丹参酮ⅡA和丹参酮Ⅰ的电子轰击与电喷雾电离质谱分析

Elucidation of tanshinone ⅡA and tanshinone Ⅰ by electron spray ionization mass spectrometry and electron ionization mass spectrometry

采用电喷雾电离质谱(ESI-MS)和电子轰击质谱(EI-MS)两种质谱技术分别对传统中药丹参的主要脂溶性活性成分丹参酮ⅡA和丹参酮Ⅰ的化学结构和裂解途径进行系统研究。采用EI-MS从丹参酮ⅡA获得m/z 294[M]+、279、261、233、207等特征质谱峰,从丹参酮Ⅰ获得m/z 276[M]+、248、233、219、205等特征质谱峰;采用ESI-MS从丹参酮ⅡA获得m/z 295[M+H]+、280、278、262、249等特征质谱峰,从丹参酮Ⅰ获得m/z 277[M+H]+、259、249、231、221、193等特征质谱峰,并用Mass Frontier 3.0软件辅助解析了其中的主要特征碎片离子以及可能的裂解途径;比较了丹参酮ⅡA和丹参酮Ⅰ的电喷雾电离质谱和电子轰击质谱裂解规律,本研究为研究丹参二萜醌类主要特征活性成分的生物转化与结构修饰提供了依据。

Electron spray ionization mass spectrometry （ESI-MS） and electron ionization mass spectrometry （Ei-MS） were used to elucidate the structures and fragmentation pathway of tanshinone Ⅱ A and tanshinone 1 , major fat-soluble components of traditional Chinese herbal medicine called ＂DanShen＂. Ion peaks m/z 294[ M]^＋ , 279, 261, 233, 207 were detected for tanshinone Ⅱ A and ion peaks m/z 276[M]^＋ , 248, 233, 219, 205 were detected for tanshinoneⅠ by EI-MS. Ion peaks m/z 295 [ M ＋ H] ^＋ , 280, 278, 262, 249 were detected for tanshinone Ⅱ A and ion peaks m/z 277[M ＋ H]^＋ , 259, 249, 231, 221, 193 were detected for tanshinone Ⅰ by ESI-MS. The fragmentation pathway of tanshinone Ⅱ A and tanshinone Ⅰ was explained with the aid of the program of mass frontier 3.0. And we compare the EI, ESI fragmentation mechanisms of tanshinone Ⅱ A and tanshinone Ⅰ , the results provide important information for the drug metabolism and structural modification of diterpenoid tanshinone from roots of Salvia mihiorrhiza Bunge.