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

Abstract

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.