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

Abstract

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.

Amine Enrichment of Thin-Film Composite Membranes via Low Pressure Plasma Polymerization for Antimicrobial Adhesion

“…[24][25] Low pressure plasma is a rapidly developing surface modification technique that has been used for almost four decades across a range of different industries. [26][27][28][29] In membrane technology, plasma treatment has been intensively studied over the last two decades in attempts to increase the hydrophilicity and improve the low-fouling properties of ultra and microfiltration membranes. 25 A challenge in applying plasma polymerization to TFC membranes is the 5 difficulty of characterizing the plasma polymerized coatings, since the functionalities of the polymerized surface can be unpredictably rearranged.…”

A microtitre chemiluminescence sensor for detection of pyrethroids based on dual‐dummy‐template molecularly imprinted polymer and computational simulation

“…In the previous reports, different parent PYs were used as templates to synthesize the MIPs for PYs (deltamethrin, cypermethrin, cyhalothrin, fenpropathrin, and fenvalerate) . Among these MIPs, the cypermethrin‐based MIP showed the broadest recognition ability recognized six PYs .…”

“…The extraction of PYs from chicken sample was according to a previous report . Briefly, the chicken muscle sample was homogenized, and 2.0 g sample homogenate was weighed into a centrifuge tube.…”

“…Therefore, there have been many articles reporting the use of MIPs as recognition elements to develop various analytical methods for the detection of different analytes, such as electrochemical sensor, pseudoimmunoassay and flow‐injection CL method . Previously, there have been some papers reporting the synthesis of MIPs for PYs, but most of the reported MIPs are used as absorbents to develop different sample extraction methods, and only two of these have been used as recognition reagents to prepare CL methods for detection of PYs …”

Construction of imprint sites in mesopores of SBA-15 via thiol-ene click reaction

“…These drawbacks arise from the high cross-linking nature of 3D MIPs. To overcome such drawbacks, different strategies, such as surface imprinting [9][10][11], preparing molecularly imprinted hollow spheres [12,13], nano-scaled imprinted materials [6,[14][15][16][17], and thin films [18,19], have been developed. The purpose of these strategies is to prepare the imprinted materials in the optimizing forms that control recognition sites to be situated at the surface or in the proximity of materials surface.…”