Abstract
Although mammalian tissues contain high levels of polyunsaturated fatty acids, our knowledge of the effects of the degree of unsaturation and double-bond location upon bilayer organization is limited. Therefore, a series of mixed-chain unsaturated phosphatidylcholines (PC) comprised of 18:0 at the sn-1 position and various unsaturates at the sn-2 position (18:1n9, 18:2n6, 18:3n6, 18:3n3, 20:2n6, 20:3n6, 20:4n6, 20:5n3, 22:4n6, 22:5n6, or 22:6n3) was studied with differential scanning calorimetry, and their gel to liquid-crystalline phase transitions yielded measurements of Tm, Tonset, delta H, and delta S. Minimal delta H values were obtained for the diene species, 1.7 and 2.9 kcal/mole for 18:2n6 and 20:2n6, respectively. These results are consistent with the dienes having an acyl chain conformation that results in perturbed chain packing. Increasing the degree of unsaturation to three or more double bonds resulted in higher delta H values, 3.7, 4.3, and 4.6 kcal/mole for 18:3n6, 20:3n6, and 20:4n6, respectively, consistent with the occurrence of a gel-state chain conformation(s), which is more tightly packed than the dienes. The 18:0,22:6n3-PC species yielded the highest delta H (6.1 kcal/mole) and delta S(22.7 cal/mol degree) of all the polyunsaturates studied. The distinctive packing properties of phospholipid bilayers containing 22:6n3 may underlie its essential role in the nervous system.
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- Applegate K. R., Glomset J. A. Computer-based modeling of the conformation and packing properties of docosahexaenoic acid. J Lipid Res. 1986 Jun;27(6):658–680. [PubMed] [Google Scholar]
- Baenziger J. E., Jarrell H. C., Smith I. C. Molecular motions and dynamics of a diunsaturated acyl chain in a lipid bilayer: implications for the role of polyunsaturation in biological membranes. Biochemistry. 1992 Apr 7;31(13):3377–3385. doi: 10.1021/bi00128a011. [DOI] [PubMed] [Google Scholar]
- Barry J. A., Trouard T. P., Salmon A., Brown M. F. Low-temperature 2H NMR spectroscopy of phospholipid bilayers containing docosahexaenoyl (22:6 omega 3) chains. Biochemistry. 1991 Aug 27;30(34):8386–8394. doi: 10.1021/bi00098a016. [DOI] [PubMed] [Google Scholar]
- Barton P. G., Gunstone F. D. Hydrocarbon chain packing and molecular motion in phospholipid bilayers formed from unsaturated lecithins. Synthesis and properties of sixteen positional isomers of 1,2-dioctadecenoyl-sn-glycero-3-phosphorylcholine. J Biol Chem. 1975 Jun 25;250(12):4470–4476. [PubMed] [Google Scholar]
- Coolbear K. P., Berde C. B., Keough K. M. Gel to liquid-crystalline phase transitions of aqueous dispersions of polyunsaturated mixed-acid phosphatidylcholines. Biochemistry. 1983 Mar 15;22(6):1466–1473. doi: 10.1021/bi00275a022. [DOI] [PubMed] [Google Scholar]
- Deese A. J., Dratz E. A., Dahlquist F. W., Paddy M. R. Interaction of rhodopsin with two unsaturated phosphatidylcholines: a deuterium nuclear magnetic resonance study. Biochemistry. 1981 Oct 27;20(22):6420–6427. doi: 10.1021/bi00525a021. [DOI] [PubMed] [Google Scholar]
- Ghosh D., Williams M. A., Tinoco J. The influence of lecithin structure on their monolayer behavior and interactions with cholesterol. Biochim Biophys Acta. 1973 Jan 26;291(2):351–362. doi: 10.1016/0005-2736(73)90488-4. [DOI] [PubMed] [Google Scholar]
- Hernandez-Borrell J., Keough K. M. Heteroacid phosphatidylcholines with different amounts of unsaturation respond differently to cholesterol. Biochim Biophys Acta. 1993 Dec 12;1153(2):277–282. doi: 10.1016/0005-2736(93)90416-w. [DOI] [PubMed] [Google Scholar]
- Holte L. L., van Kuijk F. J., Dratz E. A. Preparative high-performance liquid chromatography purification of polyunsaturated phospholipids and characterization using ultraviolet derivative spectroscopy. Anal Biochem. 1990 Jul;188(1):136–141. doi: 10.1016/0003-2697(90)90541-g. [DOI] [PubMed] [Google Scholar]
