We develop a theoretical model for the solubilization of phospholipid bilayers by micelle-forming surfactants. Cylindrical micelles, disklike micelles, and spherical micelles are considered as alternative resultant structures. The main question addressed is, what kind of micelles can be expected under various thermodynamical conditions? Our analysis is based on a theoretical model that accounts for Helfrich energy of curvature of amphiphile monolayers and for the entropy of mixing of lipids and surfactants in mixed aggregates. We conclude that for usual values of the elastic parameters of amphiphile monolayers cylindrical micelles are the most probable aggregates resulting from micellization of phospholipid by surfactants. This conclusion is consistent with available experimental data. Conditions of formation of disklike and spherical micelles are also determined.
IntroductionAmphiphiles tend to self-assemble in aqueous solutions, mostly due to the hydrophobic effect. 1 In the resultant aggregates, the amphiphilic molecules are packed as monolayers, where their hydrophobic moieties are shielded from contact with the external aqueous medium by the polar head groups. Depending on their molecular structure and interactions, the amphiphiles form aggregates of different shapes. [2][3][4] Most of the biological amphiphiles (phospholipids) self-assemble in nearly flat bilayer membranes, forming closed vesicles (liposomes). By contrast, most of the commonly used surfactants form micelles whose radii of curvature are close to the length of hydrocarbon chains. 5 While each of the pure compounds form in dilute solution aggregates of a particular type, mixtures of lipids and surfactants self-assemble in either mixed liposomes or mixed micelles, depending on the composition. [5][6][7] Transition from mixed bilayers to mixed micelles upon addition of surfactant to phospholipid vesicles is commonly denoted as solubilization of the liposomes. The resultant micelles were previously described as having either disklike (oblate ellipsoidal 8 ) or cylindrical shapes, 5 in apparent agreement with dynamic light scattering data.More recently, however, cryotransmition electron microscopy, 9,10 size-exclusion high-performance liquid chromatography, 11 small angle neutron scattering, 12 and re-evaluation of dynamic light scattering data 13 indicated that in most cases solubilization of liposomes results in formation of threadlike rather than disklike micelles.The model of disklike micelles was supported by the idea that the surfactant molecules form the rims of the micelles where the amphiphile monolayers are strongly curved, while the lipid molecules remain in flat parts of the disks. However, this qualitative consideration did not account for the entropy of mixing of the two components in the micelle, which tends to distribute uniformly the molecules of the two components over the whole surface of each micelle. The result of competition of these two tendencies is not obvious and requires a detailed theoretical analysis.Based on the more...