A novel voltammetry with a modified gold electrode for the direct determination of copper in environmental samples, without any pretreatment, is proposed in this paper. A porous disorganized monolayer was formed on the surface of the gold electrode by the self-assembly of mercaptoacetic acid (MAA), which could selectively permeate small molecules. Subtractive square wave anodic stripping voltammetry (SASV) was applied to determine copper, in which the underpotential deposition (UPD) of copper was used as the deposition step. The linear range was from 8 × 10 -7 to 1 × 10 -5 mol l -1 by the modified electrode in the presence of human serum albumin, and the determination was not interfered with common metal ions. Copper in a real environmental sample was successfully detected.

Linear sweep anodic stripping voltammetry was applied to determine the concentration of free copper ions in the process of binding copper to human serum albumin (HSA) on the mercaptoethane sulfonate modified gold electrode surface. A kinetic model of two consecutive steps for the process of binding copper to HSA was first proposed on the basis of the electrochemical results and compared with a parallel kinetic response model by using residual analysis. The experimental data of the stripping peak currents with time was fitted according to the model and the kinetic parameters, binding rate constants, k1 and k2, were estimated to be 0.411 and 0.055 min(-1), respectively.