Effect of Lipophilic Tail Architecture and Solvent Engineering on the Structure of Trehalose-Based Nonionic Surfactant Reverse Micelles

Abstract

We use small-angle X-ray scattering and dynamic light scattering to investigate the structural and dynamical properties of trehalose polyisostearate, abbreviated as TQ-n (n = 3, 5, and 7), in different organic solvents, where n represents the number of isosterate chains per surfactant molecule. TQ-n spontaneously assembles into reverse micelles without addition of water at 25 °C. We found that for TQ-5 and TQ-7, steric hindrance of the lipophilic surfactant tail causes significant reduction of the aggregation number, whose scheme is clearly distinguished from the modification of the critical packing parameter. Increasing the hydrocarbon chain length of oils from octane to hexadecane favors one-dimensional micellar growth, leading to the formation of rodlike micelles due to different penetration tendencies of oils into the lipophilic shell of the surfactant. Subtle differences in solvent polarity also plays a crucial role in the micellar size, which is decreased when liquid paraffin is replaced with squalene. A further decrease is attained in more polar mixed triglyceride oils. A rising temperature also results in the same direction. The extrapolated structure factor to the zero scattering vector, S(q → 0), for the TQ-3/decane systems almost exactly follows that predicted for hard spheres, demonstrating that osmotic compressibility of the system is well explained if accounting for the excluded volume. However, we found that the effective diffusion coefficient decreases with surfactant concentration, which is an opposite trend to what is expected for hard spheres. This apparent contradiction is likely to be due to the occurrence of transient interdigitation between the lipophilic tails of neighboring reverse micelles at higher concentration. Our data highlight the relevance of the concept of "tunable reverse micellar geometry" in the novel trehalose-based nonionic surfactant binary mixtures, in which lipophilic tail architecture, solvent engineering, concentration, and temperature act as intrinsic parameters for the structure control of the reverse micelles.