UPLC-QTRAP-MS/MS结合化学计量学方法鉴别宣木瓜与资丘木瓜

Discrimination of Xuanmugua and Ziqiumugua by UPLC-QTRAP-MS/MS Coupled with Chemometrics

目的 建立超高效液相色谱-三重四极杆/线性离子阱质谱法(UPLC-QTRAP-MS/MS)结合化学计量学方法比较宣木瓜与资丘木瓜的差异。方法 采用UPLC-QTRAP-MS/MS技术同时测定木瓜11种水溶性有机酸(莽草酸、奎宁酸、琥珀酸、苹果酸、原儿茶酸、柠檬酸、咖啡酸、丁香酸、阿魏酸、绿原酸和肉桂酸)和3种鞣质(没食子酸、儿茶素和表儿茶素)的含量,结合偏最小二乘法判别分析(PLS-DA)和系统聚类分析(HCA)对实验数据进行综合评价。结果 14个目标成分在相应浓度范围内线性关系均良好。奎宁酸(含量为3.39%~6.34%)、苹果酸(含量为1.19%~12.52%)、莽草酸(含量为0.370%~0.556%)、柠檬酸(含量为0.088%~0.430%)、绿原酸(含量为0.110%~0.397%)的含量较高。PLS-DA结果显示,琥珀酸、苹果酸、奎宁酸、丁香酸、肉桂酸、柠檬酸、咖啡酸和绿原酸为2个产地木瓜样品间的主要差异成分。以PLS-DA筛选的主要差异成分为指标进行HCA分析,结果表明组间距为25时,样品可按产地聚为两类。结论 所建立的UPLC-QTRAP-MS/MS方法结合化学计量学能有效分析宣木瓜与资丘木瓜质量的差异性,为木瓜多成分的快速测定和质量控制提供参考。

Objective To establish an ultra-high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry(UPLC-QTRAP-MS/MS) combined with chemometrics method to compare the differences between Xuanmugua(XCF, Chaenomelis Fructus from Anhui Xuancheng)and Ziqiumugua(HCF, Chaenomelis Fructus from Hubei Yichang).Methods An UPLC-QTRAP-MS/MS method was used for simultaneous determination of 11 water-soluble organic acids(shikimic acid, quinic acid, succinic acid, malic acid, protocatechuic acid,citric acid, caffeic acid, syringic acid, ferulic acid, chlorogenic acid and cinnamic acid)and 3 tannins(gallic acid,catechin and epicatechin)in Chaenomelis Fructus(CF). Partial least squares discriminant analysis(PLS-DA)and hierarchical cluster analysis(HCA)were combined to comprehensively evaluate the experimental data.Results The linearities of 14 target components in a corresponding concentration range were good, and the contents of quinic acid(3.39%-6.34%),malic acid(1.19%-12.52%),shikimic acid(0.370%-0.556%),citric acid(0.088%-0.430%)and chlorogenic acid(0.110%-0.397%)were high. The PLS-DA results showed that succinic acid,malic acid,quinic acid,syringic acid,cinnamic acid,citric acid,caffeic acid and chlorogenic acid were the main differential components between XCF and HCF. HCA analysis was carried out with the main differential components screened by PLS-DA as variables, and the samples were clustered into two groups according to the origin when the group spacing was 25.Conclusion The established UPLC-QTRAP-MS/MS method combined with chemometrics can effectively analyze the quality difference between XCF and HCF,and provide a reference for the rapid determination and quality control of CF.