title: O₂migration rates in [NiFe] hydrogenases. A joint approach combining free-energy calculations and kinetic modeling.
abstract: Hydrogenases are promising candidates for the catalytic production of green energy by means of biological ways. The major impediment to such a production is rooted in their inhibition under aerobic conditions. In this work, we model dioxygen migration rates in mutants of a hydrogenase of Desulfovibrio fructusovorans. The approach relies on the calculation of the whole potential of mean force for O2 migration within the wild-type as well as in V74M, V74F, and V74Q mutant channels. The three free-energy barriers along the entire migration pathway are converted into chemical rates through modeling based on Transition State Theory. The use of such a model recovers the trend of O2 migration rates among the series.
authors.affiliation: Institut de Chimie de Nice, UMR 7272, Université de Nice-Sophia Antipolis, CNRS , Parc Valrose, 06108 Nice Cedex 2, France.
authors.forename: Jérémie
authors.initials: J
authors.lastname: Topin
authors.forename: Julien
authors.initials: J
authors.lastname: Diharce
authors.forename: Sébastien
authors.initials: S
authors.lastname: Fiorucci
authors.forename: Serge
authors.initials: S
authors.lastname: Antonczak
authors.forename: Jérôme
authors.initials: J
authors.lastname: Golebiowski
mesh_terms: D003901:Desulfovibrio / Q000201:enzymology; D004058:Diffusion; D006864:Hydrogenase / Q000737:chemistry* / Q000235:genetics / Q000378:metabolism*; D007700:Kinetics; D056004:Molecular Dynamics Simulation; D009068:Movement; D009154:Mutation; D010100:Oxygen / Q000378:metabolism*; D011487:Protein Conformation; D013816:Thermodynamics
chemical_list: C043296:nickel-iron hydrogenase; D006864:Hydrogenase; D010100:Oxygen