Marcelo Henrique Sousa

Effect of magnetic dipolar interactions on nanoparticle heating efficiency: Implications for cancer hyperthermia

Nanostructured magnetic systems have many applications, including potential use in cancer therapy deriving from their ability to heat in alternating magnetic fields. In this work we explore the influence of particle chain formation on the normalized heating properties, or specific loss power (SLP) of both low- (spherical) and high- (parallelepiped) anisotropy ferrite-based magnetic fluids. Analysis of ferromagnetic resonance (FMR) data shows that high particle concentrations correlate with increasing chain length producing decreasing SLP. Monte Carlo simulations corroborate the FMR results. We propose a theoretical model describing dipole interactions valid for the linear response regime to explain the observed trends. This model predicts optimum particle sizes for hyperthermia to about 30% smaller than those previously predicted, depending on the nanoparticle parameters and chain size. Also, optimum chain lengths depended on nanoparticle surface-to-surface distance. Our results might have important implications to cancer treatment and could motivate new strategies to optimize magnetic hyperthermia.

Use of Raman micro-spectroscopy in the characterization of MIIFe2O4 (M = Fe, Zn) electric double layer ferrofluids

MIIFe2O4 (M = Fe, Zn) electric double layer ferrofluids (edl-ferrofluids) were investigated and characterized by Raman micro-spectroscopy as solids (powder) or in solution forming magnetic fluids. The Raman spectra showed that the nanoparticles forming the magnetic fluids have different compositions depending on the MII ion used in their preparation. In the case of FeFe2O4 edl-ferrofluid, maghemite, magnetite, an amorphous non-stoichiometric oxyhydroxide [FeOx(OH)3 − 2x, x<1] and Fe(OH)3 phases are present. In the case of the ZnFe2O4 edl-ferrofluid, a magnetite-like structure where the FeII centers were replaced by the ZnII ions is present. A model of the distribution of the different chemical phases on the nanoparticles is presented. The Raman spectrum of the FeFe2O4 edl-ferrofluid excited close to an absorption band of the sample at 650 nm presents several Raman features above 900 cm−1 that are not observed for the ZnFe2O4 edl-ferrofluid sample. These results have been interpreted considering the resonant excitation of the density of phonon states with k ≠ 0 due to quantum size effects. Copyright

Fabrication of glycine-functionalized maghemite nanoparticles for magnetic removal of copper from wastewater

Maghemite nanoparticles (MNPs) were functionalized with glycine, by a cost-effective and environmentally friendly procedure, as an alternative route to typical amine-functionalized polymeric coatings, for highly efficient removal of copper ions from water. MNPs were synthesized by co-precipitation method and adsorption of glycine was investigated as a function of ligand concentration and pH. The efficiency of these functionalized nanoparticles for removal of Cu(2+) from water has been explored and showed that adsorption is highly dependent of pH and that it occurs either by forming chelate complexes and/or by electrostatic interaction. The adsorption process, which reaches equilibrium in few minutes and fits a pseudo second-order model, follows the Langmuir adsorption model with a very high maximum adsorption capacity for Cu(2+) of 625mg/g. Furthermore, these nanoadsorbents can be used as highly efficient separable and reusable materials for removal of toxic metal ions.

Low temperature experimental investigation of finite-size and surface effects in CuFe 2 O 4 nanoparticles of ferrofluids

Abstract Size sorted magnetic nanoparticles based on copper ferrite have been chemically synthesized. Their magnetic properties have been investigated at low temperature using Mossbauer spectroscopy and magnetisation measurements. The thermal variation of the magnetization is strongly affected by finite size and surface effects. Indeed, the Mossbauer results show that the structure of the nanoparticles is made of a monodomain ordered core and a surface shell of disordered spins. Introduction Magnetic ferrite nanoparticles have been studied for the last decades from both scientific and technological point of view [1]. They are largely used as components in recording tape, flexible disc recording media, magnetic fluids as well as biomedical material. These applications require the knowledge of the properties of nanostructured systems and how bulk properties are modified as the crystal size decreases to the nanometric range [2]. As an example, in γ-Fe 2

