Pub Date : 2024-10-22DOI: 10.1021/acscatal.4c05732
Maham Liaqat, Emma McDonald, Robert Jervine Valdez Ortega, Aaron Lopes, Flavia Codreanu, Hannah Carlisle, Challa V. Kumar, Xudong Yao, James F. Rusling, Jie He
We herein report a design of artificial enzymes by incorporating a synthetic copper complex into noncatalytic bovine serum albumin (Cu-BSA) to carry out stereoselective oxidation. This Cu-BSA catalyst with stably bound Cu complex as a cofactor shows peroxidase-like activity to catalyze epoxidation of styrene with high chiral selectivity (>99%) to R-styrene epoxide. With the electrochemical conversion of Cu2+ to Cu+, Cu-BSA also exhibits oxidase-like activity to selectively reduce oxygen to hydrogen peroxide (H2O2), which can be combined with its peroxidase function to drive oxidation of C═C bonds using air. This artificial enzymatic system holds promise for chiral-selective transformations of non-natural substances and highlights the versatility of noncatalytic proteins in the design of artificial enzymes.
{"title":"Cu-Albumin Artificial Enzymes with Peroxidase and Oxidase Activity for Stereoselective Oxidations","authors":"Maham Liaqat, Emma McDonald, Robert Jervine Valdez Ortega, Aaron Lopes, Flavia Codreanu, Hannah Carlisle, Challa V. Kumar, Xudong Yao, James F. Rusling, Jie He","doi":"10.1021/acscatal.4c05732","DOIUrl":"https://doi.org/10.1021/acscatal.4c05732","url":null,"abstract":"We herein report a design of artificial enzymes by incorporating a synthetic copper complex into noncatalytic bovine serum albumin (Cu-BSA) to carry out stereoselective oxidation. This Cu-BSA catalyst with stably bound Cu complex as a cofactor shows peroxidase-like activity to catalyze epoxidation of styrene with high chiral selectivity (>99%) to R-styrene epoxide. With the electrochemical conversion of Cu<sup>2+</sup> to Cu<sup>+</sup>, Cu-BSA also exhibits oxidase-like activity to selectively reduce oxygen to hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>), which can be combined with its peroxidase function to drive oxidation of C═C bonds using air. This artificial enzymatic system holds promise for chiral-selective transformations of non-natural substances and highlights the versatility of noncatalytic proteins in the design of artificial enzymes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486827","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}
Pub Date : 2024-10-22DOI: 10.1021/acscatal.4c04454
Jun Ke, Jiaxi Zhang, Longhai Zhang, Shunyi He, Chengzhi Zhong, Li Du, Huiyu Song, Xiaoming Fang, Zhengguo Zhang, Zhiming Cui
The incorporation of high-valence metals into FeNi-based oxides has been widely accepted as an efficient approach for facilitating the alkaline oxygen evolution reaction (OER), but the corresponding structure–property relationship remains unclear due to the lack of identification of the real structure. In this study, we reveal the surface evolution processes of M-doped FeNi oxides (M is Mo, V, and W) and elucidate the role of M dissolution in enhancing oxygen evolution kinetics. Taking Mo as an example, the high-valence metal Mo was doped into FeNiOx and its leaching behavior was observed during OER. By combining in situ Raman analysis, electrochemical measurement, and first-principles calculation, it was unveiled that the electro-dissolution of Mo, in the form of MoO42–, led to preferential removal of lattice oxygen, thereby facilitating the adsorption step of OH and triggering the lattice oxygen-mediated mechanism for promoting OER. Consequently, the optimized FeNiMoOx displayed an overpotential of only 235 mV to reach 10 mA/cm2 and a 30-fold enhancement in specific activity compared with that of FeNiOx at 1.53 V. Our findings provide a different perspective on the intricate association between dissolution of high-valence metal and alkaline OER performance, elucidating the key role of the dissolution-induced structure change on promoting the OER mechanism.
