HPLC-Q-TOF-MS/MS法检测降压类中成药中非法添加的24种化学物质

摘要

目的：建立检测降压类中成药中非法添加的24种化学物质的方法。方法：采用高效液相色谱-飞行时间串联质谱法。色谱条件：色谱柱为Agilent Poroshell 120 EC-C18，流动相为0.05％甲酸溶液-甲醇（梯度洗脱），流速为0.3 ml/min，柱温为30℃，进样量为5μl。质谱条件：离子源为电喷雾电离源，毛细管电压为4.0 kV，毛细管出口电压为135 V，锥孔电压为65 V，脱溶剂温度为350℃，干燥气流速为10 L/min，雾化器压力为40 psi，碰撞能量为8～45 V，扫描范围为m/z 100～1700，检测方式为正离子模式（ESI+）。结果：卡托普利、硝苯地平、氢氯噻嗪、盐酸可乐定、利血平检测质量浓度线性范围为2.0～32μg/L，苯磺酸氨氯地平、非洛地平、缬沙坦、拉西地平、坎地沙坦酯检测质量浓度线性范围为3.0～48μg/L，其余14种化学物质检测质量浓度线性范围为2.5～40μg/L（r≥0.9959）；定量限≤2.9441 ng，检测限≤0.9885 ng；精密度、稳定性、重复性试验的RSD≤5.1％；回收率为81.5％～115.5％（RSD＝1.81％～4.86％，n＝9）。结论：该方法专属性强、灵敏度高、简便快捷，适用于降压类中成药中非法添加化学物质的检测。%OBJECTIVE:To establish a method for the detection of 24 chemical substances that illegally added into antihyper-tensive traditional Chinese medicines. METHODS:HPLC-Q-TOF-MS/MS was adopted. The chromatographic conditions were as follows,the column was Agilent Poroshell 120 EC-C18 with mobile phase of 0.05% formic acid-methanol (gradient elution) at a flow rate of 0.3 ml/min,column temperature was 30 ℃,injection volume was 5 μl. MS conditions were as follows,ion sou- rce was an electrospray ionization source,capillary voltage was 4.0 kV,capillary exit voltage was 135 V,cone voltage was 65 V,de-solvation temperature was 350 ℃,drying gas flow rate was 10 L/min,nebulizer pressure was 40 psi,collision energy was 8-45 V;scanning range was m/z 100-1 700;and detection method was positive ion mode (ESI+). RESULTS:The linear range was 2.0-32 μg/L for captopril nifedipine,hydrochlorothiazide,clonidine hydrochloride,reserpine,3.0-48 μg/L for amlodipine besylate, felodipine,valsartan,lacidipine,candesartan cilexetil and 2.5-40 μg/L for the other 14 chemical substances (r≥0.995 9);limit of quantification was not higher than 2.944 1 ng,the limit of detection was not higher than 0.988 5 ng;RSDs of precision,stability and reproducibility tests were no higher than 5.1%;recoveries were 81.5%-115.5%(RSD were 1.81%-4.86%,n=9). CONCLU-SIONS:The method is specific,sensitive,simple and rapid,and suitable for the detection of chemical substances that illegally add-ed into antihypertensive traditional Chinese medicines.