A reliable, highly selective and sensitive procedure is presented for simultaneous determination of captopril and thioguanine based on cathodic adsorptive stripping of Cu(I)-captopril and Cu(I)-thioguanine complexes on a hanging mercury drop electrode. Captopril and thioguanine were preconcentrated onto the surface of hanging mercury drop electrode using Cu(II) as a suitable probe, with accumulation time of 90 s. Then the preconcentrated complexes were analyzed by cathodic stripping differential pulse voltammetry. The effect of various parameters such as pH, concentration of copper, accumulation potential, accumulation time and scan rate on the sensitivity were studied. The optimum conditions for simultaneous determination of captopril and thioguanine include pH=3.5, 45.0 ng mL-1 copper(II) concentration, accumulation potential of -0.10 V and scan rate of 60 mV s-1. Under the optimum conditions and for an accumulation time of 90 s, the measured peak currents at about -0.15 V and -0.40 V (vs. Ag/AgCl) are proportional to the concentrations of thioguanine and captopril over the ranges of 0.15-180 and 0.5-100 nmol L-1, respectively. The limits of detection are 0.08 and 0.3 nmol L-1 for thioguanine and captopril, respectively. The relative standard deviations for five replicate analyses of 20.0 nmol L-1 captopril and thioguanine are 2.5% and 2.1%, respectively. The method was applied to the determination of captopril and thioguanine in synthetic mixed samples, pharmaceutical samples and human serum with satisfactory results.
captopril; thioguanine; copper(II); adsorptive cathodic stripping voltammetry
