Dr. Nicusor IACOB

The precise control of the magnetic compensation temperature (theta c) in ferrimagnetic garnets is essential for the development of cutting-edge ultrafast customizable spintronic devices. In this work we demonstrate how fine variation in stoichiometry and cation distribution in iron gadolinium garnets significanty influences theta c. Two samples of Gd3Fe5O112 garnets synthesized via a new hydrothermal method and a conventional solid-state reaction, respectively, were considered. The complex study was carried out using a complex approach combining X-ray diffraction, magnetometry, and M & ouml;ssbauer spectroscopy. Atomic-scale analysis revealed with unprecedent accuracy a cationic inversion between Fe3+ ang Gd3+ at octahedral and dodecahedral sites in both samples, and their chemical compositions were determined as Gd2.70Fe4.76O11.9 and Gd2.96Fe4.68O11.5, respectively. These local rearrangements have been shown to have a consistent influence on theta c (290 K and 317 K, respectively) around room temperature, emphasizing the high sensitivity of exchange interactions to internal atomic order. Results clearly illustrate the strong correlation between the processing, atomic configuration and macroscopic magnetic behavior, establishing a new paradigm for the design of garnet-based materials with tunable theta c. The strategy for the accurate determination of cation inversion illustrated in this work exhibits great potential in guiding material innovations for next-generation spintronics.

In recent decades, magnetic hyperthermia (MH) has gained considerable scientific interest in cancer treatment due to its ability to heat tumor tissues deeply localized inside the body. Functionalizing magnetic nanoparticles (MNPs) with vector molecules via specific organic molecules that coat the particle surface has enabled targeting particular tissues, thereby increasing the specificity of MH. MH relies on applying radiofrequency (RF) magnetic fields to a magnetic nanoparticle distribution injected in a tumor tissue. The RF field energy is converted into thermal energy through specific relaxation mechanisms and magnetic hysteresis-driven processes. This increases the tumor tissue temperature over the physiological threshold, triggering a series of cellular apoptosis processes. Additionally, the mechanical effects of low-frequency AC fields on anisotropic MNPs have been shown to be highly effective in disrupting the functional cellular components. From the macroscopic perspective, a crucial parameter measuring the efficiency of magnetic nanoparticle systems in MH is the specific absorption rate (SAR). This parameter is experimentally evaluated by different calorimetric and magnetic techniques and methodologies, which have specific drawbacks and may induce significant errors. From a microscopic perspective, MH relies on localized thermal and kinetic effects in the nanoparticle proximity environment. Studying MH at the cellular level has become a focused research topic in the last decade. In the context of these two perspectives, inevitable questions arise: could the thermal and kinetic effects exhibited at the cellular scale be linked by the macroscopic SAR parameter, or should we find new formulas for quantifying them? The present work offers a general perspective of MH, highlighting the experimental pitfalls encountered in SAR evaluation and motivating the necessity of standardizing the devices and protocols involved. It also discusses the challenges that arise in MH performance evaluation at the cellular level.

A methodology for the quantitative estimation of the drug loading of iron oxide-based magnetic nanoparticles by corroborating magnetometry and M & ouml;ssbauer spectroscopy investigations is reported. The proposed methodology is exemplified in the case of two series of nanoparticles, namely Fe3O4 nanoparticles covered with citric acid molecules and further functionalized with doxorubicin, and Fe3O4 nanoparticles covered with L-Cysteine molecules and further functionalized with doxorubicin. The general idea of the proposed methodology is to probe the real magnetic structure of the magnetic core via low-temperature M & ouml;ssbauer spectroscopy for the correct estimation of the spontaneous magnetization of the magnetic core. It subsequently uses the ratio between the spontaneous magnetization of the covered nanoparticles and that of the magnetic core for the reliable and nondestructive evaluation of the nanoparticle loading by organic molecules. Although the methodology is exemplified in the case of magnetite-based nanoparticles, it can be successfully considered for a large class of medicine-loaded Fe-containing magnetic nanoparticles where 57Fe M & ouml;ssbauer spectroscopy can be applied.

