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.