Chitosan-based magnetic molecularly imprinted polymer: synthesis and application in selective recognition of tricyclazole from rice and water samples

A tricyclazole selective chitosan/Fe₃O₄ magnetic molecularly imprinted polymer (MMIP) was synthesized using non-covalent binding polymerization involving methacrylic acid (MAA) as functional monomer, divinylbenzene (DVB-80) as crosslinker, 2,2'-azobisisobutyronitrile as initiator, acetonitrile/toluene (75:25, v/v) as porogenic solvent and tricyclazole as template. Surface morphology and magnetic characterization of the prepared imprinted and non-imprinted polymers were done using scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry and vibrating sample magnetometry, respectively. The adsorption kinetic data fitted best in pseudo-second-order model. The adsorption equilibrium was achieved in 30 min and the maximum binding capacity was 4579.9 µg/g. The Freundlich isotherm model was found suitable for explaining the binding isotherm data (R²?>?0.99). Negative values of thermodynamic parameters ?G (Gibb’s free energy), ?H (enthalpy), and ?S (entropy) revealed exothermic and spontaneous nature of adsorption processes. It also revealed decreased randomness at the solid–liquid interface during sorption. The scatchard plot analysis suggested heterogeneity of binding sites on MMIPs. The molecular recognition selectivity of MMIPs towards tricyclazole was much higher, as compared to its structural analogues, tebuconazole (α?=?28.58) and hexaconazole (α?=?37.16). The MMIPs were successfully applied to separate and enrich tricyclazole from fortified samples of rice and water, with a recovery percentage of 89.4% and 90.9%, respectively. These reusable imprinted polymers possessing high selectivity and specificity can be utilized as an adsorbent for solid-phase extraction in sample preparation for tricyclazole residue analysis in complex environmental matrices.