Redox properties of desulfovibrio-gigas [fe3s4] and [fe4s4] ferredoxins and heterometal cubane-type clusters formed within the [fe3s4] core - square-wave voltammetric studies

The same polypeptide chain (58 amino acids, 6 cysteines) is used to build up two ferredoxins in Desulfovibrio gigas a sulfate reducing organism. Ferredoxin II (FdII) contains a single [Fe3S4] core and ferredoxin I (FdI) mainly a [Fe4S4] core. The [Fe3S4] core can readily be interconverted into a [Fe4S4] complex (J. J. G. Moura, I. Moura, T. A. Kent, J. D. Lipscomb, B. H. Huynh, J. LeGall, A. V. Xavier, and E. Munck, J. Biol. Chem. 257, 6259 (1982)). This interconversion process suggested that the [Fe3S4] core could be used as a synthetic precursor for the formation of heterometal clusters. Co, Zn, Cd, and Ni derivatives were produced (I. Moura, J. J. G. Moura, E. Munck, V. Papaephthymiou, and J. LeGall, J. Am. Chem. Soc. 108, 349 (1986), K. Surerus, E. Munck, I. Moura, J. J. G. Moura, and J. LeGall, J. Am. Chem. Soc. 109, 3805 (1986), and A. L. Macedo, I. Moura, J. J. G. Moura, K. Surerus, and E. Munck, unpublished results). The redox properties of a series of heterometal clusters (MFe3S4] are accessed using direct electrochemistry (square wave voltammetry-SWV) promoted by Mg(II) at a glassy carbon electrode (derivatives: Cd ( - 495 mV), Fe ( - 420 mV), Ni ( - 360 mV), and Co ( - 245 mV) vs normal hydrogen electrode (NHE)). In parallel, the electrochemical behavior (cyclic voltammetry-CV, differential pulse voltammetry-DPV and SWV) of FdI and FdII were investigated as well as the cluster interconversion process. In addition to the +1 0 (3Fe cluster) and +2 +1 (4Fe cluster) redox transitions, a very negative redox step, at -690 mV, was detected for the 3Fe core, reminiscent of a postulated further 2e- reduction step, as proposed for D. africanus ferredoxin III by F. A. Armstrong, S. J. George, R. Cammack, E. C. Hatchikian, and A. J. Thomson, Biochem. J. 264, 265 (1989). The electrochemical redox potential values are compared with those determined by independent methods (namely by electron paramagnetic resonance (EPR) and visible spectroscopy).