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

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.

Preparation of magnetic molecularly imprinted polymer based on multiwalled carbon nanotubes for selective dispersive micro-solid phase extraction of fenitrothion followed by ion mobility spectrometry analysis.

A novel molecularly imprinted polymer based on magnetic multiwalled carbon nanotubes was fabricated and applied for selective dispersive micro-solid phase extraction of fenitrothion prior its determination by ion mobility spectrometry. The composite was synthesized using magnetic multiwalled carbon nanotubes as the support. Methacrylic acid was used as the functional monomer, fenitrothion as the template, ethylene glycol dimethacrylate as the cross-linker, and 2,2-azoisobutyronitrile as the initiator. The resultant polymer was characterized by FTIR spectroscopy, X-ray diffraction, field emission scanning electron microscopy, Brunauer-Emmet-Teller analysis, thermogravimetric analysis, and vibrating sample magnetometer techniques. Experimental factors affecting the extraction efficiency such as pH and amount of sorbent were evaluated. Under optimum experimental conditions, the developed method displayed the linear range of 5-220 µg/L with a detection limit of 1.3 µg/L. The intra- and interday relative standard deviations for determination of fenitrothion were 3.6 and 4.7% (n = 6), respectively. Ultimately, the proposed method was used to monitor trace amounts of fenitrothion in fruits, vegetables, and water samples.

Temperature-controlled liquid-liquid microextraction combined with high-performance liquid chromatography for the simultaneous determination of diazinon and fenitrothion in water and fruit juice samples.

A simple, environmentally benign, and rapid method based on temperature-controlled liquid-liquid microextraction using a deep eutectic solvent was developed for the simultaneous extraction/preconcentration of diazinon and fenitrothion. The method involved the addition of deep eutectic solvent to the aqueous sample followed by heating the mixture in a 75°C water bath until the solvent was completely dissolved in the aqueous phase. Then, the resultant solution was cooled in an ice bath and a cloudy solution was formed. Afterward, the mixture was centrifuged and the enriched deep eutectic solvent phase was analyzed by high-performance liquid chromatography with ultraviolet detection for quantification of the analytes. The factors affecting the extraction efficiency were optimized. Under the optimized extraction conditions, the limits of detection for diazinon and fenitrothion were 0.3 and 0.15 µg/L, respectively. The calibration curves for diazinon and fenitrothion exhibited linearity in the concentration range of 1-100 and 0.5-100 µg/L, respectively. The relative standard deviations for five replicate measurements at 10.0 µg/L level of analytes were less than 2.8 and 4.5% for intra- and interday assays, respectively. The developed method was successfully applied to the determination of diazinon and fenitrothion in water and fruit juice samples.

Preparation of magnetic mesoporous silica composite for the solid-phase microextraction of diazinon and malathion before their determination by high-performance liquid chromatography.

A novel magnetic mesoporous silica material was synthesized and used as the sorbent for the magnetic solid-phase microextraction of diazinon and malathion before their quantification by high-performance liquid chromatography with UV detection. The sorbent was synthesized by a surfactant-templated one-pot sol-gel procedure using SiO2 -coated Fe3 O4 as the magnetic support, cetyltrimethylammonium bromide as the template and tetraethyl orthosilicate as the silicon source. The characteristics of the prepared sorbent were investigated using Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction. The sorbent exhibited a high maximum adsorption capacity of 19.2 and 9.4 mg/g for diazinon and malathion, respectively. The parameters affecting the microextraction were optimized by the MultiSimplex method. Under the optimized conditions, the calibration graphs were linear in the concentration ranges of 0.3-50.0 and 0.5-50 µg/L with the limits of detection of 0.09 and 0.14 µg/L for diazinon and malathion, respectively. The relative standard deviations (n = 5) at a concentration level of 10.0 µg/L of analytes were less than 2.5 and 4% for intra and interday, respectively. The developed method was successfully used for the determination of diazinon and malathion in apple, tomato, cucumber, tap water, and well water samples.