Influence of sphingosine on the thermal phase behaviour of neutral and acidic phospholipid liposomes.

The physical state of lipids is known to have pronounced effects on membrane functions. We studied the influence of sphingosine, a modulator of diverse cellular processes on the thermal phase behaviour and molecular packing of neutral and acidic phospholipids. Differential scanning calorimetry of multilamellar liposomes as well as the monolayer technique were employed. Inclusion of sphingosine in diacylphosphatidylcholine liposomes increased their pretransition temperature Tp until at about 10 mol% sphingosine this transition was abolished. For these liposomes a gradual increase in both the temperature Tm and enthalpy delta Hm of the main transition caused by sphingosine was observed. In contrast to diacylphosphatidylcholines, the Tp for dihexadecylphosphatidylcholine was lowered by sphingosine, demonstrating that the latter destabilizes the interdigitated gel phase. Inclusion of sphingosine in dimyristoylphosphatidic acid and dipalmitoylphosphatidylserine liposomes first elevated the Tm without significant changes in delta Hm, while at sphingosine contents > 50 mol% the appearance of complex melting profiles was evident. The transition temperature for the egg yolk phosphatidic acid was shifted from below 0 to 29 degrees C when mixed with sphingosine in a molar ratio of 1:1. Sphingosine also condensed the eggPA monolayers residing on an air-buffer interface. Accordingly, besides introducing a positive surface charge allowing the binding or activation of some proteins, sphingosine could influence membrane-mediated cellular processes by altering the organization and state of membrane lipids.