UPLC-LTQ-Orbitrap MS结合分子网络技术鉴别铁线莲属植物中三萜皂苷类成分

Identification on triterpenoid saponins of Clematis species by UPLC-LTQ-Orbitrap MS combined with molecular network

目的构建铁线莲属6种植物中皂苷类成分的分子网络与快速分析。方法超高效液相色谱-线性离子阱-静电场轨道阱质谱联用技术(UHPLC-LTQ Orbitrap MS)采集质谱信息,将信息上传至GNPS数据平台计算分析,借助Cytoscape软件生成可视化分子网络图,根据对照品的裂解规律和文献分析鉴定铁线莲植物中皂苷类成分。结果从6种植物中鉴别出常春藤和齐墩果酸型皂苷共25个,其中16个为常春藤型皂苷、9个为齐墩果酸型皂苷,根据代表各成分节点的颜色及比例,得到各成分在铁线莲属6种植物中的分布情况。鉴定的25个三萜皂苷中,20个为2种或2种以上铁线莲共有成分,其中化合物clematichinenoside A和oleanolic acid 3-O-ribopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside为5种铁线莲共有成分;6个三萜皂苷只在单种铁线莲中存在。结论基于UPLC-LTQ-Orbitrap MS的分子网络技术与传统分析方法比较,其可快速、可视化的区分6种植物中三萜皂苷的差异;6种植物中三萜皂苷类成分相似之中又有不同,为药材替代提供参考依据。

Objective To construct molecular network and analyze rapidly the saponins of six species of Clematis plants. Methods The mass spectral data, acquired with UHPLC-LTQ Orbitrap MS, were uploaded to the GNPS analysis platform to build molecular network, visualized by Cytoscape software. On the other hand, the triterpenoid saponins from six plants were identified on the basis of the fragmentation regularity of the standard and the reported literature. Results Twenty-five triterpenoid saponins, including 16 hederagenin saponins and nine oleanolic acid-type saponins, were determined from six kinds of plants. The distribution of the triterpenoid saponins in the six kinds of plants were profiled by the pie chart of each node in molecular network. Twenty compounds were found in at least two species of Clematis. Clematichinenoside A and oleanolic acid 3-O-ribopyranosyl-(1 →3)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside were the common constituents in five species. Six saponins were distributed in in single species of Clematis. Conclusion Compared with traditional phytochemical methods, the molecular network technology of UPLC-LTQ-Orbitrap MS can quickly and visually distinguish different triterpenoid saponins in six kinds of plants. There are similarities and differentiates among the triterpenoid saponins in the six kinds of plants, which provides the basis for the substitution of medicinal materials.