液相色谱-串联质谱法测定蜂王浆中新型烟碱类药物及其代谢物残留量

Simultaneous Determination of Neonicotinoid Insecticides and Two Metabolites in Royal-jelly by LC-MS/MS

  • 摘要: 采用QuEChERS净化-液相色谱-串联质谱法(QuEChERS-LC-MS/MS)测定蜂王浆中新型烟碱类药物吡蚜酮、呋虫胺、烯啶虫胺、噻虫嗪、氟啶虫酰胺及代谢物4-(三氟甲基)烟酰胺、吡虫啉、噻虫胺、氯噻啉、啶虫脒及代谢物N-去甲基啶虫脒和噻虫啉的残留量。样品经水稀释,甲醇沉淀蛋白并提取,以N-丙基乙二胺(PSA)、C18和无水硫酸镁作为分散剂进行QuEChERS净化,采用液相色谱-串联质谱法进行检测(电喷雾离子源,正离子模式,多反应监测模式),以同位素内标法和外标法进行定量分析。结果表明,该方法定量限以S/N=10计,吡呀酮、呋虫胺为2.5 μg/kg,烯啶虫胺、氯噻啉、啶虫脒、噻虫啉为5.0 μg/kg,噻虫嗪、氟啶虫酰胺、吡虫啉、噻虫胺、4-(三氟甲基)烟酰胺、N-去甲基啶虫脒为12.5 μg/kg。线性相关系数大于0.996。对空白蜂王浆进行添加回收实验,回收率为81.2%~119%;相对标准偏差为1.7%~12.2%。该方法简便、快捷,定量限能够满足目前国内外最大残留限量的要求,可作为蜂王浆中新型烟碱类药物及其代谢物残留量的测定方法。

     

    Abstract: Pymetrozine, dinotefuran, nitenpyram, thiamethoxam, flonicamid and its metabolite (4-trifluoromethylnicotinamide), imidacloprid, clothianidin, imidaclothiz, acetamiprid and its metabolite (N-desmethylacetamiprid)) and thiacloprid residues in royal-jelly were detected by QuEChERS-LC-MS/MS. The royal-jelly samples were diluted by water, the protein of royal-jelly was precipitated by methanol and then the methanol supernatant solution was cleaned up with PSA, C18 and MgSO4 by QuEChERS method, the supernatant solution was evaporated to dryness and reconstituted in methanol-0.15% formic acid solution (1∶9, V/V), and then filtered through nylon membrane into a glass LC vial for LC-MS/MS analysis. The solution was separated by Agilent Eclipse XDB-C18 column (150 mm×4.6 mm×5 μm) and the quantitative detection was performed on LC-MS/MS by multiple reaction monitoring (MRM) mode under positive electrospray ionization mode (ESI+). Isotopes internal standard method (dinotefuran, thiamethoxam, imidacloprid, clothianidin, acetamiprid and thiacloprid) and external standard method (pymetrozine, nitenpyram, flonicamid, 4-trifluoromethylnicotinamide, imidaclothiz and N-desmethylacetamiprid) were used for quantitation analysis. The limits of quantification (LOQs, S/N=10) of pymetrozine, dinotefuran are 2.5 μg/kg, nitenpyram, imidaclothiz, acetamiprid, thiacloprid are 5.0 μg/kg, thiamethoxam, flonicamid, imidacloprid, clothianidin, 4-trifluoromethylnicotinamide, N-desmethylacetamiprid are 12.5 μg/kg, respectively. The correlation coefficients are more than 0.996, the recoveries and the relative standard deviations (RSD) are 81.2%-119% and 1.7%-12.2%, respectively. This method is convenient, rapid and effective, QuEChERS(quick, easy, cheap, effective and rugged) is suitable for determination and confirmation of pymetrozine, dinotefuran, nitenpyram, thiamethoxam, flonicamid and its metabolite (4-trifluoromethylnicotinamide), imidacloprid, clothianidin, imidaclothiz, thiacloprid, acetamiprid and its metabolite (N-desmethylacetamiprid).

     

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