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

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-MS(n) in positive and negative-ion modes has been developed for the direct structural elucidation of steroid saponins of this kind in plant extracts.

Qualitative and quantitative determination of major saponins in Paris and Trillium by HPLC-ELSD and HPLC–MS/MS

“…In the MS, the steroid saponins exhibited quasi-molecular ions [M+H] + , [M−H] − , or whilst in the MS n spectra fragment ions were formed by successive or simultaneous loss of saccharide groups, H 2 O or CH 3 OH. The detailed fragmentation pathways have been discussed before [25].…”

“…Highest sensitivity, relatively short analysis time, considerable structural information, low amount of sample and on line identification of separated saponins should be recommended as their competitive advantages. In our previous research, we identified 23 steroid saponins from P. yunnanensis and deduced their fragmentation pathways [25]. In the present paper, we used LC-MS/MS to identify the common steroid saponins and compared their ingredient variability in Paris and Trillium plants.…”

Simultaneous quantification of Polyphyllin D and Paris H, two potential antitumor active components in Paris polyphylla by liquid chromatography–tandem mass spectrometry and the application to pharmacokinetics in rats

“…Due to the above potential biological effects, it is necessary to carry out the bioanalysis and pharmacokinetic studies on Polyphyllin D and Paris H. The in vitro quantitative methods of Polyphyllin D and Paris H analysis have been carried out in the last several years mainly by liquid chromatography with both reversed phase columns coupled to diode array detector (DAD) and evaporative light scattering detector (ELSD) [17][18][19][20]. None of these methods meets the requirements for the analysis of biological fluids with respect to an efficient clean-up procedure, shorter running time and higher sensitivity.…”

Preparative separation and purification of steroidal saponins inParis polyphyllavar.yunnanensisby macroporous adsorption resins

“…The analytical process was completed in 60 min. According to the profile of dried rhizomes of the PPY extract, the main ingredients found were Paris VII, Paris H, formosanin C, gracillin and polyphyllin D (Kang et al, 2012;Liu et al, 2013;Man et al, 2009a). Therefore, those five saponins were used as the quantitative criteria in the study of this separation process.…”

“…It appeared with the name ''ZaoXiu'', and many wellknown formulary Chinese Medicines contain Rhizoma Paridis, such as Yunnan Baiyao Powder and Gongxuening Capsules produced by Yunnan Baiyao Group Ltd. Co. (Yunnan, China), Loulian Capsules (Tonghua Wantong Pharmaceutical Ltd. Co., Tonghua, China), Jidesheng Sheyao Tablet (Nantong Jinghua Pharmaceutical Ltd. Co., Nantong, China). Rhizoma Paridis saponins (RPS) (Man et al, 2009a), as steroidal saponins, are the main and the active components in PPY (Liu et al, 2012;Qin et al, 2012;Zhang et al, 2010). They recently attracted particular interests because modern pharmacology research indicated these steroidal saponins appeared to exhibit a variety of biological activities, such as antitumor (Man et al, 2009b(Man et al, , 2011a, antifungal activity (Deng et al, 2008), inhibitory activities against abnormal uterine bleeding (Fu et al, 2008) and anthelmintic activity (Wang et al, 2010).…”