Dual-template imprinted polymer electrochemical sensor for simultaneous determination of malathion and carbendazim using graphene quantum dots

Abstract

Malathion (MAL) and carbendazim (CBZ) are organophosphate pesticides and fungicides, respectively. They are often used simultaneously in agriculture, and both have been shown to have harmful effects on humans and animals. Therefore, it is important to be able to measure both of these toxins simultaneously in order to assess their potential risks. This study aims to design a dual template electrochemical sensor using a cost-effective graphite-epoxy composite electrode (GECE) modified with molecularly imprinted polymers (MIPs) coated on graphene quantum dots (GQDs) for simultaneous detection of MAL and CBZ in real samples. GQDs were synthesized initially, and their surface was coated with MIPs that were formed using MAL and CBZ as the template molecules, ethylene glycol dimethyl acrylate as the cross-linker, and methacrylic acid as the functional monomer. The GQDs@MIP were characterized using Fourier transform infrared spectroscopy, field-emission scanning electron microscopy, and X-ray scattering spectroscopy. Parameters affecting the sensor response, such as the percentage of GQDs@MIP in the fabricated electrode, the pH of the rebinding solution and analysis solution, and the incubation time, were optimized. The optimum pH values of the rebinding solution were verified using density functional theory (DFT) calculations. Under the optimized conditions, differential pulse voltammetry (DPV) response calibration curves of MAL and CBZ were generated, and the results showed that the sensor had a linear response to MAL in the range of 0.02–55.00 μM with a limit of detection (LOD) of 2 nM (S/N = 3) and to CBZ in the range of 0.02–45.00 μM with a low LOD of 1 nM (S/N = 3). The results also demonstrated the proposed sensor's long-term stability and anti-interference capability. The practical applicability of the fabricated electrode was evaluated for real sample analysis, and good recovery values were obtained.