Redox couples of inducible nitric oxide synthase

We report direct electrochemistry of the iNOS heme domain in a DDAB film on the surface of a basal plane graphite electrode. Cyclic voltammetry reveals FeIII/II and FeII/I couples at -191 and -1049 mV (vs Ag/AgCl). Imidazole and carbon monoxide in solution shift the FeIII/II potential by +20 and +62 mV, while the addition of dioxygen results in large catalytic waves at the onset of FeIII reduction. Voltammetry at higher scan rates (with pH variations) reveals that the FeIII/II cathodic peak can be resolved into two components, which are attributable to FeIII/II couples of five- and six-coordinate hemes. Digital simulation of our experimental data implicates water dissociation from the heme as a gating mechanism for ET in iNOS.