Rajaa Farran, Y. Mekmouche, Nhat Tam Vo, C. Herrero, Annamaria Quaranta, Marie Sircoglou, F. Banse, P. Rousselot‐Pailley, A. Simaan, A. Aukauloo, T. Tron, W. Leibl
{"title":"Tracking Light-Induced Electron Transfer Towards O 2 in a Hybrid Photoredox-Laccase System","authors":"Rajaa Farran, Y. Mekmouche, Nhat Tam Vo, C. Herrero, Annamaria Quaranta, Marie Sircoglou, F. Banse, P. Rousselot‐Pailley, A. Simaan, A. Aukauloo, T. Tron, W. Leibl","doi":"10.2139/ssrn.3778327","DOIUrl":null,"url":null,"abstract":"Photobiocatalysis is an interesting approach to use light to perform specific chemical transformations in a selective and efficient way. The intention is to couple a photoredox cycle with an enzyme performing multielectronic catalytic activity. Laccase, a robust multicopper oxidase, can be envisioned as a tool to use dioxygen as a clean electron sink when coupled to an oxidation photocatalyst. Here, we provide a detailed study of the coupling of a [Ru(bpy)3]2+ photosensitizer to laccase. We demonstrate that efficient laccase reduction requires using an electron relay like methyl viologen. In the presence of dioxygen, electrons transiently stored in superoxide ions (O2●–) are scavenged by laccase leading to formation of water instead of H2O2. The net result is the photo accumulation, in an essentially irreversible way, of highly oxidizing [Ru(bpy)3]3+. This study provides a global scheme for the future use of laccase, in tandem with a light-driven oxidative process, using O2 as both a one-electron transfer relay and a 4-electron substrate to become the sustainable final electron acceptor in a such a hybrid photocatalytic process.","PeriodicalId":9858,"journal":{"name":"Chemical Engineering (Engineering) eJournal","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2021-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Engineering (Engineering) eJournal","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.2139/ssrn.3778327","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 1
Abstract
Photobiocatalysis is an interesting approach to use light to perform specific chemical transformations in a selective and efficient way. The intention is to couple a photoredox cycle with an enzyme performing multielectronic catalytic activity. Laccase, a robust multicopper oxidase, can be envisioned as a tool to use dioxygen as a clean electron sink when coupled to an oxidation photocatalyst. Here, we provide a detailed study of the coupling of a [Ru(bpy)3]2+ photosensitizer to laccase. We demonstrate that efficient laccase reduction requires using an electron relay like methyl viologen. In the presence of dioxygen, electrons transiently stored in superoxide ions (O2●–) are scavenged by laccase leading to formation of water instead of H2O2. The net result is the photo accumulation, in an essentially irreversible way, of highly oxidizing [Ru(bpy)3]3+. This study provides a global scheme for the future use of laccase, in tandem with a light-driven oxidative process, using O2 as both a one-electron transfer relay and a 4-electron substrate to become the sustainable final electron acceptor in a such a hybrid photocatalytic process.