Although the DPPH (2,2-diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl) radical is known for its indefinite stability, both in solid and in solution, and therefore no dimerization reaction occurs, the DPPH-dimer has been obtained by an alternative synthesis. Oxidation of the DPPH-dimer led to the corresponding DPPH-diradical, practically exhibiting all of the known properties of the simple DPPH radical. The structures were confirmed using 1H and 13C NMR, IR, UV-vis, HR-MS, and electron spin resonance (for the diradical) analyses. Additionally, cyclic voltammetry and superconducting quantum interference device (SQUID) measurements were performed to investigate the electrochemical and magnetic properties of the DPPH-diradical. DFT calculations revealed that the ground state was an open-shell singlet. The diradical character y of the ground state and vertical S-T gap were 0.279 and -5.81 kcal mol-1, respectively.

Present work reports a systematic study on the evaluation of magnetic inhomogeneities in non-stoichiometric Mg0 & sdot;5Ca0 & sdot;5Fe2O4 nanoferrite (MCNF) by conducting exhaustive dc -magnetization, ac -susceptibility and Fe-57 Mossbauer spectroscopic measurements and exchange bias investigations using training protocol down to 6 K. Rietveld fitting to PXRD established the formation of anticipated spinel fcc phase of MCNF (non-stoichiometric) along with a minute impurity phase of calcite. Scherrer method and HRTEM micrographs illustrated broad size distribution of MCNF nanoparticles with an average nanocrystallite size of -15 nm. Combined 57Fe Mo center dot ssbauer spectroscopic and dc -magnetization analysis establishes coexistence of ferrimagnetic (67 %) & superparamagnetic (33 %) states at 300 K with notable M-s = 22 emu/g, M-r = 4 emu/g & H-c = 130 Oe and blocking of most of the nanoparticles of MCNF below 300 K. The coercivity followed the size -modified Kneller law for ferrimagnetic nanoparticles and the saturation magnetization abides the Bloch law. Moreover the frequencydependent ac -susceptibility investigations revealed two magnetic transitions: (i) A transition at - 330 K in the low frequency data attributed to the relaxation of blocked particles of bigger sizes under the superparamagnetic (SPM) regime and (ii) an irregularity at low temperatures is assigned to surface spin glass freezing. Surface spin glass freezing was further affirmed by the ageing experiments and dynamic scaling law. Furthermore, even the best fit to the dynamic scaling couldn't assert the existence of conventional spin glass phase due to slower spin -flip time of surface spins. A soft ferrimagnetic core of MCNF is enveloped with disordered surface spins, which manifest spin glass state. Concurrently, the findings of exchange bias at 30 K and training effect at 6 K affirmed that MCNF nanoparticles are presenting themselves as FM core- SG shell system. Our experimental findings suggested magnetic inhomogeneities comprised of superparamagnetism, ferrimagnetism and disordered surface spin glass state in the non-stoichiometric MCNF.

In the present work, we report the synthesis and investigations of La0.9K0.1MnO3 and La0.8K0.1Pb0.1MnO3 bulk samples which could be potential magnetocaloric materials for magnetic refrigeration close to room temperature. A flash combustion reaction and sintering at 1200 degrees C for 10 h are used to prepare the bulk materials. Both compounds crystallized into a rhombohedral structure with R3\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\overline{3 }$$\end{document}c space group confirmed by X-ray powder diffraction results. Scanning electron microscopy analysis, combined with XRD peak profiles is performed to estimate the particle/crystallite size of the samples. Moreover, the Curie temperature, TC, is found to be higher in lead-rich sample due to the enhancement of the grain size and the Mn3+-O-Mn4+ double exchange (DE) interaction. Therefore, the bulk sample La0.8K0.1Pb0.1MnO3 shows a room temperature phase transition of 289 K as well as a higher saturation magnetization. The La0.8K0.1Pb0.1MnO3 bulk compound exhibits a high and sharp peak in magnetic entropy change up to 5.5 Jkg-1 K-1 under 5 T at the magnetic transition temperature TC. To compare the magnetocaloric performances of the studied compounds, relative cooling power (RCP) was employed. The obtained experimental results revealed that the increase in particle size influences severely the magnetocaloric properties.

