Ratiometric sensing interface for glutathione determination based on electro-polymerized copper-coordinated molecularly imprinted layer supported on silver/porous carbon hybrid

A novel molecularly imprinted ratiometric-based sensor was designed for highly selective and ultrasensitive electrochemical detection of glutathione (GSH). The sensor consists of porous carbon co-doped with nitrogen and sulfur formed on the surface of graphite electrode (N, S@PC/GE). Silver nanoparticles (Ag) were grown on the surface of N, S@PC/GE to improve the conductivity/surface area of the sensor and represent an internal reference signal for ratiometric response. The monomer (pyrrole-4-carboxylic acid, Py-COOH) was electro-polymerized on the surface of Ag/N, S@PC/GE in the presence of Cu (II) to form Cu-MIP@Ag/N, S@PC/GE. Addition of GSH decreased the signal of Ag at 0.18 V (oxidation of Ag) due to coordination complexation, while the signal response at 0.83 V (oxidation of Ag-GSH complex) was increased. Under optimum conditions, the ratio response (IGSH/IAg) was increased with increasing the concentration of GSH in the range of 0.01-500 nM with a detection limit (S/N = 3) of 0.003 nM. The electrochemical sensor exhibits many advantages including low LOD, high selectivity, good reproducibility, and satisfactory stability. The sensor was successfully applied to determine GSH in dietary supplements and human serum samples with recoveries % ranged from 97.4 to 101.8% and relative standard deviation % (RSD %) did not exceed 3.8%. This research paper introduces new information for the construction of molecular imprinted ratiometric-based electrochemical sensors for highly selective and sensitive detection of (bio) molecules.