Recent advances in molecular-imprinting-based solid-phase microextraction for determination of pharmaceutical residues

Abstract

Pharmaceutical residues usually exist in various complicated matrices at trace levels, but pose potential threats to human health and ecological environment. Recognition and determination of the residues are important and urgent. Therefore, efficient sample pretreatment techniques become a research hotspot for the sensitive and precise determination by chromatography and mass spectrometry. Molecular-imprinting-based solid-phase microextraction (MI-SPME) combines the rapidity, high enrichment and solvent-free property of SPME with the specific recognition and selective adsorption ability of molecularly imprinted polymers (MIPs), and shows significant advantages in the highly selective separation and enrichment of drug residues in complex samples. Herein, we review recent advances in MI-SPME for determination of pharmaceutical residues since 2019. Firstly, the basic characteristics and operation process of SPME are briefly introduced, and then the polymerization methods of MIPs including free radical polymerization, in-situ polymerization and sol-gel polymerization, and new imprinting technologies and strategies including surface imprinting, nano-imprinting, dummy template, multi-template/functional monomer imprinting and stimuli-responsive imprinting, are comprehensively overviewed. Then, various modes of MI-SPME device are meticulously discussed, mainly including MIPs-coated fiber SPME, MIPs-based in-tube SPME, dispersible SPME, MIPs in-tip SPME, MIPs stir bar sorptive extraction, and MIPs thin film microextraction. Subsequently, typical application cases of MI-SPME coupled with chromatography and mass spectrometry for the determination of drug residues are summarized, in the fields of food safety, biological medicine and environmental monitoring, specially mentioning chiral drug detection and matrix effects and interferences. Finally, the possible challenges of MI-SPME in drug residue detection are presented, and the research prospects and development trends of MI-SPME are proposed.