基于液相色谱-飞行时间质谱联用和质量亏损过滤技术的黄葵黄酮类成分系统分析  

Systematic Screening and Assignment of Flavones in Total Flavones of Abelmoschus Manihot Based on High-performance Liquid Chromatography Time-of-Flight Mass Spectrometry Analysis and Mass Defect Filter

作　　者：高芯 万瑶瑶 李长印[1] 段徐彬 丁选胜[2] 居文政[1] GAO Xin;WAN Yao-Yao;LI Chang-Yin;DUAN Xu-Bin;DING Xuan-Sheng;JU Wen-Zheng(Department of Clinical Pharmacology,Affiliated Hospital of Nanjing University of Chinese Medicine,Nanjing 210029,China;School of Pharmacy,China Pharmaceutical University,Nanjing 211198,China)

机构地区：[1]南京中医药大学附属医院临床药理实验室,南京210029 [2]中国药科大学药学院,南京211198

出　　处：《分析化学》2020年第2期262-268,共7页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.81503300);江苏省卫生健康委医学科研项目(No.H2019092);江苏省中医院高峰人才项目(No.y2018rc22);江苏高校优势学科建设工程项目(苏政办发[2018]87号);南京中医药大学中医学优势学科三期项目开放课题(No.ZYX03KF030)资助~~

摘　　要：采用液相色谱-飞行时间质谱联用(High-performance liquid chromatography time-of-flight mass spectrometry,LC-TOF-MS)分析黄葵总黄酮(Total flavones of Abelmoschus maniho t L.Medic,TFA)提取物,采集其正负离子模式下的LC-TOF-MS分析数据。借助质量亏损过滤(Mass defect filter,MDF)技术提取原始数据中黄酮类相关特征离子,通过TOF-MS精确分子量归属各离子的元素组成及离子类型,根据元素组成和离子类型的相关性合并可能源自同一个化合物的准分子离子和碎片离子,依据不少于2个准分子离子的出现筛选确认目标化合物。借助标准品比对、文献查阅、数据库搜索等手段解析选定的目标化合物的母离子和子离子图谱,对其结构进行鉴定或合理归属。最终从TFA中筛选并初步鉴定出49种黄酮类化合物。鉴定结果表明,TFA中黄酮类化合物的形成主要涉及糖基化、甲基化、甲酰化、乙酰化和葡萄糖醛酸化等转化反应。本研究丰富了对黄葵化学物质基础的认识,可为全面评价黄葵制剂质量、深入开展黄葵药效学研究提供重要参考;同时也表明LC-TOF-MS分析结合MDF技术是一种适用于中药化学成分的系统筛选方法。High-performance liquid chromatography time-of-flight mass spectrometry(HPLC-TOF-MS)was employed to analyze the extract of total flavones of Abelmoschus manihot L.Medic(TFA)in both positive and negative ion mode.The raw LC-MS data were filtered by a well-established mass defect filter(MDF)approach to screen the flavone-related ions,and then,each screened ion was assigned by TOF-MS accurate mass measurement to certain elemental composition and ion type.Next,the co-eluted ions from one single compound were attempted to be combined,and the presence of each compound was confirmed by at least two quasi-molecular ions.Aided by authentic standards comparison and searching literature and databases,the targeted compounds were tentatively identified or assigned according to their parent and fragment ions.Finally,49 flavones were screened and tentatively identified or assigned from the TFA extract.The results showed that,glycosylation,methylation,formylation,acetylation and glucuronidation were considered to be the major conversion involved in the formation of the TFA flavones.The current study not only provided the sufficient chemical substance for further studies of TFA,such as quality control and pharmacological activity,but also demonstrated the potential of the combination of LC-TOF-MS and MDF for systematically screening the constituents of herbal medicines.

关 键 词：黄葵 黄酮 液相色谱-飞行时间质谱 质量亏损过滤 成分系统筛选 结构鉴定 

分 类 号：R284[医药卫生—中药学] O657.63[医药卫生—中医学]