Molecular structure of maltoside surfactants controls micelle formation and rheological behavior

The anomeric configuration (α or β) of n-hexadecyl-d-maltopyranoside (C₁₆G₂) has been shown to affect the morphology of the micelle, from elongated for α-C₁₆G₂ to worm-like micelles for β-C₁₆G₂. The entanglement of worm-like micelles often leads to strong modifications of the rheological behavior of the system and, as such, the anomeric configuration of C₁₆G₂ could also provide the possibility of controlling this. Furthermore, mixing these surfactants are hypothesized to result in mixed micelles allowing to finely tune the rheology of a system containing these sustainable surfactants.

The rheology of α- and β-C₁₆G₂, and mixtures of those, was determined by rotational and oscillatory rheology at different temperatures and surfactant concentrations. Micelle structure and composition for these systems were characterized using contrast variation small-angle neutron scattering and small-angle X-ray scattering. The results from these were connected in order to elaborate a molecular understanding of the rheological response of the system.

The self-assembly of these surfactants have been found to result in different rheological properties. β-C₁₆G₂ show a high viscosity with a non-Newtonian viscoelastic behavior, which was linked to the formation of worm-like micelles. In contrast, α-C₁₆G₂ self-assembled into short cylindrical micelles, resulting in a Newtonian fluid with low viscosity. Furthermore, mixtures of these two surfactants lead to systems with intermediate rheological properties as a result of the formation of micelles with intermediate morphology to those of the pure anomers. These results also show that the rheological properties of the system can be tuned to change the micelle morphology, which in turn depends on the anomeric configuration of the surfactant. Also, surfactant concentration, temperature of the system, and micelle composition for surfactant mixtures provide control over the rheological properties of the system in a wide temperature range. Therefore, these results open new possibilities in the development of sustainable excipients for formulation technology, where the characteristics of the system can be easily tailored through geometric variations in the monomer structure whilst maintaining the chemical composition of the system.