Skip to main content
SpringerLink
Log in

Novel Cyclopropane Fatty Acids from the Phospholipids of the Caribbean Sponge Pseudospongosorites suberitoides

  • Original Article
  • Published:
Lipids

Abstract

The cyclopropane fatty acids 17-methyl-trans-4,5-methyleneoctadecanoic acid, 18-methyl-trans-4,5-methylenenonadecanoic acid, and 17-methyl-trans-4,5-methylenenonadecanoic acid were characterized for the first time in nature in the phospholipids (mainly PE, PG and PS) of the hermit-crab sponge Pseudospongosorites suberitoides. Pyrrolidine derivatization was the key in identifying the position of the cyclopropyl and methyl groups in the acyl chains and 1H NMR was used to determine the trans stereochemistry of the cyclopropane ring. The phospholipids from the sponge also contained an interesting series of iso-anteiso Δ5,9 fatty acids with chain-lengths between 17 and 21 carbons, with the fatty acids (5Z,9Z)-18-methyl-5,9-nonadecadienoic acid and the (5Z,9Z)-17-methyl-5,9-nonadecadienoic acid being described for the first time in sponges. The anteiso α-methoxylated fatty acid 2-methoxy-12-methyltetradecanoic acid was also identified for the first time in nature in the phospholipids of this interesting marine sponge. The novel cyclopropyl fatty acids could have originated from the phospholipids of a cyanobacterium living in symbiosis with the sponge.

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

Similar content being viewed by others

Abbreviations

ATCC:

American type culture collection

ECL:

Equivalent chain length

FAME:

Fatty acid methyl ester

GC–MS:

Gas chromatography–mass spectrometry

PE:

Phosphatidylethanolamine

PG:

Phosphatidylglycerol

PS:

Phosphatidylserine

References

  1. Gunstone FD (1994) Cyclic acids, In: Gunstone FD, Harwood JL, Padley FB (eds) The lipid handbook, 2nd edn, Chapman and Hall, London, pp 13–14

    Google Scholar 

  2. Grogan DW, Cronan JE Jr (1997) Cyclopropane ring formation in membrane lipids of bacteria. Microbiol Mol Biol Rev 61:429–441

    PubMed  CAS  Google Scholar 

  3. Cox AD, Wilkinson SG (1989) Polar lipids and fatty acids of Pseudomonas cepacia. Biochim Biophys Acta 1001:60–67

    PubMed  CAS  Google Scholar 

  4. Holz GG Jr, Beach DH, Singh BN, Fish WR (1983) Biosynthesis of the novel fatty acid, 17-methyl-cis-9,10-methyleneoctadecanoic acid, by the parasitic protozoan Herpetomonas megaseliae. Lipids 18:607–610

    Article  PubMed  CAS  Google Scholar 

  5. Saito T, Ochiai H (1998) Fatty acid composition of the cellular slime mold Polysphondylium pallidum. Lipids 33:327–332

    Article  PubMed  CAS  Google Scholar 

  6. Gontier E, Boussouel N, Terrasse C, Jannoyer M, Menard M, Thomasset B, Bourgaud F (2000) Litchi chinensis fatty acid diversity: occurrence of the unusual cyclopropanoic fatty acids. Biochem Soc Trans 28:578–580

    Article  PubMed  CAS  Google Scholar 

  7. Fish WR, Holz GG Jr, Beach DH, Owen E, Anekwe GE (1981) The cyclopropane fatty acid of trypanosomatids. Mol Biochem Parasitol 3:103–115

    Article  PubMed  CAS  Google Scholar 

  8. Lankelma J, Ayanoglu E, Djerassi C (1983) Double-bond location in long-chain polyunsaturated fatty acids by chemical ionization-mass spectrometry. Lipids 18:853–858

    Article  CAS  Google Scholar 

  9. Nemoto T, Yoshino G, Ojika M, Sakagami Y (1997) Amphimic acids and related long-chain fatty acids as DNA Topoisomerase I inhibitors from an Australian sponge, Amphimedon sp.; isolation, structure, synthesis, and biological evaluation. Tetrahedron 53:16699–16710

    Article  CAS  Google Scholar 

  10. MacMillan JB, Molinski TF (2005) Majusculoic acid, a brominated cyclopropyl fatty acid from a marine cyanobacterial mat assemblage. J Nat Prod 68:604–606

    Article  PubMed  CAS  Google Scholar 

  11. Diaz MC, Pomponi SA, Van Soest RWM (1993) A systematic revision of the Central West Atlantic Halichondrida (Demospongiae, Porifera). Part III: description of valid species. Sci Mar 57:283–306

