Skip to main content
SpringerLink
Log in

LC-ESI MS/MS profiling of polar steroid metabolites of the Far Eastern starfish Patiria (=Asterina) pectinifera

  • Original Article
  • Published:
Metabolomics Aims and scope Submit manuscript

Abstract

Profiling of asterosaponins, polyhydroxysteroids and glycosides of polyhydroxysteroids of the common in the Far Eastern sea waters starfish Patiria (=Asterina) pectinifera was performed by LC-ESI MS and LC-APPI MS. The 72 polar steroid metabolites, including 35 asterosaponins, 22 polyhydroxysteroids and 15 sulfated glycosides of polyhydroxysteroids, were detected and identified using the LC–MS and LC–MS/MS spectra. The steroid metabolome of P. pectinifera is characterized by large number of sulfated and non-sulfated highly oxidized compounds with cholestane, ergostane and stigmastane skeleton systems of aglycones. Some peculiarities of biosynthesis of the starfish polar steroids were discussed. It was suggested that biosynthesis of asterosaponins from diet sterols is executed in a mosaic type manner with transformations in aglycone moieties and elongation of carbohydrate chains proceeding independently from each other and simultaneously.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • D’Auria, M. V., Iorizzi, M., Minale, L., Riccio, R., & Uriarte, E. (1990). Starfish saponins, Part 41. Structure of two new steroidal glycoside sulfates (miniatosides A and B) and two new polyhydroxysteroids from the starfish Patiria miniata. Journal of Natural Products, 53, 94–101.

    Article  Google Scholar 

  • Demeyer, M., De Winter, J., Caulier, G., Eeckhaut, I., Flammang, P., & Gerbauxa, P. (2014). Molecular diversity and body distribution of saponins in the sea star Asterias rubens by mass spectrometry. Comparative Biochemistry and Physiology Part B, 168, 1–11.

    Article  CAS  Google Scholar 

  • Domon, B., & Costello, C. E. (1988). A systematic nomenclature for carbohydrate fragmentations in FAB-MS/MS spectra of glycoconjugates. Glycoconjugate Journal, 5, 397–409.

    Article  CAS  Google Scholar 

  • Dong, G., Xuc, T., Yanga, B., et al. (2011). Chemical constituents and bioactivities of starfish. Chemistry & Biodiversity, 8, 740–791.

    Article  CAS  Google Scholar 

  • Dubois, M. A., Higuchi, R., Komori, T., & Sasaki, T. (1988a). Structures of two new oligoglycoside sulfates, pectiniosides E and F, and biological activities of the six new pectiniosides. Liebigs Annalen der Chemie, 9, 845–850.

    Article  Google Scholar 

  • Dubois, M. A., Noguchi, Y., Higuchi, R., & Komori, T. (1988b). Structures of two new oligoglycoside sulfates: pectinioside C and pectinioside D. Liebigs Annalen der Chemie, 6, 495–500.

    Article  Google Scholar 

  • Griffiths, W. J. (2003). Tandem mass spectrometry in the study of fatty acids, bile acids, and steroids. Mass Spectrometry Reviews, 22, 81–152.

    Article  CAS  PubMed  Google Scholar 

  • Higuchi, R., Noguchi, Y., Komori, T., & Sasaki, T. (1988). 1H NMR spectroscopy and biological activities of polyhydroxylated steroids from the starfish Asterina pectinifera Muller et Troschel. Liebigs Annalen der Chemie, 1, 1185–1189.

    Article  Google Scholar 

  • Hwang, I. H., Kim, D. W., Kim, S. J., et al. (2011). Asterosaponins isolated from the starfish Asterias amurensis. Chemical & Pharmaceutical Bulletin, 59(1), 78–83.

    Article  CAS  Google Scholar 

  • Iorizzi, M., Minale, L., & Riccio, R. (1990). Starfish saponins. Part 39. Steroidal oligoglycoside sulphates and polyhydroxysteroids from the starfish Asterina pectinifera. Gazzetta Chimica Italiana, 120, 147–153.

