基于UHPLC Q-Exactive Orbitrap MS/MS和分子网络技术快速鉴定开心散化学成分  

Rapid Identification of Chemical Components in KaiXinSan by UHPLC Q-Exactive Orbitrap MS/MS and Molecular Network Analysis

作　　者：白云凤 黄智兴 唐雅楠 董爱 邓欣祺 王春国 徐砚通 BAI Yunfeng;HUANG Zhixing;TANG Yanan;DONG Ai;DENG Xinqi;WANG Chunguo;XU Yantong(School of Life Sciences,Beijing University of Chinese Medicine,Beijing 102488,China;School of Chinese Materia Medica,Beijing University of Chinese Medicine,Beijing 102488,China;Institute of Chinese Materia Medica,China Academy of Chinese Medical Sciences,Beijing 100700,China;Beijing Research Institute of Chinese Medicine,Beijing University of Chinese Medicine,Beijing 102488,China)

机构地区：[1]北京中医药大学生命科学学院,北京102488 [2]北京中医药大学中药学院,北京102488 [3]中国中医科学院中药研究所,北京100700 [4]北京中医药大学北京中医药研究院,北京102488

出　　处：《中国现代中药》2025年第2期258-273,I0007-I0009,共19页Modern Chinese Medicine

基　　金：北京中医药大学实验技术类项目(2023-syjs-01);国家重点研发计划项目(2023YFC3504100);中国中医科学院中药研究所人才引进项目课题(ZXKT22059);中国中医科学院青年科技人才培养专项(ZZ16-XRZ-071)。

摘　　要：目的:建立基于高分辨质谱法(HR-MS)、分子网络和Glycomol技术整合策略的中药复杂化学成分快速分析方法,对开心散中化学成分进行系统分析。方法:采用超高效液相色谱-四级杆-静电场轨道阱高分辨质谱法(UHPLC Q-Exactive Orbitrap MS/MS)对开心散及其中的10个对照品进行质谱数据采集和裂解行为研究,计算MS/MS碎片模式的相似性并通过全球天然产物分子网络数据库(GNPS)创建分子网络,根据对照品的质谱裂解规律、高分辨质谱一级和二级质谱数据对分子网络中结构相似的分子簇及开心散中主要的化合物类别的结构进行确证;通过Glycomol技术对同分异构体进行精准区分。结果:在正、负离子扫描模式下分析了开心散中102个化学成分,其中人参的主要成分为皂苷类化合物,共25个;远志的成分包括皂苷类、寡糖酯类、酮类等化合物,共58个;石菖蒲相关化合物16个;茯苓中的化合物检出3个。通过GNPS分子网络进行分类得到人参皂苷、远志皂苷、远志糖酯共3类网络。通过Glycomol技术准确鉴别人参皂苷Rg_(2)、人参皂苷F_(2)、人参皂苷Rg_(3)3种同分异构体,并推测出其他同分异构体的结构。结论:建立的HR-MS、分子网络和Glycomol技术整合策略分析开心散化学成分方法可为其进一步的质量控制、药效物质及药效机制研究等提供数据参考,为中药复方化学成分的快速分析提供借鉴。Objective:To establish a method for rapid identification of complex chemical components in KaiXinSan by integrating high resolution mass spectrometry(HR-MS),molecular network analysis,and Glycomol.Methods:Ultra-high performance liquid chromatography-quadrupole-Exactive Orbitrap-tandem mass spectrometry(UHPLC Q-Exactive Orbitrap MS/MS)was employed to collect MS data and study the fragmentation patterns of KaiXinSan components and 10 reference substances.The similarity of the fragmentation patterns of MS/MS was calculated,and the Global Natural Products Social Molecular Networking(GNPS)was employed to create the molecular network.Based on the fragmentation patterns obtained by MS and the MS and MS/MS data obtained by HR-MS for the reference substances,the molecular clusters with similar structures in the molecular network and the main compounds in KaiXinSan were identified.The isomers were distinguished by Glycomol.Results:A total of 102 chemical components in KaiXinSan were detected in positive and negative ion scanning modes.The main components of Ginseng Radix et Rhizoma were saponins(25 compounds),and 58 compounds were identified in Polygalae Radix,including saponins,oligosaccharides,and xanthones.In addition,16 compounds of Acori Tatarinowii Rhizoma and three compounds of Poria were detected.The GNPS analysis yielded three networks of ginsenosides,onjisaponins,and tenuifolioses.The three isomers,ginsenosides Rg_(2),ginsenosides F_(2),and ginsenosides Rg_(3),were accurately identified by Glycomol,and the structures of other isomers were deduced.Conclusion:The strategy of integrating HR-MS,molecular network analysis,and Glycomol established in this study provides reference data for the quality control and the research on the pharmacodynamic substances and mechanism of KaiXinSan.Moreover,it provides a reference for the rapid identification of chemical components in traditional Chinese medicine compound prescriptions.

关 键 词：开心散 分子网络 裂解规律 结构鉴定 Glycomol技术 

分 类 号：R284[医药卫生—中药学]