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Characterization of tanshinones in the roots of Salvia miltiorrhiza (Dan‐shen) by high‐performance liquid chromatography with electrospray ionization tandem mass spectrometry
Author(s) -
Yang Min,
Liu Aihua,
Guan Shuhong,
Sun Jianghao,
Xu Man,
Guo Dean
Publication year - 2006
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.2447
Subject(s) - chemistry , salvia miltiorrhiza , electrospray ionization , fragmentation (computing) , tandem mass spectrometry , molecule , chromatography , substituent , mass spectrometry , medicinal chemistry , organic chemistry , medicine , alternative medicine , pathology , traditional chinese medicine , computer science , operating system
The qualitative analysis of tanshinones in the roots of Salvia miltiorrhiza (Dan‐shen in Chinese) was performed using high‐performance liquid chromatography with electrospray ionization tandem mass spectrometry (ESI‐MS n ). Tanshinones are the major bioactive constituents of Dan‐shen, which is used in China for the treatment of haematological abnormalities and cardiovascular diseases. The ESI‐MS n fragmentation behavior of tanshinones was investigated. For tanshinones with the tanshinone I nucleus, the fragmentation was triggered by loss of a molecule of CO except bearing a substituent at C 17 or C 18 , followed by sequential eliminations of CO. If C 15–16 was a saturated bond, the fragmentation was triggered by elimination of a molecule of H 2 O. For tanshinones with the tanshinone IIA nucleus, the fragmentation was triggered by loss of a molecule of H 2 O, followed by successive eliminations of CO. Ions corresponding to loss of a molecule of propylene (Δ m = 42) were also observed. Moreover, when C 15–16 was a saturated bond, ions corresponding to losses of CH 3 , H 2 O and propylene were more abundant. If no D‐ring existed, the presence of isopropyl resulted in an elimination of a molecule of H 2 O with an adjacent CO or OH. In addition, the extension of the π ‐conjugation in the A‐ring (especially at C 1–2 ) induced the fragmentation by loss of a molecule of CO. These fragmentation rules were applied to the identification of tanshinones in a chloroform/methanol (3:7) extract of Dan‐shen, which was separated on a C 18 column with gradient elution. A total of 27 tanshinones were identified, including five new constituents. The established method could be used for the sensitive and rapid identification of tanshinones in the Dan‐shen drug and its pharmaceutical preparations. Copyright © 2006 John Wiley & Sons, Ltd.