Selective recognition and enrichment of sterigmatocystin in wheat by thermo-responsive imprinted polymer based on magnetic halloysite nanotubes

Abstract

Two thermo-responsive molecularly imprinted polymers (MHNTs@MIP and MCNTs@MIP) for the selective extraction of sterigmatocystin have been prepared on the surface of the magnetic halloysite nanotubes (MHNTs) and magnetic carbon nanotubes (MCNTs), respectively. 1, 8-dihydroxyanthraquinone, n-isopropyl acrylamide, methacrylic acid, ethylene dimethacrylate and dimethyl sulfoxide were used as the dummy template, thermo-sensitive functional monomer, co-monomer, cross-linker and porogen, respectively. The magnetic properties, adsorption properties as well as the temperature responsive behaviors of MHNTs@MIP and MCNTs@MIP were systematically studied and compared for the first time. Enough saturation magnetizations of MHNTs@MIP (9.42 emu/g) and MCNTs@MIP (10.54 emu/g) were obtained. MHNTs@MIP and MCNTs@MIP also showed controllable adsorption and release behaviors to sterigmatocystin in response to the temperature change (35 °C and 20 °C). Compared with MCNTs@MIP, MHNTs@MIP had higher adsorption affinity (KL = 0.120 L/mg), higher adsorption kinetic (K2 = 0.0100 g/(mg•min)) and higher imprinting factor (5.22) to sterigmatocystin. These results indicated that MHNTs@MIP was favorable adsorbent for the selective separation of sterigmatocystin. Furthermore, the elution conditions of MHNTs@MIP were optimized by response surface methodology. Under the optimal conditions, MHNTs@MIP coupled with high performance liquid chromatography were successfully applied to the selective recognition, purification, enrichment and detection of sterigmatocystin in wheat samples. The recoveries were calculated from 88.62% to 102.9% with RSDs less than 3.5 % and limit of detection of 1.1 μg/kg. This work provided a suitable carrier for the preparation of imprinted polymers and a practical approach for highly selective recognition and determination of analytes in real samples.