Biochemical Signal‐Induced Supramolecular Hydrogelation for Structured Free‐Standing Soft Material Formation

Cells coordinate their activity and regulate biological processes in response to chemical signals. Mimicking natural processes, control over the formation of artificial supramolecular materials is of high interest for their application in biology and medicine. Supramolecular material that can form in response to chemical signals is important for the development of autonomously responsive materials. Herein, a supramolecular hydrogel system is reported enabling in situ generation of hydrogelators in response to a specific chemical signal. Using self-immolative chemistry, spatial control over the formation of supramolecular hydrogel material and structured free-standing hydrogel objects via providing H₂O₂ locally is demonstrated. In addition, a hybrid system is developed enabling in situ generation of the H₂O₂ by the action of an enzyme and glucose, providing an extra handle for the development of an intelligent soft material. This generic design should enable the use of various (chemical)stimuli that can be obtained via coupling different stimuli and various chemical and/or biological markers and appears a versatile approach for the design of smart artificial soft materials that can find application in theranostic purposes.