Investigation on NMR Relaxivity of Nano-Sized Cyano-Bridged Coordination Polymers

We present the first comparative investigation of the Nuclear Magnetic Resonance (NMR) relaxivity of a series of nanosized cyano-bridged coordination networks stabilized in aqueous solution. These Ln<sup>3+</sup>/[Fe­(CN)<sub>6</sub>]<sup>3‑</sup> (Ln = Gd, Tb, Y) and M<sup>2+</sup>/[Fe­(CN)<sub>6</sub>]<sup>3‑</sup> (M = Ni, Cu, Fe) nanoparticles with sizes ranging from 1.4 to 5.5 nm are stabilized by polyethylene glycols (MW = 400 or 1000), polyethylene glycol functionalized with amine groups (MW = 1500), or by N-acetyl-d-glucosamine. The evaluation of NMR relaxivity allowed estimation of the Magnetic Resonance Imaging (MRI) contrast efficiency of our systems. The results demonstrate that Gd<sup>3+</sup>/[Fe­(CN)<sub>6</sub>]<sup>3‑</sup> nanoparticles have <i>r</i><sub>1p</sub> and <i>r</i><sub>2p</sub> relaxivities about four times higher than the values observed in the same conditions for the commercial Contrast Agents (CAs) ProHance or Omniscan, regardless of the stabilizing agent used, while nanoparticles of Prussian blue and its analogues M<sup>2+</sup>/[Fe­(CN)<sub>6</sub>]<sup>3‑</sup> (M = Ni, Cu, Fe) present relatively modest values. The influence of the chemical composition of the nanoparticles, their crystal structure, spin values of lanthanide and transition metal ions, and stabilizing agent on the relaxivity values are investigated and discussed.