Large-Scale Synthesis of Ultrathin Manganese Oxide Nanoplates and Their Applications to T1 MRI Contrast Agents

Lamellar structured ultrathin manganese oxide nanoplates have been synthesized from thermal decomposition of manganese(II) acetylacetonate in the presence of 2,3-dihydroxynaphthalene, which promoted two-dimensional (2-D) growth by acting not only as a strongly binding surfactant but also as a structure-directing agent. Ultrathin manganese oxide nanoplates with a thickness of about 1 nm were assembled into a lamellar structure, and the width of the nanoplates could be controlled from 8 to 70 nm by using various coordinating solvents. X-ray absorption near-edge structure (XANES) spectra at the Mn K edge clearly showed that the nanoplates are mainly composed of Mn(II) species with octahedral symmetry. These hydrophobic manganese oxide nanoplates were ligand-exchanged with amine-terminated poly(ethyleneglycol) to generate water-dispersible nanoplates and applied to T1 contrast agents for magnetic resonance imaging (MRI). They exhibited a very high longitudinal relaxivity (r1) value of up to 5.5 mM–1s–1 derived from their high concentration of manganese ions exposed on the surface, and strong contrast enhancement of in vitro and in vivo MR images was observed with a very low dose.