{"title":"Role of High-Valence Metal Dissolution in Oxygen Evolution Kinetics of the Advanced FeNiOx Catalysts","authors":"Jun Ke, Jiaxi Zhang, Longhai Zhang, Shunyi He, Chengzhi Zhong, Li Du, Huiyu Song, Xiaoming Fang, Zhengguo Zhang, Zhiming Cui","doi":"10.1021/acscatal.4c04454","DOIUrl":"https://doi.org/10.1021/acscatal.4c04454","url":null,"abstract":"The incorporation of high-valence metals into FeNi-based oxides has been widely accepted as an efficient approach for facilitating the alkaline oxygen evolution reaction (OER), but the corresponding structure–property relationship remains unclear due to the lack of identification of the real structure. In this study, we reveal the surface evolution processes of M-doped FeNi oxides (M is Mo, V, and W) and elucidate the role of M dissolution in enhancing oxygen evolution kinetics. Taking Mo as an example, the high-valence metal Mo was doped into FeNiO<sub><i>x</i></sub> and its leaching behavior was observed during OER. By combining in situ Raman analysis, electrochemical measurement, and first-principles calculation, it was unveiled that the electro-dissolution of Mo, in the form of MoO<sub>4</sub><sup>2–</sup>, led to preferential removal of lattice oxygen, thereby facilitating the adsorption step of OH and triggering the lattice oxygen-mediated mechanism for promoting OER. Consequently, the optimized FeNiMoO<sub><i>x</i></sub> displayed an overpotential of only 235 mV to reach 10 mA/cm<sup>2</sup> and a 30-fold enhancement in specific activity compared with that of FeNiO<sub><i>x</i></sub> at 1.53 V. Our findings provide a different perspective on the intricate association between dissolution of high-valence metal and alkaline OER performance, elucidating the key role of the dissolution-induced structure change on promoting the OER mechanism.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486830","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}
Metal halide perovskite nanocrystals (PNCs) have demonstrated remarkable photocatalytic properties in diverse photochemical reactions owing to their high absorption coefficients and long photogenerated carrier lifetimes. However, their catalytic applications have been severely hindered by their structural incompatibility with polar solvents, water in particular, due to the labile ionic nature of the perovskite. Realization of the photocatalytic performance of PNCs in an aqueous medium would significantly expand their potential in photocatalysis. Herein, judiciously designed CsPbBr3 NCs stabilized on Al2O3 nanoflowers (denoted as A-CsPbBr3 NCs) are utilized as water-stable photocatalysts for aqueous photomediated reversible addition–fragmentation chain transfer (photo-RAFT) polymerization. The A-CsPbBr3 NCs exhibited exceptional water stability and photostability owing to the stabilization effect endowed by Al2O3 nanoflowers without sacrificing their charge/carrier transport properties. Consequently, aqueous photo-RAFT polymerization was successfully performed by leveraging A-CsPbBr3 NCs as photocatalysts under visible light illumination, which was inaccessible to conventional short-ligand-capped PNCs. The effects of the excitation wavelength, catalyst loading, and architectures of PNCs on the visible-light-mediated polymerization were scrutinized to reveal the polymerization via a photoinduced electron-/energy-transfer mechanism, yielding polymers/copolymers with well-defined compositions, well-controlled molecular weights, low polydispersity, and high chain-end fidelity.
