Raphae 1l Riva, Ste ´phanie Schmeits, Christine Je ´ro ˆme, Robert Je ´ro ˆme,* and

Azide pendent groups of aliphatic polyesters have been derivatized into tertiary amines, ammonium salts and poly(ethylene oxide) grafts. The experimental conditions have been optimized (organic solvent, 35 degrees C), such that the aliphatic polyesters are not degraded, including even poly(lactide) which is very sensitive to attack by weak nucleophiles.

Recent progress in the synthesis of aliphatic polyesters, substituted by pendent functional groups, has been reviewed. Two main strategies have to be distinguished. The first route consists of the ring‐opening polymerization of ε‐caprolactone substituted by various functional groups, protected if needed, in α‐ or γ‐position. In a second strategy, the functional groups are grafted onto preformed polyesters chains in α‐position of the carbonyl groups. α‐chloro‐ε‐caprolactone is quite an interesting monomer because, after polymerization, the activated chloride can be easily derivatized by atom transfer radical addition and “click” chemistry, respectively. Similarly, γ‐acrylic‐ε‐caprolactone is precursor of (co)polyesters well‐suited to derivatization of the pendent double bonds by Michael addition.

No abstract

In previous works, poly(D,L-lactide-co-ɛCL-poly(ethylene glycol) (poly(D,L-La-co-αPEGɛCL) amphiphilic graft-copolymers were successfully synthesized according to a copper azide-alkyne cycloaddition (CuAAC) strategy. This paper aims at reporting on the behavior of this amphiphilic copolymer in water, which was not studied in the previous paper. Moreover, the ability of the copolymer to stabilize a PLA nanoparticles aqueous suspension is presented. For this purpose, dynamic light scattering (DLS) and transmission electron microscopy (TEM) are proposed to characterize the nanoparticles in solution. Otherwise, the strategy developed for the synthesis of the amphiphilic copolymers was adapted and extended to the synthesis of PLA-based degradable hydrogel, potentially applicable as drug-loaded degradable polymer implant.