ELECTROCHEMICAL MIMICKING OF REDUCED RUBREDOXIN BY IRON(II) COMPLEXESOF CYSTEINE PEPTIDE THIOLATE IN AQUEOUS MICELLE SOLUTION

The electrochemical properties of Fe(II) complexes with a number of cy steine-containing oligopeptides were investigated in aqueous Triton X- 100 (10%) micelle solution. The complexes with an aromatic ring such a s [Fe(Z-cys-Pro-Leu-cys-Gly-NH-C6H4-p -F)(2)](2-), Z-cys-Pro-Leu-Cys-G ly-NH-CH2-CH2-C6H4-p-F)(2)](2-) and [Fe(Z-cys-Pro-Leu-cys-Gly-Phe-OMe) (2)](2-) exhibit their redox potentials at -0.28, -0.30 and -0.26 V vs . SCE, respectively, in aqueous Triton X-100 (10%) micelle solution wi th good reversibility. The potentials are very close to that of native rubredoxin (-0.31 V vs. SCE in aqueous solution). A para-substituent effect was observed for the redox potentials of [Fe(Z-cys-Pro-Leu-cys- Gly-NH-C6H4-p-X)(2)](2-) (X = OMe, H, F and CN) in aqueous micelle sol ution. The most positively shifted potential was found at -0.26 V vs. SCE for the complex with the strongest electron-withdrawing cyano (CN) substituent. The results show that the complexes with an aromatic rin g are quite stable in such aqueous micelle solutions. (C) 1998 Elsevie r Science S.A. All rights reserved.