Covalent organic framework-based magnetic solid-phase extraction coupled with gas chromatography-tandem mass spectrometry for the determination of trace phthalate esters in liquid foods

Covalent organic framework-coated magnetite particles (Fe₃O₄@COF) were synthesized and applied as the adsorbent to the selective capture of phthalate esters (PAEs) in liquid foods. Combined with the magnetic solid-phase extraction (MSPE) technology, a gas chromatography-tandem mass spectrometry (GC-MS/MS) method was employed for the separation and quantification of PAEs. Following optimization of the magnetic extraction and elution parameters, the developed analytical method offered a satisfactory linear range (0.1-5 μg L^-1) with determination coefficients ranging from 0.9934 to 0.9975 for the five different PAEs studied. The limits of detection (LOD) were in the range 1.9-12.8 ng L^-1. The recoveries ranged from 70.0 to 119.8% with a relative standard deviation (RSD) less than 9.7%. Density functional theory (DFT) calculations established that the dominant adsorption mechanism used by the COF to bind PAEs involved π-π stacking interactions. Results encourage the wider use of COF-based adsorbents and MSPE methods in the analytical determination of PAEs in foods.