Equilibrium between inactive ready Ni-SIr and active Ni-SIa states of [NiFe] hydrogenase studied by utilizing Ni-SIr-to-Ni-SIa photoactivation

Abstract

Previously, the Ni-SI_r state of [NiFe] hydrogenase was found to convert to the Ni-SI_a state by light irradiation. Herein, large activation energies and a large kinetic isotope effect were obtained for the reconversion of the Ni-SI_a state to the Ni-SI_r state after the Ni-SI_r-to-Ni-SI_a photoactivation, suggesting that the Ni-SI_a state reacts with H₂O and leaves a bridging hydroxo ligand for the Ni-SI_r state.