Molecular Stereocomplexation for Enhancing the Stability of Nanoparticles Encapsulated in Polymeric Micelles for Magnetic Resonance Imaging

A generalizable approach for improving the stability of polylactide-based (PLA-based) micelles for encapsulating nanoparticles (NPs) is demonstrated, using stereocomplexation between a pair of poly (ethylene glycol)-b-poly(d-lactide)/poly(ethylene glycol)-b-poly(l-lactide) block copolymer blends. Three different superparamagnetic ferrite-based NPs with distinct nanostructures are first prepared by the high-temperature pyrolysis method, including spherical MnFe2O4, cubic MnFe2O4, and core-shell MnFe2O4@Fe3O4. The diameters of these NPs are approximately 7-10 nm as revealed by transmission electron microscopy. These hydrophobic NPs can be encapsulated within self-assembled, stereocomplexed PLA (sc-PLA) micelles. All sc-PLA micelle systems loaded with three different NPs exhibit enhanced stability at elevated temperatures (20-60 °C) and with extended storage time (∼96 h) compared with analogous samples without stereocomplex formation, confirmed by dynamic light scattering measurements. The magnetic NP-loaded micelles with mean diameters of approximately 150 nm show both biocompatibility and superparamagnetic property. Under a 1.5 T magnetic field, cubic MnFe2O4 (c-MnFe2O4)-loaded micelles exhibit an excellent negative contrast enhancement of MR signals (373 mM-1·s-1), while core-shell MnFe2O4@Fe3O4-loaded micelles show a slightly lower signal for MR imaging (275 mM-1·s-1). These results suggest the potential of using sc-PLA-based polymer micelles as universal carriers for magnetic resonance imaging contrast agents with improved stability for different applications such as cancer diagnosis.