Electrocatalytic oxidation of NADH at the self-assembled monolayer of nickel(II) macrocycle on gold electrode

Abstract

Electroactive self-assembled monolayers (SAMs) of macrocyclic Ni(II) complex (1) were fabricated on gold electrode and its electrochemistry has been studied in different supporting electrolytes. Substantial stabilization of tervalent nickel and a significant negative shift of formal potential of the Ni^3+/2+ couple have been observed when the supporting electrolyte is changed from nitrate to phosphate. Coordination of supporting electrolyte anion with the Ni(III) complex shifts the formal potential and thus tervalent nickel is stabilized. SAM of 1 electrode shows an excellent electrocatalytic activity towards the oxidation of NADH in aqueous NaNO₃ solution, whereas it scarcely catalyzes the oxidation of NADH in aqueous phosphate buffer solution. The electrocatalytic oxidation of NADH in Na₂SO₄ solution is less efficient than that in NaNO₃ solution. The anion-dependent electrocatalysis has been discussed on the basis of the difference in the coordinating ability of the anions with the tervalent nickel centers. Steady-state current has been measured for the oxidation of NADH and it was proportional to the concentration of NADH.