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KMID : 0352720190430030368
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Journal of Ginseng Research
2019 Volume.43 No. 3 p.368 ~ p.376
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Differentiation and identification of ginsenoside structural isomers by two-dimensional mass spectrometry combined with statistical analysis
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Xiu Yang
Ma Li
Zhao Huanxi
Sun Xiuli
Li Xue
Liu Shuying
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Abstract
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Background: In the current phytochemical research on ginseng, the differentiation and structural identification of ginsenosides isomers remain challenging. In this paper, a two-dimensional mass spectrometry (2D-MS) method was developed and combined with statistical analysis for the direct differentiation, identification, and relative quantification of protopanaxadiol (PPD)-type ginsenoside isomers.
Methods: Collision-induced dissociation was performed at successive collision energy values to produce distinct profiles of the intensity fraction (IF) and ratio of intensity (RI) of the fragment ions. To amplify the differences in tandem mass spectra between isomers, IF and RI were plotted against collision energy. The resulting data distributions were then used to obtain the parameters of the fitted curves, which were used to evaluate the statistical significance of the differences between these distributions via the unpaired t test.
Results: A triplet and two pairs of PPD-type ginsenoside isomers were differentiated and identified by their distinct IF and RI distributions. In addition, the fragmentation preference of PPD-type ginsenosides was determined on the basis of the activation energy. The developed 2D-MS method was also extended to quantitatively determine the molar composition of ginsenoside isomers in mixtures of biotransformation products.
Conclusion: In comparison with conventional mass spectrometry methods, 2D-MS provides more direct insights into the subtle structural differences between isomers and can be used as an alternative approach for the differentiation of isomeric ginsenosides and natural products.
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KEYWORD
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Differentiation, Ginsenoside isomers, Relative quantification, Two-dimensional mass spectrometry
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