ACS Catalysis 最新文献

{"title":"Encapsulating Ru Nanoclusters for Reductive Imination of Biomass-Based Furfural by Shape-Selective Catalysis","authors":"Hongtao Zou, Yuxin Jin, Limin Chen, Jinzhu Chen","doi":"10.1021/acscatal.4c07371","DOIUrl":"https://doi.org/10.1021/acscatal.4c07371","url":null,"abstract":"Reductive imination of aldehydes to the corresponding secondary imines, while attractive and promising, remains a big challenge due to consecutive hydrogenation and hydroammonolysis of the in situ formed imine. Herein, we describe a strategy of shape-selective catalysis for the reductive imination of biomass-derived furfural with H₂NOH and H₂ by using Ru nanoclusters confined within the regular micropores of ZSM-5 (Ru@ZSM-5). The Ru@ZSM-5 features a consecutive furfural oxime-hydrogenation and furfurylimine-hydrogenation due to their closed molecular sizes to the pore apertures (5.3 × 5.6 Å) of the ZSM-5. In contrast, the in situ formed secondary imine (4.3 × 11.2 Å) with a large molecular size could not pass through ZSM-5 micropores to reach the active Ru sites, thus remaining unaffected without further hydrogenation and hydroammonolysis. The shape-selectivity of Ru@ZSM-5 is further confirmed by catalyst-passivation and hydrogen-spillover experiments. The Ru@ZSM-5 shows high activity and shape-selectivity with good recyclability and is easily extended to reductive imination of a variety of aldehydes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"205 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990878","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":"Diastereo- and Enantioselective Chemoenzymatic Synthesis of Chiral Tricyclic Intermediate of Anti-HIV Drug Lenacapavir","authors":"Wenzhen Fu, An Liu, Yang Yang","doi":"10.1021/acscatal.4c07464","DOIUrl":"https://doi.org/10.1021/acscatal.4c07464","url":null,"abstract":"Despite its great potential, the development and implementation of scalable new-to-nature biocatalytic transformations in the chemoenzymatic synthesis of clinically significant pharmaceuticals still present a considerable challenge. We developed a chemoenzymatic synthesis of the very recently developed anti-HIV drug lenacapavir’s 5/5/3 fused tricyclic fragment featuring an unusual chiral cyclopropane moiety. Key to this development is a biocatalyst-controlled, fully diastereo- and enantiodivergent cyclopropanation of a highly functionalized vinylpyrazole substrate, granting access to all four possible stereoisomers of lenacapavir cyclopropane. High-throughput experimentation led to the discovery of heme-dependent globins, including nitrous oxide dioxygenase (NOD) and protoglobin (Pgb), as promising cyclopropanation biocatalysts. Directed evolution furnished a highly diastereo- and enantioselective cyclopropanation (up to 99:1 d.r. and 99:1 e.r.). Further developed downstream chemical cyclization afforded the desired lenacapavir 5/5/3 fused tricycle with great stereochemical purity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"74 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990879","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":"Reshaping the Substrate-Binding Pocket of Ene-Reductase for Enhanced and Inverted Stereoselectivity: A Concise Access to the Stereocomplementary Chiral GABA Derivatives","authors":"An Huang, Xian-Heng Song, Lin-Lin Song, Shuang-Shuang Pan, Jia-Xin Tian, Peng-Fei Wang, Shu-Yun Ju, Ya-Jun Wang","doi":"10.1021/acscatal.4c06784","DOIUrl":"https://doi.org/10.1021/acscatal.4c06784","url":null,"abstract":"Despite the availability of numerous natural and engineered ene-reductases (ERs), enantiocomplementary synthesis of the sterically hindered molecules by ERs is still limited by poor substrate acceptance, particularly due to the insufficient complementary stereoselectivity. Herein, we reshaped the substrate-binding pocket of <i>Se</i>ER from <i>Saccharomyces eubayanus</i> through semirational design, enabling ERs capable of stereocomplementary hydrogenating of the challenging substituted β-cyano cinnamic esters. Compared to the wild type, the variants exhibited enhanced activity (up to 161-fold) and catalytic efficiency <i>k</i>_cat/<i>K</i>_M (up to 358-fold), displaying potential in synthesizing various chiral β-cyano esters with high stereoselectivity (up to 99% <i>ee</i>). Molecular dynamics simulations demonstrated that the key for the superior catalytic performance of variants is the well-tuned substrate-binding pocket, which