A new core–shell magnetic mesoporous surface molecularly imprinted composite and its application as an MSPE sorbent for determination of phthalate esters

Abstract

In this study, a new core–shell magnetic mesoporous surface molecularly imprinted polymer (Fe₃O₄@SiO₂@mSiO₂-MIPs) which has specific adsorption and rapid adsorption rate for phthalate esters (PAEs) was prepared by a convenient method. Based on this composite as a magnetic solid phase extraction (MSPE) material, a rapid, efficient and sensitive matrix dispersion magnetic solid-phase extraction gas chromatography-mass spectrometry method (DMSPE-GC/MS) was developed for the determination of PAEs in multiple liquid samples. It is the first time that Fe₃O₄@SiO₂@mSiO₂-MIPs have been prepared by bonding amino groups on the surface of a double layer silicon substrate with diisononyl phthalate (DINP) as virtual template and 3-(2-aminoethyl)-aminopropyl trimethoxymethylsilane (TSD) as functional monomer. FT-IR, TEM, EDS, SEM, XRD, BET and VSM were used to characterize the composite. The adsorption isotherm and kinetics of Fe₃O₄@SiO₂@mSiO₂-MIPs showed that it possessed fast adsorption rates (approximately 5 min to reach equilibrium), high adsorption capacities (523.9 mg g⁻¹) and good recognition of PAEs. The real samples were preconcentrated by Fe₃O₄@SiO₂@mSiO₂-MIPs, under the optimum DMSPE-GC/MS conditions. Validation experiments showed that the method presented good linearity (R² > 0.9971), satisfactory precision (RSD < 5.7%) and high recovery (92.1–105.8%), and the limits of detection ranged from 1.17 ng L⁻¹ to 3.03 ng L⁻¹. The results indicated that the novel method had good sensitivity, high efficiency and wide sample application and was suitable for the determination of PAEs in liquid drink samples such as water, alcohol, beverages and so on.