Programming Intrinsic States of Solvent-Free Glycolipids through Molecular Architecture and Thermal History.

Amphiphilic molecules enable the formation of diverse ordered structures across soft materials systems. The solution-phase self-assembly of glycolipids has been extensively investigated. However, the structural organization of these materials in the absence of solvent remains less systematically understood. It remains unclear whether solvent-free intrinsic states are uniquely dictated by molecular architecture or permit processing-dependent state selection. By systematically varying sugar headgroup identity and alkyl-chain multiplicity under solvent-free conditions, the effects of molecular architecture and thermal history on intrinsic states are mapped. Time-temperature mapping across the glycolipid series distinguishes structure-dominated systems that converge toward a single outcome from transitional regimes where prior temperature-time history influences intrinsic state selection. Within the processing-sensitive regime, designed heat-treatment trajectories direct structural development and generate distinct mesoscale organizations. Spectroscopic analysis further reveals that this trajectory-dependent structural evolution involves strengthened intermolecular hydrogen-bonding networks within the constrained packing environment of the double-tail architecture. The resulting physical states range from viscous liquids to gels with tunable domain architectures. Rheological measurements demonstrate that bulk mechanical response is governed by mesoscale organization, with mechanical strength spanning approximately 3 orders of magnitude without altering chemical composition. These findings establish a structure-processing-property framework for solvent-free glycolipids and position thermal history as a programmable design parameter for engineering adaptive soft materials.