{"title":"Water-Stable Perovskite Nanocrystals to Overcome the Photocatalysis–Stability Trade-Off in Aqueous Photo-RAFT Polymerization","authors":"Mengqiang Zhang, Jingyi Hao, Chengli Wang, Yue Zhang, Xiaomeng Zhang, Zhe Cui, Peng Fu, Minying Liu, Ge Shi, Xiaoguang Qiao, Yajing Chang, Yanjie He, Xinchang Pang","doi":"10.1021/acscatal.4c03407","DOIUrl":"https://doi.org/10.1021/acscatal.4c03407","url":null,"abstract":"Metal halide perovskite nanocrystals (PNCs) have demonstrated remarkable photocatalytic properties in diverse photochemical reactions owing to their high absorption coefficients and long photogenerated carrier lifetimes. However, their catalytic applications have been severely hindered by their structural incompatibility with polar solvents, water in particular, due to the labile ionic nature of the perovskite. Realization of the photocatalytic performance of PNCs in an aqueous medium would significantly expand their potential in photocatalysis. Herein, judiciously designed CsPbBr<sub>3</sub> NCs stabilized on Al<sub>2</sub>O<sub>3</sub> nanoflowers (denoted as A-CsPbBr<sub>3</sub> NCs) are utilized as water-stable photocatalysts for aqueous photomediated reversible addition–fragmentation chain transfer (photo-RAFT) polymerization. The A-CsPbBr<sub>3</sub> NCs exhibited exceptional water stability and photostability owing to the stabilization effect endowed by Al<sub>2</sub>O<sub>3</sub> nanoflowers without sacrificing their charge/carrier transport properties. Consequently, aqueous photo-RAFT polymerization was successfully performed by leveraging A-CsPbBr<sub>3</sub> NCs as photocatalysts under visible light illumination, which was inaccessible to conventional short-ligand-capped PNCs. The effects of the excitation wavelength, catalyst loading, and architectures of PNCs on the visible-light-mediated polymerization were scrutinized to reveal the polymerization via a photoinduced electron-/energy-transfer mechanism, yielding polymers/copolymers with well-defined compositions, well-controlled molecular weights, low polydispersity, and high chain-end fidelity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486557","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}
Combining abiotic photocatalytic modules with enzymatic conversion to reform biomass represents a compelling way for sustainable energy schemes but faces marked challenges on the electron and proton transport corresponding to the cofactor regeneration and shuttling between biotic and abiotic partners. Herein, we report a consecutive photoinduced electron-transfer approach to reform biomass into fuels and active H-source for nitroarene reduction by grafting a cage-dye-NADH (nicotinamide adenine dinucleotide) clathrate with glucose dehydrogenase (GDH). Under light irradiation, the cage-dye-NADH clathrate acts as a photoactive relay to conduct two photoinduced 1e– electron-transfer reactions consecutively with a 2e– oxidation of NADH to NAD+, guaranteeing an orderly path related to cofactor regeneration. When the clathrate is positioned inside the pocket of GDH to join a biotic NAD+-mediated synthesis, the metal–organic artificial enzyme facilitates fast cofactor generation and shuttling between the artificial clathrate and the native enzyme within one working module. The grafting enzyme combines artificial photocatalysis and enzymatic dehydrogenation to endow an efficient conversion of biomass feedstocks into green H-source, innovating a unique paradigm for the sustainable energy scheme that combines energy of two photons in one turnover cycle. The superiority of the grafting enzyme allows the direct hydrogenation and reduction of fine chemicals and enables tandem nitroarene reduction with a turnover number reaching 15,000, providing a distinguished avenue for biomass utilization and solar energy conversion.
