Abstract
The fatty acid compositions of the seed lipids from four Ephedra species, E. nevadensis, E. viridis, E. przewalskii, and E. gerardiana (four gymnosperm species belonging to the Cycadophytes), have been established with an emphasis on Δ5-unsaturated polymethylene-interrupted fatty acids (Δ5-UPIFA). Mass spectrometry of the picolinyl ester derivatives allowed characterization of 5,9- and 5,11–18∶2; 5,9,12–18∶3; 5,9,12,15–18∶4; 5,11–20∶2; 5,11,14–20∶3; and 5,11,14,17–20∶4 acids. Δ5-UPIFA with a Δ11-ethylenic bond (mostly C20 acids) were in higher proportions than δ5-UPIFA with a δ9 double bond (exclusively C18 acids) in all species. The total δ5-UPIFA content was 17–31% of the total fatty acids, with 5, 11, 14–20∶3 and 5, 11, 14, 17–20∶4 acids being the principal δ5-UPFIA isomers. The relatively high level of cis-vaccenic (11–18∶1) acid found in Ephedra spp. seeds, the presence of its δ5-desaturation product, 5, 11–18∶2 acid (proposed trivial name: ephedrenic acid), and of its elongation product, 13–20∶1 acid, were previously shown to occur in a single other species, Ginkgo biloba, among the approximately 170 gymnosperm species analyzed so far. Consequently, Ephedraceae and Coniferophytes (including Ginkgoatae), which have evolved separately since the Devonian period (≈300 million yr ago), have kept in common the ability to synthesize C18 and C20 δ5-UPIFA. We postulate the existence of two δ5-desaturases in gymnosperm seeds, one possibly specific for unsaturated acids with a δ9-ethylenic bond, and the other possibly specific for unsaturated acids with a δ11-ethylenic bond. Alternatively, the δ5-desaturases might be specific for the chain length with C18 unsaturated acids on the one hand and C20 unsaturated acids on the other hand. The resulting hypothetical pathways for the biosynthesis of δ5-UPIFA in gymnosperm seeds are only distinguished by the position of 11–18∶1 acid. Moreover, 13C nuclear magnetic resonance spectroscopy of the seed oil from two Ephedra species has shown that δ5-UPIFA are essentially excluded from the internal position of triacylglycerols, a characteristic common to all of the Coniferophytes analyzed so far (more than 30 species), with the possibility of an exclusive esterification at the sn-3 position. This structural feature would also date back to the Devonian period, but might have been lost in those rare angiosperm species containing δ5-UPIFA.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
Abbreviations
- Ag-TLC:
-
argentation thin-layer chromatography
- FAME:
-
fatty acid methyl ester
- GLC:
-
gas-liquid chromatography
- MS:
-
mass spectrometry
- NMR:
-
nuclear magnetic resonance
- TAG:
-
triacylglycerol
- UPIFA:
-
unsaturated polymethylene-interrupted fatty acid
References
Page, C.N. (1990) Gymnosperms: Coniferophytina (Conifers and Ginkgoids), in The Families and Genera of Vascular Plants, K. Kubitzki, ed., Pteridophytes and Gymnosperms (Kramer, K.U., and Green, P.S., eds.) Springer-Verlag, Berlin, Vol. 1, pp. 279–391.
Ehrendorfer, F. (1971) Systematik und Evolution: Spermatophyta. Samenpflanzen, in Lehrbuch der Botanik für Hochschulen (“Strasburger”) G. Fischer, Stuttgart.
Takagi, T., and Itabashi, Y. (1982) cis-5 Olefinic Unusual Fatty Acids in Seed Lipids of Gymnospermae and Their Distribution in Triacylglycerols, Lipids 17, 716–723.
Wolff, R.L., and Bayard, C.C. (1995) Fatty Acid Composition of Some Pine Seed Oils, J. Am. Oil Chem. Soc. 72, 1043–1046.
