A New Benzyl Phenethanolamine-β-Cyclodextrin Bonded Phase: Chiral Chromatography Performance and Application for LC-MS/MS Analysis of Pesticide Enantiomers in Fruits and Vegetables

Abstract

Abstract Background At present, the research on achiral drug and pesticide residue detection methods is still the mainstay at home and abroad, and there is still a lack of systematic research on the enantiomeric analysis of chiral drugs and pesticides. Objective In order to prepare a novel chiral stationary phase, whose “multi-mode” chiral separation chromatographic performance and its utility was verified. Method An S-(-)-2-benzylamino-1-phenylethanol mono-derivative β-cyclodextrin bonded stationary phase (BzCSP) was prepared based on the “thiol-ene” addition reaction. The chiral compounds including four types of chiral compounds were used as “probes,” and their chiral chromatographic properties were evaluated. Furthermore, a new LC-MS/MS method for the determination of the enantiomeric residues of three chiral pesticides in five kinds of fruits and vegetables was established. Results The study found that the novel stationary phase was suitable for a variety of chromatographic modes (normal phase mode, reversed-phase mode, polar organic mode). The resolutions of hexaconazole (Hex), tebuconazole (Teb), and triticonazole (Trit) enantiomers could be up to 2.31, 1.68, and 1.48, respectively, within 30 min under reversed-phase chromatography. Based on the optimal chromatographic and mass spectrum conditions, a new LC-MS/MS quantitative method for the Hex, Teb, and Trit enantiomers was established by multi-reaction positive ion monitoring (MRM). The detection limits (LODs) of enantiomers were less than 0.89 µg/kg for Hex, 0.93 µg/kg for Teb, and 0.93 µg/kg for Trit, and the averaged recoveries of enantiomers were in the range of 75.8–106.3% for Hex, 77.4–116.3% for Teb, and 78.7–113.4% for Trit. The method had good reproducibility with the RSDs (<5%) for intraday and (<7%) for interday. Conclusions The established method had the characteristics of good selectivity, high sensitivity, strong resistance to matrix interference, and good reproducibility. It is indicated that the stationary phase prepared by the “thiol-ene” addition reaction is a new type of multi-mode stationary phase, which has a good development value. Highlights The study reported a new method for the rapid preparation of a rare “multi-mode” chiral stationary phase BzCSP based on the “thiol-ene” addition reaction and verified the practicability of BzCSP including good selectivity, high sensitivity, strong resistance to matrix interference, and good reproducibility.