Thermodynamic parameters of electrochemical oxidation of L-DOPA: experimental and theoretical studies.

Electrode potential and thermodynamic parameters of the electrochemical reaction of L-DOPA in aqueous solution are obtained experimentally by cyclic voltammetry method and also calculated theoretically using accurate ab initio calculations (G3MP2//B3LYP) along with the available solvation model of CPCM. The pH dependence of the redox activity of L-DOPA in aqueous solution at temperatures in the range of 10-30 °C was used for the experimental determination of the standard reduction potential, changes of entropy, enthalpy, and Gibbs free energy for the studied reaction. The experimental formal redox potential of the two-proton-two-electron reduction process was obtained to be 0.745 V versus standard hydrogen electrode (SHE). The theoretical and experimental values (0.728 and 0.745 V) for the standard electrode potential of L-DOPA are in agreement with each other. The difference between the peak potential of the L-DOPA and the products, which are produced by chemical reactions, has been measured experimentally and also calculated theoretically. There is also an agreement between experimental and theoretical potential difference. Also in this work, the changes of thermodynamic functions of solvation are calculated from the differences between the solution-phase experimental values and the gas-phase theoretical values.