IntroductionDioctadecyldimethylammonium salts (DODAX, X being usually Br -or Cl -) are long (C 18 ) double chain cationic surfactants which associate in water, above the gel-to-liquid-crystalline phase transition temperature, T m , as bilayer structures (T m =45°C, for DODABr) [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. The molecular organization of DODAX depends on the surfactant concentration, the temperature and the solvent condition. Since DODAX molecules are poorly soluble in water at room temperature, energy-input-based methods are required to form high-curvature vesicles. The most common vesicle preparation protocols consist of sonicating [8] or extruding [14] the homogeneous surfactant aqueous dispersion, or dissolving the surfactant in an appropriate organic solvent (e.g., chloroform, dichloromethane or ethanol) and then injecting it in the desired solvent (usually water or electrolytic aqueous solution) above the evaporation temperature of the organic solvent [8]. These protocols usually introduce contaminants in the surfactant dispersion. Exceptions are bath sonication and extrusion since the flask or syringe containing the dispersion may be sealed or isolated, but the loss of surfactant, retained in the extrusion membrane, is a problem to be overcome. Thus, the formation of spontaneous vesicles seems to be the best way to form vesicles with good control of Abstract High-curvature and stabilized vesicles of dioctadecyldimethylammonium bromide (DODABr) can be formed spontaneously in aqueous electrolytic solution. It is shown by cryo-transmission electron microscopy that 5.0 mM DODABr molecules associate in water at a temperature above its gel-to-liquidcrystalline phase transition temperature (T m »45°C) in a variety of complex bilayer structures. However, in the presence of NaCl the preferred structures formed are unilamellar and bilamellar vesicles with high curvature and the dispersion is polydisperse in size and geometry, but the main vesicle population contains spherical, flattened and smoothed structures. It is, however, less polydisperse than the corresponding salt-free dispersion, and the size polydispersity and the vesicle curvature radius tend to decrease with NaCl concentration. Long cylindrical bilamellar vesicles, with a very thin water layer separating the bilayers are also formed in the presence of 10 mM NaCl. The effect of the ionic strength on T m , obtained by differential scanning calorimetry, is shown to depend on the nature of the counterion: Br -decreases, whereas Cl -increases T m of DODABr, indicating different affinity of these counterions for the vesicle surfaces.Progr Colloid Polym Sci (2004) 128: 163-168 DOI 10.1007/b97125 Ó Springer-Verlag 2004 Eloi