Fuel-Driven and Enzyme-Regulated Redox-Responsive Supramolecular Hydrogels

Chemical reaction networks (CRN) embedded in hydrogels can transform responsive materials into complex self-regulating materials that generate feedback to counter the effect of external stimuli. This study presents hydrogels containing the beta-cyclodextrin (CD) and ferrocene (Fc) host-guest pair as supramolecular crosslinks where redox-responsive behavior is driven by the enzyme-fuel couples horse radish peroxidase (HRP)-H2O2 and glucose oxidase (GOx)-d-glucose. The hydrogel can be tuned from a responsive to a self-regulating supramolecular system by varying the concentration of added reduction fuel d-glucose. The onset of self-regulating behavior is due to formation of oxidation fuel in the hydrogel by a cofactor intermediate GOx[FADH(2)]. UV/Vis spectroscopy, rheology, and kinetic modeling were employed to understand the emergence of out-of-equilibrium behavior and reveal the programmable negative feedback response of the hydrogel, including the adaptation of its elastic modulus and its potential as a glucose sensor.