Determination of trace bisphenols in milk based on Fe3O4@NH2-MIL-88(Fe)@TpPa magnetic solid-phase extraction coupled with HPLC

Abstract

Herein, a covalent organic framework (COF) was grown on a magnetic metal-organic framework (MOF) by a solvothermal method for the efficient extraction of bisphenols (BPs). The magnetic solid-phase extraction (MSPE) of four bisphenols (bisphenol A, bisphenol B, bisphenol AF and bisphenol C) was carried out without adjusting the pH and salt concentration. When 30 mg Fe3O4@NH2-MIL-88(Fe)@TpPa was used to adsorb for 25 min, 6 mL methanol was used to elute for 20 min, and the extract was detected by high-performance liquid chromatography (HPLC). The proposed method has a low detection limit of 0.011–0.036 ng mL−1, a wide linear range of 0.05–100 ng mL−1, and a correlation coefficient (R2) of 0.9980–0.9998. The intra-day and inter-day precisions are 0.74–2.54% and 1.68–3.72%, respectively. Bisphenol A was determined by applying the proposed method to the determination of actual milk samples. The standard addition experiment showed that the relative recovery of the four bisphenols was 85.70–119.7%. Pseudosecond-order, first-order, Langmuir and Freundlich models were applied to explore the adsorption characteristics of Fe3O4@NH2-MIL-88(Fe)@TpPa. In general, the established Fe3O4@NH2-MIL-88(Fe)@TpPa-MSPE-HPLC-UV method exhibits attractive sensitivity, simple manipulation, and excellent reusability, and it has excellent prospects for the detection of trace BPs in complex milk matrices.