Wolff, R.L., Deluc, L.G., and Marpeau, A.M. (1996) Conifer Seeds: Oil Content and Fatty Acid Distribution, J. Am. Oil Chem. Soc. 73, 765–771.
Wolff, R.L., Comps, B., Deluc, L.G., and Marpeau, A.M. (1997) Fatty Acids of the Seeds from Pine Species of the Ponderosa-Banksiana and Halepensis Sections. The Peculiar Taxonomic Position of Pinus pinaster, J. Am. Oil Chem. Soc. 75, 45–50.
Wolff, R.L., Deluc, L.G., Marpeau, A.M., and Cops, B. (1997) Chemotaxonomic Differentiation of Conifer Families and Genera Based on the Seed Oil Fatty Acid Compositions: Multivariate Analyses, Trees 12, 57–65.
Wolff, R.L., Comps, B., Marpeau, A.M., and Deluc, L.G. (1997) Taxonomy of Pinus Species Based on the Seed Oil Fatty Acid Compositions, Trees 12, 113–118.
Wolff, R.L., and Marpeau, A.M. (1997) δ5-Olefinic Acids in the Edible Seeds of Nut Pine (Pinus cembroides edulis) from the United States, J. Am. Oil Chem. Soc. 74, 613–614.
Wolff, R.L., Pédrono, F., and Marpeau, A.M. (1999) Fatty Acid Composition of Edible Pine Seeds with Emphasis on North American and Mexican Pines of the Cembroides Subsection, Oléagineaux Corps Gras Lipides 6, 107–110.
Wolff, R.L., Pédrono, F., Marpeau, A.M., Christie, W.W., and Gunstone, F.D. (1998) The Seed Fatty Acid Composition and the Distribution of δ5-Olefinic Acids in the Triacylglycerols of Some Taxaceae (Taxus and Torreya). J. Am. Oil Chem. Soc. 75, 1637–1641.
Wolff, R.L., Pédrono, F., Marpeau, A.M., and Gunstone, F.D. (1999) The Seed Fatty Acid Composition and the Distribution of δ5-Olefinic Acids in the Triacylglycerols of Some Taxares (Cephalotaxus and Podocarpus), J. Am. Oil Chem. Soc. 76, 469–473.
Wolff, R.L., Christie, W.W., and Marpeau, A.M. (1999) Reinvestigation of the Polymethylene-Interrupted 18∶2 and 20∶2 Acids in Ginkgo biloba Seed Lipids, J. Am. Oil Chem. Soc. 76, 273–276.
Wolff, R.L., Pédrono, F., and Marpeau, A.M. (1999) Fokienia hodginsii Seed Oil, Another Source of All-cis 5, 9, 12, 15–18∶4 (Coniferonic) Acid, J. Am. Oil Chem. Soc. 76, 535–536.
Jamieson, G.R., and Reid, E.H. (1972) The Leaf Lipid of Some Conifer Species, Phytochemistry 11, 269–275.
Smith, C.R., Jr., Kleiman, R., and Wolff, I.A. (1968) Caltha palustris L. Seed Oil. A Source of Four Fatty Acids with cis-5-Unsaturation, Lipids 3, 37–42.
Aitzetmüller, K., and Tsevegsüren, N. (1994) Seed Fatty Acids, “Front-End”—Desaturases and Chemotaxonomy—A Case Study in the Ranunculaceae, J. Plant Physiol. 143, 538–543.
Aitzetmüller, K. (1997) Seed Oil Fatty Acids in the Labiatae, Lamiales Newsletter 5, 3–5.
Smith, C.R., Jr., Freidinger, R.M., Hagemann, J.W., Spencer, G.F., and Wolff, I.A. (1969) Teucrium depressum Seed Oil: A New Source of Fatty Acids With Delta-5-Unsaturation, Lipids, 4, 462–465.
