Abstract
The partial phase diagram and the hydration properties of the 1-palmitoyl-2-oleoyl-phosphatidylethanolamine (POPE)-water system, in the absence and presence of 30 mol% cholesterol, have been investigated by solid state phosphorus NMR of the lipid and deuterium NMR of heavy water. The POPE-D2O phase diagram resembles other phosphatidylethanolamine (PE)-water systems: below water-to-lipid molar ratios (Ri) of 3 the lamellar gel (Lβ or Lc)-to-hexagonal type II (HII) phase sequence is observed on increasing the temperature. For Ri≥3 the thermotropic sequence (Lβ or Lc)-Lα-HII is detected. On increasing hydration from Ri=3, the HII phase is detected from 40°C to 85°C whereas the gel phase is observed from 40°C to 30°C. The limiting hydrations of the gel, Lα and HII phases are Ri ≈ 3, 17 and 20, respectively. The number of bound water molecules per lipid is ca. 8 in both the La and HII phases. The presence of cholesterol stabilizes the hexagonal phase 20°C below temperatures at which it is observed in its absence and reduces the limiting hydration of the fluid and hexagonal phases to Ri ≈ 9 and 14, respectively. The structure and/or dynamics of the water bound to the interface are markedly modified on going from the Lα to the HII phase.
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Abbreviations
- NMR:
-
Nuclear magnetic resonance
- DDPE:
-
1,2-Didodecyl-rac-glycerol-3-phosphoethanol-amine
- DHPE:
-
1,2-Dihexadecyl-sn-glycerol-3-phosphoethanol-amine
- DOPE:
-
1,2-Dioleoyl-sn-glycerol-3-phosphoethanol-amine
- POPE:
-
1-Palmitoyl-2-oleoyl-sn-glycerol-3-phosphoetha-nolamine
- DAPE:
-
1,2-Diarachinoyl-sn-glycerol-3-phosphoethanol-amine
- DMPC:
-
1,2-Dimyristol-sn-glycerol-3-phosphocholine
- DPPC:
-
1,2-Dipalmitoyl-sn-glycerol-3-phosphocholine
- Tc :
-
lamellar gel-to-lamellar fluid transition temperature
- Th :
-
lamellar fluid-to-hexagonal transition temperature
References
Arvidson G, Brentel I, Kahn A, Lindblom G, Fontell K (1985) Eur J Biochem 152:753
Batenburg AM, Van Esch JH, De Kruijff B (1988) Melittin-induced changes of the macroscopic structure of phosphatidylethanolamines. Biochemistry 27:2324–2331
Blaurock AE (1982) Evidence of bilayer structure and of membrane interactions from X-ray diffraction analysis. Biochim Biophys Acta 650:167–207
Boggs JM, Stamp D, Hughes DW, C.M. D. (1981) Influence of ether linkage on the lamellar to hexagonal phase transition of ethanolamine phospholipids. Biochemistry 20:5728–5735
Caffrey M (1985) Kinetics of the lamellar gel/lamellar liquid-crystal and lamellar/inverted hexagonal phase transition in phosphatidylethanolamine: a real-time X-ray diffraction study using synchrotron radiation. Biochemistry 24:4826–4844
Cullis PR, De Kruijff B (1978) Polymorphic phase behaviour of lipid mixtures as detected by 31P NMR. Biochim Biophys Acta 507:207–218
Cullis PR, De Kruijff B (1979) Lipid polmorphism and the functional roles of lipids in biological membranes. Biochim Biophys Acta 559:399–420
Cullis PR, De Kruyff B, Richards RE (1976) Factors affecting the motion of the polar headgroup in pospholipid bilayers. A31P NMR study of unsonicated phosphatidylcholine liposomes. Biochim Biophys Acta 426:433–446
Cullis PR, Kruijff B (1978) The polymorphic phase behaviour of phosphatidylethanolamines of natural and synthetic origin. Biochim Biophys Acta 513:31–42
Davis JH (1983) The description of membrane lipid conformation, order and dynamics by2H-NMR. Biochim Biophys Acta 737:117–171
Davis JH, Jeffrey KR, Bloom M, Valic MI, Higgs TP (1976) Quadrupolar echo deuteron magnetic resonance spectroscopy in orderted hydrocarbon chains. Chem Phys Letters 42:390–394
Dufourc EJ, Mayer C, Stohrer J, Althoff G, Kothe G (1992) Dynamics of phosphate head groups in biomembranes. A comprehensive analysis using phosphorus-31 nuclear magnetic resonance lineshape and relaxation time measurements. Biophysical J 61:42–57