- Keough K. M., Giffin B., Kariel N. The influence of unsaturation on the phase transition temperatures of a series of heteroacid phosphatidylcholines containing twenty-carbon chains. Biochim Biophys Acta. 1987 Aug 7;902(1):1–10. doi: 10.1016/0005-2736(87)90129-5. [DOI] [PubMed] [Google Scholar]
- Keough K. M., Kariel N. Differential scanning calorimetric studies of aqueous dispersions of phosphatidylcholines containing two polyenoic chains. Biochim Biophys Acta. 1987 Aug 7;902(1):11–18. doi: 10.1016/0005-2736(87)90130-1. [DOI] [PubMed] [Google Scholar]
- Kim H. Y., Salem N., Jr Application of thermospray high-performance liquid chromatography/mass spectrometry for the determination of phospholipids and related compounds. Anal Chem. 1987 Mar 1;59(5):722–726. doi: 10.1021/ac00132a009. [DOI] [PubMed] [Google Scholar]
- Kim H. Y., Sawazaki S., Salem N., Jr Lipoxygenation in rat brain? Biochem Biophys Res Commun. 1991 Jan 31;174(2):729–734. doi: 10.1016/0006-291x(91)91478-u. [DOI] [PubMed] [Google Scholar]
- Knapp H. R., Salem N., Jr Formation of PGI3 in the rat during dietary fish oil supplementation. Prostaglandins. 1989 Nov;38(5):509–521. doi: 10.1016/0090-6980(89)90145-7. [DOI] [PubMed] [Google Scholar]
- Ladbrooke B. D., Chapman D. Thermal analysis of lipids, proteins and biological membranes. A review and summary of some recent studies. Chem Phys Lipids. 1969 Dec;3(4):304–356. doi: 10.1016/0009-3084(69)90040-1. [DOI] [PubMed] [Google Scholar]
- Litman B. J., Lewis E. N., Levin I. W. Packing characteristics of highly unsaturated bilayer lipids: Raman spectroscopic studies of multilamellar phosphatidylcholine dispersions. Biochemistry. 1991 Jan 15;30(2):313–319. doi: 10.1021/bi00216a001. [DOI] [PubMed] [Google Scholar]
- Mitchell D. C., Straume M., Litman B. J. Role of sn-1-saturated,sn-2-polyunsaturated phospholipids in control of membrane receptor conformational equilibrium: effects of cholesterol and acyl chain unsaturation on the metarhodopsin I in equilibrium with metarhodopsin II equilibrium. Biochemistry. 1992 Jan 28;31(3):662–670. doi: 10.1021/bi00118a005. [DOI] [PubMed] [Google Scholar]
- Salem N., Jr, Abood L. G., Hoss W. Separation of brain phosphatidylserines according to degree of unsaturation by thin-layer chromatography. Anal Biochem. 1976 Dec;76(2):407–415. doi: 10.1016/0003-2697(76)90335-3. [DOI] [PubMed] [Google Scholar]
- Salem N., Jr, Ward G. R. Are omega 3 fatty acids essential nutrients for mammals? World Rev Nutr Diet. 1993;72:128–147. doi: 10.1159/000422334. [DOI] [PubMed] [Google Scholar]
- Slater S. J., Kelly M. B., Taddeo F. J., Ho C., Rubin E., Stubbs C. D. The modulation of protein kinase C activity by membrane lipid bilayer structure. J Biol Chem. 1994 Feb 18;269(7):4866–4871. [PubMed] [Google Scholar]
- Straume M., Litman B. J. Equilibrium and dynamic structure of large, unilamellar, unsaturated acyl chain phosphatidylcholine vesicles. Higher order analysis of 1,6-diphenyl-1,3,5-hexatriene and 1-[4-(trimethylammonio)phenyl]- 6-phenyl-1,3,5-hexatriene anisotropy decay. Biochemistry. 1987 Aug 11;26(16):5113–5120. doi: 10.1021/bi00390a033. [DOI] [PubMed] [Google Scholar]
- Stubbs C. D., Smith A. D. The modification of mammalian membrane polyunsaturated fatty acid composition in relation to membrane fluidity and function. Biochim Biophys Acta. 1984 Jan 27;779(1):89–137. doi: 10.1016/0304-4157(84)90005-4. [DOI] [PubMed] [Google Scholar]
- Wiedmann T. S., Pates R. D., Beach J. M., Salmon A., Brown M. F. Lipid-protein interactions mediate the photochemical function of rhodopsin. Biochemistry. 1988 Aug 23;27(17):6469–6474. doi: 10.1021/bi00417a041. [DOI] [PubMed] [Google Scholar]