目的 建立大宗中药材酸枣仁的多指标含量测定方法，为准确发现酸枣仁和理枣仁中差异性质量控制成分提供参考。方法 采用UPLC-MS/MS多反应监测（multiple reaction monitoring，MRM）正、负离子切换扫描模式，ACQUITY UPLC HSS T3色谱柱（150 mm×2.1 mm，1.8 μm）进行分离，流动相为0.1%甲酸水（A）-乙腈（B），进行梯度洗脱，测定16批酸枣仁和13批理枣仁中乌药碱、木兰花碱、维采宁II、斯皮诺素、当药黄素、山柰酚-3-O-芸香糖苷、6'''-阿魏酰斯皮诺素、酸枣仁皂苷A和酸枣仁皂苷B的含量，并结合主成分分析（principal component analysis，PCA）和偏最小二乘判别分析（partial least squares discrimination analysis，PLS-DA）评价酸枣仁和理枣仁中9种成分的差异。结果 9种成分在相应的浓度范围内线性关系良好，相关系数（r）>0.9991，仪器精密度RSD<4.69%，平均加样回收率为95.41%～106.25%，RSD<3.75%。含量测定结果表明酸枣仁中乌药碱、木兰花碱、当药黄素、山柰酚-3-O-芸香糖苷、酸枣仁皂苷A和B的含量显著高于理枣仁（P<0.01），而理枣仁中斯皮诺素、维采宁II和6'''-阿魏酰斯皮诺素的含量显著高于酸枣仁（P<0.01）。PCA和PLS-DA结果表明，酸枣仁和理枣仁可明显分开，两者组内样品成分具有很强的相似性，而组间差异较大。结论 建立了专属性强、灵敏度高的酸枣仁和理枣仁质量差异性评价方法，为两者质量差异性评价的指标成分选择提供依据，为阐明理枣仁可否作为酸枣仁的代用品提供实验基础。

Objective To establish a method for simultaneous quantification of multiple components of Ziziphi Spinosae Semen (ZSS), in order to provide an applicable strategy to screen out the different marker components between ZSS and Ziziphi Mauritianae Semen (ZMS). Methods A UPLC-MS/MS method was developed and validated for simultaneous quantification of coclaurine, magnoflorine, vicenin II, spinosin, swertisin, kaempferol-3-O-rutinoside, 6'''-feruylspinosin, jujuboside A, and jujuboside B using multiple reaction monitoring (MRM). Chromatographic separation was achieved with a reversed‐phase Acquity UPLC HSS T3 column (150 mm×2.1 mm, 1.8 µm). Gradient elution was performed with a mobile phase consisting of 0.1% formic acid in Milli‐Q ultrapure water (A) and acetonitrile (B). In addition, chemometrics methods, including principal component analysis (PCA), and partial least squares discriminant analysis (PLS-DA), were used to evaluate the differences between ZSS and ZMS. Results All the compounds showed good linearity (r>0.9991) with a relatively wide concentration range, acceptable recovery at 95.41%－106.25%, and RSD% less than 3.75%. The contents of coclaurine, magnoflorine, swertisin, kaempferol-3-O-rutinoside, jujuboside A, and jujuboside B were significantly higher in ZSS than that in ZMS, while the contents of vicenin II, spinosin, and 6'''-feruylspinosin in ZSS were significantly lower than that in ZMS. The results from PCA and PLS-DA suggested that ZSS and ZMS could be clearly separated. The sample components in the two groups had strong similarity, but the difference between the two groups was large. Conclusion A stable and reliable quality evaluation method of ZSS and ZMS was established, which provided a reference for quality marker components and the scientific basis for the feasibility of ZMS to substitute ZSS.

R286.2

国家自然科学基金青年基金资助项目（81603289）；国家自然科学基金青年基金资助项目（81603251）；山西省研究生联合培养基地人才培养项目（2017JD01）；山西省科技攻关计划振东专项（2016ZD0105）；山西省青年科技人员培优计划（05）