title: Bio-inspired electron-delivering system for reductive activation of dioxygen at metal centres towards artificial flavoenzymes.
abstract: Development of artificial systems, capable of delivering electrons to metal-based catalysts for the reductive activation of dioxygen, has been proven very difficult for decades, constituting a major scientific lock for the elaboration of environmentally friendly oxidation processes. Here we demonstrate that the incorporation of a flavin mononucleotide (FMN) in a water-soluble polymer, bearing a locally hydrophobic microenvironment, allows the efficient reduction of the FMN by NADH. This supramolecular entity is then capable of catalysing a very fast single-electron reduction of manganese(III) porphyrin by splitting the electron pair issued from NADH. This is fully reminiscent of the activity of natural reductases such as the cytochrome P450 reductases with kinetic parameters, which are three orders of magnitude faster compared with other artificial systems. Finally, we show as a proof of concept that the reduced manganese porphyrin activates dioxygen and catalyses the oxidation of organic substrates in water.
authors.affiliation: Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Univ Paris Sud, Université Paris Saclay, rue du doyen Georges Poitou, 91405 Orsay, France.
authors.forename: Yoann
authors.initials: Y
authors.lastname: Roux
authors.affiliation: Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Univ Paris Sud, Université Paris Saclay, rue du doyen Georges Poitou, 91405 Orsay, France.
authors.forename: Rémy
authors.initials: R
authors.lastname: Ricoux
authors.affiliation: Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Univ Paris Sud, Université Paris Saclay, rue du doyen Georges Poitou, 91405 Orsay, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Avenier
authors.affiliation: Laboratoire de Chimie Bioorganique et Bioinorganique, Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Univ Paris Sud, Université Paris Saclay, rue du doyen Georges Poitou, 91405 Orsay, France.
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Mahy
mesh_terms: D002384:Catalysis; D004579:Electron Transport; D005486:Flavin Mononucleotide / Q000737:chemistry / Q000378:metabolism*; D007700:Kinetics; D008345:Manganese / Q000378:metabolism*; D009243:NAD / Q000378:metabolism; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism*; D011166:Porphyrins / Q000378:metabolism
chemical_list: D011166:Porphyrins; D009243:NAD; D008345:Manganese; D005486:Flavin Mononucleotide; D010100:Oxygen