Simulation of the electrochemical behavior of multi‐redox systems: Current potential studies on multiheme cytochromes

The direct unmediated electrochemical response of the tetrahemic cytochrome c₃ isolated from sulfate reducers Desulfovibrio baculatus (DSM 1743) and D. vulgaris (strain Hildenborough), was evaluated using different electrode systems [graphite (edge cut), gold, semiconductor (InO₂) and mercury)] and different electrochemical methods (cyclic voltammetry and differential pulse voltammetry). A computer program was developed for the theoretical simulation of a complete cyclic voltammetry curve, based on the method proposed by Nicholson and Shain [Nicholson, R. S. & Shain, I. (1964) Anal. Chem. 36, 706–723], using the Gauss‐Legendre method for calculation of the integral equations. The experimental data obtained for this multi‐redox center protein was deconvoluted in to the four redox components using theoretically generated cyclic voltammetry curves and the four mid‐point reduction potentials determined. The pH dependence of the four reduction potentials was evaluated using the deconvolution method described.