{"title":"Merging Consecutive PET Processes within a Metal–Organic Cage for Abiotic–Biotic Combined Photocatalytic Biomass Reforming","authors":"Zhefan Li, Junkai Cai, Lingxiao Wang, Chunying Duan","doi":"10.1021/acscatal.4c06018","DOIUrl":"https://doi.org/10.1021/acscatal.4c06018","url":null,"abstract":"Combining abiotic photocatalytic modules with enzymatic conversion to reform biomass represents a compelling way for sustainable energy schemes but faces marked challenges on the electron and proton transport corresponding to the cofactor regeneration and shuttling between biotic and abiotic partners. Herein, we report a consecutive photoinduced electron-transfer approach to reform biomass into fuels and active H-source for nitroarene reduction by grafting a cage-dye-NADH (nicotinamide adenine dinucleotide) clathrate with glucose dehydrogenase (GDH). Under light irradiation, the cage-dye-NADH clathrate acts as a photoactive relay to conduct two photoinduced 1e<sup>–</sup> electron-transfer reactions consecutively with a 2e<sup>–</sup> oxidation of NADH to NAD<sup>+</sup>, guaranteeing an orderly path related to cofactor regeneration. When the clathrate is positioned inside the pocket of GDH to join a biotic NAD<sup>+</sup>-mediated synthesis, the metal–organic artificial enzyme facilitates fast cofactor generation and shuttling between the artificial clathrate and the native enzyme within one working module. The grafting enzyme combines artificial photocatalysis and enzymatic dehydrogenation to endow an efficient conversion of biomass feedstocks into green H-source, innovating a unique paradigm for the sustainable energy scheme that combines energy of two photons in one turnover cycle. The superiority of the grafting enzyme allows the direct hydrogenation and reduction of fine chemicals and enables tandem nitroarene reduction with a turnover number reaching 15,000, providing a distinguished avenue for biomass utilization and solar energy conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486828","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}
Pub Date : 2024-10-22DOI: 10.1021/acscatal.4c06044
Samir Chattopadhyay, Mun Hon Cheah, Reiner Lomoth, Leif Hammarström
Rhenium bipyridine tricarbonyl complexes, fac-[Re(bpy)(CO)3X]n+, are highly effective in selectively converting CO2 to CO under electrochemical and photochemical conditions. Despite numerous mechanistic studies aimed at understanding its CO2 reduction reaction (CO2RR) pathway, the intermediates further into the catalytic cycle have escaped detection, and the steps leading to product release remained elusive. In this study, employing stopped-flow mixing coupled with time-resolved infrared spectroscopy, we observed, for the first time, the reduced Re-tetracarbonyl species, [Re(bpy)(CO)4]0, with a half-life of approximately 55 ms in acetonitrile solvent. This intermediate is proposed to be common in both electrochemical and photochemical CO2RR. Furthermore, we directly observed the release of the product (CO) from this intermediate. Additionally, we detected the accumulation of [Re(bpy)(CO)3(CH3CN)]+ as a byproduct following product release, a significant side reaction under conditions with a limited supply of reducing equivalents mirroring photochemical conditions. The process could be unambiguously attributed to an electron transfer-catalyzed ligand substitution reaction involving [Re(bpy)(CO)4]0 by simultaneous real-time detection of all involved species. We believe that this side reaction significantly impacts the CO2RR efficiency of this class of catalysts under photochemical conditions or during electrocatalysis at mild overpotentials.
{"title":"Direct Detection of Key Intermediates during the Product Release in Rhenium Bipyridine-Catalyzed CO2 Reduction Reaction","authors":"Samir Chattopadhyay, Mun Hon Cheah, Reiner Lomoth, Leif Hammarström","doi":"10.1021/acscatal.4c06044","DOIUrl":"https://doi.org/10.1021/acscatal.4c06044","url":null,"abstract":"Rhenium bipyridine tricarbonyl complexes, <i>fac</i>-[Re(bpy)(CO)<sub>3</sub>X]<sup><i>n</i>+</sup>, are highly effective in selectively converting CO<sub>2</sub> to CO under electrochemical and photochemical conditions. Despite numerous mechanistic studies aimed at understanding its CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) pathway, the intermediates further into the catalytic cycle have escaped detection, and the steps leading to product release remained elusive. In this study, employing stopped-flow mixing coupled with time-resolved infrared spectroscopy, we observed, for the first time, the reduced Re-tetracarbonyl species, [Re(bpy)(CO)<sub>4</sub>]<sup>0</sup>, with a half-life of approximately 55 ms in acetonitrile solvent. This intermediate is proposed to be common in both electrochemical and photochemical CO<sub>2</sub>RR. Furthermore, we directly observed the release of the product (CO) from this intermediate. Additionally, we detected the accumulation of [Re(bpy)(CO)<sub>3</sub>(CH<sub>3</sub>CN)]<sup>+</sup> as a byproduct following product release, a significant side reaction under conditions with a limited supply of reducing equivalents mirroring photochemical conditions. The process could be unambiguously attributed to an electron transfer-catalyzed ligand substitution reaction involving [Re(bpy)(CO)<sub>4</sub>]<sup>0</sup> by simultaneous real-time detection of all involved species. We believe that this side reaction significantly impacts the CO<sub>2</sub>RR efficiency of this class of catalysts under photochemical conditions or during electrocatalysis at mild overpotentials.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486573","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}
