2013 Volume 62 Issue 7 Pages 489-498
Cationic gemini surfactants having a quaternary ammonium headgroup have been synthesized from oleic acid. The hydrocarbon chain is covalently bound to the terminal carbonyl group of oleic acid via an amide bond, while the quaternary ammonium headgroup is introduced onto the cis double bond of oleic acid. The Krafft temperature of these surfactants drops below room temperature (ca. 25°C) when the counterion is exchanged from Br– to Cl–. The aqueous solution properties of the Cl series of surfactants have been assessed by means of pyrene fluorescence, dynamic light scattering (DLS), and static surface tension measurements. An increased hydrocarbon chain length results in a lower critical micelle concentration (cmc) and a higher adsorption efficiency at the air/aqueous solution interface. Surface tension measurements suggest the formation of premicelles at concentrations below cmc, whereas, above cmc, DLS indicates the formation of micellar aggregates whose diameter ranges from 5 to 10 nm. We, furthermore, characterized the adsorption of these surfactants to the silica/aqueous solution interface and observed their spontaneous adsorption to the solid surface by electrostatic and intermolecular hydrophobic interactions. The combination of soft-contact imaging atomic force microscopy (AFM) and force-curve data suggests bilayer formation above cmc, which is reflective of the large packing parameter of the gemini surfactants. Interestingly, we found the repulsive interaction observed during compression of the adsorbed layer to be relatively weak, as a result of the low adsorption density and/or the loose molecular packing arrangement, which arises from the asymmetric structure.
