Synthetic polyester elastomeric constructs have become increasingly important for a range of healthcare applications, due to tunable soft elastic properties that mimic those of human tissues. A number of these constructs require intricate mechanic design to achieve a tunable material with controllable curing. Here, we present the synthesis and characterization of poly(itaconate-co-citrateco-octanediol) (PICO), which exhibits tunable formation of elastomeric networks through radical crosslinking of itaconate in the polymer backbone of viscous polyester gels. Through variation of reaction times and monomer molar composition, we were able to generate materials with modulation of a wide range of elasticity (36-1476 kPa), indicating the tunability of materials to specific elastomeric constructs. This correlated with measured rapid and controllable gelation times. As a proof-of-principle, we developed scaffold support for cardiac tissue patches, which presented visible tissue organization and viability with appropriate elastomeric support from PICO materials. These formulations present potential application in a range of healthcare applications with requirement for elastomeric support with controllable, rapid gelation under mild conditions.

With the objective of generating photo-responsive polymers, carbonate monomers with pendant cinnamoyl or coumarin moieties, which are capable of photo-reversible dimerization, were synthesized.

Biohybrid networks have the potential to have stiffnesses equivalent to that of native soft connective tissues as well as cell-mediated degradation behavior.

The ring-opening polymerization kinetics of 5-[2-(2-methoxyethoxy)ethoxymethyl]-5-methyl-1,3-dioxa-2-one (TMOE-2) and 5-[2-{2-(2-methoxyethoxy) ethyoxy}-ethoxymethyl]-5-methyl-1,3-dioxa-2-one (TMOE-3) was investigated using different catalysts with the aim to improve control over molecular weight. The possibility of monomer impurities driving the variability in molecular weight that has been seen in different reports, was assessed and evidence of catalysis via an imidazole impurity was found. The catalysts 1,5,7-triazobicyclo(4.4.0)dec-5-ene (TBD), hydrogen chloride in diethyl ether (HClÁEt 2 O), stannous 2-ethylhexanoate (SnOct 2), and catalyst free thermal polymerizations were conducted to understand the mechanisms influencing the molecular weight. TBD and HClÁEt 2 O consistently achieved high conversion of the monomer; however, molecular weights greater than 7,000 Da could not be achieved due to competing side reactions. SnOct 2 catalyzed and catalyst free thermal polymerizations were highly influenced by monomer purity and achieved lower conversion than TBD and HClÁEt 2 O. Understanding these mechanisms will guide future synthesis of poly(TMOE-2) and poly(TMOE-3) for biomedical applications.