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SCIENCE CHINA Chemistry, Volume 60, Issue 6: 748-753(2017) https://doi.org/10.1007/s11426-016-0439-6

A novel catalytic application of heteropolyacids: chemical transformation of major ginsenosides into rare ginsenosides exemplified by Rg1

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  • ReceivedOct 29, 2016
  • AcceptedDec 5, 2016
  • PublishedMar 20, 2017

Abstract

High performance liquid chromatography coupled with quadruple-time-of-flight mass spectrometry (HPLC-Q-TOF-MS) method was developed for analyzing the hydrolytic mixtures of ginsenoside Rg1 in acidic conditions (pH 3). Three catalysts, a heteropolyacid (H4SiW12O40, SiW12 for short), its complex with γ-CD (SiW12/γ-CD for short) and formic acid, were used for comparison. The chemical transformation products were identified based on the accurate mass measurement and the fragment ions obtained from tandem mass spectrometry. It was concluded that the catalytic efficiency of SiW12 (»SiW12/γ-CD) is ca. 410 times higher than that of formic acid, thus becoming the most efficient catalyst for chemical transformations of ginsenosides.


Funded by

National Natural Science Foundation of China(21371025)

National Basic Research Program of China(2014CB932103)

111 Project(B07012,the Fundamental Research Grant (20121942006)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21371025), the 111 Project (B07012) and the degree and postgraduate education development research project (YJYJG2015B07) by Beijing Institute of Technology.


Interest statement

The authors declare that they have no conflict of interest.


Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Scheme 1

    The chemical structure and the nomenclature for fragmentation of Rg1.

  • Figure 1

    HPLC extracted ion chromatograms of the ginsenoside Rg1 hydrolyzed by SiW12 and formic acid, and ESI-MS spectra of each peak in negative-ion mode (pH 3.0, reaction time=5 h, temperature=60 °C) (color online).

  • Figure 2

    The ESI-MS/MS spectra of each chemical transformation product of Rg1 in negative-ion mode. The precursor ion in each case is shown in a red box (color online).

  • Figure 3

    Chemical transformation pathways of ginsenoside Rg1.

  • Table 1   Comparison of catalytic efficiency for the chemical transformation of R by SiW, SiW/γ-CD complex and formic acid

    Entry

    Cat.

    Concentration (×10−6 mol/L)

    Conv. (mol%)

    Catalyst

    Rg1

    1

    HCOOH

    227.5

    1.3

    75.7

    2

    SiW12

    0.6

    1.3

    86.5

    3

    SiW12/γ-CD

    0.6

    1.3

    85.5

    Reaction condition: pH 3; reaction time=5 h; temperature=60 °C. Determined by LC-MS.

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