A novel synthetic route for high-index faceted iron oxide concave nanocubes with high T(2) relaxivity for in vivo MRI applications.

Iron oxide nanoparticles (IONPs) with high-index facets have shown great potential as high performance T(2) contrast agents for MRI. Previous synthetic approaches focused mainly on ion-directed or oxidative etching methods. Herein, we report a new synthetic route for preparing high-index faceted iron oxide concave nanocubes using a bulky coordinating solvent. Through the systematic replacement of a non-coordinating solvent, 1-octadecene, with trioctylamine, the solvent interaction with the nanoparticle surface is modified, thereby, promoting the growth evolution of the IONPs from spherical to concave cubic morphology. The presence of the bulky trioctylamine solvent results in particle size increase and the formation of nanoparticles with enhanced shape anisotropy. A well-defined concave nanocube structure was evident from the early stages of particle growth, further confirming the important role of bulky coordinating solvents in nanoparticle structural development. The unique concave nanocube morphology has a direct influence on the magnetic properties of the IONPs, ultimately leading to an ultra-high T(2) relaxivity (862.2 mM(-1) s(-1)), and a 2-fold enhancement in T(2)(*)-weighted in vivo MRI contrast compared to spherical IONP analogs.