Controlled Clustering of Superparamagnetic Nanoparticles Using Block Copolymers: Design of New Contrast Agents for Magnetic Resonance Imaging

Abstract

When polyelectrolyte-neutral block copolymers are mixed in aqueous solutions with oppositely charged species, stable complexes are found to form spontaneously. The mechanism is based on electrostatics and on the compensation between the opposite charges. Electrostatic complexes exhibit a core−shell microstructure. In the core, the polyelectrolyte blocks and the oppositely charged species are tightly bound and form a dense coacervate microphase. The shell is made of the neutral chains and surrounds the core. In this paper, we report on the structural and magnetic properties of such complexes made from 6.3 nm diameter superparamagnetic nanoparticles (maghemite γ-Fe₂O₃) and cationic-neutral copolymers. The copolymers investigated are poly(trimethylammonium ethylacrylate methyl sulfate)-b-poly(acrylamide), with molecular weights 5000-b-30000 g mol^-1 and 110000-b-30000 g mol^-1. The mixed copolymer−nanoparticle aggregates were characterized by a combination of light scattering and cryo-transmission electron microscopy. Their hydrodynamic diameters were found in the range 70−150 nm, and their aggregation numbers (number of nanoparticles per aggregate) from tens to hundreds. In addition, Magnetic Resonance Spin−Echo measurements show that the complexes have a better contrast in Magnetic Resonance Imaging than single nanoparticles and that these complexes could be used for biomedical applications.