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Differentiation of common diastereoisomeric ursane‐type triterpenoids by high‐performance liquid chromatography/tandem mass spectrometry
Author(s) -
Gao Jie,
Shi Jianmei,
Lu Xiaomeng,
Sun Cuirong,
Pan Yuanjiang
Publication year - 2011
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.4978
Subject(s) - chemistry , tandem mass spectrometry , mass spectrometry , epimer , fourier transform ion cyclotron resonance , electrospray ionization , chromatography , electrospray , tandem , analytical chemistry (journal) , stereochemistry , materials science , composite material
A rapid and stable method consisting of high‐performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry was established for the identification and differentiation of common diastereoisomeric ursane‐type triterpenoids at the C‐3 position. Two characteristic fragment ions, [M–H–H 2 O–CO 2 ] – and [M–H–H 2 O–HCOOH] – , exhibited significant stereochemical effects and were utilized to distinguish 3‐OH epimers. Based on reference standards, the abundance of the fragment ion [M–H–H 2 O–HCOOH] – in 3β‐OH compounds in the MS 3 experiment was dramatically higher compared to [M–H–H 2 O–CO 2 ] – ; however, for 3α‐OH compounds, the product ion [M–H–H 2 O–CO 2 ] – was noted to be higher than [M–H–H 2 O–HCOOH] – . Energy‐resolved mass spectrometric experiments were carried out to support the differentiation of these diastereoisomeric triterpenoids at the C‐3 position. Using this method, a total of nine ursane‐type triterpenoids from a plant crude extract, including four pairs of epimers at the C‐3 position, were identified and distinguished rapidly. Furthermore, offline Fourier transform ion cyclotron resonance tandem mass spectrometry was also performed to assign accurate elemental compositions. Copyright © 2011 John Wiley & Sons, Ltd.