Incorporation of Glutamic Acid or Amino-Protected Glutamic Acid into Poly(Glycerol Sebacate): Synthesis and Characterization

Abstract

Poly(glycerol sebacate) (PGS), a soft, tough elastomer with excellent biocompatibility, has been exploited successfully in many tissue engineering applications. Although tunable to some extent, the rapid in vivo degradation kinetics of PGS is not compatible with the healing rate of some tissues. The incorporation of L-glutamic acid into a PGS network with an aim to retard the degradation rate of PGS through the formation of peptide bonds was conducted in this study. A series of poly(glycerol sebacate glutamate) (PGSE) containing various molar ratios of sebacic acid/L-glutamic acid were synthesized. Two kinds of amino-protected glutamic acids, Boc-L-glutamic acid and Z-L-glutamic acid were used to prepare controls that consist of no peptide bonds, denoted as PGSE-B and PGSE-Z, respectively. The prepolymers were characterized using 1H-NMR spectroscopy. Cured elastomers were characterized using FT-IR, DSC, TGA, mechanical testing, and contact angle measurement. In vitro enzymatic degradation of PGSE over a period of 28 days was investigated. FT-IR spectroscopy confirmed the formation of peptide bonds. The glass transition temperature for the elastomer was found to increase as the ratio of sebacic acid/glutamic acid was increased to four. The decomposition temperature of the elastomer decreased as the amount of glutamic acid was increased. PGSE exhibited less stiffness and larger elongation at break as the ratio of sebacic acid/glutamic acid was decreased. Notably, PGSE-Z was stiffer and had smaller elongation at break than PGSE and PGSE-B at the same molar ratio of monomers. The results of in vitro enzymatic degradation demonstrated that PGSE has a lower degradation rate than does PGS, whereas PGSE-B and PGSE-Z degrade at a greater rate than does PGS. SEM images suggest that the degradation of these crosslinked elastomers is due to surface erosion. The cytocompatibility of PGSE was considered acceptable although slightly lower than that of PGS. The altered mechanical properties and retarded degradation kinetics for PGSE reflect the influence of peptide bonds formed by the introduction of L-glutamic acid. PGSE displaying a lower degradation rate compared to that for PGS can be used as a scaffold material for the repair or regeneration of tissues that are featured by a low healing rate.

Keywords

• poly(glycerol sebacate)
• poly(ester amide)
• elastomer
• lipase
• π-π stacking interactions
• pi stacking