采用超高效合相色谱四极杆飞行时间质谱,建立了手性农药腈菌唑对映体在苹果、葡萄和茶叶中的对映体拆分与残留分析方法。样品采用乙腈提取,Cleanert TPT或Pesti Carb柱净化,优化合相色谱条件将腈菌唑对映体进行分离,四极杆飞行时间质谱基质外标法定量测定。对合相色谱的影响因素进行了优化,确定最佳条件为:Chromega Chrial CCA色谱柱,流动相采用CO_2-异丙醇(95∶5),流速2.0 m L/min,动态背压13.79 MPa,柱温30℃,柱后离子化辅助溶剂为含2 mmol/L甲酸铵的甲醇-水(1∶1)溶液。结果表明:在0.01~1.00 mg/L浓度范围内,标准曲线满足线性关系,相关系数在0.98以上;在0.005,0.025,0.25 mg/kg加标水平下,苹果和葡萄中腈菌唑对映体的平均回收率(n=6)为62.5%~103.0%,相对标准偏差均不大于9.9%,方法定量下限为0.005 mg/kg;在0.01,0.05,0.5 mg/kg加标水平下,红茶中腈菌唑对映体的平均回收率(n=6)为84.1%~86.4%,相对标准偏差均小于9.6%,方法定量下限为0.01 mg/kg。
A separation and residue determination method for myclobutanil enantiomers in apple, grape and black tea was firstly developed by ultra performance convergence chromatography combined with quadrupole time - of - flight mass spectrometry ( UPC2 - QTOF/MS). Samples were extracted with acetonitrile, purified with Cleaneert TPT or Cleanert PestiCarb solid-phase extraction(SPE) col- umns, and separated in the optimum condition of convergence chromatography, then analyzed by UPC2 - QTOF/MS with the matrix external standard method. All the influence factors of convergence chromatography( chromatographic column, mobile phase modifier and proportion, column temperature, automated backpressure regulator, and post-column auxiliary solvent) were optimized. The best conditions were as iollows: ChromegaChrial CCA column with a mobile phase of CO2 - isopro- panol(95 : 5), a flow rate of 2.0 mL/min, an automated baekpressure regulator(ABPR) of 13.79MPa, a column temperature of 30 ℃, and a post-column auxiliary solvent of methanol - water( 1 : 1 ) containing 2 mmol/L ammonium formate. The results showed that the linear ranges of myclobutanil enantiomers were in the range of 0.01 - 1.00 mg/L, and the correlation coefficients were above 0. 98. The reeoveries of myclobutanil enantiomers at three spiked levels of 0. 005, 0. 025, 0.25 mg/kg in fruit matrix were in the range of 62.5% - 103.0% with relative standard deviations ( RS- Ds, n =6) not more than 9.9% , and the limits of quantitation (LOQ) of enantiomers were 0. 005 mg/kg. The recoveries of myelobutanil enantiomers at three spiked levels of 0.01, 0. 05, 0.5 mg/ kg in black tea matrix were 84. 1% - 86.4% with RSDs(n =6) less than 9.6% , and the LOQ for these two enantiomers were 0. 01 mg/kg. The method was rapid, convenient and reliable, and could meet the requirement for residue analysis.