Mixed lipid aggregates containing gangliosides impose different 2H-NMR dynamical parameters on water environment depending on their lipid composition.

Water dynamics in samples of ceramide tetrasaccharide (Gg4Cer) vesicles and GM1 ganglioside micelles at 300:1 water/lipid mole ratio were studied by using deuterium nuclear magnetic resonance (2H-NMR). GM1 imposes a different restriction on water dynamics that is insensitive to temperatures either above or below its phase transition temperature or below the freezing point of water. The calculated correlation times are in the range of 10(-10) s, typical of water molecules near to the polar groups. Pure GM1 micelles have two distinct water microenvironments dynamically characterized. Their dynamic parameters remain constant with temperature ranging from -18 to 32 degrees C, but the amount of strongly associated water is modified. By contrast, a mixture of single soluble carbohydrates corresponding to GM1 polar head group does not preserve the dynamic parameters of water hydration when the temperature is varied. Incorporation of cholesterol or lysophosphatidylcholine into GM1 micelles substantially increases the mobility of water molecules compared with that found in pure GM1 micelles. The overall results indicate that both the supramolecular organization and the local surface quality (lipid-lipid interaction) strongly influence the interfacial water mobility and the extent of hydration layers in glycosphingolipid aggregates.

Ganglioside hydration study by 2H-NMR: dependence on temperature and water/lipid ratio.

Dynamic properties of 2H2O in samples of ganglioside aggregates hydrated at water/lipid ratios ranging from 25:1 to 8000:1 mole/mole were studied by using deuterium nuclear magnetic resonance (2H-NMR). We present a physical model for the interpretation of the measured spin-spin relaxation times (T2). For all the concentrations studied the model provides evidence for the existence of at least two kinds of water environments: one in which the rotational correlation time is in the range of 10(-9) to 10(-8) s, and a second in which it lies between 10(-11) to 10(-10) s. A detailed study on the temperature dependence was performed for two of the concentrations, one corresponding to the hexagonal phase (100:1 mole/mole) and the other involving a micellar phase (200:1 mole/mole). In the 100:1 2H2O/ganglioside molar ratio sample, most of the water is tightly bound to long cylindrical structures. For the 200: 1 sample, there are on average approximately 30 water molecules tightly bound to the polar head group of each ganglioside molecule. The relative number and dynamics of molecules in this environment are essentially insensitive to temperature variations in the range 220-300K The rest of water molecules are also influenced by the aggregate, having a different mobility from that observed in the free liquid state.