RESUMO
Living systems use dissipative processes to enable precise spatiotemporal control over various functions, including the transient modulation of the stiffness of tissues, which, however, is challenging to achieve in soft materials. Here, we report a new platform to program hydrogel films with tunable, time-dependent mechanical properties under out-of-equilibrium conditions, powered by electricity. We show that the lifetime of the transient network of a surface-confined hydrogel film can be effectively controlled by programming the generation of an electrochemically oxidized mediator in the presence of a chemical or photoreducing agent in solution. It is, therefore, electrically possible to direct the transient stiffening or softening of the hydrogel film, enabling high modularity of the material functions with precise spatiotemporal control. Temporally controlled operations of the hydrogel films are demonstrated for the on-demand, dose-controlled release of multiple model protein payloads from electrode arrays using the present electrically powered dissipative system. This demonstration of electrically driven transient modulation of the stiffness properties of hydrogel films represents an important step toward the engineering of dissipative materials for developing future biomedical applications that can harness the temporal, adaptive properties of this new class of materials.
RESUMO
A Fe3+-ion cross-linked carboxymethyl cellulose, Fe3+-CMC, redox-active gel exhibiting dissipative, transient stiffness properties is introduced. Chemical or photosensitized reduction of the higher-stiffness Fe3+-CMC to the lower-stiffness Fe2+-CMC gel, accompanied by the aerobic reoxidation of the Fe2+-CMC matrix, leads to the dissipative, transient stiffness, functional matrix. The light-induced, temporal, transient release of a load (Texas red dextran) and the light-triggered, transient mechanical bending of a poly-N-isopropylacrylamide (p-NIPAM)/Fe3+-CMC bilayer construct are introduced, thus demonstrating the potential use of the dissipative Fe3+-CMC gel for controlled drug release or soft robotic applications.
RESUMO
Achieving specific mechanical properties of hydrogels, especially when used as thin films, can be crucial in diverse applications, including tissue engineering and bioelectronics. Here, a novel electrochemical approach for fabricating uniform and robust hydrogel films based on carboxymethyl cellulose cross-linked by Fe3+ ions (Fe-CMC), exhibiting tunable, dynamic properties is introduced. High modulation of the mechanical properties of the film is achieved by applying multiple electrochemical pulses of oxidative voltage during hydrogel deposition. Our study shows also a remarkable effect of the ionic strength on the properties of the electrodeposited hydrogel films. We found that switching from a salt solution to water enhanced the stiffness of the hydrogels, thereby regulating the permeability of the films. These results are supported by molecular dynamics (MD) simulations, showing that an increase in the ionic strength induces a weakening of the Fe-CMC interactions, ultimately affecting the network strength. Finally, the robustness of these electrodeposited hydrogel films enables their delamination from the electrode without any damage, thereby expanding their potential applications as freestanding smart membranes. By providing fundamental insights into the dynamics of metal-coordinated bonds and their response at the macroscopic scale, we have demonstrated the versatility of electrochemical gelation for the fabrication of robust hydrogel films with tunable mechanical properties, which could serve as smart platforms for a variety of biomedical applications.