Magnetic solid-phase extraction modified Quick, Easy, Cheap, Effective, Rugged and Safe method combined with pre-column derivatization and ultra-high performance liquid chromatography-tandem mass spectrometry for determination of estrogens and estrogen mimics in pork and chicken samples

Abstract

In this study, conventional Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method was modified by magnetic solid-phase extraction (MSPE) for purification/pre-concentration of eleven estrogens and estrogen mimics from the extracts of pork and chicken muscles, prior to dansyl chloride (DNS-Cl) derivatization coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) assay. Dual octadecyl- and 2-aminoethyl-3-aminopropyl- groups functionalized mesoporous silica core-shell magnetic nanoparticles (C18/NH2-Fe3O4@mSiO2 MNPs) were synthesized and employed as MSPE sorbent with remarkable aqueous compatibility in comparison with conventional C18 functionalized sorbent. The proposed MSPE is easier to handle than the traditional SPE purification process in QuEChERS method. The lab-prepared MNPs were characterized by transmission electron microscope (TEM), brunner-emmet-teller (BET), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA) and vibrating sample magnetometer (VSM). Pre-column derivatization was conducted to significantly enhance the sensitivity of the analytes in MS/MS via analyzing their derivatives in positive ion mode instead of analyzing their original forms in negative ion mode. Under the optimal sample pretreatment and instrumental analysis conditions, the approach showed low limits of detection (LODs, 0.02‒3.00 µg kg–1), appropriate recoveries (81.1‒115.4%) and acceptable precisions (0.48‒15.1%, n = 6), with good feasibility and future prospect of trace compounds analysis in complex food samples.