    CAS  Google Scholar 

  • Iorizzi, M., Minale, L., Riccio, R., & Yasumoto, T. (1993). Starfish saponins, Part 51. Steroidal oligoglycosides from the starfish Distolasterias nipon. Journal of Natural Products, 56(10), 1786–1798.

    Article  CAS  PubMed  Google Scholar 

  • Ivanchina, N. V., Kicha, A. A., Kalinovsky, A. I., et al. (2000). Hemolytic polar steroidal constituents of the starfish Aphelasterias japonica. Journal of Natural Products, 63, 1178–1181.

    Article  CAS  PubMed  Google Scholar 

  • Ivanchina, N. V., Kicha, A. A., Kalinovsky, A. I., Dmitrenok, P. S., Prokof’eva, N. G., & Stonik, V. A. (2001). New steroid glycosides from the starfish Asterias rathbuni. Journal of Natural Products, 64, 945–947.

    Article  CAS  PubMed  Google Scholar 

  • Ivanchina, N. V., Kicha, A. A., & Stonik, V. A. (2011). Steroid glycosides from marine organisms. Steroids, 76, 425–454.

    Article  CAS  PubMed  Google Scholar 

  • Ivanchina, N. V., Kicha, A. A., Malyarenko, T. V., Kalinovsky, A. I., Dmitrenok, P. S., & Stonik, V. A. (2013). Biosynthesis of polar steroids from the Far Eastern starfish Patiria (=Asterina) pectinifera. Cholesterol and cholesterol sulfate are converted into polyhydroxylated sterols and monoglycoside asterosaponin P1 in feeding experiments. Steroids, 78, 1183–1191.

    Article  CAS  PubMed  Google Scholar 

  • Kicha, A. A., Kalinovsky, A. I., Levina, E. V., Stonik, V. A., & Elyakov, G. B. (1983a). Polyhydroxylated steroids from digestive organs of the starfish Patiria pectinifera. Bioorganicheskaia Khimiia, 9, 975–977.

    CAS  Google Scholar 

  • Kicha, A. A., Kalinovsky, A. I., Levina, E. V., Stonik, V. A., & Elyakov, G. B. (1983b). Asterosaponin P1 from the Starfish Patiria pectinifera. Tetrahedron Letters, 24, 3893–3896.

    Article  CAS  Google Scholar 

  • Kicha, A. A., Kalinovsky, A. I., & Levina, E. V. (1984). Polyhydroxylated steroids from the starfish Patiria pectinifera. Khimiya Prirodnykh Soedinenii, 6, 738–741.

    Google Scholar 

  • Kicha, A. A., Ivanchina, N. V., Kalinovsky, A. I., Dmitrenok, P. S., & Stonik, V. A. (2000). Asterosaponin P2 from the Far-Eastern starfish Patiria (Asterina) pectinifera. Russian Chemical Bulletin, 49, 1794–1795.

    Article  CAS  Google Scholar 

  • Kicha, A. A., Ivanchina, N. V., Gorshkova, I. A., Ponomarenko, L. P., Likhatskaya, G. N., & Stonik, V. A. (2001a). The distribution of free sterols, polyhydroxysteroids and steroid glycosides in various body components of the starfish Patiria (=Asterina) pectinifera. Comparative Biochemistry and Physiology Part B, 128, 43–52.

    Article  CAS  Google Scholar 

  • Kicha, A. A., Ivanchina, N. V., Kalinovsky, A. I., Dmitrenok, P. S., & Stonik, V. A. (2001b). Sulfated steroid compounds from the starfish Aphelasterias japonica of the Kuril population. Russian Chemical Bulletin, 50(4), 724–727.

