Magnetic molecular imprinted covalent organic framework composite for the magnetic solid-phase extraction of bisphenol AF

Abstract

A magnetic molecular imprinted covalent organic framework composite (MCOF-MIP) that possessed the ‘dual-selectivity’ of a covalent organic framework and molecular imprinted polymer (MIP) with rapid response performance was successfully prepared for the removal of bisphenol AF (BPAF) from real water and blood samples. First, the MCOF was separately synthesized using magnetic Fe3O4 as the magnetic core, 1,3,5-triaminobenzene and 2,5-dibromobenzene-1,4-diformaldehyde as precursors and a deep eutectic solvent (DES) as the solvent using a solvothermal synthesis method. The MCOF showed high crystallinity and good adsorption capacities for BPAF (107.4 mg g−1), bisphenol A (113.6 mg g−1), bisphenol S (120.0 mg g−1) and bisphenol F (82.1 mg g−1). To further improve the selectivity for BPAF, an MIP, which uses BPAF as a template, was introduced to form the MCOF-MIP. Due to the dual selectivity of MCOF and MIP, the MCOF-MIP exhibited relatively high selective adsorption capacity to BPAF (243.1 mg g−1) compared to that for the MCOF (107.4 mg g−1), while the adsorption capacities (149.7–109.4 mg g−1) for the other three compounds were not significantly improved. Furthermore, a magnetic solid-phase extraction (MSPE) method was established, and MSPE parameters such as adsorbent dosage, adsorption time, desorption solvent and desorption time were optimized. Combined with high-performance liquid chromatography with diode-array detection (HPLC-DAD) analysis, a rapid and sensitive method was developed to detect BPAF, which showed good linearity (r > 0.9969) ranging from 0.1 to 400 μg mL–1. Low limits of detection (0.04 μg mL–1, S/N = 3) and quantitation (0.1 μg mL–1, S/N = 10) and good precision with low relative SDs (<1.2 % for intra-day and <1.1 % for inter-day) were also obtained. Finally, MSPE coupled with HPLC-DAD was employed for the analysis of BPAF in water and blood samples, and the recoveries of BPAF were satisfactory (91.1–112.6 %).