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Issue 4, 2014
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Facile synthesis of thiol-functionalized amphiphilic polylactide–methacrylic diblock copolymers

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Abstract

Biodegradable amphiphilic diblock copolymers based on an aliphatic ester block and various hydrophilic methacrylic monomers were synthesized using a novel hydroxyl-functionalized trithiocarbonate-based chain transfer agent. One protocol involved the one-pot simultaneous ring-opening polymerization (ROP) of the biodegradable monomer (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (L-lactide, LA) and reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) or oligo(ethylene glycol) methacrylate (OEGMA) monomer, with 4-dimethylaminopyridine being used as the ROP catalyst and 2,2′-azobis(isobutyronitrile) as the initiator for the RAFT polymerization. Alternatively, a two-step protocol involving the initial polymerization of LA followed by the polymerization of DMA, glycerol monomethacrylate or 2-(methacryloyloxy)ethyl phosphorylcholine using 4,4′-azobis(4-cyanovaleric acid) as a RAFT initiator was also explored. Using a solvent switch processing step, these amphiphilic diblock copolymers self-assemble in dilute aqueous solution. Their self-assembly provides various copolymer morphologies depending on the block compositions, as judged by transmission electron microscopy and dynamic light scattering. Two novel disulfide-functionalized PLA-branched block copolymers were also synthesized using simultaneous ROP of LA and RAFT copolymerization of OEGMA or DMA with a disulfide-based dimethacrylate. The disulfide bonds were reductively cleaved using tributyl phosphine to generate reactive thiol groups. Thiol–ene chemistry was utilized for further derivatization with thiol-based biologically important molecules and heavy metals for tissue engineering or bioimaging applications, respectively.

Graphical abstract: Facile synthesis of thiol-functionalized amphiphilic polylactide–methacrylic diblock copolymers

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Publication details

The article was received on 17 Oct 2013, accepted on 14 Nov 2013 and first published on 27 Nov 2013


Article type: Paper
DOI: 10.1039/C3PY01446K
Citation: Polym. Chem., 2014,5, 1405-1417
  • Open access: Creative Commons BY license
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    Facile synthesis of thiol-functionalized amphiphilic polylactide–methacrylic diblock copolymers

    E. Themistou, G. Battaglia and S. P. Armes, Polym. Chem., 2014, 5, 1405
    DOI: 10.1039/C3PY01446K

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