Bioactive hydrogel coatings of complex substrates using diffusion-mediated redox initiation

Hydrogels have long been established as materials with tunable stiffness and chemistry that enable controlled cellular interactions. When applied as coatings, hydrogels can be used to introduce biofunctionality to medical devices with minimal effect on bulk properties. However, it remains challenging to uniformly apply hydrogel coatings to three dimensional geometries without substantially changing the manufacturing process and potentially affecting device function. Herein, we report a new redox-based crosslinking method for applying conformable hydrogel coatings with tunable thickness and chemistry. This new diffusion-mediated strategy of redox initiation and hydrogel crosslinking enabled coating of a variety of three dimensional substrates without changing the primary fabrication process. Following adsorption of the reducing agent to the construct, hydrogel coating thickness was readily controlled by immersion time with desorption and diffusion of the reducing agent initiating hydrogel crosslinking from the surface. The process was used to generate a range of hydrogel properties by varying the macromer molecular weight and concentration. In addition, we demonstrated that these coatings can be applied sequentially to generate multilayered constructs with distinct features. Finally, incorporation of proteins into the bulk of the hydrogel coating or as a final surface layer permitted the controlled introduction of bioactivity that supported cell attachment. This work provides a versatile method for assembling bioactive coatings with a simple post-fabrication process that is amenable to diverse geometric substrates and chemistries.