Facile synthesis of magnetic molecularly imprinted polymer: Perphenazine template and its application in urine and plasma analysis

Synthesis of magnetic iron oxide nanoparticles and its surface modification with methacrylic acid (MAA) was performed simultaneously by adding Fe2+/Fe3+ to an alkaline MAA solution under nitrogen atmosphere. MAA coated magnetite (Fe3O4@MAA) has abundant reactive double bonds on the surface that can initiate polymerization. Magnetic molecularly imprinted polymers (MMIPs) were synthesized through distillation⿿precipitation polymerization of MAA as monomer, perphenazine (PPZ) as template, and ethylene glycol di-methacrylate (EGDMA) as cross linker on Fe3O4@MAA, with concise control of experimental conditions in about 90 min. The produced super paramagnetic MMIPs can be separated from the solution in the presence of external magnetic field in less than 1 min. Characterizations of the synthesized particles were performed by electron microscopes, thermo-gravimetric analysis (TGA), vibrating sample magnetometer (VSM), Fourier transform infrared (FT-IR) spectroscopy, and BET. The data showed that Fe3O4@MAA was well encapsulated in the polymer shell. The MMIPs showed high porosity. Moreover, MMIPs were used for rapid pre-concentration and separation of PPZ in human plasma and urine without any dilution and pretreatments using high performance liquid chromatography equipped with a photo diode array detector (HPLC-PDA). The calibration curve in urine and plasma has shown the same slope as the external calibration curve. Linear range of 20⿿5000 ng mL⿿1, and a detection limit of 5.3 ng mL⿿1 was obtained. The results showed 97.92% recovery along with the relative standard deviation of 6.07% (n = 6) for 1 μg mL⿿1 PPZ. Pre-concentration factor was 13. The MMIPs adsorbed PPZ in 1 min and then desorbed it by MeOH:HOAc in 2 min.