Effects of axial ligand replacement on the redox potential of cytochrome c.

The formal potentials (E0') and electron transfer numbers (n) of imidazole (Im), 1-methylimidazole (1-MeIm), and 1-ethylimidazole (1-EtIm) complexes of cytochrome c have been determined for the first time using optically transparent thin-layer spectroelectrochemistry. In comparing these results with the E0' value of the cytochrome c, their potentials at infinite dilution have been calculated, which indicate that axial replacement of methionine-80 by Im, 1-MeIm, and 1-EtIm gives rise to 426, 359, and 327 mV negative shifts relative to that of native cytochrome c, respectively. Thereby, the origins of the effects of axial substitution on redox potential are discussed.