Planta Med 2014; 80(04): 321-329
DOI: 10.1055/s-0033-1360330
Analytical Studies
Original Papers
Georg Thieme Verlag KG Stuttgart · New York

Characterization of Steroidal Saponins from Dioscorea villosa and D. cayenensis Using Ultrahigh Performance Liquid Chromatography/Electrospray Ionization Quadrupole Time-of-Flight Mass Spectrometry

Bharathi Avula
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, The University of Mississippi, University, MS, USA
,
Yan-Hong Wang
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, The University of Mississippi, University, MS, USA
,
Mei Wang
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, The University of Mississippi, University, MS, USA
,
Zulfiqar Ali
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, The University of Mississippi, University, MS, USA
,
Troy J. Smillie
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, The University of Mississippi, University, MS, USA
,
Jerry Zweigenbaum
2   Agilent Technologies, Wilmington, DE, USA
,
Ikhlas A. Khan
1   National Center for Natural Products Research, Research Institute of Pharmaceutical Sciences, The University of Mississippi, University, MS, USA
3   Department of Pharmacognosy, School of Pharmacy, The University of Mississippi, University, USA
› Author Affiliations
Further Information

Publication History

received 20 September 2013
revised 30 December 2013

accepted 04 January 2014

Publication Date:
07 February 2014 (online)

Abstract

Yam (Dioscorea spp.) is an important edible tuber plant used for medicinal purposes to promote health and longevity in Chinese tradition. Steroidal saponins were reported to be the major physiologically active constituents in yams. In this current work, the structural characteristics of steroidal saponins in methanolic extracts from dried rhizomes of two Dioscorea species (D. villosa L. and D. cayenensis Lam.) and dietary supplements have been identified and analyzed using UHPLC/QTOF-MS in both negative and positive ion modes. The fragmentation patterns of reference standards were determined and the steroidal saponins in the extracts were identified or tentatively characterized from their retention times and mass spectra. The fragments produced by collision-induced dissociation (CID) revealed the characteristic cleavage of glycosidic bonds, and the fragmentation pattern provided structural information about the sugars. Twenty-one saponins, including four tentatively identified compounds, were detected in the crude extracts of two Dioscorea species. These saponins can be used to distinguish D. villosa from D. cayenensis. For example, asperin and gracillin are found only in D. cayenensis, and dioscoreavilloside A and B and parvifloside are only found in D. villosa. This can be used to determine the presence or absence of D. villosa in commercial products, which may help determine the spiking of plant material, and/or prevent the use of potentially mislabeled or misidentified “Dioscorea” material. The analytical method also provided an alternative, fast method for quality control of Dioscorea species in dietary supplements. Principal component analysis showed that Dioscorea species and commercial products were easily distinguished. From this a partial least squares model was constructed to determine what species are in different products.

