Bunyamin Karagoz, Jonathan Yeow, Lars Esser, Shyam M. Prakash, Rhiannon P. Kuchel, Thomas P. Davis, Cyrille Boyer
We report a versatile synthetic method for the in situ self-assembly of magnetic-nanoparticle-functionalized polymeric nanomorphologies, including spherical micelles and rod-like and worm-like micelles and vesicles. Poly(oligoethylene glycol methacrylate)-block-(methacrylic acid)-block-poly(styrene) (POEGMA-b-PMAA-b-PST) triblock copolymer chains were simultaneously propagated and self-assembled via a polymerization-induced self-assembly (PISA) approach. Subsequently, the carboxylic acid groups in the copolymers were used to complex an iron ion (FeII/FeIII) mixture. Iron oxide nanoparticles were then formed in the central block, within the polymeric nanoparticles, via alkaline coprecipitation of the iron(II) and (III) salts. Nanoparticle morphologies, particle sizes, molecular weights, and chemical structures were then characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), size exclusion chromatography (SEC), and 1H NMR measurements. TEM micrographs showed that the average size of the magnetic nanoparticles was 7 nm at the hydrophobic/hydrophilic nexus contained within the nanoparticles. In addition, XRD was used to confirm the formation of iron oxide nanoparticles. Importantly, the polymeric nanoparticle morphologies were not affected by the coprecipitation of the magnetic nanoparticles. The hybrid nanoparticles were then evaluated as negative MRI contrast agents, displaying remarkably high transverse relaxivities (r2, greater than 550 mM1 s1 at 9.4 T); a result, that we hypothesize, ensues from iron oxide nanoparticle clustering at the hydrophobichydrophilic interface. This simple synthetic procedure is highly versatile and produces nanocarriers of tunable size and shape with high efficacy as MRI contrast agents and potential utility as theranostic delivery vectors.