Impact of metallic trace elements on relaxivities of iron-oxide contrast agents

In this work, well-defined 3 nm-sized Ca²⁺, Fe³⁺, Na⁺, Mg²⁺, Zn²⁺, Ni²⁺, Co²⁺, and Cd²⁺ cation-adsorbed Fe₃O₄/γ-Fe₂O₃ nanoparticles were used as prototype systems to investigate the influence of metallic trace elements in body fluids on the relaxivities of iron-oxide contrast agents. It was found that surface-adsorbed cations formed a deterioration layer to induce pronounced relaxivity loss. Theoretical study showed that such relaxivity loss can be well described by a modified GCAS function, taking into account the harmonic cation oscillations around Fe₃O₄/γ-Fe₂O₃ nanoparticles. Quantum mechanics analyses revealed that even-parity and odd-parity states of harmonic oscillations are dominant in r ₁ and r ₂ relaxivities, respectively. Moreover, the harmonic oscillations of Na⁺ and Mg²⁺ cations around Fe₃O₄/γ-Fe₂O₃ nanoparticles are found to be classical forbidden, which are quite different from their counterparts located in the classical permissive area.