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 <i>trans-cis</i> photoisomerization under UV irradiation. Remarkably, when assembled in aqueous media, they autonomously revert to the <i>trans</i> 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.