Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS...Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS-based semiconductors are promising for the photosynthesis of H_(2)O_(2) owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process,however,they suffer from fast H_(2)O_(2) decomposition on the surface of pristine CdS.Therefore,[Cp*Rh(bpy)H_(2)O]2+,a highly selective proton-coupled electron transfer catalyst,was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H_(2)O_(2),mitigating the surface issue of pristine CdS,increasing light absorption,accelerating photonic carrier separation,and enhancing oxygen reduction reaction selectivity to H_(2)O_(2).This photocatalyst promoted the light driven H_(2)O_(2) generation rate up to 1345μmol·L^(-1)·g^(-1)·h^(-1),which was 2.4 times that of pristine CdS.The constructed heterojunction photocatalyst could supply H_(2)O_(2) in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene,achieving a yield of 81%and an ee value of 99%under optimum conditions.A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system,achieving the corresponding chiral alcohols in good yield(51%–88%)and excellent enantioselectivity(90%–99%ee).展开更多
Cytochrome P450 monooxygenases(P450s)play crucial roles in the oxyfunctionalization of non-activated hydrocarbons,thus bridging the gap between simple molecules and high value-added fine chemicals.The introduction of ...Cytochrome P450 monooxygenases(P450s)play crucial roles in the oxyfunctionalization of non-activated hydrocarbons,thus bridging the gap between simple molecules and high value-added fine chemicals.The introduction of P450s into artificially designed cascade reactions provides an exciting opportunity to accomplish challenging reactions and access organic compounds that cannot be achieved by traditional chemical catalysts or by natural metabolic pathways.The main objective of this review is to provide an overview of different types of artificially designed multi-step cascades in which P450s are involved as key catalysts in the biosynthesis of various organic molecules.The different efforts include in vitro multi-enzymatic biocatalytic cascades,in vivo biocatalytic cascades as well as chemo-enzymatic hybrid cascades.Overall,this work provides an overview of cascade reactions involving P450s with various potential applications for the industrial production of food,cosmetics,polymers and pharmaceuticals.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22378096)the Natural Science Foundation of Hebei Province(Grant No.B2023202014)+1 种基金the Science Technology Research Project of Higher Education of Hebei Province(Grant Nos.QN2021045,and QN2023207)the Tianjin Science and Technology Project(Grant No.22KPHDRC00260).
文摘Unspecific peroxygenases exhibit high activity for the selective oxyfunctionalization of inert C(sp3)–H bonds using only H_(2)O_(2) as a clean oxidant,while also exhibiting sensitivity to H_(2)O_(2) concentration.CdS-based semiconductors are promising for the photosynthesis of H_(2)O_(2) owing to their adequately negative potential for oxygen reduction reaction via a proton-coupled electron transfer process,however,they suffer from fast H_(2)O_(2) decomposition on the surface of pristine CdS.Therefore,[Cp*Rh(bpy)H_(2)O]2+,a highly selective proton-coupled electron transfer catalyst,was anchored onto a supramolecular polymer-grafted CdS nanoflower to construct an efficient integrated photocatalyst for generating H_(2)O_(2),mitigating the surface issue of pristine CdS,increasing light absorption,accelerating photonic carrier separation,and enhancing oxygen reduction reaction selectivity to H_(2)O_(2).This photocatalyst promoted the light driven H_(2)O_(2) generation rate up to 1345μmol·L^(-1)·g^(-1)·h^(-1),which was 2.4 times that of pristine CdS.The constructed heterojunction photocatalyst could supply H_(2)O_(2) in situ for nonspecific peroxygenases to catalyze the C–H oxyfunctionalization of ethylbenzene,achieving a yield of 81%and an ee value of 99%under optimum conditions.A wide range of substrates were converted to the corresponding chiral alcohols using this photo-enzyme catalytic system,achieving the corresponding chiral alcohols in good yield(51%–88%)and excellent enantioselectivity(90%–99%ee).
基金This study was supported by the National Key Research and Development Program of China(No.2019YFA09005000)the National Natural Science Foundation of China(Nos.21977026&21702052)Research Program of State Key Laboratory of Biocatalysis and Enzyme Engineering。
文摘Cytochrome P450 monooxygenases(P450s)play crucial roles in the oxyfunctionalization of non-activated hydrocarbons,thus bridging the gap between simple molecules and high value-added fine chemicals.The introduction of P450s into artificially designed cascade reactions provides an exciting opportunity to accomplish challenging reactions and access organic compounds that cannot be achieved by traditional chemical catalysts or by natural metabolic pathways.The main objective of this review is to provide an overview of different types of artificially designed multi-step cascades in which P450s are involved as key catalysts in the biosynthesis of various organic molecules.The different efforts include in vitro multi-enzymatic biocatalytic cascades,in vivo biocatalytic cascades as well as chemo-enzymatic hybrid cascades.Overall,this work provides an overview of cascade reactions involving P450s with various potential applications for the industrial production of food,cosmetics,polymers and pharmaceuticals.