Fabrication and extensive characterization of hard-soft nanocomposites composed of hard magnetic low-temperature phase LTP-MnBi and amorphous Fe70Si10B20 soft magnetic phase for bulk magnets are reported. Samples with compositions Mn55Bi45 + x center dot(Fe70Si10B20) (x = 0, 3, 5, 10, 20 wt.%) were prepared by spark plasma sintering of powder mixtures. Characterization has been performed by X-ray diffraction, scanning and transmission electron microscopy, magnetometry and Fe-57 Mossbauer spectroscopy. It was shown that samples contain crystallized and nanometric LTP-MnBi phases with various elemental compositions depending on the degree of Bi clustering. Complex correlations between starting compositions, processes during fabrication, and functional magnetic characteristics were observed. Unexpected special situations of the relation between microstructure and magnetic coupling mechanisms are discovered. Exchange spring effects of different strengths occur, being very sensitive to morpho-structural and compositional features, which in turn are controlled by processing conditions. An in-depth analysis of related microscopic characteristics is provided. Results of this work suggest that fabrication by powder metallurgy routes, such as spark plasma sintering of hard and soft magnetic powder mixtures, of MnBi-based composites with exchange spring phenomena have a high potential in designing and optimization of suitable materials with tunable magnetic properties towards rare-earth-free permanent magnet applications.

We report on the Matrix Assisted Pulsed Laser Evaporation, laser technology for depositing biocompatible, antimicrobial, hydrophilic, and biodegradable complex hybrid polymeric system loaded with essential cypress-oil and magnetite nanoparticles as resorbable implants, capable of targeting possible hyperthermia applications, an anticancer moderate field heating therapy. Magnetite nanoparticles based on iron oxide (Fe3O4) coated with Cypress essential oil (denoted: Fe3O4- Cypress) and embedded in PLGA (poly(lactic-co-glycolic acid) (denoted: PLGA-Fe3O4- Cypress-) and PLGA - poly(3,4ethylene dioxythiophene) doped with poly(styrene sulfonate) anions) (PEDOT: PSS) mixture (denoted: PLGA-Fe3O4- Cypress- PEDOT: PSS) were used as MAPLE targets. The controlled drug delivery of the active Cypress oil, an antimicrobial therapeutic agent from Fe3O4- Cypress nanoparticles could be possible by applying an external radio frequency (RF) magnetic field. The Fe3O4-Cypress-based powders as well as the final hybrid coatings have been characterized in terms of stoichiometry, morphology, magnetic, antimicrobial properties, biocompatibility, and response to external physical stimuli. FTIR analyses confirmed the quasi-stoichiometric laser transfer of organic compounds while the XRD evidenced the semicrystalline structure of deposited thin films. SEM and AFM images evidence that conductive polymer addition led to the films' relief flattening and a decrease in the coatings' thickness and roughness by changing the polymeric packaging. The samples containing conductive polymer exhibited 3 times higher current and corrosion rate values. All coatings are hydrophilic and revealed enhanced cellular viability when cultured with osteoblast-like MG-63 cells. The composite structures exhibited significant antimicrobial activity against Gram-positive (Staphylococcus aureus), and Gram -negative (Escherichia coli ) bacteria, as well as to the opportunistic yeast Candida albicans.

