Dispersive liquid‒liquid microextraction combined with enzyme-linked immunosorbent assay for the analysis of chlorpyrifos in cereal samples.

In this paper, an analysis method for chlorpyrifos (CPF) in cereal samples was proposed using dispersive liquid‒liquid microextraction combined with an enzyme-linked immunosorbent assay. In the dispersive liquid‒liquid microextraction, deep eutectic solvents and fatty acids were used as solvents to extract, purify, and concentrate CPF in cereals. In the enzyme-linked immunosorbent assay, gold nanoparticles were utilized to enrich and conjugate more antibodies and horseradish peroxidase, while magnetic beads were used as solid supports to amplify the signal and shorten the detection time of CPF. The linearity range was 0.002-1 µg kg-1, and the limit of detection was 0.0006 µg kg-1. The extraction recoveries were 86.7-99.9% with a relative standard deviation of less than 7.0%. The proposed method was successfully used to analyze CPF in cereal samples (rice, wheat, maize, and millet) and has prospects for the pretreatment and detection of CPF residues in other food samples.

Hydrophilic and hydrophobic deep eutectic solvent-based extraction to determine parathion in cereals by digital image colorimetry integrated with smartphones.

To determine parathion in cereals, hydrophilic and hydrophobic deep eutectic solvents (DESs) were used by digital image colorimetry with smartphones. In the solid-liquid extraction part, hydrophilic DESs were used as extractants to extract parathion from cereals. In the liquid-liquid microextraction part, hydrophobic DESs dissociated into terpineol and tetrabutylammonium bromide in situ. The dissociated hydrophilic tetrabutylammonium ions reacted with parathion extracted in hydrophilic DESs under alkaline conditions to produce a yellow product, which was extracted and concentrated by dispersed organic phase terpinol. Digital image colorimetry integrated with the use of a smartphone was used for quantitative analysis. The limit of detection and quantification were 0.003 mg kg-1 and 0.01 mg kg-1, respectively. The recoveries for parathion were 94.8-106.2% with a relative standard deviation less than 3.6%. The proposed method was applied to analyze parathion in cereal samples: the method has the potential to be applied to pesticide residue analysis in food products.

Deep eutectic solvent-based adhesive tape extraction combined with enzyme inhibition assay for the determination and distinction of dithiocarbamate pesticides in food samples.

A simple, green extraction method of dithiocarbamate (DTC) pesticides in food samples was developed using adhesive tapes and a green deep eutectic solvent (DES). A rapid and convenient determination and distinction method of DTC pesticides was established using tyrosinase inhibition assay. First, DTC pesticides were extracted by pasting and peeling off the adhesive tape, then eluted by the DES synthesized from xylitol and ethylene glycol. Second, determination of DTC pesticides was conducted by inhibiting the activity of tyrosinase which can catalyze the oxidation of catechol. Less colored products were generated in the reaction system (tyrosinase, catechol, and 4-aminoantipyrine), leading to weak absorbance. In addition, different DTC pesticides (ziram, propineb, zineb, mancozeb, thiram, metiram, and ferbam) were successfully distinguished by sensor arrays (tyrosinase, phenolic compounds, and 4-aminoantipyrine) through principal component analysis. The limit of detection was found to be 0.2 µg kg-1, and the limit of quantification was 0.6 µg kg-1. The recoveries ranging from 89.4% to 103.8% were obtained in vegetable, fruit, and cereal, with a relative standard deviation of less than 4.2%. The method is simple, rapid, and convenient and shows good application prospects in the determination of pesticides in a variety of food samples.

Deep eutectic solvent-based dispersive liquid-liquid microextraction followed by smartphone digital image colorimetry for the determination of carbofuran in water samples.

A detection method of carbofuran (CBF) in water samples was reported using deep eutectic solvent (DES)-based dispersive liquid-liquid microextraction (DLLME) combined with digital image colorimetry (DIC), which was environmentally friendly, solvent-saving, rapid, and convenient. Under alkaline conditions, the green and multifunctional extractant DESs dissociated into linalool and heptanoic acid, and CBF was hydrolyzed to 2,3-dihydro-2,2-dimethyl-7-benzofuranol and further coupled with fast blue BB salt to form an azo derivative. Heptanoic acid led to the dispersion of linalool to extract the orange-red azo derivative; DIC was used for quantitative analysis using a smartphone with its associated ease of data-acquisition. This experiment optimized the types, molar ratios, and volumes of DESs and the amounts of sodium carbonate and sodium chloride. Under optimal conditions, the limits of detection (LOD) and quantitation (LOQ) were 0.024-0.032 mg L-1 and 0.081-0.108 mg L-1, respectively. The extraction recoveries in real samples (tap, pond, and river water) were 92.4-101.0% with a relative standard deviation below 4.6%. This method has successfully analyzed CBF in different water samples and shows prospects for the monitoring and control of CBF residues in other environmental samples.