Spencer, G.F., and Earle, F.R. (1972) The Abundance of cis-5-Octadecenoic Acid in Dioscoreophyllum cumminsii Seed Oil, Lipids 7, 435–536.
Knapp, S.J., and Crane, J. (1995) Fatty Acid Diversity of Section Inflexae Limnanthes (Meadowfoam), Ind. Crops Prod. 4, 219–227.
Badami, R.C., and Patil, K.B. (1981) Structure and Occurrence of Unusual Fatty Acids in Minor Seed Oils, Prog. Lipid Res. 19, 119–153.
Aitzetmüller, K. (1995) Fatty Acid Patterns of Ranunculaceae Seed Oils: Phylogenetic Relationships, Plant Syst. Evol. 9, 229–240.
Pohl, P., and Wagner, H. (1972) Fettsaüren im Pflanzen- und Tierreich (eine übersicht) II: Trans-ungesättigte, Alkin-, Hydroxy-, Epoxy, Oxo-, Cyclopropan- und Cyclopropen-Fettsaüren, Fette Seifen Anstrichm. 74, 541–550.
Hegnauer, R. (1990) Chemotaxonomie der Pflanzen, Birkhäuser, Basel.
Aitzetmüller, K. (1996) Seed Fatty Acids, Chemotaxonomy and Renewable Sources, in Oils-Fats-Lipids 1995: Proceedings of the 21st World Congress of the International Society for Fat Research, Barnes & Associates, High Wycombe, U.K., Vol. 1, pp. 117–120.
Kleiman, R., Spencer, G.F., Earle, F.R., and Wolff, I.A. (1967) Fatty Acid Composition of Ephedra campylopoda Seed Oil, Chem. Ind., 1326–1327.
Plattner, R.D., Spencer, G.F., and Kleiman, R. (1976) Double Bond Location in Polyenoic Fatty Esters through Partial Oxymercuration, Lipids 11, 222–227.
Schlenk, H., and Gelleman, J.L. (1965) Arachidonic, 5, 11, 14, 17-Eicosatetraenoic and Related Acids in Plants-Identification of Unsaturated Fatty Acids, J. Am. Oil Chem. Soc. 42, 504–511.
Litchfield, C. (1968) Triglyceride Analysis by Consecutive Liquid-Liquid Partition and Gas-Liquid Chromatography. Ephedra nevadensis Seed Fat, Lipids 3, 170–177.
Daulatabad, C.D., Hiremath, S.C., and Ankalgi, R.F. (1985) Component Fatty Acids of Welwitschia mirabilis, Hook, f. Seed Oil, Fette Seifen Anstrichm. 87, 171–172.
Mustafa, J., Gupta, A., Ahmad, M.S., Jr., Ahmad, F., and Osman, S.M. (1986) Cyclopropenoid Fatty Acids in Gnetum scandens and Sterculia pallens Seed Oils, J. Am. Oil Chem. Soc. 63, 1191–1192.
Berry, S.K. (1980) Cyclopropene Fatty Acids in Gnetum gnemon (L.) Seeds and Leaves, J. Sci. Food Agric. 31, 657–662.
Vickery, J.R., Whifield, F.B., Ford, G.L., and Kennett, B.H. (1984) The Fatty Acid Composition of Gymnospermae Seed and Leaf Oils, J. Am. Oil Chem. Soc. 61, 573–575.
Gunstone, F.D., Seth, S., and Wolff, R.L. (1995) The Distribution of 5 Polyene Fatty Acids in Some Pine Seed Oils Between the α- and β-Chains by 13C-NMR Spectroscopy, Chem. Phys. Lipids 78, 89–96.
Blaise, P., Tropini, V., Farine, M., and Wolff, R.L. (1997) Positional Distribution of δ5-Unsaturated Polymethylene-Interrupted Fatty Acids in Triacylglycerols from Conifer Seeds as Determined by Partial Chemical Cleavage, J. Am. Oil Chem. Soc. 74, 165–168.
