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Directed Evolution of a Modular Polyketide Synthase Thioesterase for Generation of a Hybrid Macrocyclic Ring System
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-11 DOI: 10.1021/acscatal.4c07922
Maria L. Adrover-Castellano, Brian J. Curtis, Jennifer J. Schmidt, Hannah A. Boesger, Carolyn A. Glasser, Damilola E. Olukorede, Fengrui Qu, David H. Sherman
Modular type I polyketide synthases (PKSs) comprise a family of enzymes that synthesize a diverse class of natural products with medicinal applications. The biochemical features of these systems include the extension and processing of polyketide chains in a stepwise, stereospecific manner, organized by a series of modules divided into distinct catalytic domains. Previous work revealed that a primary hurdle for utilizing PKS modules to create diverse macrolactones hinges on the selectivity of the thioesterase (TE) domain. Herein, we generated hybrid 12-membered macrolactone/lactam ring systems employing unnatural amide-containing hexaketide intermediates in conjunction with an engineered TE S148C mutant from the pikromycin (Pik) biosynthetic pathway. Specifically, unnatural macrocycle (3) was initially formed in severely attenuated yields compared to the native product generated from the natural hexaketide substrate. A stepwise directed evolution campaign generated Pik TE variants with enhanced selectivity for macrocycle formation over hydrolysis. Over three rounds of evolution, a series of mutant Pik TE proteins were identified, and further combinations of beneficial mutations carried from each round produced a composite variant with 6-fold enhanced isolated yield of the hybrid macrocycle compared to the parent TE S148C mutant enzyme. This study offers insights into the range of amino acid residues, both proximal and distal to the active site, that impart improved selectivity and yield against the unnatural polyketide substrate and overcoming a key PKS pathway gatekeeper.
{"title":"Directed Evolution of a Modular Polyketide Synthase Thioesterase for Generation of a Hybrid Macrocyclic Ring System","authors":"Maria L. Adrover-Castellano, Brian J. Curtis, Jennifer J. Schmidt, Hannah A. Boesger, Carolyn A. Glasser, Damilola E. Olukorede, Fengrui Qu, David H. Sherman","doi":"10.1021/acscatal.4c07922","DOIUrl":"https://doi.org/10.1021/acscatal.4c07922","url":null,"abstract":"Modular type I polyketide synthases (PKSs) comprise a family of enzymes that synthesize a diverse class of natural products with medicinal applications. The biochemical features of these systems include the extension and processing of polyketide chains in a stepwise, stereospecific manner, organized by a series of modules divided into distinct catalytic domains. Previous work revealed that a primary hurdle for utilizing PKS modules to create diverse macrolactones hinges on the selectivity of the thioesterase (TE) domain. Herein, we generated hybrid 12-membered macrolactone/lactam ring systems employing unnatural amide-containing hexaketide intermediates in conjunction with an engineered TE S148C mutant from the pikromycin (Pik) biosynthetic pathway. Specifically, unnatural macrocycle (<b>3</b>) was initially formed in severely attenuated yields compared to the native product generated from the natural hexaketide substrate. A stepwise directed evolution campaign generated Pik TE variants with enhanced selectivity for macrocycle formation over hydrolysis. Over three rounds of evolution, a series of mutant Pik TE proteins were identified, and further combinations of beneficial mutations carried from each round produced a composite variant with 6-fold enhanced isolated yield of the hybrid macrocycle compared to the parent TE S148C mutant enzyme. This study offers insights into the range of amino acid residues, both proximal and distal to the active site, that impart improved selectivity and yield against the unnatural polyketide substrate and overcoming a key PKS pathway gatekeeper.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385451","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
Reply to Comment on “Assessment of the Reaction Location of Skeletal 1-Butene Isomerization over Ferrierite”
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.5c00776
Pawel A. Chmielniak, Karoline L. Hebisch, Urim Pearl Kim, Jeffrey C. Kenvin, Carsten Sievers
The solution presented by Deng et al. is true for the general case. Our work describes a specific subset, and we were therefore able to make a simplifying assumption.
