Tuneable Transient Thermogels Mediated by a pH‐ and Redox‐Regulated Supramolecular Polymerization

We present a multi-stimuli responsive transient supramolecular polymerization of s-sheet encoded dendritic peptide monomers in water. The glutamic acid and methionine containing amphiphiles undergo a glucose oxidase-catalyzed, glucose-fueled transient hydrogelation in response to an interplay of pH- and oxidation-stimuli, promoted by the production of reactive oxygen species (ROS). By adjusting the enzyme and glucose concentration we tune the assembly and the disassembly rates of the supramolecular polymers, which dictate the stiffness and transient stability of the hydrogels. The incorporation of triethylene glycol chains introduces thermoresponsive properties to the materials. We further show that repair enzymes are able to reverse the oxidative damage in the methionine-based thioether side chains. Since ROS play an important role in signal transduction cascades, our strategy offers great potential for applications of these dynamic biomaterials in redox microenvironments.