O₂migration rates in [NiFe] hydrogenases. A joint approach combining free-energy calculations and kinetic modeling

J Phys Chem B. 2014 Jan 23;118(3):676-81. doi: 10.1021/jp4093964. Epub 2014 Jan 13.

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Desulfovibrio / enzymology
  • Diffusion
  • Hydrogenase / chemistry*
  • Hydrogenase / genetics
  • Hydrogenase / metabolism*
  • Kinetics
  • Molecular Dynamics Simulation*
  • Movement
  • Mutation
  • Oxygen / metabolism*
  • Protein Conformation
  • Thermodynamics

Substances

  • nickel-iron hydrogenase
  • Hydrogenase
  • Oxygen