{"title":"Reply to Comment on “Assessment of the Reaction Location of Skeletal 1-Butene Isomerization over Ferrierite”","authors":"Pawel A. Chmielniak, Karoline L. Hebisch, Urim Pearl Kim, Jeffrey C. Kenvin, Carsten Sievers","doi":"10.1021/acscatal.5c00776","DOIUrl":"https://doi.org/10.1021/acscatal.5c00776","url":null,"abstract":"The solution presented by Deng et al. is true for the general case. Our work describes a specific subset, and we were therefore able to make a simplifying assumption.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"162 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375289","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
Automated Engineering Protein Dynamics via Loop Grafting: Improving Renilla Luciferase Catalysis
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.4c06207
Joan Planas-Iglesias, Marika Majerova, Daniel Pluskal, Michal Vasina, Jiri Damborsky, Zbynek Prokop, Martin Marek, David Bednar
Engineering protein dynamics is a challenging and unsolved problem in protein design. Loop transplantation or loop grafting has been previously employed to transfer dynamic properties between proteins. We recently released a LoopGrafter Web server to execute the loop grafting task, employing eight computational tools and one database. The LoopGrafter method relies on the prediction of the local dynamic behavior of the elements to be transplanted and has successfully reconstructed previously engineered sequences. However, it was unclear whether catalytically competitive previously uncharacterized designs could be obtained by this method. Here, we address this question, showing how LoopGrafter generates viable loop-grafted chimeras of luciferases, how these chimeras encompass the activity of interest and unique kinetic properties, and how all this process is done fully automatically and agnostic of any previous knowledge. All constructed designs proved to be catalytically active, and the most active one improved the activity of the template enzyme by 4 orders of magnitude. The computational details and parameter optimization of the sequence pairing step of the LoopGrafter workflow are revealed. The optimized and experimentally validated loop grafting workflow available as a fully automated Web server represents a powerful approach for engineering catalytically efficient enzymes by modification of protein dynamics.
{"title":"Automated Engineering Protein Dynamics via Loop Grafting: Improving Renilla Luciferase Catalysis","authors":"Joan Planas-Iglesias, Marika Majerova, Daniel Pluskal, Michal Vasina, Jiri Damborsky, Zbynek Prokop, Martin Marek, David Bednar","doi":"10.1021/acscatal.4c06207","DOIUrl":"https://doi.org/10.1021/acscatal.4c06207","url":null,"abstract":"Engineering protein dynamics is a challenging and unsolved problem in protein design. Loop transplantation or loop grafting has been previously employed to transfer dynamic properties between proteins. We recently released a LoopGrafter Web server to execute the loop grafting task, employing eight computational tools and one database. The LoopGrafter method relies on the prediction of the local dynamic behavior of the elements to be transplanted and has successfully reconstructed previously engineered sequences. However, it was unclear whether catalytically competitive previously uncharacterized designs could be obtained by this method. Here, we address this question, showing how LoopGrafter generates viable loop-grafted chimeras of luciferases, how these chimeras encompass the activity of interest and unique kinetic properties, and how all this process is done fully automatically and agnostic of any previous knowledge. All constructed designs proved to be catalytically active, and the most active one improved the activity of the template enzyme by 4 orders of magnitude. The computational details and parameter optimization of the sequence pairing step of the LoopGrafter workflow are revealed. The optimized and experimentally validated loop grafting workflow available as a fully automated Web server represents a powerful approach for engineering catalytically efficient enzymes by modification of protein dynamics.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"36 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385453","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
In2Cu3O6 Nanocluster in Siliceous Zeolite for Efficient CO2 Methanation
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.4c07480
Yanbin Zhu, Xiaoju Yang, Yan Wei, Peize Li, Shujie Liu, Muqin Wang, Xuan Yang, Yongqing Fu, Yan Shen, Mingkui Wang
This work reports CO2 methanation with high Faraday efficiency and production selectivity on In2Cu3O6 nanoclusters encapsulated in siliceous MFI zeolite (In2Cu3O6@zeolite) by modulating the pH and buffering capacity of electrolytes. Using an aqueous electrolyte of KHCO3 and K2CO3 saturated with CO2, the In2Cu3O6@zeolite electrode achieves a superior electrocatalytic Faraday efficiency of 74.1% for CO2 methanation and a retention rate of ∼90% after a 40 h long stability test. This represents one of the highest Faraday efficiency values for CO2 methanation. In situ spectroscopic characterization of intermediates shows that the high selectivity for methanation in aqueous electrolytes is due to the enriched protonation and associated pH buffering effect enabled by the encapsulation of In2Cu3O6 nanoclusters in MFI zeolite channels. When such an In2Cu3O6@zeolite catalyst is used as the cathode of an aprotic Li-CO2 battery, a high full-discharge capacity of 28,992 mAh g–1 at 100 mA g–1 and excellent cycling performance over 200 cycles at 400 mA g–1 can be achieved.