Constructing compact direct Z- and S-scheme heterostructures is an efficient strategy for realizing a highly efficient charge separation and photocatalytic performance. However, the stochastic nature of interface orientation and lattice mismatch often results in a blind region for effective inner charge transfer, which hinders the logical design of compact heterojunctions. Here, experimental results and theoretical research unveiled that complicated internal charges can be directly transferred to an intermediate cocrystal plane for electron–hole recombination in compact S-scheme heterostructures, called “bone-joint” heterostructures, which facilitate the establishment of an inherent electric field to drive charge transfer. Moreover, those bone-joint structures adjust the inherent chemical and energetic interactions that manipulate the reactant adsorption mode and surface reaction energy. As a result, a synthesized catalyst displayed a remarkable hydrogen peroxide production performance and stability. This offers a paradigm for intrinsic charge transfer dynamics in heterostructures and a guiding philosophy for designing efficient heterostructures.
构建紧凑的直接 Z 型和 S 型异质结构是实现高效电荷分离和光催化性能的有效策略。然而，界面取向和晶格失配的随机性往往会导致有效内部电荷转移的盲区，从而阻碍了紧凑型异质结的合理设计。在此，实验结果和理论研究揭示了在紧凑型 S 型异质结构（称为 "骨连接 "异质结构）中，复杂的内部电荷可直接转移到中间共晶平面上进行电子-空穴重组，这有利于建立内在电场来驱动电荷转移。此外，这些骨连接结构还能调整固有的化学和能量相互作用，从而操纵反应物的吸附模式和表面反应能。因此，合成的催化剂显示出卓越的过氧化氢生产性能和稳定性。这为异质结构中的内在电荷转移动力学提供了一个范例，也为设计高效异质结构提供了一个指导思想。
{"title":"Unveiling Intrinsic Charge Transfer Dynamics in Bone-Joint S-Scheme Heterostructures To Promote Photocatalytic Hydrogen Peroxide Generation","authors":"Yuhui Liu, Xiaoxu Deng, Yi Wang, Qin Luo, Yunxia Liu, Shuang-Feng Yin, Peng Chen","doi":"10.1021/acscatal.4c05031","DOIUrl":"https://doi.org/10.1021/acscatal.4c05031","url":null,"abstract":"Constructing compact direct Z- and S-scheme heterostructures is an efficient strategy for realizing a highly efficient charge separation and photocatalytic performance. However, the stochastic nature of interface orientation and lattice mismatch often results in a blind region for effective inner charge transfer, which hinders the logical design of compact heterojunctions. Here, experimental results and theoretical research unveiled that complicated internal charges can be directly transferred to an intermediate cocrystal plane for electron–hole recombination in compact S-scheme heterostructures, called “bone-joint” heterostructures, which facilitate the establishment of an inherent electric field to drive charge transfer. Moreover, those bone-joint structures adjust the inherent chemical and energetic interactions that manipulate the reactant adsorption mode and surface reaction energy. As a result, a synthesized catalyst displayed a remarkable hydrogen peroxide production performance and stability. This offers a paradigm for intrinsic charge transfer dynamics in heterostructures and a guiding philosophy for designing efficient heterostructures.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451888","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}
Ligand engineering is one of the most important, but labor-intensive processes in the development of transition metal catalysis. Historically, this process has been guided by ligand descriptors such as Tolman’s electronic parameter and the cone angle. Analyzing reaction outcomes in terms of these parameters has enabled chemists to identify the most important properties for controlling catalytic pathways and thus designing better ligands. However, typical strategies for these analyses rely on regression approaches, which often require extensive experimental studies to identify trends across chemical space and understand outliers. Here, we introduce the virtual ligand-assisted optimization (VLAO) method, a computational approach for reactivity-directed ligand engineering. In this method, important features of ligands are identified by simple mathematical operations on equilibrium structures and/or transition states of interest, and derivative values of arbitrary objective functions with respect to ligand parameters are obtained. These derivative values are then used as a guiding principle to optimize ligands within the parameter space. The VLAO method was demonstrated in the optimization of monodentate and bidentate phosphine ligands including asymmetric quinoxaline-based ligands. In addition, we successfully found an optimal ligand for the α-selective hydrogermylation of a terminal ynamide, applying the design principle suggested by the VLAO method. These results highlight the practical utility of the VLAO method, with the potential for directed optimization of a wide variety of ligands for transition metal catalysis.
