title: Mechanism of protection of catalysts supported in redox hydrogel films.
abstract: The use of synthetic inorganic complexes as supported catalysts is a key route in energy production and in industrial synthesis. However, their intrinsic oxygen sensitivity is sometimes an issue. Some of us have recently demonstrated that hydrogenases, the fragile but very efficient biological catalysts of H2 oxidation, can be protected from O2 damage upon integration into a film of a specifically designed redox polymer. Catalytic oxidation of H2 produces electrons which reduce oxygen near the film/solution interface, thus providing a self-activated protection from oxygen [Plumeré et al., Nat Chem. 2014, 6, 822-827]. Here, we rationalize this protection mechanism by examining the time-dependent distribution of species in the hydrogenase/polymer film, using measured or estimated values of all relevant parameters and the numerical and analytical solutions of a realistic reaction-diffusion scheme. Our investigation sets the stage for optimizing the design of hydrogenase-polymer films, and for expanding this strategy to other fragile catalysts.
authors.affiliation: †Laboratoire de Bioénergétique et Ingénierie des Protéines, Aix Marseille Université, CNRS, BIP UMR 7281, 13402 Marseille, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Fourmond
authors.forename: Stefanie
authors.initials: S
authors.lastname: Stapf
authors.forename: Huaiguang
authors.initials: H
authors.lastname: Li
authors.forename: Darren
authors.initials: D
authors.lastname: Buesen
authors.affiliation: ∥Max-Planck-Institut für Chemische Energiekonversion, Stiftstr 34-36, 45470 Mülheim an der Ruhr, Germany.
authors.forename: James
authors.initials: J
authors.lastname: Birrell
authors.affiliation: ∥Max-Planck-Institut für Chemische Energiekonversion, Stiftstr 34-36, 45470 Mülheim an der Ruhr, Germany.
authors.forename: Olaf
authors.initials: O
authors.lastname: Rüdiger
authors.affiliation: ∥Max-Planck-Institut für Chemische Energiekonversion, Stiftstr 34-36, 45470 Mülheim an der Ruhr, Germany.
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Lubitz
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Schuhmann
authors.forename: Nicolas
authors.initials: N
authors.lastname: Plumeré
authors.affiliation: †Laboratoire de Bioénergétique et Ingénierie des Protéines, Aix Marseille Université, CNRS, BIP UMR 7281, 13402 Marseille, France.
authors.forename: Christophe
authors.initials: C
authors.lastname: Léger
mesh_terms: D015374:Biosensing Techniques; D002384:Catalysis; D016969:Desulfovibrio vulgaris / Q000201:enzymology*; D004583:Electrons; D004800:Enzymes, Immobilized / Q000378:metabolism*; D020100:Hydrogels / Q000737:chemistry*; D006859:Hydrogen / Q000378:metabolism; D006864:Hydrogenase / Q000378:metabolism*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism
chemical_list: D004800:Enzymes, Immobilized; D020100:Hydrogels; D006859:Hydrogen; D006864:Hydrogenase; D010100:Oxygen