Magnetic particle spectroscopy and magnetic particle imaging of zinc and cobalt ferrite nanoparticles: Distinct relaxation mechanisms

Magnetic particle imaging (MPI) is an emerging imaging method based on the nonlinear response of superparamagnetic tracers to a sinusoidal AC magnetic field. Higher harmonics obtained by the Fourier transform of acquired signals form a so-called magnetic particle spectrum, whereby straightforward evaluation of different nanoparticles as potential MPI tracers can be carried out. The shape of the spectra is largely dictated by the combined Néel and Brownian relaxation of superspins, whose relative contributions vary significantly depending on the tracer properties. The present study is focused on the comparison of several Zn ferrite and Co ferrite samples, selected for their different magnetic behaviors, together with the commercial tracer Resovist® (SH U 555 A). A new custom-made magnetic particle spectrometer and a commercial MPI system (Bruker) with comparable AC field amplitudes (∼14 mT) and frequencies (∼25 kHz) are used. Magnetic nanoparticles of Zn and Co ferrites have been synthesized by the thermal decomposition method and by the solvothermal/hydrothermal route, achieving four different samples of magnetic cores with the mean crystallite size in the range of 8–16 nm. From all of them, well-comparable silica-coated particles with a shell thickness of 5–6 nm have been prepared. To analyse the effect of the coating layer and hydrodynamic size, three additional samples have been supplemented: solvothermal Zn ferrite nanoparticles stabilized with a citrate monolayer, the same particles coated with 17 nm thick silica shell, and silica-coated Zn ferrite particles from the thermal decomposition with a higher degree of agglomeration. Fundamental characterizations of the nanomaterials by XRD, XRF, TEM, and DLS are followed by detailed investigations of their magnetic properties and structural peculiarities by SQUID magnetometry and ⁵⁷Fe Mössbauer spectroscopy. Magnetic particle spectroscopy and subsequent MPI study demonstrate: (i) superior properties of Zn ferrite nanoparticles compared to their Co ferrite counterparts, (ii) only negligible to weak effect of the type/thickness of the coating on signal of Zn ferrite nanoparticles, (iii) comparable performance of the solvothermal Zn ferrite particles with a thin silica shell and of the Resovist® tracer, and importantly, (iv) that suitable choice of the magnetic phase enables to separate the contributions of the Néel and Brownian relaxation on the timescale of MPI.