strengthens and stabilizes substrate recognition. Furthermore, we elucidated the practicality of the <i>Se</i>ER variants in asymmetric synthesis of the chiral GABA derivatives (e.g., Phenibut, Baclofen, and Tolibut) via chemo-enzymatic cascade reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989811","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":"Recent Progress in Chiral Quaternary Ammonium Salt-Promoted Asymmetric Nucleophilic Additions","authors":"Xiaoqun Yang, Youlin Deng, Dan Ling, Tingting Li, Lingzhu Chen, Zhichao Jin","doi":"10.1021/acscatal.4c06497","DOIUrl":"https://doi.org/10.1021/acscatal.4c06497","url":null,"abstract":"Chiral quaternary ammonium ion-pair organocatalysis has been widely used in the facile synthesis of chiral molecules with challenging stereocenters. Especially, numerous asymmetric nucleophilic addition reactions have been facilitated with this strategy. This review systematically summarizes the asymmetric nucleophilic additions promoted by chiral quaternary ammonium salts in the past decade. The content is organized according to the types of electrophiles involved in these catalytic transformations. Our own perspectives on future development within this highly active research field are also provided.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"74 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989810","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 the Fungal Peroxygenase for Efficient and Regioselective Hydroxylation of Vitamin Ds and Sterols","authors":"Yawen Huang, Jie Zhang, Fuqiang Chen, Yu Fu, Han Liu, Zhiyou Zong, Quanshun Li, Yalan Zhang, Huanhuan Li, Xiang Sheng, Weidong Liu, Wuyuan Zhang","doi":"10.1021/acscatal.4c06429","DOIUrl":"https://doi.org/10.1021/acscatal.4c06429","url":null,"abstract":"Hydroxylation of C25 C–H bonds (referring to sterols) is of great importance <i>in vivo</i> for metabolizing sterols and vitamin Ds. The biocatalytic hydroxylation of C25 C–H bonds is restricted by the selectivity and activity of the enzymes due to the inertness of these bulky compounds. Herein, we employed fungal unspecific peroxygenase from <i>Agrocybe aegerita</i> (<i>Aae</i>UPO) as the catalyst to develop efficient and selective <i>Aae</i>UPO variants through protein engineering. After three rounds of evolution using semirational design, 2 variants, G195A/G241V/G318V (Stev) and Q72K/G195A/G241V (Veco), were determined to be the ideal catalysts, showing a 25- to 27-fold increase in enzyme activity and an improvement in selectivity from 25% to over 93% in gram-scale conversion of vitamin D₃ to 25-hydroxyvitamin D₃. These two variants exhibited overall enhanced catalytic performance in hydroxylating the C25 C–H bonds of the other 24 sterol and vitamin D analogues. This work provides an enzymatic toolbox to synthesize the highly important vitamins and sterols into the compounds of interest under mild conditions with remarkable regioselectivity and enzyme activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"45 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989495","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":"Molecular Design of Perylene Diimide Derivatives for Photocatalysis","authors":"Zibin Li, Feng Liu, Yanrong Lu, Jiatong Hu, Jiajing Feng, Hong Shang, Bing Sun, Wei Jiang","doi":"10.1021/acscatal.4c07066","DOIUrl":"https://doi.org/10.1021/acscatal.4c07066","url":null,"abstract":"Perylene diimides (PDIs) and their derivatives represent a kind of most promising photocatalytic materials due to their strong visible light absorption, ease of functionalization, excellent thermal/photostability, as well as tunable electronic structures and energy levels. However, several challenges persist in the development of PDI photocatalysts, including low electron–hole separation efficiency, slow charge transfer, and rapid carrier recombination. In this perspective, we focus on enhancing the performance of PDI photocatalysts through a molecular design. We provide a comprehensive overview of various improvement strategies: (1) precise modulation of molecular dipole moments by altering the polarity of side chains to strengthen the built-in electric field, (2) utilization of steric hindrance and noncovalent interactions of side chains to construct nanoscale, highly ordered supramolecular nanostructures, (3) modification of the perylene core to adjust molecular energy levels and increase the number of active sites, (4) integration of