Photocrosslinkable biodegradable elastomers based on cinnamate-functionalized polyesters

Abstract

Synthetic biodegradable elastomers are an emerging class of materials that play a critical role in supporting innovations in bioabsorbable medical implants. This work describes the synthesis and characterization of poly (glycerol-co-sebacate)-cinnamate (PGS-CinA), a biodegradable elastomer based on hyperbranched polyesters derivatized with pendant cinnamate groups. PGS-CinA can be prepared via photodimerization in the absence of photoinitiator using monomers that are found in common foods. The resulting network exhibits a Young’s modulus of 50.5 to 152.1 kPa and a projected in vitro degradation half-life time between 90 and 140 days. PGS-CinA elastomers are intrinsically cell adherent and support rapid proliferation of fibroblasts. Spreading and proliferation of fibroblasts are loosely governed by the substrate stiffness within the range of Young’s moduli in PGS-CinA networks that were prepared. The thermo-mechanical properties, biodegradability, and intrinsic support of cell attachment and proliferation suggest that PGS-CinA networks abroadly applicable for use in next generation bioabsorable materials including temporary medical devices and scaffolds for soft tissue engineering.

Synthesis, Characterization and 3D Micro-Structuring via 2-Photon Polymerization of Poly(glycerol sebacate)-Methacrylate–An Elastomeric Degradable Polymer

“…Similar results have been reported for PGS-acrylate and PGScinnamate, with increased addition of the functional groups resulting in an increase in Young's modulus and UTS [19,20,23,26]. These reported values were also comparable with those produced by PGS-M. PGS-acrylate demonstrated Young's modulus values ranging from 0.6 to 13.2 MPa for degrees of functionalisation (comparable to DM) from 21 to 88%.…”

“…After a further 24 h in methanol, no significant reduction in mass was seen in any sample. These results are consistent with other photocurable PGS polymers and thermally crosslinked PGS also [20,26,29,30]. The molecular structure of the PGS-M was examined using ATR-FTIR.…”

“…Alternatively, the functionalization of PGS with cinnamate groups has also been examined. This produces a prepolymer that photocures directly on exposure to ultraviolet light, however this requires long exposure times (2 h) [20].…”

Photo-irradiation paradigm: Mapping a remarkable facile technique used for advanced drug, gene and cell delivery

“…Also the thiolene moiety functional systems is working through the excitation of free radicals, but, proceed through step-growth mechanism [65]. Whereas cinnamate [62,66] and anthracene [67] moieties undergo reversible photodimerization upon light irradiation. Less commonly used moieties are epoxidized moiety that forms ether bridges in the presence of iodonium salt as a PI [68] and the styrylpyridinium moiety which undergoes cycloaddition reactions upon exposure to photo-irradiation [69].…”

“…At the same time a good PIS should provide the following: complete stability i.e. does not initiate spontaneous reaction when mixed with the photoreactive molecules [62]; shows a rapid and high initiation efficacy to maximize utilization of undissociated PI that degrade the quality of the formulated pharmaceutical carrier [56]; and appropiate with the incorporation of proteins/peptides or the encapsulation of viable cells [56]. Also, it cannot be overlooked here that some delivery carriers can be photo-formulated without using a PI, instead they depend on long time exposure of the photo-responsive molecules to the light energy.…”