Zn1-xFexO nanoparticles with the iron concentrations level in the dilute regime (x = 0.001---0.01) were produced by a sol-gel route from acetate precursors along with an un-doped and 3 at.% Fe-doped reference. The X-ray diffraction of the un-doped and 0.1-1 at.% Fe-doped samples reveal the reflections for only the ZnO wurtzite structure. Fe doping enhances the a-axis lattice constant, the unit cell volume and the microstrain. Iron doping reduces the average crystallite/particle size (confirmed by Scanning Electron Microscopy), improving the surface-to-volume ratio or the concentration of defective surface sites. XPS identifies the iron in both Fe3+ and Fe2+ states. XPS and Fe-57 Mossbauer spectroscopy indicate a broad distribution (distortion) of Fe3+ sites on the surface of ZnO nanoparticles. The blue shift and broadening of the UV emission, and quenching of defect-related photoluminescence in the Fe-doped samples verify the presence of iron in the ZnO lattice and surface intrinsic defects. 0.1-1 at.% Fe-doped ZnO show room temperature ferromagnetism, RTFM, characteristic of dilute magnetic semiconductors, DMS. The magnetization measurements with temperature evidence an antiferromagnetic alignment and an increase of ferromagnetic contribution with Fe doping up to 1 at.%. Zn0.97Fe0.3O reference is a superparamagnetic ZnO/ZnFe2O4 nanocomposite with a blocking temperature of 20 K; HRTEM shows (ultra)fine ZnFe2O4 particles at the surface of ZnO nanoparticles. The analysis of experimental data of 0.1-1 at.% Fe-doped ZnO was done in terms of iron coupling with intrinsic defects, which can generate surface Fe3+ states with geometries similar to the Fe3+ in inverse spinel ZnFe2O4. The superexchange interaction (resembling that in the inverse spinel ZnFe2O4) between the Fe3+ sites with distorted configuration resulting in ferrimagnetism was hypothesised as a possible mechanism of RTFM. Experimental (structural, local chemical, magnetic, optical) and interpretation results can be used to optimize the processing conditions for Fe-doped ZnO to serve as an effective DMS, e.g. for spintronic applications.

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe3O4-L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, Mossbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe3O4-L-Cys-Dox nanoparticles. Moreover, by means of a FO-SPR sensor, we evidenced and confirmed the binding of Dox to L-Cys. Biological tests on mouse (B16F10) and human (A375) metastatic melanoma cells evidenced the internalization of magnetic nanoparticles delivering Dox. Half maximum inhibitory concentration IC50 values of Fe3O4-L-Cys-Dox were determined for both cell lines: 4.26 mu g/mL for A375 and 2.74 mu g/mL for B16F10, as compared to 60.74 and 98.75 mu g/mL, respectively, for unloaded controls. Incubation of cells with Fe3O4-L-Cys-Dox modulated MAPK signaling pathway activity 3 h post-treatment and produced cell cycle arrest and increased apoptosis by 48 h. We show that within the first 2 h of incubation in physiological (pH = 7.4) media, similar to 10-15 mu M Dox/h was released from a 200 mu g/mL Fe3O4-L-Cys-Dox solution, as compared to double upon incubation in citrate solution (pH = 3), which resembles acidic environment conditions. Our results highlight the potential of Fe3O4-L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy.

The phosphate KCoCr-(PO4)(2) and iron-substitutedvariants KCoCr1-x Fe x (PO4)(2) (x =0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route,while a high substitution level of Fe was achieved. Their structureswere refined using powder X-ray diffraction and indexed in a monoclinicsystem with a P2(1)/n spacegroup. A 3D framework with six-sided tunnels parallel to the [101]direction was formed in which the K atoms are located. Mo''ssbauerspectroscopy confirms the exclusive presence of octahedral paramagneticFe(3+) ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopyconfirmed the presence of paramagnetic Cr3+ ions. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present higher ionic activity. Relative to the electrochemicalactivity of K, these materials could be good candidates for positiveand/or negative electrode materials for energy storage applications. The synthesized phosphate KCoCr-(PO4)(2) and Fe-substituted variants KCoCr1-x Fe x (PO4)(2) (x = 0.25, 0.5, and 0.75) present a 3D frameworkwith six-sided tunnels in which the K atoms are located. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present improved ionic activity, making these materials goodcandidates for positive and/or negative electrode materials for energystorage applications.

Novel (1-x) SrFe12O19 - x BNT-BT0.08 (x = 0; 0.5; 0.8; 1) nanocomposites were explored in this study. The samples were produced by sol-gel method and compacted by conventional sintering. The composition, morphology, local structure, dielectric and magnetic properties were investigated by X-ray diffraction, Transmission Electron Microscopy, Impedance Analysis, Mossbauer spectroscopy, and SQUID magnetometry. The desired composition and the presence of the magnetoplumbite SrFe12O19 and perovskite BNT-BT structures were verified by X-ray diffraction. Irregular morphology and large size distributions are evidenced in the electron microscopy micrographs. The reported room temperature dielectric constants in this study are the highest values obtained in multiferroic composites at room temperature: giant dielectric constants (similar to 1.3 x 10(6)) were obtained, relative to 0.13 x 10(4) in BNT-BT. The hyperfine parameters allowed the identification of the Wyckoff positions of the Fe ions corresponding closely to the theoretical case. The hard magnetic character of the SrFe12O19 phase is evidenced from the magnetic measurements. For the first time in multifermic composites, superdielectric characteristics are evidenced at room temperature.

