Degradable and Comb-Like PEG-Based Copolymers by Nitroxide-Mediated Radical Ring-Opening Polymerization

Vianney Delplace (1) , Antoine Tardy (2) , Simon Harrisson (1) , Simona Mura , Didier Gigmes (2) , Yohann Guillaneuf (2) , Julien Nicolas (1)

1 IGPS - Institut Galien Paris-Sud
2 ICR - Institut de Chimie Radicalaire

Three cyclic ketene acetals, 2-methylene-1,3-dioxepane (MDO), 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), and 2-methylene-4-phenyl-1,3-dioxolane (MPDL), have been copolymerized with oligo(ethylene glycol) methyl ether methacrylate and a small amount of acrylonitrile (or styrene) at 90 °C by nitroxidemediated radical ring-opening polymerization, as a convenient way to prepare degradable PEG-based copolymers for biomedical applications. MPDL was the best candidate, enabling high monomer conversions to be reached and well-defined PEG-based copolymers with adjustable amount of ester groups in the main chain to be synthesized, leading to nearly complete hydrolytic degradation (5% KOH aqueous solution, ambient temperature). The noncytotoxicity of the obtained copolymers was shown on three different cell lines (i.e., fibroblasts, endothelial cells and macrophages), representing a promising approach for the design of degradable precursors for PEGylation and bioconjugation via the NMP technique.

Domains: Chemical Sciences

Vianney Delplace, Antoine Tardy, Simon Harrisson, Simona Mura, Didier Gigmes, et al.. Degradable and Comb-Like PEG-Based Copolymers by Nitroxide-Mediated Radical Ring-Opening Polymerization. Biomacromolecules, 2013, 14 (10), pp.3769--3779. ⟨10.1021/bm401157g⟩. ⟨hal-01460454⟩