α-Gel formation by amino acid-based gemini surfactants

Ternary mixtures being composed of surfactant, long-chain alcohol, and water sometimes form a highly viscous lamellar gel with a hexagonal packing arrangement of their crystalline hydrocarbon chains. This molecular assembly is called "α-crystalline phase" or "α-gel". In this study, we have characterized α-gels formed by the ternary mixtures of amino acid-based gemini surfactants, 1-hexadecanol (C16OH), and water. The surfactants used in this study were synthesized by reacting dodecanoylglutamic acid anhydride with alkyl diamines and abbreviated as 12-GsG-12 (s: the spacer chain length of 2, 5, and 8 methylene units). An amino acid-based monomeric surfactant, dodecanoylglutamic acid (12-Glu), was also used for comparison. At a fixed water concentration the melting point of the α-gel increased with increasing C16OH concentration, and then attained a saturation level at the critical mole ratio of 12-GsG-12/C16OH = 1/2 under the normalization by the number of hydrocarbon chains of the surfactants. This indicates that, to obtain the saturated α-gel, a lesser amount of C16OH is required for the gemini surfactants than for the monomeric one (the critical mole ratio of 12-Glu/C16OH = 1/3). Small- and wide-angle X-ray scattering measurements demonstrated an increase in the long-range d-spacing of the saturated α-gels in the order 12-Glu <12-G8G-12 < 12-G5G-12 < 12-G2G-12. In the three gemini surfactant systems, the decreased spacer chain length resulted in the increased maximum viscosity and elastic modulus of the saturated α-gels at a given water concentration. This is caused by the decreased amount of excess water being present outside the α-gel structure (or the increased amount of water incorporated between the surfactant-alcohol bilayers). To the best of our knowledge, this is the first report focusing on the formation of α-gel in gemini surfactant systems.