超高效液相色谱-串联质谱-电喷雾离子源测定柑橘中灭螨醌和羟基灭螨醌残留

Determination of acequinocyl and hydroxyacequinocyl residues in Citrus by ultra performance liquid chromatography-tandem mass spectrometry-electrospray ionization

中文关键词:  灭螨醌  羟基灭螨醌  QuEChERS  液相色谱-串联质谱法  电喷雾离子源  残留分析

英文关键词:acequinocyl  hydroxyacequinocyl  QuEChERS  UPLC-MS/MS  ESI  residue analysis

中文摘要:

      目的 建立柑橘中灭螨醌及其代谢物羟基灭螨醌残留的超高效液相色谱-串联质谱-电喷雾离子源（ultra performance liquid chromatography-tandem mass spectrometry-electrospray ionization, UPLC-MS/MS-ESI）检测方法。方法 样品经0.5%甲酸乙腈提取，氟罗里硅土吸附剂和无水硫酸镁净化，以0.1%甲酸溶液和甲醇为流动相进行梯度洗脱，经ACQUITY UPLC BEH C18 (100 mm×2.1 mm, 1.7 μm)色谱柱分离。采用电喷雾正离子模式，多重反应监测（multiple reaction monitoring, MRM）模式进行检测，基质匹配外标法定量。结果 灭螨醌及羟基灭螨醌在0.0025~0.0500 mg/L质量浓度范围内线性关系良好，相关系数r≥0.9984。在0.005~0.500 mg/kg加标水平下，灭螨醌及羟基灭螨醌在柑橘全果和果肉中的平均回收率为70%~93%，最大相对标准偏差（relative standard deviation, RSD）为12.0%，方法定量限（limit of quantitation, LOQ）为0.005 mg/kg。结论 基于改良QuEChERS法，采用UPLC-MS/MS-ESI检测，方法更方便高效且正确度、精密度和灵敏度均较好，能够满足柑橘中灭螨醌和羟基灭螨醌的残留分析要求。

英文摘要:

      Objective To establish an analysis method of acequinocyl and its metabolite hydroxyacequinocyl residues detected by ultra performance liquid chromatography-tandem mass spectrometry-electrospray ionization (UPLC-MS/MS-ESI). Methods The citrus samples were extracted with 0.5% formic acid acetonitrile, purified with florisil absorbents and magnesium sulfate anhydrous, eluted with the mobile phase of 0.1% formic acid solution and methanol, separated on the ACQUITY UPLC BEH C18 (100 mm×2.1 mm, 1.7 μm) column. Then analyzed in positive ion mode of electrospray ionization source under multiple reaction monitoring (MRM) mode, quantified by matrix matching curve external standard. Results The correlation coefficient (r) was no less than 0.9984 within the mass concentration range from 0.0025 to 0.0500 mg/L, which indicated a satisfied linear relation of acequinocyl and hydroxyacequinocyl in citrus. Meanwhile, the average recoveries of acequinocyl and hydroxyacequinocyl in whole fruit and pulp of citrus were 70%~93% with the maxium relative standard deviations (RSD) of 12.0% at the spiked concentration of 0.005 to 0.500 mg/kg. The limit of quantitation (LOQ) of this method was 0.005 mg/kg. Conclusion This method is more convenient and efficient applied modified QuEChERS and UPLC-MS/MS-ESI. Moreover, the accuracy, precision and sensitivity are satisfied to accord the request of residue analysis of acequinocyl and hydroxyacequinocyl in citrus.