhihui Shao, Yi Jin","doi":"10.1021/acscatal.5c00841","DOIUrl":"https://doi.org/10.1021/acscatal.5c00841","url":null,"abstract":"Herein, the construction of acyclic quaternary carbon chiral centers through carbene insertions in a chiral metal carbene mechanism is reported. Carbene insertion products can be obtained with high chemical selectivity, regioselectivity, <i>Z/E</i> selectivity, and enantioselectivity using α-diazo esters and enone-hydrazones under the conditions of a chiral dirhodium catalyst. The mechanism verification experiments demonstrate that the benzene ring, originating from the enone-hydrazones, can shield the O and NH coordination atoms of the enone-hydrazones. This shielding effect is crucial for the asymmetric C–C bond insertion reaction catalyzed by a chiral metal carbene complex derived from a chiral dirhodium. Additionally, the results of the controlled experiments indicate that achieving the asymmetric version of the traditional C–C insertion substrate is challenging. This challenge arises from the coordination of the substrate with the Rh1 site of the chiral dirhodium catalyst, which subsequently leads to carbene precursor activation occurring at the Rh2 site, resulting in poor stereoselectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"69 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619062","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":"Cocatalyst-Dependent Divergent Amination of Alkylgold Intermediates with Azodicarboxylates","authors":"Yuan Haoxuan, Ming Bao, Kewei Chen, Jingjing Huang, Yue Pan, Dorota Gryko, Xinfang Xu","doi":"10.1021/acscatal.5c00495","DOIUrl":"https://doi.org/10.1021/acscatal.5c00495","url":null,"abstract":"The asymmetric electrophilic amination using azodicarboxylates as the <i>N</i>-source for the construction of the C–N bond has attracted much attention over the past decades. However, the use of in situ formed nucleophilic intermediates, rather than bench-stable reagents, for the asymmetric amination remains elusive and challenging. Herein, we disclose an enantioselective electrophilic amination reaction of in situ generated alkylgold species with azodicarboxylates under a gold complex and chiral quinine-derived squaramide (QN-SQA) synergetic catalysis, leading to chiral alkylideneoxazolines with a nitrogen-containing tertiary carbon stereocenter in good to high yields and enantioselectivities. Moreover, starting from the same reagents, the oxazoles incorporating an aminomethyl group on the 5-position could be obtained by gold and Brønsted acid relay catalysis via alkylideneoxazoline species. This method offers a complementary approach for the electrophilic amination through interception of in situ formed alkylgold species. With this strategic protocol, further synthetic applications can be envisioned for the catalytic construction of C–C and C–X bonds.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608447","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":"Structural Modulation and Adsorptive Behavior of CuFe-LDHs-derived Catalysts through Mn Doping: Dual Enhancement of Low-Temperature Catalytic Performance and Sulfur Resistance","authors":"Jun Liu,&nbsp;Bin Jia,&nbsp;Xiaoqing Liu,&nbsp;Ying Wang,&nbsp;Yuqiong Zhao,&nbsp;Guoqiang Li,&nbsp;Qiang Ren,&nbsp;Guojie Zhang* and Junhua Li*,&nbsp;","doi":"10.1021/acscatal.4c0719310.1021/acscatal.4c07193","DOIUrl":"https://doi.org/10.1021/acscatal.4c07193https://doi.org/10.1021/acscatal.4c07193","url":null,"abstract":"<p >Addressing the activity and resistance to toxicity of sintered flue gas at low temperatures is crucial. This study focuses on the design of Mn-doped Cu₃Fe₁-LDHs as a bifunctional catalyst for synergistic CO oxidation in NH₃–SCR. Compared with the Cu₃Fe₁O_<i>x</i> catalysts, the Mn-doped Cu₃Mn_0.25Fe_0.75O_<i>x</i> catalysts achieved dual enhancement of NO_<i>x</i> and CO conversion at low temperature and oxygen-enriched conditions, albeit with lower N₂ selectivity. They also demonstrated good sulfur-resistant performance. Confirming by theoretical calculations and characterization techniques, the chemical bonding configuration of Cu₃Fe₁O_<i>x</i> was verified. Mn is uniformly distributed in the catalyst and formed a solid solution with Cu²⁺ and Fe³⁺ in the crystal lattice. This contributed to the stable growth of the crystals during synthesis, thus improving the size and morphology of the crystals and providing more active sites. Mn introduction also promoted charge transfer between Cu²⁺ and Fe³⁺, and enhanced the catalyst’s adsorption capacity and reactivity. Chemisorption analysis revealed that the incorporation of Mn significantly improved the catalyst’s reduction capacity, oxygen adsorption ability, and acidic sites. Furthermore, in situ DRIFTS and DFT calculations demonstrated that Mn doping improved NH₃ and CO adsorption, thereby improving the catalyst’s overall performance. The SO₂ adsorption results showed that Mn doping enhanced the surface acidity of the catalyst, reducing SO₂ adsorption and sulfate formation. The development of this catalyst has important industrial application value for ultralow emission of sintering flue gas.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 6","pages":"5123–5141 5123–5141"},"PeriodicalIF":11.3,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143667166","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":"Comparing and Combining Alternative Strategies for Enhancing Cytochrome P450 Peroxygenase Activity","authors":"Matthew N. Podgorski,&nbsp; and ,&nbsp;Stephen G. Bell*,&nbsp;","doi":"10.1021/acscatal.4c0748610.1021/acscatal.4c07486","DOIUrl":"https://doi.org/10.1021/acscatal.4c07486https://doi.org/10.1021/acscatal.4c07486","url":null,"abstract":"<p >Cytochrome P450 monooxygenase (CYP) enzymes have advantageous properties over chemical catalysts. However, it is often not feasible to use CYPs in larger-scale synthesis as they require additional cofactors (NAD(P)H) and electron transfer proteins. This could be overcome by transforming CYPs into peroxygenases that use H₂O₂. Recently, multiple strategies have been reported for converting CYPs into peroxygenases. Mutating the residues of the acid–alcohol pair in the oxygen-binding groove to those found in natural peroxygenases can promote the desired H₂O₂-driven activity. Another strategy is to enlarge the enzyme’s solvent channels to allow H₂O₂ easier access into the active site, to enhance peroxygenase activity. Here, we evaluate these different strategies by comparing the peroxygenase activities of the double I-helix mutant D251Q/T252E (the QE mutant) and the F182A mutant of the bacterial enzyme CYP199A4. We also assess whether the peroxygenase activity can be further improved by combining these mutations (to give the F182AQE mutant). The F182A mutant exhibited the highest activity toward a selection of smaller substrates that undergo <i>O</i>-demethylation, <i>S</i>-oxidation, and epoxidation reactions. All the mutants converted 4-vinylbenzoic acid into the (<i>S</i>)-epoxide, with the F182A mutant having the highest stereoselectivity (&gt;99% ee). The F182A mutant was unable to oxidize 4-<i>t</i>-butylbenzoic acid, while the F182AQE mutant could with high activity. The F182A mutation was found to substantially alter the selectivity of the reaction with 4-ethylbenzoic acid, increasing hydroxylation activity over desaturation. The F182A mutant catalyzed significant further oxidation reactions of the primary metabolites before all the substrate had been consumed, demonstrating a relaxed substrate specificity. X-ray crystal structures of the F182A and F182AQE mutants with the substrates revealed changes in substrate binding and solvent access providing insights into these experimental observations.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 6","pages":"5191–5210 5191–5210"},"PeriodicalIF":11.3,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666851","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}