Fe₃O₄@rGO doped molecularly imprinted polymer membrane based on magnetic field directed self-assembly for the determination of amaranth.

Based on magnetic field directed self-assembly (MDSA) of Fe3O4@rGO composites, a novel magnetic molecularly imprinted electrochemical sensor (MIES) was fabricated and developed for the determination of the azo dye amaranth. Fe3O4@rGO composites were obtained by a one-step approach involving the initial intercalating of iron ions between the graphene oxide layers via the electrostatic interaction, followed by the reduction with hydrazine hydrate to deposit Fe3O4 nanoparticles onto the reduced oxide graphene nanosheets. In molecular imprinting, the complex including the function monomer of aniline, the template of amaranth and Fe3O4@rGO was pre-assembled through π-π stacking and hydrogen bonding interactions, and then was self-assembled on the surface of magnetic glassy carbon electrode (MGCE) with the help of magnetic field induction before electropolymerization. The structures and morphologies of Fe3O4@rGO and the doped molecularly imprinted polymers (MIPs) were investigated by Fourier transform infrared spectrometer (FT-IR), Raman spectra and scanning electron microscope (SEM). Besides, the characterization by differential pulse voltammetry (DPV) showed that Fe3O4@rGO composites promoted the electrical conductivity of the imprinted sensors when doped into the MIPs. The adsorption isotherms and adsorption kinetics were employed to evaluate the performances of MIES. The detection of amaranth was achieved via the redox probe K3[Fe(CN)6] by blocking the imprinted cavities, which avoided the interferences of oxidation products and analogs of amaranth. Furthermore, the prepared MIES exhibited good sensitivity, selectivity, reproducibility and efficiency for detecting amaranth in fruit drinks. The average recoveries were 93.15-100.81% with the RSD <3.0%.