We report the first amine-bearing cyclic ketene acetals (CKAs) for radical ring-opening polymerisation (RROP). The resulting polyesters and their corresponding nanoparticles were biodegradable and showed the desired pH sensitive behaviour.
Radical ring opening polymerization is a powerful tool to achieve a polyester via radical polymerization. We used it to obtain a dimethylated version of poly(caprolactone) (PdmCL) from dimethylated MDO (DMMDO). First, we revisited monomer synthesis and achieved a milder synthetic protocol by introducing a cobalt-based catalyst. We also developed a new route towards DMMDO via a cyclic carbonate using the Petasis chemistry. Amphiphilic blockcopolymers were then generated by free radical polymerization of DMMDO with a PEG-based macroinitiator. The resulting polyesters self-assembled into nanoparticles that were biodegradable as well as biocompatible. The nanoparticles proved to be an effective protective shell for an entrapped enzyme that was released upon degradation of the polyester by esterase. We are confident that our results will spur further research into block-copolymers resulting from RROP. not affect cell viability, making them interesting candidates for drug delivery. Our data shows that polyesters from RROP are already readily available and are especially promising in applications involving self-assembled nanoparticles. ASSOCIATED CONTENT Supporting Information. Details on the applied chemicals, synthetic protocols, NMR data, GC data on monomer synthesis, GPC traces protocols for the enzymatic reactions and cell tests are available in the supporting information. This material is available free of charge via the Internet at http://pubs.acs.org.
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