Journal of the American Oil Chemists' Society

, Volume 76, Issue 11, pp 1333–1341 | Cite as

Structural analogy between β′ triacylglycerols and n-alkanes. Toward the crystal structure of β′-2 p.p+2.p triacylglycerols

  • Jacco van de Streek
  • Paul Verwer
  • René de Gelder
  • Frank Hollander
Article

Abstract

The structural elements of the β′-2 polymorph of 1,3-dilauroyl-2-myristoylglycerol as found by Birker et al. (J. Am. Oil Chem. Soc. 68:895–906, 1991) were also observed in the crystal structures of other long-chain compounds. This analogy led to the assembly of a β′-2 structure at the atomic level from known crystallographic data. The structure was optimized by molecular mechanics and was consistent with experimental data, including satisfactory reproduction of the X-ray powder pattern. To the best of our knowledge, this is the first β′ structure with a 1,2 configuration and an intramolecular orthorhombic subcell which is fully optimized by molecular mechanics to date. It shows all structural elements found earlier by Birker et al.

Key words

β′ crystal structure fat molecular modeling powder diffraction triacylglycerol 

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References

  1. 1.
    De Jong, S., Ph.D. Thesis, University of Utrecht, The Netherlands, 1980, p. 5.Google Scholar
  2. 2.
    Larsson, K., The Crystal Structure of the β-Form of Trilaurin, Ark. Kemi 23:1–15 (1965).Google Scholar
  3. 3.
    Jensen, L.H., and A.J. Mabis, Refinement of the Structure of β-Tricaprin, Acta Crystallogr. 21:770–781 (1966).CrossRefGoogle Scholar
  4. 4.
    Gibon, V., P. Blanpain, B. Norberg, and F. Durant, New Data about Molecular Structure of β-Trilaurin, Bull. Soc. Chim. Belg. 93:27–34 (1984).CrossRefGoogle Scholar
  5. 5.
    Van Langevelde, A., K. van Malssen, F. Hollander, R. Peschar, and H. Schenk, Structure of Mono-Acid Even-Numbered β-Triacylglycerols, Acta Crystallogr. B55:114–122 (1999).Google Scholar
  6. 6.
    Birker, P.J.M.W.L., S. de Jong, E.C. Roijers, and T.C. van Soest, Structural Investigations of β′ Triacylglycerols: An X-Ray Diffraction and Microscopic Study of Twinned β′ Crystals, J. Am. Oil Chem. Soc. 68:895–906 (1991).Google Scholar
  7. 7.
    Van Langevelde, A., K. van Malssen, E. Sonneveld, R. Peschar, and H. Schenk, Crystal Packing of a Homologous Series β′-Stable Triacylglycerols, Ibid., 603–609 (1999).CrossRefGoogle Scholar
  8. 8.
    Boistelle, R., B. Simon, and G. Pèpe, Polytypic Structures of n-C28H58 (octacosane) and n-C36H74 (hexatriacontane), Acta Crystallogr. B32:1240–1243 (1976).Google Scholar
  9. 9.
    Goto, M., D.R. Kodali, D.M. Small, K. Honda, K. Kozawa, and T. Uchida, Single Crystal Structure of a Mixed-Chain Triacylglycerol: 1,2-Dipalmitoyl-3-acetyl-sn-glycerol, Proc. Nat. Acad. Sci. USA 89:8083–8086 (1992).CrossRefGoogle Scholar
  10. 10.
    Cerius2 User Guide, Version 3.5, Molecular Simulations Inc., San Diego, 1998.Google Scholar
  11. 11.
    Allen, F.H., and O. Kennard, 3D Search and Research Using the Cambridge Structural Database, Chem. Design Autom. News 8:1,31–337 (1993).Google Scholar
  12. 12.
    Pascher, I., S. Sundell, and H. Hauser, Glycerol Conformation and Molecular Packing of Membrane Lipids. The Crystal Structure of 2,3-Dilauroyl-d-glycerol, J. Mol. Biol. 153:791–806 (1981).CrossRefGoogle Scholar
  13. 13.