    Google Scholar 

  12. Sitachitta N, Gerwick WH (1998) Grenadadiene and grenadamide, cyclopropyl-containing fatty acid metabolites from the marine Cyanobacterium Lyngbya majuscula. J Nat Prod 61:681–684

    Article  PubMed  CAS  Google Scholar 

  13. Privett OS, Dougherty KA, Erdahl WL, Stolyhwo A (1973) Lipid composition of developing soybeans. J Am Oil Chem Soc 50:516–520

    PubMed  CAS  Google Scholar 

  14. Carballeira NM, Alicea J (2001) The first naturally occurring α-methoxylated branched-chain fatty acids from the phospholipids of Amphimedon complanata. Lipids 36:83–87

    Article  PubMed  CAS  Google Scholar 

  15. Djerassi C, Lam WK (1991) Sponge Phospholipids. Acc Chem Res 24:69–75

    Article  CAS  Google Scholar 

  16. Carballeira NM, Maldonado ME, Rivera E, Porras B (1989) The fatty acid 4,8,12-trimethyltridecanoic as a common constituent of the phospholipids of the sponge families Spirastrellidae and Clionidae. Biochem Syst Ecol 17:311–314

    Article  CAS  Google Scholar 

  17. Andersson BA (1978) Mass spectrometry of fatty acid pyrrolidides. Prog Chem Fats Lipids 16:279–308

    Article  CAS  Google Scholar 

  18. Knothe G (2006) NMR characterization of dihydrosterculic acid and its methyl ester. Lipids 41:393–396

    Article  PubMed  CAS  Google Scholar 

  19. Carballeira NM, Alicea J (2002) Novel methoxylated FA from the Caribbean sponge Spheciospongia cuspidifera, Lipids 37:305–308

    Article  PubMed  CAS  Google Scholar 

  20. Carballeira NM, Cruz H, Kwong CD, Wan B, Franzblau S (2004) 2-Methoxylated fatty acids in marine sponges: defense mechanism against Mycobacteria? Lipids 39:675–680

    Article  PubMed  CAS  Google Scholar 

  21. Bergquist PR, Lawson MP, Lavis A, Cambie RC (1984) Fatty acid composition and the classification of the Porifera. Biochem Syst Ecol 12:63–84

    Article  CAS  Google Scholar 

  22. Walkup RD, Jamieson GC, Ratcliff MR, Djerassi C (1981) Phospholipid studies of marine organisms: 2. Phospholipids, Phospholipid-bound fatty acids and free sterols of the sponge Aplysina fistularis (Pallas) forma fulva (Pallas) (=Verongia thiona). Isolation and structure elucidation of unprecedented branched fatty acids Lipids 16:631–646

    Article  CAS  Google Scholar 

  23. Thiel V, Blumenberg M, Hefter J, Pape T, Pomponi SA, Reed J, Reitner J, Wörheide G, Michaelis W (2002) A chemical view of the most ancient metazoa-biomarker chemotaxonomy of hexactinellid sponges. Naturwissenschaften 89:60–66

    Article  PubMed  CAS  Google Scholar 

  24. Hartmann S, Minnikin DE, Römming HJ, Baird MS, Ratledge C, Wheeler PR (1994) Synthesis of Methyl 3-(2-octadecylcyclopropen-1-yl)propanoate and methyl 3-(2-Octadecylcyclopropen-1-yl)pentanoate and cyclopropane fatty acids as possible inhibitors of mycolic acid biosynthesis. Chem Phys Lipids 71:99–108

    Article  PubMed  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by a grant from the SCORE program of the National Institutes of Health (grant no. S06GM08102). J. Vicente thanks the NIH-MARC program for an undergraduate fellowship.

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Puerto Rico, Río Piedras Campus, PO Box 23346, San Juan, 00931-3346, Puerto Rico

    Néstor M. Carballeira, Nashbly Montano, Jan Vicente & Abimael D. Rodriguez

Authors
  1. Néstor M. Carballeira
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nashbly Montano
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jan Vicente
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Abimael D. Rodriguez
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Néstor M. Carballeira.

About this article

Cite this article

Carballeira, N.M., Montano, N., Vicente, J. et al. Novel Cyclopropane Fatty Acids from the Phospholipids of the Caribbean Sponge Pseudospongosorites suberitoides . Lipids 42, 519–524 (2007). https://doi.org/10.1007/s11745-007-3047-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11745-007-3047-3

Keywords

Search

Navigation