    Article  CAS  Google Scholar 

  • Kicha, A. A., Ivanchina, N. V., & Stonik, V. A. (2003). Seasonal variations in the levels of polyhydroxysteroids and related glycosides in the digestive tissues of the starfish Patiria (=Asterina) pectinifera. Comparative Biochemistry and Physiology Part B, 136, 897–903.

    Article  Google Scholar 

  • Kicha, A. A., Ivanchina, N. V., & Stonik, V. A. (2004). Seasonal variations in polyhydroxysteroids and related glycosides from digestive tissues of the starfish Patiria (=Asterina) pectinifera. Comparative Biochemistry and Physiology Part B, 139, 581–585.

    Article  Google Scholar 

  • Kicha, A. A., Ivanchina, N. V., Huong, T. T., et al. (2010). Two new asterosaponins, archasterosides A and B, from the Vietnamese starfish Archaster typicus and their anticancer properties. Bioorganic & Medicinal Chemistry Letters, 20, 3826–3830.

    Article  CAS  Google Scholar 

  • Levina, E. V., Kalinovsky, A. I., Dmitrenok, P. S., Martyyas, E. A., & Stonik, V. A. (2010). Two new steroidal saponins, hylodoside A and novaeguinoside Y from starfishes Leptasterias hylodes reticulata and Culcita novaeguineae (juvenile). Natural Products Communications, 5(11), 1737–1742.

    CAS  Google Scholar 

  • Li, Z., Chen, G., Lu, X., Wang, H., Feng, B., & Pei, Y. (2013). Three new steroid glycosides from the starfish Asterina pectinifera. Natural Product Research, 27, 1816–1822.

    Article  CAS  PubMed  Google Scholar 

  • Malyarenko, T. V., Kicha, A. A., Ivanchina, N. V., et al. (2014). Asterosaponins from the Far Eastern starfish Leptasterias ochotensis and their anticancer activity. Steroids, 87, 119–127.

    Article  CAS  PubMed  Google Scholar 

  • Minale, L., Riccio, R., & Zollo, F. (1993). Steroidal oligoglycosides and polyhydroxysteroids from Echinoderms. Fortschritte der Chemie Organischer Naturstoffe, 62, 75–308.

    CAS  PubMed  Google Scholar 

  • Noguchi, Y., Higuchi, R., Marubayashi, N., & Komori, T. (1987). Steroidal oligoglycosides from the starfish Asterina pectinifera Muller and Troschel. Structures of two new saponins and two new oligoglycoside sulfates: pectinioside A and pectinioside B. Liebigs Annalen der Chemie, 4, 341–348.

    Article  Google Scholar 

  • Pal’yanova, N. V., Pankova, T. M., Starostina, M. V., et al. (2006). Neurotrophic effects of polyhydroxylated steroids and steroid glycosides in cultured neuroblastoma cells. Bulletin of Experimental Biology and Medicine, 141, 584–587.

    Article  PubMed  Google Scholar 

  • Pal’yanova, N. V., Pankova, T. M., Starostina, M. V., Kicha, A. A., Ivanchina, N. V., & Stonik, V. A. (2013). Neuritogenic and neuroprotective effects of polar steroids from the Far East starfishes Patiria pectinifera and Distolasterias nipon. Marine Drugs, 11, 1440–1455.

    Article  Google Scholar 

  • Peng, Y., Zheng, J., Huang, R., et al. (2010). Polyhydroxy steroids and saponins from China sea starfish Asterina pectinifera and their biological activities. Chemical & Pharmaceutical Bulletin, 58, 856–858.

    Article  CAS  Google Scholar 

  • Popov, R. S., Ivanchina, N. V., Kicha, A. A., Malyarenko, T. V., Dmitrenok, P. S., & Stonik, V. A. (2014). Metabolite profiling of polar steroid constituents in the Far Eastern starfish Aphelasterias japonica using LC–ESI MS/MS. Metabolomics, 10, 1152–1168.

