建立了以气相色谱-正化学源-串联三重四极杆质谱(gas chromatography-positive chemical ionization-tandem triple quadruple mass spectrometry, GC-PCI-MS/MS)测定面包中氨基甲酸乙酯含量的方法。面包样品添加氨基甲酸乙酯同位素内标后,经10 g/100 mL(质量浓度)乙酸铅水溶液提取及沉淀蛋白,Cleanert EC碱性硅藻土固相萃取柱净化后,利用气相色谱-正化学源-串联质谱法检测提取溶液,利用多反应监测模式(multiple reaction monitoring,MRM)分析,内标法定量。结果表明,氨基甲酸乙酯在0.5～50.0 μg/L范围内,线性良好,相关系数为0.999 5,检出限(limit of detection, LOD)为0.12 μg/kg,定量限(limit of quantification,LOQ)为0.40 μg/kg。在阴性样品添加的质量浓度分别为2.0、10.0、50.0 μg/kg三个加标水平试验中,回收率为89.3%～95.6%,日内精密度为1.3%～4.6%,日间精密度为4.5%～9.9%。该方法高效、准确、选择性强,灵敏度和精密度均满足面包中氨基甲酸乙酯痕量检测要求。
Gas chromatography-positive chemical ionization-tandem triple quadruple mass spectrometry (GC-PCI-MS/MS) was established for the determination of ethyl carbonate in breads. After spiked with internal standard of ethyl carbamate, samples were extracted and precipitated by 10% lead acetate solution, purified by Cleanert EC alkaline diatomite solid phase extraction column. The extracted solution was detected by GC-PCI-MS/MS in multiple reaction monitoring (MRM) mode. And the internal standard method was used for quantification. The results showed that the developed method exhibited good linear over the range from 0.5 μg/L to 50.0 μg/L with a correlation coefficient of 0.999 5. The limit of detection (LOD) was 0.12 μg/kg and the limit of quantification (LOQ) was 0.40 μg/kg. The recoveries at three spiked levels of 2.0, 10.0 and 50.0 μg/kg were between 89.3% and 95.6% with the intra-day relative standard deviations (RSD) (n=6) from 1.3% to 4.6% and the inter-day relative standard deviations (RSD) (n=6) from 4.5% to 9.9%. The proposed method is rapid, accurate, has strong selectivity and characterized with acceptable sensitivity and accuracy to meet the requirements of ethyl carbonate analysis in breads.
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