Bifurcated ubihydroquinone oxidation in the cytochrome bc1 complex by proton-gated charge transfer

Abstract

The unique bifurcation of electron flow at the ubihydroquinone-oxidation center of the cytochrome bc1 complex is the energy-conserving reaction of the protonmotive Q- cycle and is prerequisite to vectorial proton translocation. The widely accepted Q-cycle reaction scheme describes the overall electron and proton pathways, but does not address the detailed chemistry of this central step. Based on a model of the ubihydroquinone-oxidation pocket containing two ubiquinone molecules in a stacked configuration, a detailed model for the reactions during steady-state catalysis is proposed. In this proton-gated charge-transfer mechanism the reaction is controlled by the deprotonation of the substrate ubihydroquinone.