O2Migration Rates in [NiFe] Hydrogenases.A Joint Approach Combining Free-Energy Calculations and Kinetic Modeling.

Hydrogenases are promising candidatesfor the catalytic productionof green energy by means of biological ways. The major impedimentto such a production is rooted in their inhibition under aerobic conditions.In this work, we model dioxygen migration rates in mutants of a hydrogenaseof Desulfovibrio fructusovorans. The approach relieson the calculation of the whole potential of mean force for O2migration within the wild-type as well as in V74M, V74F,and V74Q mutant channels. The three free-energy barriers along theentire migration pathway are converted into chemical rates throughmodeling based on Transition State Theory. The use of such a modelrecovers the trend of O2migration rates among the series. [ABSTRACT FROM AUTHOR]