Raman spectroscopy as a powerful technique in the characterization of ferrofluids

Raman spectroscopy has been used to get some insight into the chemical composition and structure of magnetic fluids based on ferrites. The inner as well as the surface structure of Fe-maghemite and Zn-maghemite have characterized by Raman spectroscopy. It has been shown that different chemical species are present on the maghemite surface by changing the laser excitation energy. Maghemites modified by the adsorption of aspartic and glutamic acids as well as those modified by the adsorption of methylene blue(MB) have also been investigated by Raman spectroscopy. It has been shown that while FTIR (Fourier transform infrared) spectroscopy gives almost no information regarding to the surface species, Raman spectroscopy in and off resonance gives suitable information regarding to the adsorbate structure and bonding. The Raman spectroscopy study of the modified maghemites have shown that the organic acids adsorb on the maghemite surfarce as glutamate and aspartate chemically bounded to Fe(III) ions on the maghemite surface, and that MB, a cation, adsorbs on the maghemite surface as a monomer by ion pair formation with coadsorbed nitrate.

Magnetic ionic liquids produced by the dispersion of magnetic nanoparticles in 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2).

̀This paper reports on the advancement of magnetic ionic liquids (MILs) as stable dispersions of surface-modified γ-Fe(2)O(3), Fe(3)O(4), and CoFe(2)O(4) magnetic nanoparticles (MNPs) in a hydrophobic ionic liquid, 1-n-butyl 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf(2)). The MNPs were obtained via coprecipitation and were characterized using powder X-ray diffraction, transmission electron microscopy, Raman spectroscopy and Fourier transform near-infrared (FT-NIR) spectroscopy, and magnetic measurements. The surface-modified MNPs (SM-MNPs) were obtained via the silanization of the MNPs with the aid of 1-butyl-3-[3-(trimethoxysilyl)propyl]imidazolium chloride (BMSPI.Cl). The SM-MNPs were characterized by Raman spectroscopy and Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy and by magnetic measurements. The FTIR-ATR spectra of the SM-MNPs exhibited characteristic absorptions of the imidazolium and those of the Fe-O-Si-C moieties, confirming the presence of BMSPI.Cl on the MNP surface. Thermogravimetric analysis (TGA) showed that the SM-MNPs were modified by at least one BMSPI.Cl monolayer. The MILs were characterized using Raman spectroscopy, differential scanning calorimetry (DSC), and magnetic measurements. The Raman and DSC results indicated an interaction between the SM-MNPs and the IL. This interaction promotes the formation of a supramolecular structure close to the MNP surface that mimics the IL structure and is responsible for the stability of the MIL. Magnetic measurements of the MILs indicated no hysteresis. Superparamagnetic behavior and a saturation magnetization of ~22 emu/g could be inferred from the magnetic measurements of a sample containing 50% w/w γ-Fe(2)O(3) SM-MNP/BMI.NTf(2).

Citrate-capped iron oxide nanoparticles impair the osteogenic differentiation potential of rat mesenchymal stem cells