Dufourc EJ, Mayer C, Stohrer J, Kothe G (1992)31P and1H-NMR pulse sequences to measure lineshapes, T1Z and T2E relaxation times in biological membranes. J Chim Phys 89:243–252
Ellens H, Bentz J, Szoka FC (1986) Destabilization of phosphatidylethanolamine liposomes at the hexagonal phase transition temperature. Biochemistry 25:287–294
Faure C, Tranchant JF, Dufourc EJ (1996) Comparative effects of cholesterol and cholesterol sulfate on hydration and ordering of DMPC membranes. Biophysical J 70:1380–1390
Finer (1973) Phospholipid hydration studied by deuteron magnetic resonance spectroscopy. Chem Phys Lipids 12:1–16
Gaillard S, Dufourc EJ, Bonnet M, Renou JP (1992) Dantrolene prevents or repairs the halothane induced membrane restructuration. A31P-NMR and DSC study. Eur Biophys J 21:13–19
Gawrisch K, Parsegian VA, Hajduk DA, Tate MW, Gruner SM, Fuller NL, Rand RP (1992) Energetics of a hexagonal-lamellar-hexagonal-phase transition sequence in dioleoylphosphatidylethanolamine membranes. Biochemistry 31:2856–2864
Grabielle-Mandelmont C, Perron R (1983a) Calorimetric studies of phospholipid-water systems. I. DL-dipalmitoylphosphatidylcholine (DPPC)-water system. J Colloid Interface Sci 95:471–482
Grabielle-Mandelmont C, Perron R (1983b) Calorimetric studies of phospholipd-water systems. II. Study of water behavior. J Colloid Interface Sci 95:483–493
Harlos K, Eibl H (1981) Hexagonal phases in phospholipids with satured chains: Phosphatidylethanolamines and phosphatidic acids. Biochemistry 20:2888–2892
Israelachvili JN, Mitchell DJ, Ninham BW (1977) Theory of self-assembly of lipid bilayers and vescicles. Biochim Biophys Acta 470:185–201
Janiak MJ, Small DM, Shipley GG (1976) Nature of the thermal pretransition of synthetic phospholipids: dimyristoyl- and dipalmitoyllecithin. Biochemistry 15:4575–4580
Killian JA (1992) Gramicidin and gramicidin-lipid interactions. Biochim Biophys Acta 1113:391–425
König S, Sackmann E, Richter D, Zorn R, Carlile C, Bayerl TM (1994) Molecular dynamics of water in oriented DPPC multilayers studied by quasielastic neutron scattering and deuterium nuclear magnetic resonance relaxation. J Chem Phys 100:3307–3315
Laroche G, Dufourc EJ, Pézolet M, Dufourcq J (1991) Structure and dynamics of dimyristoylphosphatidic acid/calcium complexes by2H-NMR, Infrared, and Raman spectroscopies and small-angle X-ray diffraction. Biochemistry 30:3105–3114
Luzzati V (1968) X-ray diffraction studies of lipid-water systems. Academic Press, London New York
Marsh D (1990) CRC Handbook of Lipid Bilayers. CRC Press, Boca Raton, Florida
Rance M, Byrd RA (1983) Obtaining high-fidelity spin-1/2 powder spectra in anisotropic media: Phase-Cycled Hahn echo spectroscopy. J Magn Res 52:221–240
Seddon JM, Cevc G, Kaye RD, Marsh D (1984) X-Ray diffraction study of the polymorphism of hydrated diacyl and dialkylphosphatidylethanolamines. Biochemistry 23:2634–2644
Seddon JM, Cevc G, Marsh D (1983) Calorimetric studies of the gelfluid (Lβ-Lα) and lamellar-inverted hexagonal (Lα-HII) phase transitions in dialkyl and diacylphosphatidylethanolamines. Biochemistry 22:1280–1289
Seelig J (1978) Phosphorus-31 nuclear magnetic resonance and the head-group structure of phospholipids in membranes. Biochim Biophys Acta 515:105–140
Ulmius H, Wennerstrom G, Lindbloom G, Arvidson G (1977) Deuteron NMR studies of phases equilibria in a lecithin water system. Biochemistry 16:5742–5745
Verkleij AJ (1984) Lipidic intramembraneous particles. Biochim Biophys Acta 779:43–63
Vist MR, Davis JH (1990) Phase equilibria of cholesterol dipalmitoylphosphatidylcholine mixtures:2H-nuclear magnetic resonance and differential scanning calorimetry. Biochemistry 29:451–464
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Marinov, R., Dufourc, E.J. Thermotropism and hydration properties of POPE and POPE-cholesterol systems as revealed by solid state2H and31P-NMR. Eur Biophys J 24, 423–431 (1996). https://doi.org/10.1007/BF00576714
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DOI: https://doi.org/10.1007/BF00576714