Wolff, R.L., Dareville, E., and Martin, J.C. (1997) Positional Distribution of δ5-Olefinic Acids in Triacylglycerols from Conifer Seed Oils: General and Specific Enrichment in the sn-3 Position, J. Am. Oil Chem. Soc. 74, 515–523.
Hirata, Y., Sekiguchi, R., Saitoh, M., Kubota, K., and Kayama, M. (1994) Components of Pine Seed Lipids, Yukagaku 43, 579–582 (in Japanese).
Blaise, P., Wolff, R.L., and Farines, M. (1997) Etude Régiospecifique de Triacylglycérols d'Huiles Végétales par Clivage Chimique et RMN 13C Haute Résolution, Oléagineux Corps Gras Lipides 4, 135–141 (in French).
Aitzetmüller, K. (1997) Recent Developments in the Analysis of Food Lipids and Other Lipids, Oléagineux Corps Gras Lipides 4, 8–19.
Gunstone, F.D., and Wolff, R.L. (1996) Conifer Seed Oils: Distribution of 5δ Acids Between the α-and β-Chains by 13C-Nuclear Magnetic Resonance Spectroscopy, J. Am. Oil Chem. Soc. 73, 1611–1613.
Rutar, V., Kovac, M., and Lahajnar, G. (1989) Nondestructive Study of Liquids in Single Fir Seeds Using Nuclear Magnetic Resonance and Magic Angle Sample Spinning, J. Am. Oil Chem. Soc. 66, 961–965.
Lie Ken Jie, M.S.F., Lam, C.C., and Khisar Pasha, M. (1996) 13C Nuclear Magnetic Resonance Spectroscopic Analysis of the Triacylglycerol Composition of Biota orientalis and Carrot Seed Oil, J. Am. Oil Chem. Soc. 73, 557–662.
Aitzetmüller, K. (1993) Capillary GLC Fatty Acid Fingerprints of Seed Lipids—A Tool in Plant Chemotaxonomy?, J. High Resolut. Chromatogr. 16, 488–490.
Berdeaux, O., and Wolff, R.L. (1996) Gas-Liquid Chromatography-Mass Spectrometry of the 4,4-Dimethyloxazoline Derivatives of δ5-Unsaturated Polymethylene-Interrupted Fatty Acids from Conifer Seed Oils, J. Am. Oil Chem. Soc. 73, 1323–1326.
Tsevegsüren, N., and Aitzetmüller, K. (1997) Unusual δ5cis-Fatty Acids in Seed Oils of Cimicifuga Species, J. High Resolut. Chromatogr. Commun. 20, 237–241.
Christie, W.W. (1998) Mass Spectrometry of Fatty Acids with Methylene-Interrupted Ene-Yne Systems, Chem. Phys. Lipids 94, 35–41.
Aitzetmüller, K., and Vosmann, K. (1998) Cyclopropenoic Fatty Acids in Gymnosperms: The Seed Oil of Welwitschia, J. Am. Oil Chem. Soc. 75, 1761–1765.
Chamberlain, C.J. (1961) in Gymnosperms, Structure and Evolution, University of Chicago Press, Chicago.
Christie, W.W. (1997) Structural Analysis of Fatty Acids, in Advances in Lipid Methodology-Four (Christie, W.W., ed.) Oily Press, Dundee, pp. 119–169.
Christie, W.W. (1998) Gas Chromatography-Mass Spectrometry Methods for Structural Analysis of Fatty Acids, Lipids 33, 343–353.
Nikolova Damyanova, B., Christie, W.W., and Herslöf, B. (1990) The Structure of the Triacylglycerols of Meadowfoam Oil, J. Am. Oil Chem. Soc. 67, 503–507.
Aitzetmüller, K. (1998) Komaroffia Oils—An Excellent New Source of δ5-Unsaturated Fatty Acids, J.Am. Oil Chem. Soc. 75, 1897–1899.