    Dorset, D.L., and W.A. Pangborn, Polymorphic Forms of 1,2-Dipalmitoyl-sn-glycerol: A Combined X-ray and Electron Diffraction Study, Chem. Phys. Lipids 48:19–28 (1988).CrossRefGoogle Scholar
  14. 14.
    Harlos, K., H. Eibl, I. Pascher, and S. Sundell, Conformation and Packing Properties of Phosphatidic Acid: The Crystal Structure of Monosodium Dimyristoylphosphatidate, Ibid.:115–126 (1984).CrossRefGoogle Scholar
  15. 15.
    Hitchcock, P.B., R. Mason, K.M. Thomas, and G.G. Shipley, Structural Chemistry of 1,2 Dilauroyl-Dl-phosphatidylethanolamine: Molecular Conformation and Intermolecular Packing of Phospholipids, Proc. Nat. Acad. Sci. USA 71:3036–3040 (1974).CrossRefGoogle Scholar
  16. 16.
    Pascher, I., and S. Sundell, Membrane Lipids: Preferred Conformational States and Their Interplay. The Crystal Structure of Dilauroylphosphatidyl-N,N-dimethylethanolamine, Biochim. Biophys. Acta 855:68–78 (1986).CrossRefGoogle Scholar
  17. 17.
    Pearson, R.H., and I. Pascher, The Molecular Structure of Lecithin Dihydrate, Nature 281:499–501 (1979).CrossRefGoogle Scholar
  18. 18.
    Hernqvist, L., On the Crystal Structure of the β′1-Form of Triglycerides and the Mechanism Behind the β′1 → β Transition of Fats, Fat Sci. Technol. 90:451–454 (1988).Google Scholar
  19. 19.
    Hagemann, J.W., and J.A. Rothfus, Effects of Chain Length, Conformation and α-Form Packing Arrangement on Theoretical Monoacid Triglyceride β′-Forms, J. Am. Oil Chem. Soc. 65:638–646 (1988).CrossRefGoogle Scholar
  20. 20.
    Mayo, S.L., B.D. Olafson, and W.A. Goddard III, DREIDING: A Generic Force Field for Molecular Simulations, J. Phys. Chem. 94:8897–8909 (1990).CrossRefGoogle Scholar
  21. 21.
    Piesczek, W., G.R. Strobl, and K. Malzahn, Packing of Paraffin Chains in the Four Stable Modifications of n-Tritriacontane, Acta Crystallogr. B30:1278–1288 (1974).Google Scholar
  22. 22.
    Birker, P.J.M.W.L., and J.C.G. Blonk, Alkyl Chain Packing in a β′ Triacylglycerol Measured by Atomic Force Microscopy, J. Am. Oil Chem. Soc. 70:319–321 (1993).CrossRefGoogle Scholar
  23. 23.
    Van de Streek, J., P. Verwer, R. de Grelder, and F. Hollander, New Evidence for β′ p.p+2.p Triacylglycerol Crystal Structure, Ibid. 77, in press.Google Scholar
  24. 24.
    Nyburg, S.C., and J.A. Potworowski, Prediction of Units Cells and Atomic Coordinates for the n-Alkanes, Acta Crystallogr. B29:347–352 (1973).Google Scholar
  25. 25.
    Kaneko, F., M. Kobayashi, Y. Kitagawa, Y. Matsuura, K. Sato, and M. Suzuki, Structure of the Low-Melting Phase of Petroselinic Acid, Acta Crystallogr. C48:1054–1057 (1992).Google Scholar
  26. 26.
    Buchheim, W., and E. Knoop, Elektronenbeugungs-Untersuchung von Trilaurin, Naturwissenschaften 56:560–561 (1969).CrossRefGoogle Scholar
  27. 27.
    Spek, A.L., PLATON, an Integrated Tool for the Analysis of the Results of a Single Crystal Structure Determination, Acta Crystallogr. A46:C-34 (1990).Google Scholar

Copyright information

© AOCS Press 1999

Authors and Affiliations

  • Jacco van de Streek
    • 3
    • 1
  • Paul Verwer
    • 3
  • René de Gelder
    • 2
  • Frank Hollander
    • 1
  1. 1.Department of Solid State ChemistryUniversity of NijmegenNijmegenThe Netherlands
  2. 2.Crystallography LaboratoryUniversity of NijmegenNijmegenThe Netherlands
  3. 3.CAOS/CAMM CenterUniversity of NijmegenNijmegenThe Netherlands

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