一种新型苄基苯乙醇胺-β-环糊精键合固定相：手性色谱性能及其在 LC-MS/MS 分析果蔬中农药对映体中的应用。
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.
机构信息
School of Ecology and Environment, Yuzhang Normal University, No. 1999, Meiling Ave., Honggutan Dist., Nanchang, Jiangxi 330103, China.
Physical and Chemical Hygiene Inspection, Nanchang Center for Disease Control and Prevention, No. 833, Lijing Rd., Honggutan Dist., Nanchang, Jiangxi 330038, China.
出版信息
J AOAC Int. 2022 Sep 6;105(5):1319-1329. doi: 10.1093/jaoacint/qsac047.
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.
背景
目前，国内外对手性药物和农药残留检测方法的研究仍以非手性药物和农药残留检测方法为主，对手性药物和农药的对映体分析还缺乏系统研究。
目的
为制备一种新型手性固定相，验证其“多模式”手性分离色谱性能及其实用性。
方法
基于“巯基-烯”加成反应，制备 S-(-)-2-苄基氨基-1-苯乙醇单衍生物β-环糊精键合固定相（BzCSP）。以四种类型的手性化合物为“探针”，评价其手性色谱性能。此外，建立了一种用于测定五种水果和蔬菜中三种手性农药对映体残留量的新型 LC-MS/MS 方法。
结果
研究发现，新型固定相适用于多种色谱模式（正相模式、反相模式、极性有机模式）。在反相色谱下，30 min 内可达到 2.31、1.68 和 1.48 的对映体分离度，分别为 hexaconazole（Hex）、tebuconazole（Teb）和 triticonazole（Trit）对映体。在最佳色谱和质谱条件下，建立了多反应正离子监测（MRM）对手性化合物对映体的 LC-MS/MS 定量方法。Hex、Teb 和 Trit 对映体的检测限（LOD）均小于 0.89 μg/kg，Hex、Teb 和 Trit 对映体的平均回收率在 75.8%-106.3%之间。Teb 为 77.4%-116.3%，Trit 为 78.7%-113.4%。该方法日内和日间重复性良好，相对标准偏差（<5%）和（<7%）。
结论
所建立的方法具有选择性好、灵敏度高、基质干扰抗性强、重现性好等特点。结果表明，采用“巯基-烯”加成反应制备的固定相是一种新型的多模式固定相，具有良好的发展前景。
亮点
本研究报道了一种快速制备新型“多模式”手性固定相 BzCSP 的新方法，基于“巯基-烯”加成反应，验证了 BzCSP 包括良好的选择性、高灵敏度、强基质干扰抗性和良好的重现性在内的实用性。
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