Highly permselective membrane surface modification by cold plasma-induced grafting polymerization of molecularly...

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 μg/kg and 0.77 to 1.27 μg/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.