AuxFe1-x nanophase thin films of different compositions and thicknesses were prepared by co-deposition magnetron sputtering. Complex morpho-structural and magnetic investigations of the films were performed by X-ray Diffraction, cross-section Transmission Electron Microscopy, Selected Area Electron Diffraction, Magneto Optical Kerr Effect, Superconducting Quantum Interference Device magnetometry and Conversion Electron Mossbauer Spectroscopy. It was proven that depending on the preparation conditions, different configurations of defect alpha-Fe magnetic clusters, i.e., randomly distributed or auto-assembled in lamellar or filiform configurations, can be formed in the Au matrix. A close relationship between the Fe clustering process and the type of the crystalline structure of the Au matrix was underlined, with the stabilization of a hexagonal phase at a composition close to 70 at. % of Au and at optimal thickness. Due to different types of inter-cluster magnetic interactions and spin anisotropies, different types of magnetic order from 2D Ising type to 3D Heisenberg type, as well as superparamagnetic behavior of non-interacting Fe clusters of similar average size, were evidenced.

Polycrystalline La(0.8)K(0.2-x)Pb(x)MnO3 (x = 0.05, 0.10, 0.15, 0.20) ceramics were successfully prepared by flash combustion route and their structural, morphological, magnetic and magnetocaloric properties were investi-gated. Structural analyses using X-ray diffraction reveal that all samples are crystallized in the rhombohedral structure and belong to R c space group. The increase of Pb doping does not modify the crystalline structure but changes the grain size and lattice parameters. X-ray photoelectron spectroscopy (XPS) fitting results of Mn 2p peaks confirmed the coexistence of Mn3+ and Mn4+ ions which contribute to the double exchange interactions improving the ferromagnetic order in the samples. The magnetization's temperature and magnetic field de-pendences indicate a second-order ferromagnetic-paramagnetic transition of the ceramics. A significant mag-netic entropy change near room temperature was observed for La0.8K0.1Pb0.1MnO3, showing considerable magnetocaloric properties. Furthermore, electron paramagnetic resonance spectroscopy (EPR) was also used to examine the ferromagnetic-paramagnetic transition.

Exchange coupling in a SrFe12O19 - Fe3O4 nanocomposite magnet was explored in this study. The composition, microstructure, local structure and magnetic properties were investigated by XRD, SEM, Mossbauer spectroscopy, and SQUID magnetometry. The magnetoplumbite SrFe12O19 and spinel Fe3O4 structures were verified by X-ray diffraction. The morphology of the composite reveals the characteristics of the two components. The hyperfine parameters allowed the identification of the Wyckoff positions of the iron ions corresponding to the involved phases. The magnetic measurements of the composite, showing a single-phase-like magnetic hysteresis loop, confirmed the exchange coupling between the hard and soft magnetic phases.

The manipulation of magnetic anisotropy represents the fundamental prerequisite for the application of magnetic materials. Here we present the vectorial magnetic properties of nanostructured systems and thin films of Fe and FeCo prepared on linearly trenched Mo templates with thermally controlled periodicity. The magnetic properties of the nanosystems are engineered by tuning the shape, size, thickness, and composition parameters of the thin films. Thus, we control coercivity, magnetization, orientation of the easy axis of magnetization, and the long-range magnetic order of the system in the function of the temperature. We distinguish magnetic components that emerge from the complex morpho-structural features of the undulating Fe or FeCo nanostructured films on trenched Mo templates: (i) assembly of magnetic nanowires and (ii) assembly of magnetic islands/clusters. Uniaxial anisotropy at room temperature was proven, characterized, and explained in the case of all systems. Our work contributes to the understanding of magnetic properties necessary for possible further applications of linear systems and undulated thin films.