    Article  CAS  Google Scholar 

  • Rashkes, V. V., Kicha, A. A., Levina, E. V., & Stonik, V. A. (1985). Mass spectra of polyhydroxysteroids of the starfish Patiria pectinifera. Khimiya Prirodnykh Soedinenii, 3, 361–367.

    Google Scholar 

  • Riccio, R., Iorizzi, M., & Minale, L. (1986). Starfish Saponins 30. Isolation of 16 steroidal glycosides and 3 polyhydroxysteroids from the Mediterranean starfish Coscinasterias tenuispina. Bulletin des Societes Chimiques Belges, 95, 869–893.

    Article  CAS  Google Scholar 

  • Sandvoss, M., Weltring, A., Preiss, A., Levsen, K., & Wuensch, G. (2001). Combination of matrix solid-phase dispersion extraction and direct on-line liquid chromatography–nuclear magnetic resonance spectroscopy–tandem mass spectrometry as a new efficient approach for the rapid screening of natural products: application to the total asterosaponin fraction of the starfish Asterias rubens. Journal of Chromatography A, 917, 75–86.

    Article  CAS  PubMed  Google Scholar 

  • Silchenko, A. S., Kalinovsky, A. I., Avilov, S. A., et al. (2012). Triterpene glycosides from the sea cucumber Eupentacta fraudatrix. Structure and biological activity of cucumariosides B1 and B2, two new minor non-sulfated unprecedented triosides. Natural Product Communications, 7(9), 1157–1162.

    CAS  PubMed  Google Scholar 

  • Stonik, V. A. (2001). Marine polar steroids. Russian Chemical Reviews, 70, 673–715.

    Article  CAS  Google Scholar 

  • Stonik, V. A., Ivanchina, N. V., & Kicha, A. A. (2008). New polar steroids from starfish. Natural Products Communications, 3(10), 1587–1610.

    CAS  Google Scholar 

  • Viant, M. R., & Sommer, U. (2013). Mass spectrometry based environmental metabolomics: a primer and review. Metabolomics, 9, 144–158.

    Article  CAS  Google Scholar 

  • Wolfender, J.-L., Marti, G., Thomas, A., & Bertrand, S. (2015). Current approaches and challenges for the metabolite profiling of complex natural extracts. Journal of Chromatography A, 1382, 136–164.

    Article  CAS  PubMed  Google Scholar 

  • Zaia, J. (2010). Mass spectrometry and glycomics. OMICS: A Journal of Integrative Biology, 4(14), 401–418.

    Article  Google Scholar 

  • Zhang, L.-X., Fan, X., & Shi, J.-G. (2005). A novel polyhydroxyl sterol from Asterina pectinifera. Journal of Asian Natural Products Research, 7, 25–29.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

The study was supported by the Grants No. 14-04-00341-a from the RFBR and Grant of President of Russia No. 148.2014.4 supporting leading Russian scientific schools. We sincerely thank to Dr. V.G. Voinov for his assistance in editing this manuscript.

Author information

Authors and Affiliations

  1. G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far East Branch of the Russian Academy of Sciences, Pr. 100-let Vladivostoku 159, 690022, Vladivostok, Russia

    Roman S. Popov, Natalia V. Ivanchina, Alla A. Kicha, Timofey V. Malyarenko, Pavel S. Dmitrenok & Valentin A. Stonik

Authors
  1. Roman S. Popov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Natalia V. Ivanchina
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alla A. Kicha
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Timofey V. Malyarenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Pavel S. Dmitrenok
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Valentin A. Stonik
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Pavel S. Dmitrenok.

Ethics declarations

Conflict of interest

The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 300 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Popov, R.S., Ivanchina, N.V., Kicha, A.A. et al. LC-ESI MS/MS profiling of polar steroid metabolites of the Far Eastern starfish Patiria (=Asterina) pectinifera . Metabolomics 12, 21 (2016). https://doi.org/10.1007/s11306-015-0939-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11306-015-0939-8

Keywords

Search

Navigation