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.

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 FeO@COF(BAPTPDA-Dt) were characterized by various techniques including scanning electron microscopy, transmission electron microscopy, FTIR, thermogravimetric analysis, and vibrating sample magnetometer. The FeO microspheres were covered by COF shells. FeO@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 3 min), and less organic-reagent-consuming (only 4 mL of acetonitrile required). It is noteworthy that the FeO@COF(BAPTPDA-Dt) can be reutilized more than 8 times. The AFM1 and AFM2 were determined by LC-MS/MS. The LODs for AFM1 and AFM2 were in the range 0.0069 to 0.0078 μg kg. A wide linearity range (0.01-100 μg kg) with coefficients of determination (R) ranging from 0.9998 to 0.9999 was obtained. The recoveries at four spiked concentrations (0.05, 0.5, 5, and 50 μg kg) 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.