Formation of monolayers and bilayer foam films from lamellar, inverted hexagonal and cubic lipid phases.

Abstract

This study revealed large distinctions between the lamellar and non-lamellar liquid crystalline lipid phases in their spreading at the air/water interface and propensity to form bilayer foam films. Comparative measurements were made for the lamellar L(alpha), the inverted hexagonal H(II) and the bicontinuous cubic Pn3m phases of the phospholipid dipalmitoleoylphosphatidylethanolamine (DPoPE). With regard to monolayer formation, followed as the decrease of surface tension with time, the best spreading (lowest surface tension) was observed for the L(alpha) phase, and poorest spreading (highest surface tension) was recorded for the H(II) phase. The cubic Pn3m phase of DPoPE, induced by temperature cycling, retained an intermediate position between the L(alpha) and H(II) phases. According to their ability to lower surface tension and disintegrate at the air/water interface, the three phases thus order as L(alpha)>Pn3m>H(II). Clearly expressed threshold (minimum) bulk lipid concentrations, C(t), required for formation of stable foam bilayers from these phases, were determined and their values were found to correlate well with the bulk lipid phase behaviour. The C(t) values for L(alpha) and H(II) substantially increase with the temperature. Their Arrhenius plots, ln C(t) versus 1/ T, are linear and intersect at approximately 36-37 degrees C, coinciding with the onset of the bulk L(alpha)-->H(II) phase transition, as determined by differential scanning calorimetry. However, the C(t) value for the Pn3m phase, equal to 30 micro g/mL, was found to be constant over the whole range investigated between 20 degrees C and 50 degrees C. The horizontal C(t) versus T plot for the Pn3m phase crosses the respective plot for the L(alpha) phase at the temperature bounding from below the hysteretic loop of the L(alpha)<-->H(II) transition (approximately 26 degrees C), thus providing a certain insight about the thermodynamic stability of the Pn3m phase relative to the L(alpha) phase. The established strong effect of the particular lipid phase on the formation of monolayers and stable black foam films should be of importance in various in vitro and in vivo systems, where lipid structures are in contact with interfaces and disintegrate there to different extents.