title: Visible light-driven O2 reduction by a porphyrin-laccase system.
abstract: Several recent studies have shown that the combination of photosensitizers with metalloenzymes can support a light-driven multielectron reduction of molecules such as CO(2) or HCN. Here we show that the association of the zinc tetramethylpyridinium porphyrin (ZnTMPyP(4+)) photosensitizer with the multicopper oxidase (MCO) laccase allows to link the oxidation of an organic molecule to the four electrons reduction of dioxygen into water. The enzyme is photoreduced within minutes with porphyrin/enzyme ratio as low as 1:40. With a 1:1 ratio, the dioxygen consumption rate is 1.7 μmol L(-1) s(-1). Flash photolysis experiments support the formation of the triplet excited state of ZnTMPyP(4+) which reduces the enzyme to form a radical cation of the porphyrin with a k(ET) ≈ 10(7) s(-1) M(-1). The long-lived triplet excited state of the ZnTMPyP(4+) (τ(0) = 0.72 ms) accounts for a substantial electron-transfer quantum yield, φ(ET) = 0.35. Consequently, the enzyme-dependent photo-oxidation of the electron donor occurs with a turnover of 8 min(-1) for the one-electron oxidation process, thereby supporting the suitability of such enzyme/sensitizer hybrid systems for aerobic photodriven transformations on substrates. This study is the first example of a phorphyrin-sensitized four-electron reduction of an enzyme of the MCO family, leading to photoreduction of dioxygen into water.
authors: Chemistry Department, University of Crete, Voutes Campus, 71003 Heraklion, Crete, Greece.
authors: Theodore
authors: T
authors: Lazarides
authors: Igor V
authors: IV
authors: Sazanovich
authors: A Jalila
authors: AJ
authors: Simaan
authors: Maria Chrisanthi
authors: MC
authors: Kafentzi
authors: Milan
authors: M
authors: Delor
authors: Yasmina
authors: Y
authors: Mekmouche
authors: Bruno
authors: B
authors: Faure
authors: Marius
authors: M
authors: Réglier
authors: Julia A
authors: JA
authors: Weinstein
authors: Athanassios G
authors: AG
authors: Coutsolelos
authors: Thierry
authors: T
authors: Tron
mesh_terms: D042845:Laccase / Q000737:chemistry*; D008027:Light; D010100:Oxygen / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry*
chemical_list: D011166:Porphyrins; D042845:Laccase; D010100:Oxygen