沉香化气丸中非法添加松香酸的检查方法研究

摘要

目的 建立沉香化气丸中非法添加松香酸的UPLC-Q-TOF-MS定性方法和HPLC含量测定方法.方法 UPLC-Q-TOF-MS采用AQUITY UPLC BEH C18柱(2.1 mm×50 mm,1.8μm),流动相为乙腈-体积分数0.1%甲酸水(体积比75:25),流速为0.2 mL/min,柱温为30℃,进样量为1μL.离子化模式为ESI+,雾化气压力为310.275 kPa,体积流量为8.0 L/min,毛细管电压为4000 V,干燥气温度为350℃,m/z扫描范围为50~1100.经UPLC-Q-TOF-MS定性为阳性的样品进一步采用HPLC法进行含量测定,采用Phenomenex C18(4.6 mm×250 mm,5μm)色谱柱,流动相为乙腈-质量分数0.1%甲酸水(体积比75:25),流速为1.0 mL/min,检测波长为241 nm,柱温为30℃,进样量为10μL.结果 根据母离子(m/z 303.23)、其二级质谱碎片(m/z 123.11、149.13、257.22、285.22)及保留时间3个方面的信息,证实10批沉香化气丸样品中7批样品非法掺入了松香酸.松香酸的质量浓度在1.46~58.4μg/mL范围内与峰面积呈良好的线性关系(r=0.9999);平均回收率为101.7%,RSD为2.66%(n=6).结论 该方法简便、准确、重复性好,适用于沉香化气丸中非法掺入松香酸的检测.%Objective To establish UPLC-Q-TOF-MS identification and HPLC determination methods for abietic acid, an illegal additive in Chenxiang Huaqi pills. Methods UPLC-Q-TOF-MS was performed on the column of AQUITY UPLC BEH C18( 2.1 mm×50 mm, 1.8 μm) with mobile phase of acetonitrile-0.1%formic acid ( 75:25) at a flow rate of 0.2 mL/min, the detection wavelength was 241 nm, and the column temperature was 30℃ and volume injection was 1μL. The ionization mode was ESI+, and the atomization gas pressure was 310.275 kPa. The drying gas temperature was 350℃ with the flow rate of 8.0 L/min, and the capillary voltage was 4000 V, scan range was 50-1100 m/z. The determinations of abietic acid in positive samples were carried out. HPLC was performed on the column of Phenomenex C18 column ( 4.6 mm × 250 mm, 5 μm) at 30 ℃ and volume injection was 10 μL. The mobile phase was acetonitrile-0. 1%formic acid ( 75:25) with the isocratic elution at the flow rate of 1.0 mL/min. The detection wavelength was set at 241 nm. Results According to the mother ion ( m/z 303.23) , fragment ions ( m/z 123.11, 149.13, 257.22, 285. 22 ) and retention time, the identification of abietic acid was performed in ten batches Chenxiang Huaqi pills. It showed that seven samples were added the substance containing abietic acid. Good linearity was obtained for abietic acid in the range of 1.46 ~58.4μg/mL ( r=0.9999) . The average recovery was 101.7% ( RSD=2.66%, n=6) . Conclusion The method is simple and repeatable, which is helpful for the detection of abietic acid in Chenxiang Huaqi pills.