Construction of a magnetic covalent organic framework for magnetic solid-phase extraction of AFM1 and AFM2 in milk prior to quantification by LC-MS/MS.

Abstract

A magnetic covalent organic framework (M-COF) was designed and selected as sorbent for magnetic solid-phase extraction (MSPE) of AFM1 and AFM2 in milk, followed by LC-MS/MS analysis. The application of 2,5-Dihydroxy-1,4-benzenedicarboxaldehyde (Dt) and 4',5'-bis(4-aminophenyl)-[1,1':2',1″-terphenyl]-4,4″-diamine (BAPTPDA) as monomers endows M-COF excellent properties for adsorbing AFM1 and AFM2. The morphology, structure, stability, and magnetism of the Fe3O4@COF(BAPTPDA-Dt) were characterized by various techniques including scanning electron microscopy, transmission electron microscopy, FTIR, thermogravimetric analysis, and vibrating sample magnetometer. TheFe3O4 microspheres were covered by COF shells. Fe3O4@COF exhibited excellent magnetism and stability. Some parameters that may influence the adsorption efficiency of MSPE were also optimized, making the extraction process more effective, time-saving (about 3min), and less organic-reagent-consuming (only 4mL of acetonitrilerequired). It isnoteworthy that the Fe3O4@COF(BAPTPDA-Dt) canbe reutilized more than 8 times. TheAFM1 and AFM2 were determined by LC-MS/MS. The LODs for AFM1 and AFM2 were in the range 0.0069 to 0.0078μgkg-1. A wide linearity range (0.01-100μgkg-1) with coefficients of determination (R2) ranging from 0.9998 to 0.9999 was obtained. The recoveries at four spiked concentrations (0.05, 0.5, 5, and 50μgkg-1) in the milk matrix ranged from 85.2 to 106.5%. The intraday RSDs and the interday RSDs were in the range 1.74-4.58% and 2.65-6.69%, respectively. The matrix effect (9.3% for AFM1 and 6.7% for AFM2) was also significantly lower than that observed in other work. Overall, the established method has provided a powerful tool for rapid pretreatment and sensitive determination of AFM1 and AFM2 in milk with negligible matrix effect, presenting important value in toxicant determination.