{"title":"In2Cu3O6 Nanocluster in Siliceous Zeolite for Efficient CO2 Methanation","authors":"Yanbin Zhu, Xiaoju Yang, Yan Wei, Peize Li, Shujie Liu, Muqin Wang, Xuan Yang, Yongqing Fu, Yan Shen, Mingkui Wang","doi":"10.1021/acscatal.4c07480","DOIUrl":"https://doi.org/10.1021/acscatal.4c07480","url":null,"abstract":"This work reports CO<sub>2</sub> methanation with high Faraday efficiency and production selectivity on In<sub>2</sub>Cu<sub>3</sub>O<sub>6</sub> nanoclusters encapsulated in siliceous MFI zeolite (In<sub>2</sub>Cu<sub>3</sub>O<sub>6</sub>@zeolite) by modulating the pH and buffering capacity of electrolytes. Using an aqueous electrolyte of KHCO<sub>3</sub> and K<sub>2</sub>CO<sub>3</sub> saturated with CO<sub>2</sub>, the In<sub>2</sub>Cu<sub>3</sub>O<sub>6</sub>@zeolite electrode achieves a superior electrocatalytic Faraday efficiency of 74.1% for CO<sub>2</sub> methanation and a retention rate of ∼90% after a 40 h long stability test. This represents one of the highest Faraday efficiency values for CO<sub>2</sub> methanation. In situ spectroscopic characterization of intermediates shows that the high selectivity for methanation in aqueous electrolytes is due to the enriched protonation and associated pH buffering effect enabled by the encapsulation of In<sub>2</sub>Cu<sub>3</sub>O<sub>6</sub> nanoclusters in MFI zeolite channels. When such an In<sub>2</sub>Cu<sub>3</sub>O<sub>6</sub>@zeolite catalyst is used as the cathode of an aprotic Li-CO<sub>2</sub> battery, a high full-discharge capacity of 28,992 mAh g<sup>–1</sup> at 100 mA g<sup>–1</sup> and excellent cycling performance over 200 cycles at 400 mA g<sup>–1</sup> can be achieved.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"79 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375288","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
Comment on “Assessment of the Reaction Location of Skeletal 1-Butene Isomerization over Ferrierite”
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.4c05581
Baoqing Deng, Zhengzhuang Wei, Zhigang Zhang
The present publication comments on an error in the formula computing the diffusion coefficient in a recent publication by Chmielniak et al.
{"title":"Comment on “Assessment of the Reaction Location of Skeletal 1-Butene Isomerization over Ferrierite”","authors":"Baoqing Deng, Zhengzhuang Wei, Zhigang Zhang","doi":"10.1021/acscatal.4c05581","DOIUrl":"https://doi.org/10.1021/acscatal.4c05581","url":null,"abstract":"The present publication comments on an error in the formula computing the diffusion coefficient in a recent publication by Chmielniak et al.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"245 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375290","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
Correction to “Assessment of the Reaction Location of Skeletal 1-Butene Isomerization over Ferrierite”
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.5c00777
Pawel A. Chmielniak, Karoline L. Hebisch, Urim Pearl Kim, Jeffrey C. Kenvin, Carsten Sievers
This article has not yet been cited by other publications.
