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Issue 2, 2016
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Cationic and reactive primary amine-stabilised nanoparticles via RAFT aqueous dispersion polymerisation

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Abstract

The synthesis of primary amine-functionalised diblock copolymer nanoparticles via polymerisation-induced self-assembly (PISA) using a RAFT aqueous dispersion polymerisation formulation is reported. The primary amine steric stabiliser is a macromolecular chain transfer agent (macro-CTA) based on 2-aminoethyl methacrylate AMA, which can be readily polymerised in its hydrochloride salt form with good control (Mw/Mn < 1.30) using RAFT aqueous solution polymerisation. Subsequent chain extension of this macro-CTA with 2-hydroxypropyl methacrylate (HPMA) leads to the formation of relatively monodisperse spherical nanoparticles (68 to 288 nm) at pH 6. However, worms or vesicles could not be obtained, because strong lateral repulsion between the highly cationic PAMA stabiliser chains impedes the formation of these higher order copolymer morphologies. Deprotonation of the primary amine stabiliser chains at or above pH 9 results in flocculation of these spherical nanoparticles as the PAMA block becomes uncharged. Diblock copolymer spheres, worms or vesicles can be synthesised that remain stable at pH 9 by supplementing the PAMA macro-CTA with a poly(glycerol monomethacrylate) (PGMA) macro-CTA, since this non-ionic block confers effective steric stabilisation in alkaline media. A series of diblock copolymer nanoparticles with the general formula ([1 − n]PGMAx + nPAMAy)–PHPMAz can be synthesised by optimising: (i) the mean degree of polymerisation (DP, or x) of the PGMA block, (ii) the PHPMA core-forming DP (or z); (iii) the mol fraction (n) of the PAMA stabiliser; and (iv) the copolymer concentration. These spheres, worms and vesicles are both cationic at low pH and colloidally stable at high pH. Furthermore, deprotonation of the protonated primary amine groups on the PAMA stabiliser chains at high pH renders these particles susceptible to epoxy-amine conjugation. This is demonstrated by the reaction between the primary amine groups on (0.8PGMA101 + 0.2PAMA96)–PHPMA1000 diblock copolymer spheres, and epoxide-functionalised diblock copolymer nanoparticles in aqueous solution at pH 8.

Graphical abstract: Cationic and reactive primary amine-stabilised nanoparticles via RAFT aqueous dispersion polymerisation

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Publication details

The article was received on 30 Sep 2015, accepted on 31 Oct 2015 and first published on 02 Nov 2015


Article type: Paper
DOI: 10.1039/C5PY01577D
Citation: Polym. Chem., 2016,7, 384-393
  • Open access: Creative Commons BY license
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    Cationic and reactive primary amine-stabilised nanoparticles via RAFT aqueous dispersion polymerisation

    M. Williams, N. J. W. Penfold and S. P. Armes, Polym. Chem., 2016, 7, 384
    DOI: 10.1039/C5PY01577D

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