Highly Permselective Membrane Surface Modification by Cold Plasma-Induced Grafting Polymerization of Molecularly Imprinted Polymer for Recognition of Pyrethroid Insecticides in Fish

Specific molecularly imprinted membranes (MIMs) for pyrethroid insecticides were developed and characterized for the first time in this study by cold plasma-induced grafting polymerization using methacrylic acid as a functional monomer and cypermethrin (CYP) as a template. The nonimprinted membranes (NIMs) were also synthesized using the same procedure without the template. Meanwhile, AFM, XPS, ATR-FTIR, contact angle, and permselectivity experiments were conducted to elucidate the imprinting and recognition properties of MIMs. Results demonstrated that MIMs exhibited excellent imprinting effect and high permselectivity. A molecularly imprinted-membrane-assisted solvent extraction (MI-MASE) method based on the MIMs was established. The operating conditions were optimized for group-selective extraction of the five pyrethroid insecticides. Compared with NIMs, higher extraction recoveries (83.8% to 100.6%) of the five pyrethroid insecticides by gas chromatography-electron capture detector (GC-ECD) were obtained using MIMs at three spiked levels in fish samples; the RSD values were lower than 8.3%. The limits of detection (LOD) and quantification (LOQ) defined as the concentrations at which the signal-to-noise (S/N) ratio is 3:1 and 10:1, respectively, were in the range of 0.26 to 0.42 ?g/kg and 0.77 to 1.27 mu g/kg, respectively. No matrix effect of the developed MI-MASE was observed by gas chromatography/tandem mass spectrometry (GC/MS/MS). These results demonstrated a highly selective, efficient, and environment-friendly MI-MASE technique for preconcentration and purification of pyrethroid insecticides from seafood, followed by GC-ECD and GC/MS/MS. The excellent applicability and potential of MI-MASE for routine monitoring of pyrethroid pesticides in food samples has also been confirmed.