Towards the design of contrast-enhanced agents: systematic Ga3+ doping on magnetite nanoparticles.

The main objective of the preparation of the Fe3-xGaxO4 (0.14 ≤ x ≤ 1.35) system was to further the knowledge of the magnetic response of Ga3+-doped magnetite for application as MRI contrast agents. With this purpose, monodisperse nanoparticles between 7 and 10 nm with different amounts of gallium were prepared from an optimized protocol based on thermal decomposition of metallo-organic precursors. Thorough characterization of the sample was conducted in order to understand the influence of gallium doping on the structural, morphological and magnetic properties of the Fe3-xGaxO4 system. X-ray diffraction and X-ray absorption near-edge structure measurements have proved the progressive incorporation of Ga in the spinel structure, with different occupations in both tetrahedral and octahedral sites. Magnetization measurements as a function of field temperature have shown a clear dependence of magnetic saturation on the gallium content, reaching an Ms value of 110 Am2 kg-1 at 5 K for x = 0.14 (significantly higher than bulk magnetite) and considerably decreasing for amounts above x = 0.57 of gallium. For this reason, nanoparticles with moderate Ga quantities were water-transferred by coating them with the amphiphilic polymer PMAO to further analyse their biomedical potential. Cytotoxicity assays have demonstrated that Fe3-xGaxO4@PMAO formulations with x ≤ 0.57, which are the ones with better magnetic response, are not toxic for cells. Finally, the effect of gallium doping on relaxivities has been analysed by measuring longitudinal (T1-1) and transverse (T1-1) proton relaxation rates at 1.4 T revealing that nanoparticles with x = 0.14 Ga3+ content present remarkable T2 contrast and the nanoparticles with x = 0.26 have great potential to act as dual T1-T2 contrast agents.

Investigating the Size and Microstrain Influence in the Magnetic Order/Disorder State of GdCu2 Nanoparticles.

A series of GdCu 2 nanoparticles with controlled sizes ranging from 7 nm to 40 nm has been produced via high-energy inert-gas ball milling. Rietveld refinements on the X-ray diffraction measurements ensure that the bulk crystalline I m m a structure is retained within the nanoparticles, thanks to the employed low milling times ranging from t = 0.5 to t = 5 h. The analysis of the magnetic measurements shows a crossover from Superantiferromagnetism (SAF) to a Super Spin Glass state as the size decreases at NP size of 〈 D 〉 ≈ 18 nm. The microstrain contribution, which is always kept below 1%, together with the increasing surface-to-core ratio of the magnetic moments, trigger the magnetic disorder. Additionally, an extra contribution to the magnetic disorder is revealed within the SAF state, as the oscillating RKKY indirect exchange achieves to couple with the aforementioned contribution that emerges from the size reduction. The combination of both sources of disorder leads to a maximised frustration for 〈 D 〉 ≈ 25 nm sized NPs.

Magnetization reversal in circular vortex dots of small radius.

We present a detailed study of the magnetic behavior of Permalloy (Ni80Fe20 alloy) circular nanodots with small radii (30 nm and 70 nm) and different thicknesses (30 nm or 50 nm). Despite the small size of the dots, the measured hysteresis loops manifestly display the features of classical vortex behavior with zero remanence and lobes at high magnetic fields. This is remarkable because the size of the magnetic vortex core is comparable to the dot diameter, as revealed by magnetic force microscopy and micromagnetic simulations. The dot ground states are close to the border of the vortex stability and, depending on the dot size, the magnetization distribution combines attributes of the typical vortex, single domain states or even presents features resembling magnetic skyrmions. An analytical model of the dot magnetization reversal, accounting for the large vortex core size, is developed to explain the observed behavior, providing a rather good agreement with the experimental results. The study extends the understanding of magnetic nanodots beyond the classical vortex concept (where the vortex core spins have a negligible influence on the magnetic behavior) and can therefore be useful for improving emerging spintronic applications, such as spin-torque nano-oscillators. It also delimits the feasibility of producing a well-defined vortex configuration in sub-100 nm dots, enabling the intracellular magneto-mechanical actuation for biomedical applications.

Breakdown of magnetism in sub-nanometric Ni clusters embedded in Ag.

Downsizing to the nanoscale has opened up a spectrum of new magnetic phenomena yet to be discovered. In this context, we investigate the magnetic properties of Ni clusters embedded in a metallic Ag matrix. Unlike in Ni free-standing clusters, where the magnetic moment increases towards the atomic value when decreasing the cluster size, we show, by tuning the Ni cluster size down to the sub-nanoscale, that there is a size limit below which the clusters become non-magnetic when embedded in Ag. To this end, we have fabricated by DC-sputtering a system composed of sub-nanometer sized and non interacting Ni clusters embedded into a Ag matrix. A thorough experimental characterization by means of structural techniques (x-ray diffraction, x-ray absorption spectroscopy) and DC-magnetization confirms that the cluster size is in the sub-nanometric range and shows that the magnetization of the system is dramatically reduced, reaching only 38% of the bulk value. The experimental system has been reproduced by density functional theory calculations on Ni m clusters (m = 1-6, 10 and 13) embedded in Ag. The combination of the experimental and theoretical analysis points out that there is a breakdown of magnetism occurring below a cluster size of six atoms. According to our results, the loss of magnetic moment is not due to Ag-Ni hybridization but to charge transfer between the Ni sp and d orbitals, and the reduced magnetization observed experimentally is explained on the basis of the presence of a narrow cluster size-distribution where magnetic and non-magnetic clusters coexist.