Photocrosslinked PLA-PEO-PLA Hydrogels from Self-Assembled Physical Networks: Mechanical Properties and Influence of Assumed Constitutive Relationships

摘要

Poly(lactide) – block – poly(ethylene oxide) – block – poly(lactide) [PLA-PEO-PLA] triblock copolymers are known to form physical hydrogels in water, due to the polymer's amphiphilicity. Their mechanical properties, biocompatibility, and biodegradability have made them attractive for use as soft tissue scaffolds. However, the network junction points are not covalently crosslinked and in a highly aqueous environment these hydrogels adsorb more water, transform from gel to sol, and lose the designed mechanical properties. In this report, a hydrogel was formed by using a novel two step approach. In the first step end-functionalized PLA-PEOPLA triblock was self-assembled into a physical hydrogel through hydrophobic micelle network junctions, and then, in the second step, this self-assembled physical network structure was locked into place by photocrosslinking the terminal acrylate groups. In contrast to physical hydrogels, the photocrosslinked gels remained intact in phosphate buffered solution at body temperature. The swelling, degradation, and mechanical properties were characterized and demonstrated extended degradation time (~ 65 days), exponential decrease in modulus with degradation time, and tunable shear modulus (1.6 – 133 kPa) by varying concentration. We also discuss the various constitutive relationships (Hookean, Neo-Hookean, and Mooney-Rivlin) that can be used to describe the stress-strain behavior of these hydrogels. The chosen model and assumptions used for data fitting influences the obtained modulus values by as much as a factor of 3.5, demonstrating the importance of clearly stating one's data fitting parameters so that accurate comparisons can be made within the literature.