Fluidic Infiltrative Assembly of 3D Hydrogel with Heterogeneous Composition and Function

Abstract 3D hydrogels are powerful, multifunctional materials that are poised to become a building block in next‐generation systems. Modern schemes to print complex 3D hydrogels are advancing rapidly; however, they possess several limitations including—but not limited to—polymer incompatibility or difficulty in imparting continuous heterogeneity in composition or function. Here, a simple strategy of synthesizing programmable hydrogel systems with tunable form and function in 3D is presented. This approach utilizes commercially available stereolithographic printer/resin to fabricate high‐resolution molds followed by the programmed infiltration and gelation of hydrogel prepolymer. This mold is then sacrificed to yield 3D, multifunctional hydrogels exhibiting user‐defined heterogeneity. The approach is compatible with numerous in‐situ gelling polymers and modifiers ranging from interpenetrating networks of organic or synthetic polymers to functional materials possessing dense concentrations of nanomaterials or fluorescent markers. Accessible and versatile, this approach allows the fabrication of complex, multimaterial constructs with tunable 3D environmental responses inaccessible to well‐established hydrogel 3D printing methods.