Efficient enrichment and sensitive determination of endocrine disruptors in PPCPs by novel magnetic covalent organic framework extraction coupled with HPLC-MS/MS

Endocrine-disrupting chemicals (EDCs) are a growing class of pollutants commonly found in environmental matrices due to their extensive use in pharmaceuticals and personal care products (PPCPs). In this study, a novel magnetic covalent organic framework (COF), Fe 3 O 4 –COOH@TFP-BHBD, was successfully synthesized and utilized as an adsorbent for magnetic solid-phase extraction (MSPE) of EDCs from PPCPs. The core-shell structured adsorbent demonstrated a high specific surface area, strong magnetic responsiveness and excellent stability. A COF-MSPE-high-performance liquid chromatography-tandem mass spectrometry (COF-MSPE-HPLC-MS/MS) method was developed for the quantitative analysis of EDCs in PPCPs. Under the optimized condition, the detection and quantification limits of this method reached as low as 0.001–0.007 ng/mL and 0.004–0.025 ng/mL, respectively. This method was validated and proven capable to analyze real PPCP samples, while the spiked recovery rates in ranged from 85.62 to 107.83 % with RSD of 2.28–8.58 %. Moreover, the adsorption mechanism was investigated using density functional theory (DFT) calculations. The DFT results revealed that the efficient enrichment capacity of Fe 3 O 4 –COOH@TFP-BHBD for EDCs can be attributed to π-π interactions and hydrogen bondings. This proposed method provides excellent adsorption ability and sensitivity for the extraction and precise detection of EDCs in PPCPs.