Selective Adsorption of Quercetin by the Sol-Gel Surface Molecularly Imprinted Polymer.

Abstract

Quercetin, as one of the most biologically active natural flavonoids, is widely found in various vegetables, fruits and Chinese herbs. In this work, molecularly imprinted polymer (MIP) was synthesized through surface molecular imprinting technology with sol-gel polymerization mechanism on SiO2 at room temperature using quercetin as the template, SiO2 as the supporter, 3-aminopropyltriethoxysilane (APTES) as the functional monomer, and tetraethoxysilane (TEOS) as the cross-linker. The prepared MIP was characterized via scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR) and nitrogen adsorption measurements to validate its surface morphology, structure and functionality. SEM images revealed that the morphology of MIP was rough and spherical with the particle size of 260 nm larger than that of the support SiO2. In the FTIR spectra of MIP, the band around 1499 cm-1 and 2932 cm-1 were assigned to N-H and C-H groups, respectively. The results indicated that the imprinted polymer layers were grafted on the surface of SiO2 and the MIP had been successfully prepared. Since the specific surface area and pore volume of MIP were markedly higher than those of NIP and SiO2 and were 52.10 m2 g-1 and 0.150 cm3 g-1, respectively, it was evident that the imprinting process created corresponding imprinted cavities and porosity. The MIP for adsorbing quercetin was evaluated by static adsorption experiment. The results indicated that the adsorption equilibrium could be reached within 90 min and the maximum adsorption capacity was as high as 35.70 mg/g. The mechanism for adsorption kinetics and isotherm of MIP for quercetin was proved to conform the pseudo-second-order kinetics model (R2 = 0.9930) and the Freundlich isotherm model (R2 = 0.9999), respectively, revealing that chemical adsorption and heterogeneous surface with multilayer adsorption dominated. In contrast to non-imprinted polymer (NIP), the MIP demonstrated high selectivity and specific recognition towards quercetin whose selectivity coefficients for quercetin relative to biochanin A were 1.61. Furthermore, the adsorption capacity of MIP can be maintaining above 90% after five regeneration cycles, indicating brilliant reusability and potential application for selective adsorption of quercetin.