Ion-exchange voltammetry and electrocatalytic sensing capabilities of cytochrome c at polyestersulfonated ionomer coated glassy carbon electrodes

The incorporation and electrochemical behaviour of cytochrome c (Cyt C) at glassy carbon electrodes modified with the polyestersulfonated ionomer Eastman AQ 55 are examined. The presence of the polyelectrolytic coating allows the preconcentration of the protein within the polymer and the observation of the direct electrochemistry of Cyt C at the modified electrode without addition of promoters or mediators in the solutions. The dependence of voltammetric signals on typical parameters such as solution pH and nature or concentration of the supporting electrolyte supports the ion-exchange nature of the incorporation process. The relevant role of the permselectivity of the polymeric modifier is highlighted also by the study of electrocatalytic processes which take place at the modified electrode loaded with Cyt C. No electrocatalytic effect is observed when the electrogenerated dication (ferricenylmethyl)trimethylammonium is present as possible oxidant. On the contrary, electrocatalytic current enhancements are observed for anionic substrates such as Fe(CN)(6)(3-) (oxidant) and ascorbate (reductant). Catalytic currents increase with the substrate concentration, with higher sensitivity for Fe(CN)(6)(3-). Due to ionic repulsion, the reaction with anions occurs at the polymer-solution interface. In the case of chemically unstable substrates, such as superoxide anion, ionic repulsion slow down the approach rate of the substrate so that spontaneous decomposition can prevail over the reaction with Cyt C incorporated in the coating.