基于LC-Triple TOF MS/MS技术分析杜仲不同药用部位化学成分差异

为探讨杜仲不同药用部位(杜仲、杜仲叶和杜仲雄花)化学成分的差异,采用液相色谱-串联三重四极杆飞行时间高分辨质谱(LC-Triple TOF MS/MS)结合多元统计分析技术对杜仲不同药用部位的化学成分进行差异分析。通过对多级串联质谱数据进行峰匹配、峰对齐、滤噪处理等分析,提取特征峰;用聚类分析(HCA)、主成分分析(PCA)和偏最小二乘法-判别分析(PLS-DA)进行数据处理;通过一级质谱精确质荷比和二级质谱碎片信息,结合软件数据库搜索、标准品比对及相关文献进行成分鉴定。结果显示:杜仲、杜仲叶与杜仲雄花三者的化学组成可得到明显区分;初步筛选鉴定出23种差异显著的化学成分,且呈现不同的变化规律。杜仲、杜仲叶及杜仲雄花化学成分的差异及其变化规律,可为揭示三者药效差异的物质基础提供依据。

Difference of Chemical Constituents in Different Medicinal Parts of Eucommia ulmoides by LC-Triple TOF MS/MS

In order to study the difference of synthesis and accumulation of metabolites in different medicinal parts of Eucommia ulmoides Oilv. (Eucommiae Cortex, Eucommiae Folium and Eucommiae Flos Male), LC-Triple TOF MS/MS method combined with multivariate statistical analysis was used to analyze the difference of chemical constituents in different medicinal parts of Eucommia ulmoides Oilv. Through the analysis of the multistage tandem mass spectrometry, the characteristic peaks were extracted with mass spectrometry data peak matching, peak alignment, noise filtering. Hierachical cluster analysis (HCA), principal component analysis (PCA) and partial least-squares discriminant analysis (PLS-DA) were used for data processing. The constituents were identified according to MS accurate mass and MS/MS spectrometry fragmentation information, combined with the software of database search, comparison with reference standards and literature. The results showed that the chemical constituents in Eucommiae Cortex, Eucommiae Folium and Eucommiae Flos Male were clearly distinguished. Kinds of 23 differential chemical constituents are screened and indentified, including aucubin, deacetyl asperulosidic acid, guaiacyl glycerol, geniposidic acid, chlorogenic acid, cryptochlorogenic acid, geniposide, caffeic acid, pinoresinol-di-O-β-D-glucopyranoside, rutin, kaempferol-3-O-rutinoside, isoquercitrin, eucomoside B, pinoresinol-4’-O-β-D-glucopyranoside, quercetin-3-O-malonyl-β-D-glucoside, astragalin, isochlorogenic acid A, kaempferol-3-O-(6″-O-acetyl)-β-D-glucopyranoside, naringenin, kaempherol and three kinds of quercetin glycoside, which present different changing laws. The different constituents among Eucommiae Cortex, Eucommiae Folium and Eucommiae Flos Male can provide the material basis for revealing the property and efficacy of different medicinal parts of Eucommia ulmoides Oilv.