目的:建立同时测定辅助降血压类保健食品中非法添加的多个钙通道阻滞剂药物的HPLC-MS联用法。方法:色谱柱为Inertsil ODS-SP(5μm,4.6 mm×250 mm),流动相为0.1%甲酸-20 mmol.L-1甲酸铵(pH=4.8)-乙腈-甲醇,梯度洗脱;流速为1.0 mL.min-1,柱温为25℃。本文采用电喷雾离子源,西布曲明和华法林钠作为正、负离子模式下的内标物,0.2 mL.min-1的分流流速进离子阱质谱,选择离子模式(SIR)下定量检测地尔硫卓(m/z 414.75)、维拉帕米(m/z 455.14)、尼卡地平(m/z480.03)、氨氯地平(m/z 408.79)、硝苯地平(m/z 346.17)、尼群地平(m/z 360.36)、尼莫地平(m/z 417.75)、尼索地平(m/z387.27)、非洛地平(m/z 382.72)、西尼地平(m/z 491.52)、拉西地平(m/z 455.70)结果:利用本文建立的HPLC-MS法进行检测,11种化合物都有良好的线性范围和相关性(0.029~20.0μg·mL-1,R2≥0.9910),最低检出限为7.50~73μg.kg-1;回收率为64.6%~109.0%。结论:本方法选择性高,重复性好,能准确、快速、简便地应用于保健食品中非法添加钙通道阻滞剂类药物的检测。
Objective: To develop a rapid method for simultaneous determination of calcium antagonists illegally added in dietary supplements using high performance liquid chromatography-tandem mass spectrometry(HPLC MS / MS).Methods: Analytes were separated on Inertsil ODS-SP column(5 μm,4.6 mm × 250 mm) with the mobile phase of mixture of 0.1% formic acid and 20 mmol.L-1 ammonium formate buffer(pH 4.8)-acetonitrile methanol.The flow rate was 1.0 mL.min-1,and the column temperature was 25 ℃.The electrospray ionization method and SIR mode were adopted to quantitatively detect diltiazem(m / z 414.75),verapamil(m / z 455.14),nicardipine(m / z 480.03),amlodipine(m / z 408.79),nifedipine(m / z 346.17),nitrendipine(m / z 360.36),nimodipine(m / z 417.75),nisoldipine(m / z 387.27),felodipine(m / z 382.72),cilnidipine(m / z 491.52),lacidipine(m/z 455.70) with warfarin sodium and sibutramine as ESI+ and ESI-internal standard respectively.The flow rate to ion-trap mass spectrometry detector was 0.2 mL.min-1.Results: The results demonstrated good linear of the eleven compounds from 0.029 to 20.0 μg.mL-1 and the limits of detection were from 7.50 to 73 μg.kg-1.The recoveries of spiked samples ranged from 64.6% to 109%.Conclusion: The method is specific,quick and sensitive,which can be successfully applied in detecting calcium antagonists illegally added in health foods.