Advanced biomedical hydrogels: molecular architecture and its impact on medical applications

Hydrogels are cross-linked polymeric networks swollen in water, physiological aqueous solutions or biological fluids. They are synthesized by a wide range of polymerization methods that allow for the introduction of linear and branched units with specific molecular characteristics. In addition, they can be tuned to exhibit desirable chemical characteristics including hydrophilicity or hydrophobicity. The synthesized hydrogels can be anionic, cationic, or amphiphilic and can contain multifunctional cross-links, junctions or tie points. Beyond these characteristics, hydrogels exhibit compatibility with biological systems, and can be synthesized to render systems that swell or collapse in response to external stimuli. This versatility and compatibility have led to better understanding of how the hydrogel's molecular architecture will affect their physicochemical, mechanical and biological properties. We present a critical summary of the main methods to synthesize hydrogels, which define their architecture, and advanced structural characteristics for macromolecular/biological applications.