Influence of temperature on microdomain organization of mixed cationic–zwitterionic lipidic monolayers at the air–water interface

The thermodynamic behavior of mixed DOTAP–DPPC monolayers at the air–water interface has been investigated in the temperature range from 15 to 45 °C, covering the temperature interval where the thermotropic phase transition of DPPC, from solid-like to liquid-like, takes place. Based on the regular solution theory, the miscibility of the two lipids in the mixed monolayer was evaluated in terms of the excess Gibbs free energy of mixing ΔGex, activity coefficients f1f1 and f2f2 and interaction parameter ωω between the two lipids. The mixed DOTAP–DPPC film was found to have positive deviations from ideality at low DOTAP mole fractions, indicating a phase-separated binary mixture. This effect depends on the temperature and is largely conditioned by the structural chain conformation of the DPPC lipid monolayer. The thermodynamic parameters associated to the stability and the miscibility of these two lipids in a monolayer structure have been discussed in the light of the phase diagram of the DOTAP–DPPC aqueous mixtures obtained from differential scanning calorimetry measurements. The correlation between the temperature behavior of DOTAP–DPPC monolayers and their bulk aqueous mixtures has been briefly discussed.