Mechanically Tunable Hydrogels with Self-Healing and Shape Memory Capabilities from Thermo-Responsive Amino Acid-Derived Vinyl Polymers

In this study, we report the fabrication and characterization of self-healing and shape-memorable hydrogels, the mechanical properties of which can be tuned via post-polymerization crosslinking. These hydrogels were constructed from a thermo-responsive poly(N-acryloyl glycinamide) (NAGAm) copolymer containing N-acryloyl serine methyl ester (NASMe) units (5 mol%) that were readily synthesized via conventional radical copolymerization. This transparent and free-standing hydrogel is produced via multiple hydrogen bonds between PNAGAm chains by simply dissolving the polymer in water at a high temperature (~90 °C) and then cooling it. This hydrogel exhibited moldability and self-healing properties. The post-polymerization crosslinking of the amino acid-derived vinyl copolymer network with glutaraldehyde, which acts as a crosslinker between the hydroxy groups of the NASMe units, tuned mechanical properties such as viscoelasticity and tensile strength. The optimal crosslinker concentration efficiently improved the viscoelasticity. Moreover, these hydrogels exhibited shape fixation (~60%)/memory (~100%) behavior owing to the reversible thermo-responsiveness (upper critical solution temperature-type) of the PNAGAm units. Our multifunctional hydrogel, with moldable, self-healing, mechanical tunability via post-polymerization crosslinking, and shape-memorable properties, has considerable potential for applications in engineering and biomedical materials.