Effect of the Cationic Head Group on Cationic Surfactant-Based Surfactant Mediated Gelation (SMG).

The surfactant-mediated gelation (SMG) method allows us to formulate hydrogels using a water-insoluble organogelator. In this study, we formulated hydrogels using three cationic surfactants, hexadecyltrimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride (CTAC), and hexadecylpyridinium chloride (CPC)] and an organogelator (12-hydroxyoctadecanoic acid (12-HOA), and studied their structures and mechanical properties. A fiber-like structure similar to that found in the 12-HOA-based organogels was observed by optical microscopy. Small- and wide-angle X-ray scattering profiles showed Bragg peaks derived from the long- and short-spacing of the crystalline structures in the gel fibers and a correlation peak from the surfactant micelles in the small-angle region. Furthermore, the formation of micelles in the hydrogels was confirmed by UV-vis spectroscopic measurements of the gel samples in the presence of Rhodamine 6G. We concluded that the hydrogels prepared by the SMG method in the present systems are orthogonal molecular assembled systems in which two different molecular assembled structures coexist. Among the three surfactant systems, the CTAB system presented the lowest critical gelation concentration and highest sol-gel transition temperature and viscoelasticity. These differences in gel fiber formation and gel properties were discussed from the viewpoint of the degree of solubilization of the gelator molecules in micelles coexisting with gel fibers and diffusion of the gelator molecules in the gel formation process.

Hydrogelation with a water-insoluble organogelator - surfactant mediated gelation (SMG).

The low-molecular-weight gelator (LMG) 12-hydroxyoctadecanoic acid (12-HOA) is insoluble in water, but can be solubilized in surfactant micelles. We therefore solubilized 12-HOA at 80 °C in an aqueous solution of cetyltrimethylammonium bromide (CTAB) containing spherical micelles. On cooling this system down to room temperature, a hydrogel is obtained. We will refer to this process as "surfactant-mediated gelation" (SMG). The hydrogels were formed at a lower 12-HOA concentration when sodium salicylate (NaSal) was added to the CTAB system, which induced the formation of wormlike micelles. Hydrogels obtained by SMG from spherical and wormlike micelles are referred to as gelled micellar phases (GMs) and gelled wormlike micellar phases (GWLMs), respectively. Optical microscopy and transmission electron microscopy (TEM) showed that 12-HOA forms self-assembled fibrillar networks (SAFiNs) in both GMs and GWLMs. The sol-gel transition temperature, Tsol-gel, of the GWLM samples was higher than that of the GM samples. Dynamic rheological measurements revealed gel properties (G' > G'' at all angular frequencies) for both gels; however, a higher viscoelasticity was observed for the GWLM samples, which in turn, was reflected in the higher Tsol-gel. Small- and wide-angle X-ray scattering (SWAXS) showed that micelles and gel fibers coexist in the GM and GWLM samples. Our study demonstrates the gelation of aqueous micellar solutions with water-insoluble LMGs.