{"title":"Virtual Ligand-Assisted Optimization: A Rational Strategy for Ligand Engineering","authors":"Wataru Matsuoka, Taihei Oki, Ren Yamada, Tomohiko Yokoyama, Shinichi Suda, Carla M. Saunders, Bastian Bjerkem Skjelstad, Yu Harabuchi, Natalie Fey, Satoru Iwata, Satoshi Maeda","doi":"10.1021/acscatal.4c06003","DOIUrl":"https://doi.org/10.1021/acscatal.4c06003","url":null,"abstract":"Ligand engineering is one of the most important, but labor-intensive processes in the development of transition metal catalysis. Historically, this process has been guided by ligand descriptors such as Tolman’s electronic parameter and the cone angle. Analyzing reaction outcomes in terms of these parameters has enabled chemists to identify the most important properties for controlling catalytic pathways and thus designing better ligands. However, typical strategies for these analyses rely on regression approaches, which often require extensive experimental studies to identify trends across chemical space and understand outliers. Here, we introduce the virtual ligand-assisted optimization (VLAO) method, a computational approach for reactivity-directed ligand engineering. In this method, important features of ligands are identified by simple mathematical operations on equilibrium structures and/or transition states of interest, and derivative values of arbitrary objective functions with respect to ligand parameters are obtained. These derivative values are then used as a guiding principle to optimize ligands within the parameter space. The VLAO method was demonstrated in the optimization of monodentate and bidentate phosphine ligands including asymmetric quinoxaline-based ligands. In addition, we successfully found an optimal ligand for the α-selective hydrogermylation of a terminal ynamide, applying the design principle suggested by the VLAO method. These results highlight the practical utility of the VLAO method, with the potential for directed optimization of a wide variety of ligands for transition metal catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142486558","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}
Different P450 isoforms may catalyze different types of reactions on the same substrate due to differences in their protein environments. To uncover how the spatial environment within the enzyme regulates substrate reactivity, we conducted quantum mechanics/molecular mechanics (QM/MM) simulations on the CYP2A6-catalyzed 7-hydroxylation of coumarin. The results revealed that water molecules can flexibly enter the active site of CYP2A6. In the absence of water molecules, the NIH shift mechanism was found to be the most favorable reaction pathway, leading to the keto intermediate that further undergoes the isomerization to form the C7-hydroxylated product. However, when water molecules are present at the active site, the N-protonation route can be facilitated by the active site waters and thus becomes the preferred one. Both the NIH mechanism and the N-protonation can rationalize the 1,2-H shift for the aromatic hydroxylation reactions. This study highlights that P450s can employ diverse and flexible mechanisms for aromatic hydroxylation, offering deeper insight into the mechanisms of P450-catalyzed aromatic hydroxylation reactions.
