The determination of patulin from food samples using dual-dummy molecularly imprinted solid-phase extraction coupled with LC-MS/MS

A molecularly imprinted polymer (MIP) with specific adsorption for patulin was successfully polymerized by precipitation polymerization using 2-oxindole (2-oxin) and 6-hydroxynicotinic acid (6-HNA) as dummy template molecules, methylacrylic acid (MAA) as a functional monomer, trimethylolpropane trimethacrylate (TRIM) as a crosslinker, 2,2-azobis-(2-methylpropionitrile) (AIBN) as a initiator, and methanol as a porogen solvent. The molecularly imprinted solid phase extraction (MI-SPE) column was prepared using the polymer as a sorbent and applied for the selective extraction of patulin from real samples. The results showed that the MI-SPE method had high selectivity and specific adsorption towards patulin with mean recoveries ranged between 81.3% and 106.3% and a relative standard deviation (RSD) < 4.5%. Additionally, the developed MI-SPE method coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) exhibited good linearity in the range of 1-100 ng mL(-1) with correlation coefficients (R-2) > 0.998. The limits of detection (LODs, S/N = 3) were 0.05-0.2 ng g(-1), and the limits of quantification (LOQs, S/N = 10) were 0.2-0.5 ng g(-1). The developed method showed a better purification and higher patulin recovery for real samples than the quick, easy, cheap, effective, rugged, safe "QuEChERS" method.