Transient Stiffness Patterning in Hydrogels Driven by Dissipative Mechanochemical Coupling

Living systems adapt to mechanical forces through a series of biochemical feedback loops and dissipative signal transduction mechanisms across multiple length scales. By contrast, synthetic materials are static, closed systems with minimal interaction with their surroundings and lack the ability to adapt to mechanical deformations. Here, a strategy that enables a hydrogel to adapt to mechanical forces through the temporal modulation of its stiffness properties is reported. It is demonstrated that force-induced bond rupture at the disulfide linkages of the hydrogel, coupled with their chemical reoxidation leads to dissipative, transient stiffness functions. The electrochemical generation of the oxidant as the output of a feedback loop triggered by an externally applied force provides high spatiotemporal control over the dissipative process, enabling the engineering of hydrogels with out-of-equilibrium stiffness patterns. Additionally, dose-controlled, spatiotemporal transient release of model protein payloads from the hydrogel is demonstrated. The proposed concept has the potential to enhance the autonomous and interactive functionalities of hydrogels, advancing their applications in the biomedical field and soft robotics.