{"title":"Diverse Mechanisms for the Aromatic Hydroxylation: Insights into the Mechanisms of the Coumarin Hydroxylation by CYP2A6","authors":"Zhenjia Gan, Jianqiang Feng, Jiabin Yin, Juping Huang, Binju Wang, John Z.H. Zhang","doi":"10.1021/acscatal.4c05330","DOIUrl":"https://doi.org/10.1021/acscatal.4c05330","url":null,"abstract":"Different P450 isoforms may catalyze different types of reactions on the same substrate due to differences in their protein environments. To uncover how the spatial environment within the enzyme regulates substrate reactivity, we conducted quantum mechanics/molecular mechanics (QM/MM) simulations on the CYP2A6-catalyzed 7-hydroxylation of coumarin. The results revealed that water molecules can flexibly enter the active site of CYP2A6. In the absence of water molecules, the NIH shift mechanism was found to be the most favorable reaction pathway, leading to the keto intermediate that further undergoes the isomerization to form the C7-hydroxylated product. However, when water molecules are present at the active site, the N-protonation route can be facilitated by the active site waters and thus becomes the preferred one. Both the NIH mechanism and the N-protonation can rationalize the 1,2-H shift for the aromatic hydroxylation reactions. This study highlights that P450s can employ diverse and flexible mechanisms for aromatic hydroxylation, offering deeper insight into the mechanisms of P450-catalyzed aromatic hydroxylation reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142451606","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}
The limitations imposed by the high carrier recombination rate in the current photocatalytic H2O2 production system substantially restrict the rate of H2O2 generation. Herein, we successfully prepared an In2S3/HTCC dense heterojunction bridged by In–S–C bonds through in situ polymerization of glucose on In2S3. This interfacial In–S–C bond provides a fast transfer channel for electrons at the interface to achieve a highly efficient interfacial charge transfer efficiency, leading to the formation of an enhanced built-in electric field between In2S3 and HTCC, thus dramatically accelerating the rate of charge separation and effectively prolonging the lifetime of the photogenerated carriers. Moreover, the coverage of HTCC enhances the absorption of visible light and sorption of O2 by In2S3, while lowering its two-electron oxygen reduction reaction (ORR) energy barrier. Notably, our research demonstrates that In2S3/HTCC can generate H2O2 not only through the well-known two-step one-electron ORR but also via an alternative pathway utilizing 1O2 as an intermediate, thereby enhancing H2O2 production. Benefiting from these advantages, In2S3/HTCC-2 can produce H2O2 at a rate of up to 1392 μmol g–1 h–1 in a pure aqueous system, which is 18.2 and 5.2 times higher than that of pure In2S3 and HTCC, respectively. Our work not only provides a novel synthesis method of new organic/inorganic heterojunction photocatalysts based on HTCC but also offers new insights into the potential mechanism of interfacial bonding of heterostructures to regulate the photocatalytic H2O2 production activity.
