Highly sensitive determination of endocrine disrupting chemicals in foodstuffs through magnetic solid-phase extraction followed by high-performance liquid chromatography-tandem mass spectrometry.

Abstract

Endocrine disrupting chemicals (EDCs), proved to be potential carcinogenic threats to human health, have received great concerns in food field. It was essential to develop effective methods to detect EDCs in food samples. The present study proposed an efficient method to determine trace EDCs including estrone (E1), 17β-estradiol (E2), estriol (E3) and bisphenol A (BPA) based on magnetic solid-phase extraction (MSPE) coupled high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) in meat samples. Fe3 O4 @COF(TpBD)/TiO2 nanocomposites were synthesized via functionalization of magnetic covalent organic frameworks (COFs) with titanium dioxide (TiO2 ) nanoparticles, and used as absorbents of MSPE to enrich EDCs. The efficient EDCs enrichment relies on π-π stacking interaction, hydrogen bonding, and the interaction between titanium ions (IV, Ti4+ ) and hydroxyl groups in EDCs, which improves the selectivity and sensitivity. Under the optimized conditions, target EDCs were rapidly extracted through MSPE with 5 min. Combining Fe3 O4 @COF(TpBD)/TiO2 based MSPE and HPLC-MS/MS to determine EDCs, good linearities were observed with correlation coefficient (R2 ) ≥ 0.9989. The limits of detection (LODs) and limits of quantification (LOQs) were 0.13-0.41 μg kg-1 and 0.66-1.49 μg kg-1 , respectively. Moreover, the proposed method was successfully applied to real samples analysis. The established MSPE-HPLC-MS/MS method was successfully applied to determine EDCs in meat samples with rapidness, improved selectivity and sensitivity. It shows great prospects for EDCs detection in other complicated matrices. © 2020 Society of Chemical Industry.