Pure and Er-doped hematite (alpha-Fe2O3) nanorods were prepared by a two-step method involving hydrothermal synthesis and calcination of pure and Er-doped goethite (alpha-FeOOH) nanorods. Substitution of Fe3+ by Er3+ in the crystal structure of hematite caused morpho-structural changes such as expansion of the unit cell and gradual shortening and rounding of hematite nanorods towards formation of nanoellipsoids. These changes induced modification of magnetic and optical properties suggesting the possibility of a systematic control of physical properties via rare earth substitution. A decrease in the hyperfine magnetic field, coercive field and Morin transition temperature, as well as an increase of the magnetic susceptibility and a narrowing of the optical band gap were observed by substitution. Intimate mechanisms related to the formation of more and more defect-like hematite phases with decreased temperatures for the transition to the low temperature antiferromagnetic phase at increased doping level were evidenced via temperature dependent Mo center dot ssbauer spectroscopy.

The structural properties of VO2 thin films, grown on either LSAT or Si substrates by pulsed laser deposition (PLD), are elucidated by means of transmission electron microscopy (TEM) methods. The TEM observations confirmed the successful growth of VO2 by PLD in variable thicknesses, by optimizing the O-2 partial pressure and growth temperature. The films adopt a columnar polycrystalline morphology with narrow columns, up to the film thickness height. Four VO2 polymorphs have been detected by electron diffraction and high-resolution TEM (HRTEM) analysis, with M1 being by far the most abundant phase. Post-experimental strain measurements in HRTEM images have revealed that the actual residual strain is minimized due to the columnar morphology of the VO2 grains, as well as intrinsic oxide layers in the VO2/Si epitaxy. The TEM outcomes confirmed the complementary electrical and magnetic measurements in the films, where a transition from a monoclinic M1 to a rutile VO2 R phase has been identified, influenced by the initial percentage of phases in thick VO2 films.

MoO2-Fe2O3 nanoparticle systems were successfully synthesized by mechanochemical activation of MoO2 and alpha-Fe2O3 equimolar mixtures throughout 0-12 h of ball-milling. The role of the long-range ferromagnetism of MoO2 on a fraction of more defect hematite nanoparticles supporting a defect antiferromagnetic phase down to the lowest temperatures was investigated in this work. The structure and the size evolution of the nanoparticles were investigated by X-ray diffraction, whereas the magnetic properties were investigated by SQUID magnetometry. The local electronic structure and the specific phase evolution in the analyzed system versus the milling time were investigated by temperature-dependent Mossbauer spectroscopy. The substantially shifted magnetic hysteresis loops were interpreted in terms of the unidirectional anisotropy induced by pinning the long-range ferromagnetic order of the local net magnetic moments in the defect antiferromagnetic phase, as mediated by the diluted magnetic oxide phase of MoO2, to those less defect hematite nanoparticles supporting Morin transition. The specific evolutions of the exchange bias and of the coercive field versus temperature in the samples were interpreted in the frame of the specific phase evolution pointed out by Mossbauer spectroscopy. Depending on the milling time, a different fraction of defect hematite nanoparticles is formed. Less nanoparticles supporting the Morin transition are formed for samples exposed to a longer milling time, with a direct influence on the induced unidirectional anisotropy and related effects.

The present study aimed to assess the feasibility of developing low-cost multipurpose iron oxide/TiO2 nanocomposites (NCs) for use in combined antitumor therapies and water treatment applications. Larger size (approximate to 100 nm) iron oxide nanoparticles (IONPs) formed magnetic core-TiO2 shell structures at high Fe/Ti ratios and solid dispersions of IONPs embedded in TiO2 matrices when the Fe/Ti ratio was low. When the size of the iron phase was comparable to the size of the crystallized TiO2 nanoparticles (approximate to 10 nm), the obtained nanocomposites consisted of randomly mixed aggregates of TiO2 and IONPs. The best inductive heating and ROS photogeneration properties were shown by the NCs synthesized at 400 degrees C which contained the minimum amount of alpha-Fe2O3 and sufficiently crystallized anatase TiO2. Their cytocompatibility was assessed on cultured human and murine fibroblast cells and analyzed in relation to the adsorption of bovine serum albumin from the culture medium onto their surface. The tested nanocomposites showed excellent cytocompatibility to human fibroblast cells. The results also indicated that the environment (i.e. phosphate buffer or culture medium) used to disperse the nanomaterials prior to performing the viability tests can have a significant impact on their cytotoxicity.

