ELECTROCHEMICAL-BEHAVIOR OF METALLOTHIONEINS AND RELATED MOLECULES .3. METALLOTHIONEIN

The electrochemical behavior of Cd-Zn Thionein from rabbit liver and horse kidney with respect to pH of the solution at the dropping mercury electrode was studied, using differential pulse polarography (DPP). At pH 7.5 three well defined peaks were observed at a potential different from the potentials corresponding to pure Cd2+ and Zn2+. Two different electrochemical systems are involved: the oxidation of the mercury electrode in the presence of thiol groups contained in the metallothionein and the reduction of either free (pH < 4) or complexed (pH > 6) metal ions. The apparent acid-base dissociation constant of metallothionein was estimated. The apparent stability constants of the complexes CdT, ZnT and HgT were estimated at different pH values. Cadmium forms at least two complexes with thionein exhibiting different stabilities and probably different structures. Modifications in the polarograms with the addition of Cd, Zn and the peptidic fragment [56-61] MT I, a molecule intrinsic to the metallothionein structure, were studied. A diagram showing the oxide-reduction potentials corresponding to twelve different electrochemical species is given. DPP allows one to distinguish the chemical forms of compounds (speciation).