Surface modification of iron oxide nanoparticles may cause unexpected impact upon interaction with cells, such as cytotoxicity and change in the differentiation potential of stem cells. In this study, two kinds of iron oxide nanoparticles with different surface chemistries, i.e. one in its pristine form (P-NPs) without extra capping molecules and the other coated with citrate (C-NPs), and with similar sizes, ∼10 nm, as measured by transmission electron microscopy and X-ray diffractometry, were prepared. Both P-NPs and C-NPs aggregated to some extent in water, with hydrodynamic diameters of 211.4 ± 29 and 128.6 ± 6.3 nm, and surface zeta potential values of +23.5 ± 0.3 and -49.6 ± 0.5 mV, respectively. However, both NPs further aggregated to a similar extent with hydrodynamic diameters of 260 ± 5.5 and 214 ± 6.4 nm and with a slightly negative surface charge (∼-10 mV) in cell differentiation media. After being incubated with rat mesenchymal stem cells (MSCs) for 14 d, both types of NPs showed similar cell uptake kinetics and final intracellular iron content, i.e. 53.3 pg per cell for P-NPs and 59.9 pg per cell for C-NPs, and minimal cytotoxicity at a concentration below 100 μg mL-1. The adipogenic differentiation potential of MSCs was unaltered regardless of the NP types, and the P-NPs did not have an obvious impact on the osteogenic differentiation potential of MSCs. The osteogenic differentiation potential of the MSCs, however, was significantly impaired by incubation with the C-NPs, as evidenced by significantly reduced expression of osteogenic markers, namely collagen type I (COL) and osteocalcin (OCN) and calcium deposition. The uptake of C-NPs and surface-anchored citrate molecules were found to have a synergistic effect.

Static magneto optical birefringence of new Electric Double Layered Magnetic Fluids

Magnetic birefringence measurements are performed under a static field on Electric Double Layered Magnetic Fluids based on copper and zinc ferrite nanostructures. The optical birefringence is related to a single-particle effect and well described by a Langevin model which includes a log- normal distribution of particles. By the field-induced birefringence level, these new magnetic fluids are comparable to usual ones, a result which could offer a new way for biological applications.

Manganese ferrite-based nanoparticles induce ex vivo, but not in vivo, cardiovascular effects

Magnetic nanoparticles (MNPs) have been used for various biomedical applications. Importantly, manganese ferrite-based nanoparticles have useful magnetic resonance imaging characteristics and potential for hyperthermia treatment, but their effects in the cardiovascular system are poorly reported. Thus, the objectives of this study were to determine the cardiovascular effects of three different types of manganese ferrite-based magnetic nanoparticles: citrate-coated (CiMNPs); tripolyphosphate-coated (PhMNPs); and bare magnetic nanoparticles (BaMNPs). The samples were characterized by vibrating sample magnetometer, X-ray diffraction, dynamic light scattering, and transmission electron microscopy. The direct effects of the MNPs on cardiac contractility were evaluated in isolated perfused rat hearts. The CiMNPs, but not PhMNPs and BaMNPs, induced a transient decrease in the left ventricular end-systolic pressure. The PhMNPs and BaMNPs, but not CiMNPs, induced an increase in left ventricular end-diastolic pressure, which resulted in a decrease in a left ventricular end developed pressure. Indeed, PhMNPs and BaMNPs also caused a decrease in the maximal rate of left ventricular pressure rise (+dP/dt) and maximal rate of left ventricular pressure decline (−dP/dt). The three MNPs studied induced an increase in the perfusion pressure of isolated hearts. BaMNPs, but not PhMNPs or CiMNPs, induced a slight vasorelaxant effect in the isolated aortic rings. None of the MNPs were able to change heart rate or arterial blood pressure in conscious rats. In summary, although the MNPs were able to induce effects ex vivo, no significant changes were observed in vivo. Thus, given the proper dosages, these MNPs should be considered for possible therapeutic applications.

Cadmium and Tin Magnetic Nanocatalysts Useful for Biodiesel Production

Nanoparticulas magneticas compostas por oxidos mistos de ferro/cadmio (ICdO) e ferro/ estanho (ISnO) foram usadas como catalisadores em reacoes relevantes para diferentes tecnologias de producao de biodiesel. Estes compostos foram ativos para hidrolise e transesterificacao de oleo de soja, bem como para a esterificacao de acidos graxos obtidos a partir do oleo de soja. Na esterificacao mediada por ISnO foram alcancados altos rendimentos, ca. 84%, apos 1 h de reacao a 200 oC. O oxido foi recuperado magneticamente e reutilizado quatro vezes sem perda da sua atividade catalitica, enquanto que uma perda significativa foi observada quando ICdO foi usado. ISnO demonstrou tambem atividade para a producao de biodiesel a partir de oleo de macauba, um substrato altamente acido.