Exploiting spatial isomerism to modulate the assembled phase and rheological response of compositionally identical sugar-based surfactants

Abstract

For decades, extensive surfactant libraries have been developed to meet the requirements of downstream applications. However, achieving functional diversity has traditionally demanded a vast array of chemical motifs and synthetic pathways. Herein, a new approach for surfactant design based on structural isomerism is utilised to access a wide spectrum of functionalities. A library of C18-aliphatic maltosides was prepared through Koenigs–Knorr glycosylation, of which their properties were tuned through anomerism, stereoisomerism, regioisomerism, and degree of tail unsaturation. Self-assembly of the amphiphiles give rise to various morphologies, ranged from small micelles to large one-dimensional semiflexible assemblies, which were ultimately defined by the directionality of the supramolecular interactions imposed by the angular restraints of the isomeric centres. Remarkably, the microscopic phase determines the rheological behaviour of the system, which access Newtonian solutions, viscoelastic fluids, and gels with customised mechanical properties. The approach outlined in this study serves as a blueprint for the design of novel bioderived surfactants with diverse behaviour without altering the chemical composition of the surfactants, where the understanding of molecular interactions can potentially be used to predict and design the assembly and function of isomerically varied amphiphiles.