Self-Assembly in Aqueous Oppositely Charged Gemini Surfactants: A Correlation between Morphology and Solubilization...

Micellization behavior of oppositely charged gemini surfactants (anionic surfactant; phosphoric acid, P,P'-1,4-butanedieyl, P,P'-didodecylester, disodium salt (12-4-12A), and cationic surfactant; butanediyl-1,4, bis (N,N-hexadecyl ammonium) dibromide (16-4-16) or (D-isosorbate-1,4-diyl bis(N,N-dimethyl-N-hexadecylammonium acetoxy) dichloride (16-Isb-16)) has been studied (individually or of a gemini mixture) by conductivity and surface tension measurements. Critical micelle concentration (CMC) data show both synergistic (for 12-4-12A + 16-Isb-16) and antagonistic (for 12-4-12A + 16-4-16) interactions between the two components. Small angle neutron scattering (SANS) measurement shows formation of various aggregates, spherical (or ellipsoidal), rod-shaped, and vesicular, by changing the mole fraction (at fixed total surfactant concentration, 10 mM). Viscosity, zeta (ζ)-potential, and transmission electron microscopy (TEM) data are found in conformity of SANS results. Surprisingly, two morphologies (vesicles and rod-shaped micelles) show stability in a wide temperature range (303-343 K). The behavior has been explained on the basis of temperature induced dehydration and depletion of micellar charge. Aqueous gemini mixtures, of different morphologies, have been used for the determination of solubilization efficacy (using UV-visible spectrophotometer) toward polycyclic aromatic hydrocarbons (PAHs: anthracene; pyrene or fluorene). Molar solubilization ratio (MSR) data suggest that vesicles enhance the solubilization efficacy. SANS analysis shows that vesicle bilayer thickness increases upon PAH solubilization. The order of bilayer thickness increase is found to be anthracene > pyrene > fluorene, which is in the same order as the aqueous solubility of PAHs. This is the first report which correlates morphology to the solubilization efficacy.