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The post-polymerization modification of polyglycidol is of great interest for the synthesis of functional polyether-based polymeric biomaterials. We present a degradable polyglycidol-based hydrogel system using oxime click chemistry by employing a ketone-functionalized and an amino-oxy functionalized branched polyglycidol. Ratio-controlled amino-oxy functionalized species were obtained by controlling the ratio of N-hydroxy phthalimide to the hydroxyl groups attached to the polyether backbone. A similar strategy was utilized to obtain ratio-controlled keto functionalized branched polyglycidols. This unique feature will allow for the tailoring of this branched PEG-like structural motif for the synthesis of novel biomaterials with tailored biochemical and biomechanical properties. The bio-orthogonal nature of this crosslinking reaction makes these hydrogels an attractive option for load-bearing tissue engineering. Our hydrogel synthesis methodology allows for control over the properties of the resulting polymeric network, based upon the ratio between the keto and the amino-oxy functionalities. The potential of these polyether-based networks to serve as a successful delivery platform was assessed by studying their swelling and degradation profiles. Biocompatibility and cytotoxicity of the gels were studied using NIH 3T3 cells. Our preliminary results highlighting the potential of our hydrogels platform will be discussed. 

The modification of branching in polyglycidol is of great interest for the synthesis of novel polymeric biomaterials. We present the synthesis of novel ratio-controlled amino-oxy and keto functionalized branched polyglycidols. The biocompatibility and chemospecificity of the amino-oxy functional group make it particularly well suited for applications in bioconjugation, drug delivery and tissue engineering. Amino-oxy functionalized branched polyglycidol can serve as a critical building block for the synthesis of innovative biocompatible degradable hydrogels that are injectable. Ratio-controlled amino-oxy functionalized species were obtained by controlling the ratio of N-hydroxy phthalimide to the hydroxyl groups attached to the polyether backbone. A similar strategy was utilized to obtain ratio-controlled keto functionalized branched polyglycidols. This unique feature will allow for the tailoring of this branched PEG-like structural motif for the synthesis of novel biomaterials with tailored biochemical and biomechanical properties. 

Synthetic polymers have contributed significantly to the development of advanced scaffolds for load bearing tissue engineering applications. Despite this, there is still a need to create scaffolds that can simultaneously present multiple biophysical and biochemical properties to better mimic native cellular environments. Polyglycidol has been shown to be a biocompatible polyether polyol, that forms different, sometimes complex, polymeric architectures. Furthermore, it has multiple hydroxyl groups that are capable of numerous chemical modifications. However, little is known about the biocompatibility of modified polyglycidols and their resulting 3-D network. The overarching hypothesis for this project is that changes in the mechanical, structural, and compositional cues within a polyglycidol-based network can be tailored to influence cell responses. Therefore, as a crucial first step, we investigated the biocompatibility of functionalized polyglycidols, and the swelling, degradation, and mechanical properties of polyglycidol based hydrogels. Ongoing studies aim to show that a defined subset of biophysical and biochemical cues can be incorporated simultaneously within the polyglycidol hydrogel. Such an advanced scaffold would allow us to study the synergistic effects of various chemical and physical cues on cellular behavior.