A novel signal on-off glutathione (GSH) electrochemical sensor was developed based on a AuCu bimetal-decorated Zr-containing metal-organic framework (Zr-MOF), in which a signal amplification strategy promoted by solid-state electrochemistry of cuprous chloride (CuCl) was used. The Zr-MOF with a large surface area can be effectively used as the substrate for the in situ growth of AuCu bimetals to obtain the Zr-MOF@AuCu nanocomposite. The interaction between Cu in Zr-MOF@AuCu and Cl- in the solution accompanied with the formation of CuCl displays an enlarged stable oxidation current, which greatly declines with the addition of GSH owing to the specific Cu-GSH interaction. The conversion of CuCl into Cu-GSH triggered the "crowding-out effect" and resulted in a sharp drop in the peak current of CuCl, which can realize the ultrasensitive and selective detection of GSH. The detection mechanism was investigated, and the detection range was 10 pM-1 mM with the detection limit as low as 2.67 pM. The special response mechanism for the detection of GSH allows the highly selective detection of GSH in various real samples with reliable results, endowing the proposed electroanalysis sensor with broad application prospects in biological and food analysis.
Keywords: Zr-containing metal−organic framework, AuCu bimetals; crowding-out effect; glutathione; solid-state electrochemistry.