Self-Regulating Hydrogel Driven by Light-Responsive Glyco-Supramolecular Reassembly

Light-responsive supramolecular materials that operate autonomously represent a key step toward smart, energy-efficient systems. Yet, achieving intrinsic reversibility without external triggers is rare. Here, we present two azobenzene–glycoconjugate amphiphiles bearing glucose (Glc-Azo) or maltose (Mal-Azo) headgroups whose supramolecular organization is dictated by carbohydrate-mediated interactions. Both derivatives undergo efficient trans–cis photoisomerization under UV irradiation. Remarkably, when assembled in aqueous media, they autonomously revert to the trans configuration in the dark without external thermal input. This self-recovery is attributed to a hydrogen-bond-rich glycosidic microenvironment that modulates azobenzene packing and promotes structural reorganization. Incorporation of the bulkier maltose moiety affords robust, thermoreversible supramolecular hydrogels that undergo fully reversible, light-induced gel–sol transitions─dissociating upon UV exposure and spontaneously reassembling thereafter. These results reveal the power of glyco-directed supramolecular architectures to enable autonomous, energy-efficient photoresponsive soft materials, with implications for biomedical and smart-material applications.