title: Cofactor-free light-driven whole-cell cytochrome P450 catalysis.
abstract: Cytochromes P450 can catalyze various regioselective and stereospecific oxidation reactions of non-functionalized hydrocarbons. Here, we have designed a novel light-driven platform for cofactor-free, whole-cell P450 photo-biocatalysis using eosin Y (EY) as a photosensitizer. EY can easily enter into the cytoplasm of Escherichia coli and bind specifically to the heme domain of P450. The catalytic turnover of P450 was mediated through the direct transfer of photoinduced electrons from the photosensitized EY to the P450 heme domain under visible light illumination. The photoactivation of the P450 catalytic cycle in the absence of cofactors and redox partners is successfully conducted using many bacterial P450s (variants of P450 BM3) and human P450s (CYPs 1A1, 1A2, 1B1, 2A6, 2E1, and 3A4) for the bioconversion of different substrates, including marketed drugs (simvastatin, lovastatin, and omeprazole) and a steroid (17β-estradiol), to demonstrate the general applicability of the light-driven, cofactor-free system.
authors.affiliation: Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology, 335 Science Road, Daejeon 305-701 (Republic of Korea).
authors.forename: Jong Hyun
authors.initials: JH
authors.lastname: Park
authors.forename: Sahng Ha
authors.initials: SH
authors.lastname: Lee
authors.forename: Gun Su
authors.initials: GS
authors.lastname: Cha
authors.forename: Da Som
authors.initials: DS
authors.lastname: Choi
authors.forename: Dong Heon
authors.initials: DH
authors.lastname: Nam
authors.forename: Jae Hyung
authors.initials: JH
authors.lastname: Lee
authors.forename: Jung-Kul
authors.initials: JK
authors.lastname: Lee
authors.forename: Chul-Ho
authors.initials: CH
authors.lastname: Yun
authors.forename: Ki Jun
authors.initials: KJ
authors.lastname: Jeong
authors.forename: Chan Beum
authors.initials: CB
authors.lastname: Park
mesh_terms: D001426:Bacterial Proteins / Q000737:chemistry / Q000378:metabolism; D055162:Biocatalysis; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry / Q000378:metabolism*; D004579:Electron Transport; D004926:Escherichia coli / Q000378:metabolism; D004958:Estradiol / Q000737:chemistry / Q000378:metabolism; D019793:Fluorescein / Q000737:chemistry / Q000378:metabolism; D006418:Heme / Q000737:chemistry / Q000378:metabolism; D006801:Humans; D008027:Light; D008148:Lovastatin / Q000737:chemistry / Q000378:metabolism; D009853:Omeprazole / Q000737:chemistry / Q000378:metabolism; D010084:Oxidation-Reduction; D017319:Photosensitizing Agents / Q000737:chemistry / Q000378:metabolism; D017434:Protein Structure, Tertiary; D019821:Simvastatin / Q000737:chemistry / Q000378:metabolism
chemical_list: D001426:Bacterial Proteins; D017319:Photosensitizing Agents; D006418:Heme; D004958:Estradiol; D003577:Cytochrome P-450 Enzyme System; D008148:Lovastatin; D019821:Simvastatin; D009853:Omeprazole; D019793:Fluorescein
keywords: cofactors; cytochromes P450; enzymatic catalysis; photocatalysis; photoinduced electron transfer