Kim, S.J., Lee, K.H., Kim, Y.S., and Joh, Y.G. (1993) Studies on the Presence of all cis-Δ5,11,14-C20:3 Fatty Acid in the Seed Oils of Ginkgo, J. Korean Oil Chem. Soc. 10, 57–65 (in Korean).
Hierro, M.T.G., Robertson, G., Christie, W.W., and Joh, Y.G. (1996) The Fatty Acid Composition on the Seeds of Ginkgo biloba, J. Am. Oil Chem. Soc. 73, 575–579.
Wolff, R.L., Christie, W.W., and Coakley, D. (1997) The Unusual Occurrence of 14-Methylhexadecanoic Acid in Pinaceae Seed Oils Among Plants, Lipids 32, 971–973.
Itabashi, Y., and Takagi, T. (1982) Cis-5-Olefinic Nonmethylene-Interrupted Fatty Acids in Lipids of Seeds, Arils and Leaves of Japanese Yew, Yukagaku 31, 574–579.
Wolff, R.L. (1998) Clarification on the Taxonomic Position of Sciadopitys verticillata Among Coniferophytes Based on the Seed Oil Fatty Acid Compositions, J.Am. Oil Chem. Soc. 75:757–758.
Wolff, R.L., Christie, W.W., and Coakley, D. (1997) Bishomopinolenic (7, 11, 14–20∶3) Acid in Pinaceae Seed Oil, J. Am. Oil Chem. Soc. 74, 1583–1586.
Gellerman, J.L., Anderson, W.H., Richardson, D.G., and Schlenk, H. (1975) Distribution of Arachidonic Acid and Eicosapentaenoic Acids in the Lipids of Mosses, Biochim. Biophys. Acta 388, 277–290.
Groenewald, E.G., Krüger, G.H.J., de Wet, H., Botes, P.J., and van der Westhuizen, A.J. (1990) Detection of Prostaglandins F2α by Radioimmunoassay in Three South African Bryophytes and its Relation to the Occurrence of Polyunsaturated Fatty Acids, South African J. Sci. 86, 141–153.
Groenewald, E.G., and van der Westhuizen, A.J. (1997) Prostaglandins and Related Substances in Plants, Bot. Rev. 63, 199–220.
Gresti, J., Mignerot, C., Bézard, J., and Wolff, R.L. (1996) Distribution of δ5-Olefinic Acids in the Triacylglycerols from Pinus koraiensis and P. pinaster Seed Oils, J. Am. Oil Chem. Soc. 73, 1539–1547.
Imbs, A.B., Nevshupova, N.V., and Pham, L.Q. (1998) Triacyl Composition of Pinus koraiensis Seed Oil, J. Am. Oil Chem. Soc. 75, 865–870.
Wolff, R.L. (1997) New Tools to Explore Lipid Metabolism, INFORM 8, 116–119.
Phillips, B.E., Smith, C.R., Jr., and Tallent, W.H. (1971) Glyerides of Limnanthes douglasii Seed Oil, Lipids 6, 93–99.
Nikoloya-Damyanova, B., Christie, W.W., and Herslof, B. (1990) The Structure of the Triacylglycerols of Meadowfoam Oil, J. Am. Oil Chem. Soc. 67, 503–507.
Meyen, S.V. (1984) Basic Features of Gymnosperm Systematics and Phylogeny as Evidenced by the Fossil Record, Bot. Rev. 50, 1–112.
Author information
Authors and Affiliations
Corresponding author
About this article
Cite this article
Wolff, R.L., Christie, W.W., Pédrono, F. et al. Δ5-Olefinic acids in the seed lipids from four Ephedra species and their distribution between the α and β positions of triacylglycerols. Characteristics common to coniferophytes and cycadophytes. Lipids 34, 855–864 (1999). https://doi.org/10.1007/s11745-999-0433-1
Issue Date:
DOI: https://doi.org/10.1007/s11745-999-0433-1