Magnetic dual-dummy-template molecularly imprinted polymer synthesized from plant's phenolic acid-derived deep eutectic solvents for the enrichment of organophosphorus pesticides from rice samples before LC-MS/MS analysis.

Abstract

A novel magnetic molecularly imprinted polymer (MDMIP) is synthesized using deep eutectic solvents (DESs) derived from choline chloride, plant phenolic acids, and formic acid as green binary functional monomers. Choline chloride-2-naphthol and choline chloride-thymol-ethanol DESs are used as a dual-dummy template. The MDMIP is applied in magnetic solid phase extraction coupled with liquid chromatography-tandem mass spectrometry to determine seven organophosphorus pesticides in rice samples. The adsorption behavior follows the pseudo-second-order (R2 > 0.999) and Freundlich (R2 > 0.987) models, with an imprinting factor of 2.02, indicating high selectivity. The method exhibits a wide linear range (0.0010-5 μg L-1), low detection limits (0.00050-0.010 μg L-1), and satisfactory recovery rates (80.64 %-112.2 %, relative standard deviations <7.7 %). The incorporation of plant phenolic acid-based DESs offers a sustainable synthetic route while enhancing the adsorption efficiency and analytical performance of the magnetic adsorbent.