Simultaneous voltammetric determination of dopamine and ascorbic acid using multivariate calibration methodology performed on a carbon paste electrode modified by a mer-[RuCl3(dppb)(4-pic)] complex

The preparation and electrochemical characterization of a carbon paste electrode (CPE) modified with mer-[Ru0Cl3(dppb)(4-pic)] (dppb=Ph2P(CH2)4PPh2, 4-pic=CH3C5H4N), referred to as Rupic, were investigated. The CPE/Rupic system displayed only one pair of redox peaks, with a midpoint potential at 0.28 V vs. Ag/AgCl, which were ascribed to RuIII/RuII charge transfer. This modified electrode presented the property of electrocatalysing the oxidation of dopamine (DA) and ascorbic acid (AA) at 0.35 V and 0.30 V vs. Ag/AgCl, respectively. Because the oxidation for both AA and DA practically occurred at the same potential, distinguishing between them was difficult with cyclic voltammetry. This limitation was overcome using Partial Least Square Regression (PLSR), which allowed us, with the optimised models, to determine four synthetic samples with prediction errors (RMSEP) of 5.55 X 10-5 mol L-1 and 7.48 X 10-6 mol L-1 for DA and AA, respectively. (author)