{"title":"Correction to “Assessment of the Reaction Location of Skeletal 1-Butene Isomerization over Ferrierite”","authors":"Pawel A. Chmielniak, Karoline L. Hebisch, Urim Pearl Kim, Jeffrey C. Kenvin, Carsten Sievers","doi":"10.1021/acscatal.5c00777","DOIUrl":"https://doi.org/10.1021/acscatal.5c00777","url":null,"abstract":"This article has not yet been cited by other publications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"170 14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385454","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
Mechanistic Insights into the NH3 Oxidation Rate and Selectivity Hysteresis on Pt/Al2O3 Catalysts
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.4c05560
Brandon K. Bolton, Amish Chovatiya, Christopher K. Russell, Rohil Daya, Dylan S. Trandal, Lai Wei, Gunugunuri K. Reddy, Krishna Kamasamudram, Jeffrey T. Miller, William F. Schneider, Rajamani Gounder
Steady-state and transient kinetic measurements are combined with a suite of characterization techniques and a microkinetic model to provide insights into the mechanistic details of NH3 oxidation on Pt/Al2O3 samples of different Pt particle sizes and pretreatment history. Larger Pt particles show NH3 oxidation rates (per Pt) that are higher than those of smaller Pt particles. In situ X-ray absorption spectra reveal that smaller Pt particles are more susceptible to bulk oxidation state changes than large Pt particles, in part leading to an influence of the Pt particle size on the observed reactivity. A microkinetic model was developed that describes the dependence of product selectivity on ammonia conversion and rationalizes the different selectivity observed with respect to the catalyst particle size and condition history. Regardless of the Pt particle size, all samples show a temperature-dependent (450−550 K) hysteresis in reaction rates and product selectivities, with higher rates and N2O selectivity observed when the reaction temperature was previously at a higher temperature rather than a lower temperature. Differential kinetic and characterization data measured under conditions corresponding to the upper and lower branches of the rate hysteresis on Pt/Al2O3 suggest sample-history-dependent changes in the surface structure and active site characteristics, beyond those expected solely from changes to particle dispersion and the number of surface active sites.
{"title":"Mechanistic Insights into the NH3 Oxidation Rate and Selectivity Hysteresis on Pt/Al2O3 Catalysts","authors":"Brandon K. Bolton, Amish Chovatiya, Christopher K. Russell, Rohil Daya, Dylan S. Trandal, Lai Wei, Gunugunuri K. Reddy, Krishna Kamasamudram, Jeffrey T. Miller, William F. Schneider, Rajamani Gounder","doi":"10.1021/acscatal.4c05560","DOIUrl":"https://doi.org/10.1021/acscatal.4c05560","url":null,"abstract":"Steady-state and transient kinetic measurements are combined with a suite of characterization techniques and a microkinetic model to provide insights into the mechanistic details of NH<sub>3</sub> oxidation on Pt/Al<sub>2</sub>O<sub>3</sub> samples of different Pt particle sizes and pretreatment history. Larger Pt particles show NH<sub>3</sub> oxidation rates (per Pt) that are higher than those of smaller Pt particles. In situ X-ray absorption spectra reveal that smaller Pt particles are more susceptible to bulk oxidation state changes than large Pt particles, in part leading to an influence of the Pt particle size on the observed reactivity. A microkinetic model was developed that describes the dependence of product selectivity on ammonia conversion and rationalizes the different selectivity observed with respect to the catalyst particle size and condition history. Regardless of the Pt particle size, all samples show a temperature-dependent (450−550 K) hysteresis in reaction rates and product selectivities, with higher rates and N<sub>2</sub>O selectivity observed when the reaction temperature was previously at a higher temperature rather than a lower temperature. Differential kinetic and characterization data measured under conditions corresponding to the upper and lower branches of the rate hysteresis on Pt/Al<sub>2</sub>O<sub>3</sub> suggest sample-history-dependent changes in the surface structure and active site characteristics, beyond those expected solely from changes to particle dispersion and the number of surface active sites.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"62 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375287","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
Frank Partial Dislocation Pinning Effect Engineered IrNi Alloy Nanoparticles for Water Splitting
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.4c06833
Yunjie Liu, Yongbin Xu, Yu Tian, Shan Guo, Huifang Li, Xinyi Yuan, Zhijun Zhao, Binchao Xu, Xiaojun Wang, Peng Wang, Zhiming Liu