PDI with various semiconductors or metals to form composite systems that enhance the interfacial built-in electric field or create extensive delocalized charge channels, and (5) selection of suitable linker groups to build polymer photocatalysts with large dipole moments. These strategies can facilitate the separation and migration of photogenerated carriers in PDI photocatalysts, eventually boosting their photocatalytic efficiency. The relationship between molecular structure and photocatalytic performance, particularly in the context of photocatalytic degradation and water splitting, is examined in detail. Finally, the future prospects and challenges of PDI photocatalysts are thoroughly discussed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"144 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988231","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":"Stable CO2 Hydrogenation to Methanol by Cu Interacting with Isolated Zn Cations in Zincosilicate CIT-6","authors":"Yu Gao, Yonghui Fan, Hao Zhang, Peerapol Pornsetmetakul, Brahim Mezari, Jorden Wagemakers, Mahesh Ramakrishnan, Konstantin Klementiev, Nikolay Kosinov, Emiel J. M. Hensen","doi":"10.1021/acscatal.4c07496","DOIUrl":"https://doi.org/10.1021/acscatal.4c07496","url":null,"abstract":"The catalytic conversion of carbon dioxide (CO₂) to methanol over Cu/ZnO catalysts is expected to become valuable for recycling CO₂. The nature of the Cu–Zn interplay remains a subject of intense debate due to many different Zn species encountered in Cu/ZnO catalysts. In this study, we designed a Cu–Zn catalyst by ion-exchanging Cu into CIT-6, a crystalline microporous zincosilicate with the BEA* topology. The catalyst exhibited high and stable CO₂ hydrogenation rate to methanol. In contrast, its aluminosilicate counterparts Cu-Beta and CuZn-Beta mainly converted CO₂ to CO. <i>Operando</i> X-ray absorption spectroscopy combined with X-ray diffraction confirmed the stability of Zn cations in the zincosilicate framework during reduction in H₂ and reaction in CO₂/H₂. The active phase consisted of highly dispersed Cu particles. These particles located near isolated Zn²⁺ species represent a different type of active site for methanol synthesis than the active phases proposed for Cu–Zn catalysts, such as Cu–Zn alloy particles and Cu particles decorated with ZnO_<i>x</i>. In situ IR spectroscopy showed the formation of Zn-formate species during CO₂ hydrogenation, indicating that Zn²⁺ ions stabilize formate as a reaction intermediate in the hydrogenation of CO₂ to methanol.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988232","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":"Optimizing the Electronic Structure of IrOx Sub-2 nm Clusters via Tunable Metal Support Interaction for Acidic Oxygen Evolution Reaction","authors":"Qiuyan Chu, Yanpu Niu, Haolan Tao, Honglai Liu, Quan Li, Cheng Lian, Jingkun Li","doi":"10.1021/acscatal.4c06411","DOIUrl":"https://doi.org/10.1021/acscatal.4c06411","url":null,"abstract":"Iridium-based electrocatalysts are the most promising candidates for the acidic oxygen evolution reaction (OER). Considering their high cost and scarcity, it is imperative to maximize atom utilization and enhance the intrinsic activity of iridium. In this work, IrO_<i>x</i> sub-2 nm clusters are stabilized on TiO₂ supports via metal support interaction (MSI) induced by vacancy defects in TiO₂. The strength of MSI is readily tuned by the type of vacancies: oxygen vacancies in TiO₂ (V_O-TiO₂) induce the adsorbed MSI with relatively weak strength, while titanium vacancies in TiO₂ (V_Ti-TiO₂) lead to the strong embedded MSI. The tunable MSI further modulates the electronic structure of IrO_<i>x</i> sub-2 nm clusters. IrO_<i>x</i>/V_O-TiO₂ with adsorbed MSI exhibits an optimized electronic structure with a downshifted d-band center of IrO_<i>x</i>, resulting in a reduced binding energy with oxygen and a low energy barrier of the rate-determining step for OER. Consequently, IrO_<i>x</i>/V_O-TiO₂ delivers an activity twice that of commercial IrO₂ and a good stability for 120 h in a practical proton exchange membrane water electrolyzer. Our study provides a guideline for the rational design of acidic OER catalysts based on modulating the electronic structure of IrO_<i>x</i> sub-2 nm clusters via tunable MSI.