Hyperthermia of Magnetically Soft-Soft Core-Shell Ferrite Nanoparticles.

Magnetically soft-soft MnFe2O4-Fe3O4 core-shell nanoparticles were synthesized through a seed-mediated method using the organometallic decomposition of metal acetyl acetonates. Two sets of core-shell nanoparticles (S1 and S2) of similar core sizes of 5.0 nm and different shell thicknesses (4.1 nm for S1 and 5.7 nm for S2) were obtained by changing the number of nucleating sites. Magnetic measurements were conducted on the nanoparticles at low and room temperatures to study the shell thickness and temperature dependence of the magnetic properties. Interestingly, both core-shell nanoparticles showed similar saturation magnetization, revealing the ineffective role of the shell thickness. In addition, the coercivity in both samples displayed similar temperature dependencies and magnitudes. Signatures of spin glass (SG) like behavior were observed from the field-cooled temperature-dependent magnetization measurements. It was suggested to be due to interface spin freezing. We observed a slight and non-monotonic temperature-dependent exchange bias in both samples with slightly higher values for S2. The effective magnetic anisotropy constant was calculated to be slightly larger in S2 than that in S1. The magnetothermal efficiency of the chitosan-coated nanoparticles was determined by measuring the specific absorption rate (SAR) under an alternating magnetic field (AMF) at 200-350 G field strengths and frequencies (495.25-167.30 kHz). The S2 nanoparticles displayed larger SAR values than the S1 nanoparticles at all field parameters. A maximum SAR value of 356.5 W/g was obtained for S2 at 495.25 kHz and 350 G for the 1 mg/mL nanoparticle concentration of ferrogel. We attributed this behavior to the larger interface SG regions in S2, which mediated the interaction between the core and shell and thus provided indirect exchange coupling between the core and shell phases. The SAR values of the core-shell nanoparticles roughly agreed with the predictions of the linear response theory. The concentration of the nanoparticles was found to affect heat conversion to a great extent. The in vitro treatment of the MDA-MB-231 human breast cancer cell line and HT-29 human colorectal cancer cell was conducted at selected frequencies and field strengths to evaluate the efficiency of the nanoparticles in killing cancer cells. The cellular cytotoxicity was estimated using flow cytometry and an MTT assay at 0 and 24 h after treatment with the AMF. The cells subjected to a 45 min treatment of the AMF (384.50 kHz and 350 G) showed a remarkable decrease in cell viability. The enhanced SAR values of the core-shell nanoparticles compared to the seeds with the most enhancement in S2 is an indication of the potential for tailoring nanoparticle structures and hence their magnetic properties for effective heat generation.

Origin of Ferromagnetism and Magnetic Anisotropy in a Family of Copper(II) Triangles.

Previously reported ferromagnetic triangles (NnBu4 )2 [Cu3 (µ3 -Cl)2 (µ-4-NO2 -pz)3 Cl3 ] (1), (PPN)2 [Cu3 (µ3 -Cl)2 (µ-pz)3 Cl3 ] (2), (bmim)2 [Cu3 (µ3 -Cl)2 (µ-pz)3 Cl3 ] (3) and newly reported (PPh4 )2 [Cu3 (µ3 -Cl)2 (µ-4-Ph-pz)3 Cl3 ] (4) were studied by magnetic susceptometry, electron paramagnetic resonance (EPR) spectroscopy and ab initio calculations to assess the origins of their ferromagnetism and of the magnetic anisotropy of their ground S=3/2 state (PPN+ =bis(triphenylphosphine)iminium, bmim+ =1-butyl-3-methylbenzimidazolium, pz- =pyrazolate). Ab initio studies revealed the d z 2 character of the magnetic orbitals of the compressed trigonal bipyramidal copper(II) ions. Ferromagnetic interactions were attributed to weak orbital overlap via the pyrazolate bridges. From the wavefunctions expansions, the ratios of the magnetic couplings were determined, which were indeterminate by magnetic susceptometry. Single-crystal EPR studies of 1 were carried out to extend the spin Hamiltonian with terms which induce zero-field splitting (zfs), namely dipolar interactions, anisotropic exchange and Dzyaloshinskii-Moriya interactions (DMI). The data were treated through both a giant-spin model and through a multispin exchange-coupled model. The latter indicated that ≈62 % of the zfs is due to anisotropic and ≈38 % due to dipolar interactions. The powder EPR data of all complexes were fitted to a simplified form of the multispin model and the anisotropic and dipolar contributions to the ground state zfs were estimated.

Probing the origin of magnetic anisotropy in a dinuclear {Mn(III)Cu(II)} single-molecule magnet: the role of exchange anisotropy.

Using ab initio calculations all the components of the magnetic anisotropy in a dinuclear [Mn(III)Cu(II)Cl(5-Br-sap)2(MeOH)] single-molecule magnet (SMM) have been computed. These calculations reveal that apart from the single-ion anisotropy, the exchange anisotropy also plays a crucial role in determining the sign as well as the magnitude of the cluster anisotropy. Developed magneto-structural correlations suggest that a large ferromagnetic exchange can in fact reduce the ground-state anisotropy, which is an integral component in the design of SMMs.

Tailoring Interfacial Exchange Anisotropy in Hard-Soft Core-Shell Ferrite Nanoparticles for Magnetic Hyperthermia Applications.

Magnetically hard-soft core-shell ferrite nanoparticles are synthesized using an organometallic decomposition method through seed-mediated growth. Two sets of core-shell nanoparticles (S1 and S2) with different shell (Fe3O4) thicknesses and similar core (CoFe2O4) sizes are obtained by varying the initial quantities of seed nanoparticles of size 6.0 ± 1.0 nm. The nanoparticles synthesized have average sizes of 9.5 ± 1.1 (S1) and 12.2 ± 1.7 (S2) nm with corresponding shell thicknesses of 3.5 and 6.1 nm. Magnetic properties are investigated under field-cooled and zero-field-cooled conditions at several temperatures and field cooling values. Magnetic heating efficiency for magnetic hyperthermia applications is investigated by measuring the specific absorption rate (SAR) in alternating magnetic fields at several field strengths and frequencies. The exchange bias is found to have a nonmonotonic and oscillatory relationship with temperature at all fields. SAR values of both core-shell samples are found to be considerably larger than that of the single-phase bare core particles. The effective anisotropy and SAR values are found to be larger in S2 than those in S1. However, the saturation magnetization displays the opposite behavior. These results are attributed to the occurrence of spin-glass regions at the core-shell interface of different amounts in the two samples. The novel outcome is that the interfacial exchange anisotropy of core-shell nanoparticles can be tailored to produce large effective magnetic anisotropy and thus large SAR values.

Anisotropic fluoride nanocrystals modulated by facet-specific passivation and their disordered surfaces.

Rutile-type fluorides have been proven to be active components in the context of emerging antiferr-omagnetic devices. However, controlled synthesis of low-dimensional, in particular two-dimensional (2D), fluorides in a predictable and deterministic manner remains unrealized because of a lack of efficient anisotropic control, which impedes their further development in reduced dimensions. We report here that altered passivation of {110} growing facets can direct the synthesis of rutile-type fluoride nanocrystals into well-defined zero-dimensional (0D) particulates, one-dimensional (1D) rods and 2D sheets in a colloidal approach. The obtained nanocrystals show positive exchange bias and enhanced magnetic transition temperature from the coexistence of long-range antiferromagnetic order and disordered surface spins, making them strong alternatives for flexible magnetic devices and sensors.