Biodegradable polyesters, specifically poly(lactic-co-glycolic acids) (PLGAs), have generated an immense amount of interest in the fields of regenerative medicine and drug delivery due to their biocompatibility, FDA approval, and mechanical strength. However, the current methods for synthesizing PLGAs are limited to ring-opening polymerization (ROP) of cyclic ester monomers which yields unsequenced, random copolymers. In general, PLGAs prepared by ROP offer limited control over monomer sequence, degradation rates, and long-term release profiles of a target molecule. This work utilizes a novel synthetic method, segmer assembly polymerization (SAP), that generates copolymers with repeating sequences of lactic and glycolic acid whose components are interchangeable and may be tailored for a specific application. In this study, repeating sequence copolymers (RSCs) which exploit various linkage hydrolysis rates were selected and compared to commonly used random PLGA analogs. Changes in sequence, stereochemistry, and monomeric ratio were shown to have a profound effect on such properties as in vitro swelling, erosion, acidic microclimate distribution, and compressive modulus. Devices fabricated with sequenced PLGAs were shown to have enhanced structural stability both in vivo and in vitro. The results presented in this work focus on the importance of controlling monomer sequence within a copolymer to tailor a variety of properties in devices that are commonly used in high impact therapeutic applications.

Impact of monomer sequence and stereochemistry on the physico-chemical properties of biodegradable devices composed of poly(lactic-co-glycolic acid)

252nd National Meeting (2016)

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