Dislocation defects in alloy catalysts are appealing for enhancing the electrocatalytic kinetics of water splitting. However, developing high-efficiency bifunctional catalysts with stable dislocations remains a great challenge. Herein, we report a dislocation formation combined with a solid-solution strengthening strategy to achieve a Frank partial dislocation-strained IrNi alloy confined in an N-doped carbon matrix. Abundant dislocation defects can be first formed in ultrasmall IrNi nanoparticles due to nonequilibrium ultrafast thermal shock. Then, during the following high-temperature annealing, the atomic radius difference-induced solution strengthening mechanism further contributes to pinning and stabilizing the thus-formed dislocations. The experimental and theoretical analyses show that the thermodynamically strengthened dislocations induce an abundant compressive strain field into IrNi nanoparticles. This plays a crucial role in optimizing the electronic structure and tailoring the adsorption properties toward the reaction intermediates of metal centers, thus distinctly enhancing the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic activity of IrNi/N–C. Impressively, the catalyst harvests both good acidic (1.46 V@10 mA cm–2) and alkaline (1.53 V@10 mA cm–2) overall water splitting activity with superior stability, much exceeding the state-of-the-art Pt/C||RuO2 catalyst. We anticipate that the proposed dislocation formation–strengthening strategy provides an understanding of constructing high-performance catalysts.
{"title":"Frank Partial Dislocation Pinning Effect Engineered IrNi Alloy Nanoparticles for Water Splitting","authors":"Yunjie Liu, Yongbin Xu, Yu Tian, Shan Guo, Huifang Li, Xinyi Yuan, Zhijun Zhao, Binchao Xu, Xiaojun Wang, Peng Wang, Zhiming Liu","doi":"10.1021/acscatal.4c06833","DOIUrl":"https://doi.org/10.1021/acscatal.4c06833","url":null,"abstract":"Dislocation defects in alloy catalysts are appealing for enhancing the electrocatalytic kinetics of water splitting. However, developing high-efficiency bifunctional catalysts with stable dislocations remains a great challenge. Herein, we report a dislocation formation combined with a solid-solution strengthening strategy to achieve a Frank partial dislocation-strained IrNi alloy confined in an N-doped carbon matrix. Abundant dislocation defects can be first formed in ultrasmall IrNi nanoparticles due to nonequilibrium ultrafast thermal shock. Then, during the following high-temperature annealing, the atomic radius difference-induced solution strengthening mechanism further contributes to pinning and stabilizing the thus-formed dislocations. The experimental and theoretical analyses show that the thermodynamically strengthened dislocations induce an abundant compressive strain field into IrNi nanoparticles. This plays a crucial role in optimizing the electronic structure and tailoring the adsorption properties toward the reaction intermediates of metal centers, thus distinctly enhancing the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic activity of IrNi/N–C. Impressively, the catalyst harvests both good acidic (1.46 V@10 mA cm<sup>–2</sup>) and alkaline (1.53 V@10 mA cm<sup>–2</sup>) overall water splitting activity with superior stability, much exceeding the state-of-the-art Pt/C||RuO<sub>2</sub> catalyst. We anticipate that the proposed dislocation formation–strengthening strategy provides an understanding of constructing high-performance catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"86 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385457","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
Accessing Arenes via the Hydrodeoxygenation of Phenolic Derivatives Enabled by Hydrazine
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-10 DOI: 10.1021/acscatal.4c06061
Benedetta Di Erasmo, Inna Perepichka, Hui Su, Luigi Vaccaro, Chao-Jun Li
Hydrodeoxygenation (HDO) is an effective method for converting lignin and its derived phenolic compounds to value-added aromatic chemicals and fuels. Efforts to exploit molecular hydrogen have been made to remove the hydroxyl group in lignin-derived phenolic compounds to make them appealing for the chemical industry. However, these processes rely on high pressure and expensive catalysts, presenting challenges in terms of safety, hydrogen storage, and cost-effectiveness. This highlights the demand for alternatives under more accessible reaction conditions. Herein, we present a methodology for the HDO of phenols and naphthols using Pd/C as a commercial heterogeneous catalyst employing hydrazine as a dual reagent for reducing and hydrazone formation. This paper presents an applicable substrate scope for the HDO of different naphthols and phenols including pharmaceutically relevant molecules such as paracetamol. Additionally, highly challenging steroid derivatives, such as β-estradiol, have been hydrodeoxygenated.
