All salts studied effectively reduce critical micelle concentration (CMC) values of the cationic gemini surfactants. The ability to promote the surfactant aggregation decreases in the order of C(6)H(5)COONa > p-C(6)H(4)(COONa)(2) > Na(2)SO(4)> NaCl. Moreover, only C(6)H(5)COONa distinctly reduces both the CMC values and the surface tension at CMC. For 12-4-12 solution, the penetration of C(6)H(5)COO(-) anions and charge neutralization induce a morphology change from micelles to vesicles, whereas the other salts only slightly increase the sizes of micelles. The 12-4(OH)(2)-12 solution changes from the micelle/vesicle coexistence to vesicles with the addition of C(6)H(5)COONa, whereas the other salts transfer the 12-4(OH)(2)-12 solution from the micelle/vesicle coexistence to micelles. As compared with 12-4-12, the two hydroxyls in the spacer of 12-4(OH)(2)-12 promote the micellization of 12-4(OH)(2)-12 and reduce the amounts of C(6)H(5)COONa required to induce the micelle-to-vesicle transition.
Two star-like trimeric cationic surfactants with amide groups in spacers, tri(dodecyldimethylammonioacetoxy)diethyltriamine trichloride (DTAD) and tri(dodecyldimethylammonioacetoxy)tris(2-aminoethyl)amine trichloride (DDAD), have been synthesized, and the aggregation behavior of the surfactants in aqueous solution has been investigated by surface tension, electrical conductivity, isothermal titration microcalorimetry, dynamic light scattering, cryogenic transmission electron microscopy, and NMR techniques. Typically, both the surfactants form vesicles just above critical aggregation concentration (CAC), and then the vesicles transfer to micelles gradually with an increase of the surfactant concentration. It is approved that the conformation of the surfactant molecules changes in this transition process. Just above the CAC, the hydrophobic chains of the surfactant molecules pack more loosely because of the rigid spacer and intramolecular electrostatic repulsion in the three-charged headgroup. With the increase of the surfactant concentration, hydrophobic interaction becomes strong enough to pack the hydrophobic tails tightly and turn the molecular conformation into a pyramid-like shape, thus leading to the vesicle to micelle transition.
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