基于UHPLC Q-Exactive Orbitrap MS/MS和分子网络技术快速鉴定五味子中联苯环辛二烯型木脂素类化学成分

Rapid identification of dibenzocyclooctadiene lignans in Schisandra chinensis with UHPLC Q-Exactive Orbitrap MS/MS and molecular network

目的建立超高效液相色谱-四极杆/静电场轨道阱组合式高分辨质谱(UHPLC Q-Exactive Orbitrap MS/MS)技术和分子网络联合分析五味子联苯环辛二烯型木脂素类化学成分。方法采用UHPLC CORTECS C_(18)+色谱柱(4.6 mm×150 mm,2.7μm),以乙腈-0.1%甲酸水为流动相进行梯度洗脱。分别在正、负离子模式下,采集Q-Exactive Orbitrap MS/MS数据,根据MS/MS碎片模式的相似性创建GNPS分子网络,运用Cytoscape 3.6.1软件筛选结构相似的分子簇,最后根据保留时间信息、高分辨质谱精确分子量和MS/MS多级碎片信息确证五味子中的化学成分。结果共鉴定出31种联苯环辛二烯型木脂素类化学成分,其中在正离子模式下检测到的13种联苯环辛二烯型木脂素成分为在五味子中首次鉴定。结论该方法可为五味子质量控制、药效物质研究提供参考数据,为中药化学成分的快速定性分析提供借鉴。

Objective To determine the compound of dibenzocyclooctadiene lignans in Schisandra chinensis with ultra-high performance liquid chromatography-quadrupole/electrostatic field orbital trap combined high resolution mass spectrometry(UHPLC Q-Exactive Orbitrap MS/MS)and molecular network.Methods UHPLC CORTECS C_(18)+column(4.6 mm×150 mm,2.7μm)was used for the sample separation.Acetonitrile-0.1%formic acid water was used as the mobile phase for gradient elution.Q-Exactive Orbitrap MS data were collected under both positive and negative ion modes.GNPS molecular network was constructed based on the similarity of MS/MS fragmentation modes.Cytoscape 3.6.1 software was used to screen molecular clusters with similar structures.Finally,the chemical compositions of Schisandra chinensis were confirmed according to the retention time,accurate molecular weight,and MS/MS multistage fragment information.Results Totally 31 dibenzocyclooctadiene lignans were identified,13 of which detected in positive ion mode were identified for the first time in Schisandra chinensis.Conclusion This study provides reference for the quality control and pharmacodynamic substances discovery of Schisandra chinensis,and the rapid qualitative analysis of chemical components in traditional Chinese medicine.