Facile synthesis of thiol-functionalized amphiphilic polylactide-methacrylic diblock copolymers

Article English OPEN
Themistou, E. ; Battaglia, G. ; Armes, S.P. (2014)
  • Publisher: RSC Publishing

Biodegradable amphiphilic diblock copolymers based on an aliphatic ester block and various hydrophilic\ud methacrylic monomers were synthesized using a novel hydroxyl-functionalized trithiocarbonate-based\ud chain transfer agent. One protocol involved the one-pot simultaneous ring-opening polymerization\ud (ROP) of the biodegradable monomer (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (L-lactide, LA) and\ud reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-(dimethylamino)ethyl\ud methacrylate (DMA) or oligo(ethylene glycol) methacrylate (OEGMA) monomer, with 4-\ud dimethylaminopyridine being used as the ROP catalyst and 2,20-azobis(isobutyronitrile) as the initiator for\ud the RAFT polymerization. Alternatively, a two-step protocol involving the initial polymerization of LA\ud followed by the polymerization of DMA, glycerol monomethacrylate or 2-(methacryloyloxy)ethyl\ud phosphorylcholine using 4,40-azobis(4-cyanovaleric acid) as a RAFT initiator was also explored. Using a\ud solvent switch processing step, these amphiphilic diblock copolymers self-assemble in dilute aqueous\ud solution. Their self-assembly provides various copolymer morphologies depending on the block\ud compositions, as judged by transmission electron microscopy and dynamic light scattering. Two novel\ud disulfide-functionalized PLA-branched block copolymers were also synthesized using simultaneous ROP\ud of LA and RAFT copolymerization of OEGMA or DMA with a disulfide-based dimethacrylate. The disulfide\ud bonds were reductively cleaved using tributyl phosphine to generate reactive thiol groups. Thiol–ene\ud chemistry was utilized for further derivatization with thiol-based biologically important molecules and\ud heavy metals for tissue engineering or bioimaging applications, respectively.
  • References (50)
    50 references, page 1 of 5

    1 O. W. Webster, Science, 1991, 251, 887-893.

    2 M. Barz, F. K. Wolf, F. Canal, K. Koynov, M. J. Vicent, H. Frey and R. Zentel, Macromol. Rapid Commun., 2010, 31, 1492- 1500.

    3 J. Z. Du and S. P. Armes, Langmuir, 2008, 24, 13710-13716.

    4 J. Z. Du and S. P. Armes, Langmuir, 2009, 25, 9564-9570.

    5 J. Z. Du and S. P. Armes, So Matter, 2010, 6, 4851-4857.

    6 M. Hales, C. Barner-Kowollik, T. P. Davis and M. H. Stenzel, Langmuir, 2004, 20, 10809-10817.

    7 D.-H. Han and C.-Y. Pan, J. Polym. Sci., Part A: Polym. Chem., 2007, 45, 789-799.

    8 H. Kakwere and S. Perrier, J. Polym. Sci., Part A: Polym. Chem., 2009, 47, 6396-6408.

    9 C. Lefay, D. Gl´e, M. Rollet, J. Mazzolini, D. Bertin, S. Viel, C. Schmid, C. Boisson, F. D'Agosto, D. Gigmes and C. Barner-Kowollik, J. Polym. Sci., Part A: Polym. Chem., 2011, 49, 803-813.

    10 J. Li, J. Ren, Y. Cao and W. Yuan, Polymer, 2010, 51, 1301- 1310.

  • Metrics
    views in OpenAIRE
    views in local repository
    downloads in local repository

    The information is available from the following content providers:

    From Number Of Views Number Of Downloads
    White Rose Research Online - IRUS-UK 0 45
Share - Bookmark