四味土木香散化学成分HPLC-Q-Exactive-MS/MS高分辨质谱快速分析鉴定  

Rapid Analysis and Identification of Chemical Constituents from Siwei Tumuxiang San by HPLC-Q-Exactive-MS/MS

作　　者：李晓娜 董馨 李娜 张男 毛佳宝 包保全 张屏 LI Xiao-na;DONG Xin;LI Na;ZHANG Nan;MAO Jia-bao;BAO Bao-quan;ZHANG Ping(School of Pharmacy,Inner Mongolia Medical University,Hohhot 010110,China;School of Clinical Medicine,Inner Mongolia Medical University Hohhot 010110,China)

机构地区：[1]内蒙古医科大学药学院,呼和浩特010110 [2]内蒙古医科大学第一临床医学院,呼和浩特010110

出　　处：《中国实验方剂学杂志》2020年第6期121-131,共11页Chinese Journal of Experimental Traditional Medical Formulae

基　　金：国家自然科学基金地区科学项目(81460651);内蒙古自治区留学人员科技活动项目。

摘　　要：目的:运用高效液相色谱串联四极杆-静电场轨道阱高分辨质谱(HPLC-Q-Exactive-MS/MS),快速表征和识别四味土木香散中的成分。方法:采用Agilent ZORBAX SB-Aq色谱柱(4. 6 mm×150 mm,5μm),流动相5 mmol·L-1乙酸铵+0. 1%甲酸水溶液-乙腈梯度洗脱。依据Chem Spider和Chemical Book数据库检索及化学成分分离与结构鉴定等方法,建立组方药材化学成分的分子式、相对分子质量、结构式以及二级质谱信息的本地数据库;建立HPLC-Q-Exactive-MS/MS分析方法,结合Xcalibur 3. 0软件、对照品比对及裂解规律研究,对四味土木香散中的化学成分进行快速的结构鉴定。结果:利用HPLC-QExactive-MS/MS技术从四味土木香散中共鉴定了110个成分,包括来源于土木香的倍半萜内脂3个,来源于苦参的生物碱16个及异戊二烯黄酮38个,来源于悬钩子木的三萜皂苷12个、儿茶素类1个及黄酮苷类4个,并总结了主要类型化合物的质谱裂解规律,其中31个成分为首次报道质谱信息。结论:该研究可系统、准确、快速鉴定四味土木香散中目标化合物及非目标化合物,为该复方的体内分析以及药代动力学研究奠定基础。Objective: To rapidly characterize and identify the components of Siwei Tumuxiang San by using high performance liquid chromatography tandem quadrupole-electrostatic field orbitrap high resolution mass spectrometry( HPLC-Q-Exactive-MS/MS). Method: Agilent ZORBAX SB-Aq column( 4. 6 mm × 150 mm,5 μm) was adopted and 5 mmol·L-1 ammonium acetate + 0. 1% formic acid aqueous solution-acetonitrile were used as mobile phase. According to the separation and structure identification results of chemical components based on the methods of ChemSpider and ChemicalBook database retrieval, a local database of molecular formula,molecular weight,structural formula and MS/MS spectrum information of chemical components in Siwei Tumuxiang San was established. An HPLC-Q-Exactive-MS/MS analysis method was established. The complex compounds of Siwei Tumuxiang San were identified rapidly by using Xcalibar 3. 0 software,comparison of reference materials and studies on MS/MS fragment pathways. Result: A total of 110 compounds were identified from the Siwei Tumuxiang San by HPLC-Q-Exactive-MS/MS technology, including 3 sesquiterpene compounds from Inulae Radix, 16 alkaloid compunds and 38 isoprene flavonoid compounds from Sophorae Radix flavescentis,12 triterpenoid saponin compounds,1 catechin compounds and 4 flavonoid glycoside compounds from Rubus sachalinensis. The fragment pathways of the main types of compounds were summarized. Among them,mass spectrometry information of 31 compounds was reported for the first time. Conclusion: This study can be used to identify the target compounds and non-target compounds in Siwei Tumuxiang San systematically, accurately and quickly, which will lay a foundation for the in vivo analysis and pharmacokinetic study of the formulation.

关 键 词：四味土木香散 高效液相色谱串联四极杆-静电场轨道阱高分辨质谱 化学成分 结构鉴定 倍半萜内脂 生物碱 异戊二烯黄酮 

分 类 号：R284.2[医药卫生—中药学] R289[医药卫生—中医学]