超高效液相色谱-串联质谱双内标法同时测定复方杏香兔耳风胶囊中的10种有效成分

建立了同时测定复方杏香兔耳风胶囊中原儿茶酸、原儿茶醛、绿原酸、野黄芩苷、异绿原酸C、黄芩苷、木犀草素、芹菜素、白术内酯Ⅲ和白术内酯I等10种有效成分含量的超高效液相色谱-串联质谱（UPLC-MS/MS）双内标分析方法。以咖啡酸和淫羊藿苷为内标（IS），在ZORBAX RRHD Eclipse Plus C₁₈色谱柱上，以甲醇和含0.3%甲酸的水为流动相进行梯度洗脱分离，流速为0.3 mL/min。在电喷雾电离（ESI）正、负离子切换模式下，采用多重反应监测模式进行检测。结果表明，原儿茶酸、原儿茶醛、绿原酸、野黄芩苷、异绿原酸C、黄芩苷、木犀草素、芹菜素、白术内酯Ⅲ、白术内酯I的线性范围分别为0.00300~24.0 mg/L、0.0170~2.00 mg/L、0.0150~30.0 mg/L、0.00400~30.0 mg/L、0.0105~24.0 mg/L、0.00300~30.0 mg/L、0.00300~5.00 mg/L、0.00600~5.00 mg/L、0.00150~4.00 mg/L、0.000600~0.900 mg/L；检出限分别为1.0、11、5.0、1.5、3.5、1.0、1.0、2.0、0.50、0.20 μg/L。10种成分的加样回收率为92.5%~106%，相对标准偏差均不大于3.2%。该方法快速简便、灵敏度高、重复性好，已成功用于实际样品的分析。

Simultaneous determination of ten constituents in the Chinese medicinal preparation Fufangxingxiangtu’erfeng capsules by ultra performance liquid chromatography with tandem mass spectrometry

Using caffeic acid and icariin as internal standards, a method for the simultaneous determination of protocatechuic acid, protocatechuic aldehyde, chlorogenic acid, scutellarin, isochlorogenic acid C, baicalin, luteolin, apigenin, atractylenolide Ⅲ and atractylenolide I in Fufangxingxiangtu''erfeng capsules were established by ultra performance liquid chromatography with tandem mass spectrometry (UPLC-MS/MS). The separation was performed on a ZORBAX RRHD Eclipse Plus C₁₈ column (50 mm×2.1 mm, 1.8 μm) by using water containing 0.3% formic acid and methanol as mobile phases with the gradient elution at a flow rate of 0.3 mL/min. The analytes were detected by a tandem mass spectrometer in the multiple reaction monitoring (MRM) mode via the switching of positive electrospray ionization (ESI⁺) and negative electrospray ionization (ESI^-). Under optimum conditions, the calibration curves were linear in the range of 0.00300-24.0 mg/L for protocatechuic acid, 0.0170-2.00 mg/L for protocatechuic aldehyde, 0.0150-30.0 mg/L for chlorogenic acid, 0.00400-30.0 mg/L for scutellarin, 0.0105-24.0 mg/L for isochlorogenic acid C, 0.00300-30.0 mg/L for baicalin, 0.00300-5.0 mg/L for luteolin, 0.00600-1.50 mg/L for apigenin, 0.00150-4.00 mg/L for atractylenolide Ⅲ, and 0.000600-0.900 mg/L for atractylenolide I with the detection limits of 1.0, 11, 5.0, 1.5, 3.5, 1.0, 1.0, 2.0, 0.50, 0.20 μg/L, respectively. The average recoveries of the ten effective components were between 92.5% and 106% with all relative standard deviations not more than 3.2%. The developed method was rapid, simple, accurate, reproducible, and suitable for the quality control of the Fufangxingxiangtu''erfeng capsules.