Journal
JOURNAL OF CHROMATOGRAPHY A
Volume 1406, Issue -, Pages 136-144Publisher
ELSEVIER
DOI: 10.1016/j.chroma.2015.06.007
Keywords
Homolog-focused profiling; Ginsenoside; Step-wise multiple reaction monitoring; Scheduled multiple reaction monitoring; Formate anion-to-deprotonated ion pairing
Funding
- National Science Fund of China [81403073, 81222051]
- National Key Technology R&D Program New Drug Innovation of China [2013ZX09201018, 2012ZX09103201-036, 2012ZX09301002-002-002]
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Homolog-focused profiling is a favored option to bridge targeted metabolomics toward non-targeted metabolomics. In current study, an attempt was made for the large-scale ginsenoside-specific analysis in ginseng (G) and American ginseng (AG). When formic acid (0.1%, v/v) was introduced as the mobile phase additive, formate anion-to-deprotonated ion transitions ([M+HCOO](-) > [M-H](-)) with an optimal collision energy (-32 eV) could result in satisfactory responses for ginsenosides. Therefore, a step-wise multiple reaction monitoring (MRM)-based method employing [M+HCOO](-) > [M-H](-) ion pairs was constructed to screen ginsenosides among 501-1250 u (for Q1) with a step-size of 2 u, and MRM also served as a survey experiment to trigger enhanced product ion scans for MS2 spectrum acquisition on a hybrid triple quadrupole-linear ion trap mass spectrometer; then, the identification of those observed ginsenosides was achieved on the basis of the well-defined mass cracking patterns for ginsenosides; afterwards, scheduled MRM was introduced for large-scale relatively quantitative analysis of all detected ginsenosides. Finally, comparative metabolomics were performed to differentiate G, AG, and their processed products. Method validation was carried out using thirteen authentic compounds. A total of 221 ginsenosides, among which 185 ones were annotated, were observed and relatively quantitated. All crude materials were obviously classified into groups I-III. Above all, the MRM-based homolog-focused profiling of ginsenosides could be used as a reliable tool to gain an in-depth view for ginsenoside-enriched herbal products. (C) 2015 Elsevier B.V. All rights reserved.
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