Kinetic studies on the electron transfer between bacterial c-type cytochromes and metal oxides

Cyclic voltammetry was used to investigate the kinetics of the electron transfer between various soluble or solid metal oxides, and polyheme c-type cytochromes from Desulfuromonas acetoxidans and Desulfovibrio. The second order rate constant for the catalytic reduction of soluble chromate ions by Desulfuromonas acetoxidans cytochrome c₇ was found to be 6×10⁵ M^?1 s^?1. By using the membrane electrode technology, it has been shown that the catalytic process for Cr(VI) reduction is efficient even when the cytochrome is entrapped in the close vicinity of the electrode surface. Moreover, this proceeding allowed the catalytic reduction of solid metal oxides such as manganese(IV), vanadium(V) and iron(III) oxides to be performed. Results suggest that the metal reductase activity of a microorganism is governed by its c-type cytochrome content. Furthermore, only cytochromes with bishistidinyl heme iron coordination act as metal reducers whereas mitochondrial c-type cytochromes do not. This approach opens new pathways for the use of sulfur or sulfate bacteria in the bioremediation of metal contaminated waters and waste streams. Processes involving the use of entrapped enzymes reactors could be developed according to the metal reducing activity of their polyheme c-type cytochromes.