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989498","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":"Rational Design of β-MnO2 via Ir/Ru Co-substitution for Enhanced Oxygen Evolution Reaction in Acidic Media","authors":"Runxu Deng, Feng Liu, Shixin Gao, Zhenwei Xia, Runjie Wu, Jincheng Kong, Jin Yang, Jiahao Wen, Xiao Zhang, Chade Lv, Yuhao Wang, Xiaoguang Li, Zheng Wang","doi":"10.1021/acscatal.4c05989","DOIUrl":"https://doi.org/10.1021/acscatal.4c05989","url":null,"abstract":"The efficiency of the oxygen evolution reaction (OER) in acidic media is severely limited by the poor stability, low activity, and high cost of available catalysts. Enhancing intrinsic activity while maintaining stability and reducing reliance on precious metals is crucial. The typical adsorbate evolution mechanism (AEM) leads to high overpotentials and low activity, making the transition to alternative mechanisms, such as the lattice oxygen mechanism (LOM) or oxide path mechanism (OPM), highly desirable due to their lower overpotentials. Here, we combine density functional theory (DFT) calculations with experimental validation to enhance the activity and stability of β-MnO₂ via co-substitution with ruthenium (Ru) and iridium (Ir), enabling the transition from AEM to OPM. DFT calculations reveal that AEM is hindered by the weak nucleophilicity of water, while LOM suffers from high kinetic barriers due to structural distortions. In contrast, OPM demonstrates a significantly lower kinetic barrier, facilitated by the synergistic interaction between Ru and Ir. Experimentally, IrRuMnO_<i>x</i> was synthesized through co-precipitation and hydrothermal methods, showing an 80-fold improvement in mass activity and a 96-fold increase in stability compared to commercial IrO₂, with minimal noble metal leaching, as confirmed by inductively coupled plasma optical emission spectroscopy (ICP-OES). IrRuMnO_<i>x</i> exhibited an ultralow overpotential of 475 mV at 1 A·cm^–2 and a Tafel slope of 44.26 mV·dec^–1 in 0.5 M H₂SO₄, maintaining stable performance for over 100 h. Moreover, the IrRuMnO_<i>x</i>-based membrane electrode, with a low Ir loading of 0.075 mg_Ir·cm^–2, achieved remarkable current densities of 1.0 A·cm^–2 at 1.66 V and 2.0 A·cm^–2 at 1.91 V at 80 °C. This performance surpasses that of both unsupported and conventional supported Ir-based catalysts at comparable Ir loading levels. This study offers critical insights into OER mechanisms in acidic media and paves the way for developing efficient and durable OER electrocatalysts for hydrogen production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"116 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988229","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":"Simultaneous Engineering of the Thermostability and Activity of a Novel Aldehyde Dehydrogenase","authors":"Kangjie Xu, Qiming Chen, Haoran Fu, Qihang Chen, Jiahao Gu, Xinglong Wang, Jingwen Zhou","doi":"10.1021/acscatal.4c06840","DOIUrl":"https://doi.org/10.1021/acscatal.4c06840","url":null,"abstract":"Acetaldehyde is a toxic pollutant that can be detoxified by acetaldehyde dehydrogenases (ADAs) through its conversion to acetyl-CoA. This study developed an integrated approach combining virtual screening, rational design, and a dual scoring mechanism to identify and engineer hyperactive ADA variants. A library of 5000 <i>Dickeya parazeae</i> ADA (DpADA) homologues was created through protein BLAST, and deep learning tools predicted their <i>K</i>_cat values. The top 100 candidates were selected based on acetaldehyde binding affinity, evaluated through molecular docking and phylogenetic analysis. Among these, ADA6 from <i>Buttiauxella</i> sp. S04-F03 exhibited the highest activity, converting 57.6% of acetaldehyde to acetyl-CoA, which was 14.1 times higher than DpADA. To improve ADA6’s thermostability, folding engineering was applied, resulting in the P443C variant with an 80.7% increase in residual activity after heat treatment. Molecular dynamics simulation pinpointed I440 as a bottleneck in the substrate tunnel, guiding the design of a dual-scoring system that integrates structural adjustments and electronic optimization to evaluate mutations for improved substrate exposure and activity. The final optimized variant, P443C-I440T, achieved a conversion efficiency of 93.2%. This study demonstrates the effectiveness of combining computational tools and rational mutagenesis to enhance enzyme activity and stability in enzyme engineering.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989499","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}