Supramolecular carbohydrate-based hydrogels from oxidative hydroxylation of amphiphilic β--glycosylbarbiturates and α-glucosidase-induced hydrogelation

We describe an ecofriendly two-step synthesis of glycoamphiphiles, capable of hierarchical self-assembly into supramolecular hydrogels, consisting of Knoevenagel condensation of barbituric acid derivatives with biobased carbohydrates (glucose and maltose) and selective H 2 O 2 -mediated oxidative hydroxylation of barbiturates in water. By modifying the molecular design of glycostructures and the hydrophilic/hydrophobic balance, various glyco-nanostructures (ribbons, tapes, vesicles, helices, fibers) have been created via supramolecular self-assembly. In addition, we found that a water-soluble glycoamphiphile underwent sol-to-gel phase transition upon the addition of α-glucosidase as a result of the hydrolysis of the non-reducing-end glucose in the maltose moiety. An ecofriendly two-step synthesis in water enabled the obtention of neutral amphiphilic β- C -glycosylbarbiturates with self-assembly properties capable of supramolecular hydrogelation. And, an α-glucosidase induced sol-to-gel phase transition.