Voltammetric detection of cadmium ions at glutathione-modified gold electrodes

Abstract

An electrochemical sensor for the detection of cadmium ions is described using immobilized glutathione as a selective ligand. First, a self-assembled monolayer of 3-mercaptopropionic acid (MPA) was formed on a gold electrode. The carboxyl terminus then allowed attachment of glutathione (GSH) via carbodiimide coupling to give the MPA–GSH modified electrode. A cadmium ion forms a complex with glutathione via the free sulfhydryl group and also to the carboxyl groups. The complexed ion is reduced by linear and Osteryoung square wave voltammetry with a detection limit of 5 nM. The effect of the kinetics of accumulation of cadmium on the measured current was investigated and modeled. Increasing the temperature of accumulation and electrochemical analysis caused an increase in the voltammetric peak of approximately 4% per °C around room temperature. The modified electrode could be regenerated, being stable for more than 16 repeated uses and more than two weeks if used once a day. Some interference from Pb²⁺ and Cu²⁺ was observed but the effects of Zn²⁺, Ni²⁺, Cr³⁺ and Ba²⁺ were insignificant.