In this study, different electrospray ionization mass spectrometric (ESI-MS) methods were utilized to analyze several pairs of taxane stereoisomers including paclitaxel and 7-epi-paclitaxel. Both ESI-MS and tandem mass spectrometry (MS/MS) techniques provided stereochemically dependent mass spectra in negative-ion mode, and all studied stereoisomers could be easily distinguished based on their characteristic ions or distinct fragmentation patterns. MS/MS experiments for several taxane analogues at various collision energies were performed to elucidate potential dissociation pathways. The gas-phase deprotonation potentials were also calculated to estimate the most thermodynamically favorable deprotonation site using DFT B3LYP/6-31G(d). The results of the theoretical studies agreed well with the fragmentation patterns of paclitaxel and 7-epi-paclitaxel observed from MS/MS experiments. In addition, it was found that liquid chromatography (LC)/ESI-MS was a useful and sensitive technique for assignment of C-7 taxane stereoisomers from realistic samples. Copyright (C) 2009 John Wiley & Sons, Ltd.
关键词[WOS]:
DENSITY-FUNCTIONAL THEORY
; ANALYZER HYBRID SYSTEM
; HUMAN PLASMA
; MOLECULAR-STRUCTURE
; TRIPLE QUADRUPOLE
; PACLITAXEL TAXOL
; DOG PLASMA
; GAS-PHASE
; METABOLITES
; QUANTIFICATION
1.Chinese Acad Sci, Dalian Inst Chem Phys, Lab Pharmaceut Resource Discovery, Dalian 116023, Peoples R China 2.Chinese Acad Sci, Grad Univ, Beijing, Peoples R China 3.Dalian Univ Technol, State Key Lab Fine Chem, Dalian, Peoples R China 4.Shanghai Univ Tradit Chinese Med, Inst Chinese Mat Med, Shanghai, Peoples R China
Recommended Citation:
Ge, Guang-Bo,Zhang, Rong,Ai, Chun-Zhi,et al. Stereochemical differentiation of C-7 hydroxyltaxane isomers by electrospray ionization mass spectrometry[J]. RAPID COMMUNICATIONS IN MASS SPECTROMETRY,2009,23(3):425-432.
