Self-regulating bioinspired supramolecular photonic hydrogels based on chemical reaction networks for monitoring activities of enzymes and biofuels.

Inspired by the way many living organisms utilize chemical/biological reactions to regulate their skin and respond to stimuli in the external environment, we have developed a self-regulating hydrogel design by incorporating chemical reaction networks (CRNs) into biomimetic photonic crystal hydrogels. In this hydrogel system, we used host-guest supramolecular non-covalent bonds between beta-cyclodextrin (β-CD) and ferrocene (Fc) as partial crosslinkers and designed a CRN involving enzyme-fuel couples of horseradish peroxidase (HRP)/HO and glucose oxidase (GOD)/d-glucose, by which the responsive hydrogel was transformed into a glucose-driven self-regulating hydrogel. Due to the biomimetic structural color in the hydrogel, the progress of the chemical reaction was accompanied by a change in the color of the hydrogel. Based on this principle, the designed supramolecular photonic hydrogel (SPH) can not only achieve naked-eye detection of HO and glucose concentrations with the assistance of a smartphone but also monitor the reactions of HRP and GOD enzymes and determine their activity parameters. The sensitivity and stability of the sensor have been proven. In addition, due to the reversibility of the chemical reaction network, the sensor can be reused, thus having the potential to serve as a low-cost point-of-care sensor. The SPH was ultimately used to detect glucose in human plasma and HO in liver tumor tissue. The results are comparable with commercial assay kits. By redesigning the chemical reaction network in the hydrogel, it is expected to be used for detecting other enzymes or fuels.