Supporting Information

 
  • References

  • 1 Lacaille-Dubois MA, Wagner H. Bioactive saponins from plants: an update. Stud Nat Prod Chem 2000; 21: 633-687
  • 2 Lacaille-Dubois MA. Bioactive saponins with cancer related and immunomodulatory activity: recent developments. Stud Nat Prod Chem 2005; 32: 209-246
  • 3 Benghuzzi H, Tucci M, Eckie R, Hughes J. The effects of sustained delivery of diosgenin on the adrenal gland of female rats. Biomed Sci Instrum 2003; 39: 335-340
  • 4 Hu K, Dong AJ, Yao XS, Kobayashi H, Iwasaki S. Antineoplastic agents. Part 2. Four furostanol glycosides from rhizomes of Dioscorea collettii var. hypoglauca . Planta Med 1997; 63: 161-165
  • 5 Zhang J, Meng Z, Zhang M, Ma D, Xu S, Kodama H. Effect of six steroidal saponins isolated from Anemarrhenae rhizoma on platelet aggregation and hemolysis in human blood. Clin Chim Acta 1999; 289: 79-88
  • 6 Sauvaire Y, Ribes G, Baccou JC, Loubatieres-Marian MM. Implication of steroid saponins and sapogenins in the hypocholesterolemic effect of fenugreek. Lipids 1991; 26: 191-197
  • 7 Liu SY, Wang JY, Shyu YT, Song LM. Studies on yams (Dioscorea spp.) in Taiwan. J Chin Med 1995; 6: 111-126
  • 8 Chen Y, Wu Y. Progress in research and manufacturing of steroidal sapogenins in China. J Herb Spices Med Plants 1994; 2: 59-70
  • 9 Morgan M. Steroids. Kirk-Othmer Encyclopedia of Chemical Technology. Hoboken: John Wiley and Sons; 1997
  • 10 Sautour M, Mitaine-Offer AC, Lacaille-Dubois MA. The Dioscorea genus: a review of bioactive steroid saponins. J Nat Med 2007; 61: 91-101
  • 11 Sautour M, Miyamoto T, Lacaille-Dubois MA. Steroidal saponins and flavan-3-ol glycosides from Dioscorea villosa . Biochem Syst Ecol 2006; 34: 60-63
  • 12 Hayes PY, Lambert LK, Lehmann R, Penman K, Kitching W, De VJJ. Complete (1)H and (13)C assignments of the four major saponins from Dioscorea villosa (wild yam). Magn Reson Chem 2007; 45: 1001-1005
  • 13 Agbor-Egbe T, Treche S. Evaluation of the chemical composition of Cameroonian yam germplasm. J Food Comp Anal 1995; 8: 274-283
  • 14 Sautour M, Mitaine-Offer AC, Miyamoto T, Dongmo A, Lacaille-Dubois MA. Antifungal steroid saponins from Dioscorea cayenensis . Planta Med 2004; 70: 90-92
  • 15 Zhu J, Guo X, Fu S, Zhang X, Liang X. Characterization of steroidal saponins in crude extracts from Dioscorea zingiberensis C. H. Wright by ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry. J Pharm Biomed Anal 2010; 53: 462-474
  • 16 Sautour M, Mitaine-Offer AC, Miyamoto T, Dongmo A, Lacaille-Dubois MA. A new steroidal saponin from Dioscorea cayenensis . Chem Pharm Bull 2004; 52: 1353-1355
  • 17 Hayes PY, Lambert LK, Lehmann R, Penman K, Kitching W, De VJJ. Spectral assignments and reference data complete 1H and 13C assignments of the four major saponins from Dioscorea villosa (wild yam). Magn Reson Chem 2007; 45: 1001-1005
  • 18 Hu CC, Lin JT, Liu SC, Yang DJ. A spirostanol glycoside from wild yam (Dioscorea villosa) extract and its cytostatic activity on three cancer cells. Yaowu Shipin Fenxi 2007; 15: 310-315
  • 19 Li R, Zhou Y, Wu Z, Ding L. ESI-QqTOF-MS/MS and APCI-IT-MS/MS analysis of steroid saponins from the rhizomes of Dioscorea panthaica . J Mass Spectrom 2006; 41: 1-22
  • 20 Liang M, Zheng Z, Yuan Y, Kong L, Shen Y, Liu R, Zhang C, Zhang W. Identification and quantification of C21 steroidal saponins from Radix Cynanchi Atrati by high-performance liquid chromatography with evaporative light scattering detection and electrospray mass spectrometric detection. Phytochem Anal 2007; 18: 428-435
  • 21 Lin S, Wang D, Yang D, Yao J, Tong Y, Chen J. Characterization of steroidal saponins in crude extract from Dioscorea nipponica Makino by liquid chromatography tandem multi-stage mass spectrometry. Anal Chim Acta 2007; 599: 98-106
  • 22 Zheng Z, Zhang W, Kong L, Liang M, Li H, Lin M, Liu R, Zhang C. Rapid identification of C21 steroidal saponins in Cynanchum versicolor Bunge by electrospray ionization multi-stage tandem mass spectrometry and liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom 2007; 21: 279-285
  • 23 Lu Y, Luo J, Xu D, Huang X, Kong L. Characterization of spirostanol saponins in Solanum torvum by high-performance liquid chromatography/evaporative light scattering detector/electrospray ionization with multi-stage tandem mass spectrometry. Rapid Commun Mass Spectrom 2008; 22: 2447-2452
  • 24 Zhou DY, Zhang XL, Xu Q, Xue XY, Zhang FF, Liang XM. UPLC/Q-TOFMS/MS as a powerful technique for rapid identification of polymethoxylated flavones in Fructus aurantii . J Pharm Biomed Anal 2009; 50: 2-8
  • 25 Novak TJ, Grinberg N, Hartman B, Marcinko S, DiMichele L, Mao B. LCMS using a hybrid quadrupole time of flight mass spectrometer for impurity identification during process chemical development of a novel integrase inhibitor. J Pharm Biomed Anal 2010; 51: 78-83
  • 26 Li CM, Zhang XL, Xue XY, Zhang FF, Xu Q, Liang XM. Structural characterization of iridoid glucosides by ultra-performance liquid chromatography/electrospray ionization quadrupole time-of-flight tandem mass spectrometry. Rapid Commun Mass Spectrom 2008; 22: 1941-1954
  • 27 Zhang J, Jin Y, Dong J, Xiao Y, Feng J, Xue X, Zhang X, Liang X. Systematic screening and characterization of tertiary and quaternary alkaloids from Corydalis yanhusuo W.T. Wang using ultra-performance liquid chromatography-quadrupole-time-of-flight mass spectrometry. Talanta 2009; 78: 513-522
  • 28 Wang X, Sun W, Sun H, Lv H, Wu Z, Wang P, Liu L, Cao H. Analysis of the constituents in the rat plasma after oral administration of Yin Chen Hao Tang by UPLC/Q-TOF-MS/MS. J Pharm Biomed Anal 2008; 46: 477-490
  • 29 Li SL, Song JZ, Choi FFK, Qiao CF, Zhou Y, Han QB, Xu HX. Chemical profiling of Radix Paeoniae evaluated by ultra-performance liquid chromatography/photo-diode-array/quadrupole time-of-flight mass spectrometry. J Pharm Biomed Anal 2009; 49: 253-266
  • 30 Avula B, Wang YH, Ali Z, Smillie TJ, Khan IA. Chemical fingerprint analysis and quantitative determination of steroidal compounds from Dioscorea villosa, Dioscorea species, and dietary supplements using UHPLC-ELSD. Biomed Chromatogr 2014; 28: 281-294
  • 31 Ali Z, Smille TJ, Khan IA. Cholestane steroid glycosides from the rhizomes of Dioscorea villosa (Wild Yam). Carbohydr Res 2013; 370: 86-91