Daniela Tomasino1,Ruairi Brannigan2,Andreas Heise1
Royal College of Surgeon in Ireland1,Dublin City University2
Daniela Tomasino1,Ruairi Brannigan2,Andreas Heise1
Royal College of Surgeon in Ireland1,Dublin City University2
Polymerization-induced self-assembly (PISA) has emerged as a straightforward methodology for the <i>in situ</i> preparation of nano-objects with tuneable shape and dimensions.<sup>1,2</sup> Copper catalysed alkyne-azide cycloaddition (CuAAC) is a robust synthetic method with the aim of binding two molecular blocks together through heteroatom linkages (C-X-C).<sup>3</sup>The integration of the two techniques creates a facile strategy for the design of versatile nanoparticles.<br/>In this work, the combination of PISA and CuAAC allowed for the preparation and post-functionalization of NPs due to the incorporation of a propargylic moiety within the hydrophilic shell of the NPs. The NPs were prepared <i>via</i> aqueous dispersion single electron transfer living radical polymerization induced self-assembly (SET-LR-PISA). Poly(ethylene glycol methyl ether methacrylate)-<i>statistical</i>-poly(propargyl methacrylate) [P(PEGMA)]<sub>18</sub>-<i>s</i>-P(PgM)<sub>5</sub>] was obtained by conventional atom-transfer copolymerization (ATRP). The hydrophilic macroinitiator was then chain extended with 2-hydroxypropyl methacrylate (HPMA) <i>via</i> SET-LRP, which induced self-assembly, yielding [P(PEGMA)]<sub>18</sub>-<i>s</i>-P(PgM)<sub>5</sub>-<i>b</i>-[PHPMA] NPs. Fixing the mean molecular weight of [P(PEGMA)]<sub>18</sub>-<i>s</i>-P(PgM)<sub>5</sub>] to 6.2 kDa and varying HPMA DP, monomer conversion of the system was investigated <i>via</i> <sup>1</sup>H NMR and the stability was improved thanks to the addition of tetrabutyl ammonium salt during the reaction. The final diblock copolymer structure was analysed via <sup>1</sup>H NMR, GPC. The remaining copper concentration in the final product was assessed by inductively coupled plasma mass spectroscopy (ICP MS) analysis. After having characterized the NPs in terms of size and shape <i>via</i> dynamic light scattering (DLS) and transmission-electron microscopy (TEM), the corona was functionalized with various compounds <i>i.e.</i> fluorescein azide, methoxypolyethylen glycol azide, mannosyl derivatives; demonstrating that the system provides a unique platform for the preparation of biorelevant modifiable materials though ATRP type polymerisation.<br/><br/>1. Karagoz, B: Esser, L.; Duong, H. T.: Basuki, J. S.; Boyer, C.; Davis, T. P. Polym Chem. 2004, 5 (2), 350-355<br/>2. Blanazs, A.: Ryan, A. J.: Armes, S. P. Macromolecules 2012, 45 (12), 5099-5107<br/>3. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew Chem Int Ed Engl 2001, 40 (11), 2004-2021