分散微固相萃取-超高效液相色谱-高分辨质谱法测定葡萄酒和啤酒中多菌灵和噻菌灵

Determination of carbendazim and thiabendazole in wine and beer by ultra high performance liquid chromatographyhigh resolution mass spectrometry coupled with dispersive micro solid-phase extraction

基于强阳离子交换填料(PCX),采用分散微固相萃取前处理技术,结合超高效液相色谱-四级杆-静电场轨道阱高分辨质谱联用技术,建立了一种快速测定葡萄酒和啤酒中多菌灵和噻菌灵的方法。通过对分散微固相萃取技术中PCX用量、洗脱溶剂中氨水的体积分数、乙腈的体积分数和洗脱体积的优化,实现了样品中多菌灵和噻菌灵的有效净化。经BEH C_(18)(50 mm×2.1 mm,1.7μm)色谱柱分离后,通过静电场轨道阱质谱靶向单一离子监测(targeted single ion monitoring,tSIM)结合数据依赖的二级质谱扫描(data dependent tandem mass spectrometry,ddMS^2)采集模式进行定性定量分析。待测物多菌灵和噻菌灵在一定浓度范围内均呈良好线性关系,相关系数R^2≥0.999 9。在葡萄酒和啤酒基质中,多菌灵和噻菌灵的检出限分别为0.02和0.01μg/L,定量限分别为0.06和0.03μg/L。在0.1、1.0、100μg/L 3个添加水平下,多菌灵和噻菌灵的加标回收率分别为95.6%~110.2%和87.5%~102.8%,日内精密度(RSDr)分别为1.8%~5.2%和1.3%~4.8%,日间精密度(RSD_R)分别为4.3%~8.7%和4.8%~9.4%。该方法快速、简便、灵敏,适用于葡萄酒和啤酒中多菌灵和噻菌灵的残留检测。

A rapid method was established for the determination of carbendazim and thiaben-dazole in wine and beer by ultra high performance liquid chromatography-Q Orbitrap high reso-lution mass spectrometry and dispersive micro solid-phase extraction （DMSPE） based on a strong cation exchange adsorbent （PCX）. For the pretreatment method, the amount of PCX, the volume percentage of acetonitrile,the volume percentage of ammonium hydroxide and the volume of eluent were optimized. The analytes were separated on a BEH Cl8 column （50 mmx 2. 1 mm,1. 7 pm） and detected using targeted single ion monitoring-data dependent tandem mass spectrometry （tSIM-ddMS2） scan mode. The method showed a good linearity within a cer-tain concentration ranges with correlation coefficients R2^0. 999 9. The detection limits of car-bendazim and thiabendazole in wine and beer were 0. 02 and 0. 01 p^^L,and the quantification limits were 0. 06 and 0. 03 pg/L. The average recoveries of carbendazim and thiabendazole atthespikedlevelsof0.1,1.0and 1 0 0pg/Lwereintherangesof 95.6%-110.2%an d 87.5%- 102. 8%, with intra-day precision （RSDr） ranges from 1. 8 % -5. 2% and 1. 3 % -4. 8 % , and inter-day precision （RSDr） ranges from 4. 3 % -8. 7% and 4. 8 % -9. 4%. The method is rapid, simple and sen-sitive for the simultaneous determination of carbendazim and thiabendazole in wine and beer.