Structure and Pathway Research on Chemical Transformation of Ginsenoside Rb1 via HPLC-HRMS/MSn/QqQ Technique†

doi:10.7503/cjcu20170216

Abstract

Abstract:

Keggin-type dodeca tungstophosphoric acid(HPW) was used in the chemical transformation of ginsenoside Rb₁. The aim of this research is to analyze the structure of the transformed products and transformation pathways based on high-performance liquid chromatography coupled with three kinds of mass spectrometry(HPLC-MS), the potential of which in qualitative and quantitative analysis of natural product was also developed. Q Exactive, a kind of high-resolution MS(HRMS), was used for the rapid structural identification of transformed products. Multistage tandem MS(MSⁿ) was further applied to verifying the identified structure. Ten transformed products, 20(S)-Rg₃, 20(R)-Rg₃, 20(S)-25-OH-Rg₃, 20(R)-25-OH-Rg₃, 25-OH-Rk₁, 25-OH-Rg₅, Rg₅, Rk₁, (20S,25)-epoxy-Rg₃ and(20R,25)-epoxy-Rg₃ were rapidly identified in all. In HPW-generated acidic solution, ginsenoside Rb₁ was chemically transformed through deglycosylation, epimerization at C₂₀ as well as hydration, elimination and cyclization reactions on the aglycone. Triple quadrupole(QqQ) MS was further used in its SRM mode for the accurately quantitative analysis of the conversion of Rb₁ and the yield of 20(S)-Rg₃, 20(R)-Rg₃, Rk₁ and Rg₅. Rb₁ was completely transformed to rare ginsenosides within 40 min. Based on the quantitative analysis results, HPW exhibited a much higher activity towards the transformation of Rb₁ in comparison with biotransformation, and it is a kind of efficient reagent for the chemical transformation of ginsenoside Rb₁. What’s more, HPLC-HRMS/MSⁿ/QqQ technique was proved to be effective for the qualitative and quantitative analysis of the natural products such as ginsenosides.

Key words: Ginsenoside Rb1, HPLC-HRMS/MSn/QqQ, Heteroploy acid, Chemical transformation

CLC Number:

O657.6

TrendMD:

LI Xue, ZHAO Huanxi, MIAO Rui, LI Wenying, XIU Yang, LIU Shuying. Structure and Pathway Research on Chemical Transformation of Ginsenoside Rb₁ via HPLC-HRMS/MSⁿ/QqQ Technique^†[J]. Chem. J. Chinese Universities, 2017, 38(10): 1730.

Figures/Tables 9

Fig.1 Total ion chromatogram of chemical transformation for ginsenoside Rb1

Fig.2 MS/MS spectrum of the [M-H]- ion at m/z 1107 of ginsenoside Rb1

Fig.3 MS/MS spectrum of the [M-H]- ion at m/z 801 of ginsenoside 20(S)-25-OH-Rg3

Fig.4 MS/MS spectrum of the [M-H]- ion at m/z 783 of ginsenoside 25-OH-Rk1

Fig.5 MS/MS spectrum of the [M-H]- ion at m/z 783 of ginsenoside 20(S)-Rg3

Fig.6 MS/MS spectrum of the [M-H]- ion at m/z 783 of (20S,25)-epoxy-Rg3

Fig.7 MS/MS spectrum of the [M-H]- ion at m/z 765 of ginsenoside Rk1

Scheme 1 Chemical transformation pathways of ginsenoside Rb1 by 12-H3PW12O40

Fig.8 Conversion of ginsenosides Rb1, 20(S)-Rg3, 20(R)-Rg3, Rk1 and Rg5

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Structure and Pathway Research on Chemical Transformation of Ginsenoside Rb₁ via HPLC-HRMS/MSⁿ/QqQ Technique^†

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