Path dependence of three-phase or two-phase end points in fluid binary lipid mixtures.

The phase behavior of anionic/zwitterionic mixtures can be controlled by tuning the charge state of the anionic lipid. In the case of dioleoylphosphatidic acid (DOPA)/dioleoylphosphatidylcholine (DOPC) mixtures, demixing occurs either when DOPA is protonated or when DOPA(2-):Ca(2+) complexes form. Herein it will be shown that the final end point, a three-phase or two-phase system, depends on the order in which the charge state is manipulated. The facile accessibility of different end points is a clear demonstration of the inherent flexibility of biological systems.