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    高效液相色谱-串联质谱法同时测定干辣椒中21种琥珀酸脱氢酶抑制剂类杀菌剂的残留量

    Simultaneous Determination of Residues of 21 Succinate Dehydrogenase Inhibitor Fungicides in Dried Chilies by High Performance Liquid Chromatography-Tandem Mass Spectrometry

    • 摘要: 取粉状均质干辣椒样品2.50 g,加入10 mL 0.1%(体积分数,下同)甲酸溶液,涡旋混匀,静置10 min,加入10 mL正己烷饱和的乙腈溶液,振荡5 min,加入QuEChERS萃取盐包(含4 g无水硫酸镁、1 g氯化钠、0.5 g倍半水合柠檬酸二钠和1 g柠檬酸钠),迅速摇匀,振荡10 min,离心5 min。取1.0 mL上清液置于装有150 mg无水硫酸镁、50 mg N-丙基乙二胺、50 mg十八烷基硅烷键合硅胶和20 mg石墨化碳黑的离心管中,涡旋1 min,离心5 min,取0.5 mL上清液,加入0.5 mL水,混匀,过0.22 µm滤膜,采用高效液相色谱-串联质谱法测定滤液中21种琥珀酸脱氢酶抑制剂(SDHI)类杀菌剂的含量。以Thermo Accucore-aQ色谱柱为固定相,以不同体积比的甲醇和含0.1%甲酸的5 mmol·L−1甲酸铵溶液的混合溶液为流动相进行梯度洗脱,采用电喷雾离子(ESI)源在多反应监测(MRM)模式下进行质谱分析,基质匹配法定量。结果显示,21种SDHI类杀菌剂的质量浓度在0.001~0.5 mg·L−1内与对应定量子离子的峰面积呈线性关系,测定下限(10S/N)均为0.01 mg·kg−1。按照标准加入法进行回收试验,回收率为79.0%~108%,测定值的相对标准偏差(n=6)为0.53%~14%。方法用于分析20批干辣椒样品,21种SDHI类杀菌剂均未检出。

       

      Abstract: The homogenized powder sample of dried chili (2.50 g) was taken, and 10 mL of 0.1% (volume fraction, the same below) formic acid solution was added. The mixture was vortexed and settled for 10 min, and 10 mL of n-hexane-saturated acetonitrile solution was added. The mixture was oscillated for 5 min, and the QuEChERS extraction salt packet (containing 4 g of anhydrous magnesium sulfate, 1 g of sodium chloride, 0.5 g of disodium citrate sesquihydrate, and 1 g of sodium citrate) was added. The mixture was shaken rapidly and oscillated for 10 min. After centrifugation for 5 min, 1.0 mL of the supernatant was taken and placed into a centrifuge tube containing 150 mg of anhydrous magnesium sulfate, 50 mg of N-propylethylenediamine, 50 mg of octadecylsilane-bonded silica gel, and 20 mg of graphitized carbon black. The mixture was vortexed for 1 min and centrifuged for 5 min. Subsequently, 0.5 mL of the supernatant was taken and 0.5 mL of water was added. The solution was homogenized and passed through 0.22 μm filter membrane. The 21 succinate dehydrogenase inhibitor (SDHI) fungicides in the filtrate were determined by high performance liquid chromatography-tandem mass spectrometry using Thermo Accucore-aQ column as the stationary phase, and a mixture of methanol and 5 mmol·L−1 ammonium formate solution containing 0.1% formic acid at different volume ratios as the mobile phase for gradient elution. The electrospray ion (ESI) source was used for mass spectrometry analysis in the multiple reaction monitoring (MRM) mode, and the matrix matching method was used for quantification. As shown by the results, linear relationships between the values of the corresponding quantitative daughter ion peak area and mass concentrations of 21 SDHI fungicides were found in the range of 0.001‒0.5 mg·L−1, with the same lower limits of determination (10S/N) of 0.01 mg·kg−1. Test for recovery was made by the standard addition method, giving results in the range of 79.0%‒108%, with RSDs (n=6) of the determined values in the range of 0.53%‒14%. This method was applied to the analysis of 20 batches of dried chili samples, and 21 SDHI fungicides were not detected.

       

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