{"title":"Accessing Arenes via the Hydrodeoxygenation of Phenolic Derivatives Enabled by Hydrazine","authors":"Benedetta Di Erasmo, Inna Perepichka, Hui Su, Luigi Vaccaro, Chao-Jun Li","doi":"10.1021/acscatal.4c06061","DOIUrl":"https://doi.org/10.1021/acscatal.4c06061","url":null,"abstract":"Hydrodeoxygenation (HDO) is an effective method for converting lignin and its derived phenolic compounds to value-added aromatic chemicals and fuels. Efforts to exploit molecular hydrogen have been made to remove the hydroxyl group in lignin-derived phenolic compounds to make them appealing for the chemical industry. However, these processes rely on high pressure and expensive catalysts, presenting challenges in terms of safety, hydrogen storage, and cost-effectiveness. This highlights the demand for alternatives under more accessible reaction conditions. Herein, we present a methodology for the HDO of phenols and naphthols using Pd/C as a commercial heterogeneous catalyst employing hydrazine as a dual reagent for reducing and hydrazone formation. This paper presents an applicable substrate scope for the HDO of different naphthols and phenols including pharmaceutically relevant molecules such as paracetamol. Additionally, highly challenging steroid derivatives, such as β-estradiol, have been hydrodeoxygenated.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385452","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 Multiple Roles of Bipyridine-Nickel(II) Complex in Versatile Photoredox C(sp2)–C(sp3) Cross-Coupling
IF 12.9 1区 化学 Q1 CHEMISTRY, PHYSICAL Pub Date : 2025-02-09 DOI: 10.1021/acscatal.4c07605
Jingsheng Li, Tengfei Kang, Yi Xiao, Zhenyu Li, Yulin Xiao, Yonggang Yan, Geyang Song, Gang Li, Jianyang Dong, Chao Wang, Dong Xue
The cross-coupling reaction of low-reactivity aryl halides has been proven challenging. Herein, an efficient photochemical C(sp2)–C(sp3) cross-coupling reaction of (hetero)aryl halides and a range of C(sp3) radical precursors (organotrifluoroborates, 1,4-dihydropyridines (DHPs), redox-active esters (RA esters), Katritzky salts, hydrocarbons, and cyclic ethers) catalyzed by inexpensive and readily available Ni(II) complexes was reported, under UV light (365–370 nm) irradiation without any exogenous photosensitizer. The reaction demonstrated a broad substrate scope (>100 examples), good functional group tolerance, and the capability to scale up the reaction by 25 times, facilitating the modification and synthesis of drug molecules. Mechanistic studies and control experiments revealed that the nickel catalyst played irreplaceable multiple roles: activating the C(sp3) radical precursors and aryl halides and supporting the proposed reaction mechanism, where the bipyridine-nickel complex induces the formation of C(sp3) radicals, followed by single-electron transmetalation and subsequent reductive elimination to give the final products.
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ACS Catalysis
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