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Characterization of steroidal saponins in saponin extract from Paris polyphylla by liquid chromatography tandem multi-stage mass spectrometry

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Abstract

Rhizoma Paridis saponins are bioactive steroidal saponins derived from Paris polyphylla. Optimization of the ionization process was performed with electrospray ionization tandem mass spectrometry in both positive and negative-ion modes. Negative-ion ESI was adopted for generation of the precursor deprotonated molecules to achieve the best ionization sensitivity for the analytes. Positive ionization was used to choose the most abundant fragment ion. Furthermore, according to the characteristic fragmentation behavior of known steroidal saponins isolated from this plant (polyphyllin D, formosanin C, gracillin, Paris H, Paris VII, and dioscin), 23 constituents were structurally characterized on the basis of their retention time and ESI analyses, including four pairs of naturally occurring isomers. Five of these 23 constituents were new compounds. The analytical method of LC–MSn in positive and negative-ion modes has been developed for the direct structural elucidation of steroid saponins of this kind in plant extracts.

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Abbreviations

Ara:

α-l-arabinofuranosyl

FC:

formosanin C

Glc:

β-d-glucopyranosyl

PD:

polyphyllin D

PPY:

Paris polyphylla var. yunnanensis (Fr.) Hand.-Mazz

Rha:

α-l-rhamnopyranosyl

RPS:

Rhizoma Paridis saponins

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Acknowledgment

This work was supported by a grant 07JCZDJC05400 from the Tianjin Municipal Science and Technology Commission (Tianjin, China) and a grant 30873378 from National Natural Science Foundation of China.

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Correspondence to Wenyuan Gao.

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Yanjun Zhang and Wenyuan Gao contributed equally to this paper.

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Man, S., Gao, W., Zhang, Y. et al. Characterization of steroidal saponins in saponin extract from Paris polyphylla by liquid chromatography tandem multi-stage mass spectrometry. Anal Bioanal Chem 395, 495–505 (2009). https://doi.org/10.1007/s00216-009-2987-2

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  • DOI: https://doi.org/10.1007/s00216-009-2987-2

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