{"title":"Furan-Based HTCC/In2S3 Heterojunction Achieves Fast Charge Separation To Boost the Photocatalytic Generation of H2O2 in Pure Water","authors":"Xiaolong Tang, Changlin Yu, Jiaming Zhang, Kaiwei Liu, Debin Zeng, Fang Li, Feng Li, Guijun Ma, Yanbin Jiang, Yongfa Zhu","doi":"10.1021/acscatal.4c04341","DOIUrl":"https://doi.org/10.1021/acscatal.4c04341","url":null,"abstract":"The limitations imposed by the high carrier recombination rate in the current photocatalytic H<sub>2</sub>O<sub>2</sub> production system substantially restrict the rate of H<sub>2</sub>O<sub>2</sub> generation. Herein, we successfully prepared an In<sub>2</sub>S<sub>3</sub>/HTCC dense heterojunction bridged by In–S–C bonds through in situ polymerization of glucose on In<sub>2</sub>S<sub>3</sub>. This interfacial In–S–C bond provides a fast transfer channel for electrons at the interface to achieve a highly efficient interfacial charge transfer efficiency, leading to the formation of an enhanced built-in electric field between In<sub>2</sub>S<sub>3</sub> and HTCC, thus dramatically accelerating the rate of charge separation and effectively prolonging the lifetime of the photogenerated carriers. Moreover, the coverage of HTCC enhances the absorption of visible light and sorption of O<sub>2</sub> by In<sub>2</sub>S<sub>3</sub>, while lowering its two-electron oxygen reduction reaction (ORR) energy barrier. Notably, our research demonstrates that In<sub>2</sub>S<sub>3</sub>/HTCC can generate H<sub>2</sub>O<sub>2</sub> not only through the well-known two-step one-electron ORR but also via an alternative pathway utilizing <sup>1</sup>O<sub>2</sub> as an intermediate, thereby enhancing H<sub>2</sub>O<sub>2</sub> production. Benefiting from these advantages, In<sub>2</sub>S<sub>3</sub>/HTCC-2 can produce H<sub>2</sub>O<sub>2</sub> at a rate of up to 1392 μmol g<sup>–1</sup> h<sup>–1</sup> in a pure aqueous system, which is 18.2 and 5.2 times higher than that of pure In<sub>2</sub>S<sub>3</sub> and HTCC, respectively. Our work not only provides a novel synthesis method of new organic/inorganic heterojunction photocatalysts based on HTCC but also offers new insights into the potential mechanism of interfacial bonding of heterostructures to regulate the photocatalytic H<sub>2</sub>O<sub>2</sub> production activity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450006","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}
Pub Date : 2024-10-19DOI: 10.1021/acscatal.4c05345
Qingqin Huang, Yu-Ping Tang, Chao-Gang Zhang, Zhen Wang, Lei Dai
Helical systems have attracted considerable interest across multiple scientific fields due to not only their essential roles in biological processes but also their potential to unveil chirality-associated phenomena, properties, and functionalities. Today, the distinctive topologies of helicenes have found extensive applications in materials science, molecular recognition, and asymmetric catalysis owing to their structural diversity and unique optical and electronic characteristics. Nonetheless, in contrast to the advancements in the synthesis of optically pure point-chiral and axially chiral compounds, the catalytic enantioselective assembly of helically chiral molecules remains in its nascent stages. This Perspective delves into the latest developments in the organocatalytic asymmetric synthesis of helically chiral compounds, emphasizing both the strengths and limitations of the existing literature, with perspectives on the remaining challenges within the field. It is expected that this Perspective will serve as a catalyst for innovation, inspiring the creation of more efficient strategies to synthesize helically chiral molecules.
{"title":"Enantioselective Synthesis of Helically Chiral Molecules Enabled by Asymmetric Organocatalysis","authors":"Qingqin Huang, Yu-Ping Tang, Chao-Gang Zhang, Zhen Wang, Lei Dai","doi":"10.1021/acscatal.4c05345","DOIUrl":"https://doi.org/10.1021/acscatal.4c05345","url":null,"abstract":"Helical systems have attracted considerable interest across multiple scientific fields due to not only their essential roles in biological processes but also their potential to unveil chirality-associated phenomena, properties, and functionalities. Today, the distinctive topologies of helicenes have found extensive applications in materials science, molecular recognition, and asymmetric catalysis owing to their structural diversity and unique optical and electronic characteristics. Nonetheless, in contrast to the advancements in the synthesis of optically pure point-chiral and axially chiral compounds, the catalytic enantioselective assembly of helically chiral molecules remains in its nascent stages. This Perspective delves into the latest developments in the organocatalytic asymmetric synthesis of helically chiral compounds, emphasizing both the strengths and limitations of the existing literature, with perspectives on the remaining challenges within the field. It is expected that this Perspective will serve as a catalyst for innovation, inspiring the creation of more efficient strategies to synthesize helically chiral molecules.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142450097","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}
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