Magnetite (Fe3O4) and ferrite (MFe2O4, M = Mn, Zn) hydrophobic magnetic nanoparticles with various shapes and sizes were synthesized by high-temperature reaction of organic precursor solutions. Spherical, cubic, hexagonal, and octahedral shapes and sizes ranging from 10 to 100 nm were obtained. It has been proven that the reported high capability of tailoring the shape and the size of the surface-coated nanoparticles allows controlling a variety of properties that are relevant to many potential applications. Structurally well-formed hydrophobic magnetic nanoparticles with high saturation magnetization values are reported. The hydrophobic oleic acid shell was successfully transformed by a simple and environmentally friendly oxidative scission method into azelaic acid. The morphostructural characteristics, size distributions, chemical composition, and magnetic properties of the resulting hydrophilic nanoparticles were investigated by electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, Mossbauer spectroscopy, superconducting quantum interference device, and vibrating sample magnetometry. Magnetic hyperthermia measurements have been performed in a specially designed sample holder placed in an inductor with copper windings assuring alternating magnetic fields of safely biological amplitude-frequency products. The optimal shape with a specific size range for nanoparticles dispersed in various carriers providing the best heating efficiency is reported.

Fe-Gd amorphous thin films of different compositions and thicknesses were analyzed with respect to their magnetic and magneto-optical behavior. By preparing samples with the same Fe/Gd elemental ratio at different thicknesses, and of various Fe/Gd ratios at constant thickness, respectively, we were able to show the influences of these two parameters on the interconnected behavior of the two magnetic sub-lattices, one of Fe and the other of Gd, which are antiferromagnetically coupled. Magneto-Optical Kerr Effect (MOKE) measurements revealed reversed hysteresis loops for sample compositions crossing the magnetic compensation point. Temperature dependent magnetization curves highlighted the variation of the overall net contribution of the two magnetic sub-lattices by changing either the Fe/Gd elemental ratio or the film thickness. Fe-57 Conversion Electron Mossbauer (CEM) spectra give additional support to the specific magnetic behavior evidenced by temperature and field dependent Superconducting Quantum Interference Device (SQUID) magnetometry.

Zn-Fe-O nanoparticle systems (Z3F, Z20F and Z60F) were produced by changing the Zn:Fe ratio (0.97 : 0.03, 0.8 : 0.2 and 0.4 : 0.6 in at%, respectively) in Zn(ii)-Fe(iii)-carboxylate precursors. According to X-ray diffraction, Z60F is nearly single-phase ZnFe2O4 (5.9 nm crystallite size), Z20F is a ZnO/ZnFe2O4 nanocomposite consisting of 48.8% ZnFe2O4 (4.7 nm crystallite size), and Z3F is apparently pure ZnO (9.5 nm). We found evidence for a ZnFe2O4 spinel of high inversion degree (80-100%) and with superparamagnetic (SPM) behaviour at room temperature in all three samples by a remarkable correlation between HRTEM, FTIR, XPS, Mossbauer and magnetization analyses. Iron modifies the decomposition process of the precursor and enhances its viscosity, which appears to favour the separation of Zn- and Fe-rich phases. As a consequence, two-phase systems of individual nanocrystals/nanoparticles (ZnO and ZnFe2O4) are formed. The large anisotropy constant, 10(6)-10(7) erg cm(-3), of the ZnFe2O4 nanoparticles and the concentration dependence of their magnetic energy barrier are explained in terms of interparticle interactions interlinked with finite size effects and high inversion degree; these factors also control the other parameters of importance for applications, including the blocking temperature (13-111 K), saturation magnetization (1.08-17.7 emu g(-1) at 300 K, 4.6-44.8 emu g(-1) at 5 K) and coercivity (85.4-491 Oe at 5 K). Magnetic dynamic results, particularly modelled by the Neel-Brown and Vogel-Fulcher laws, yield fitting parameters which validate the presence of concentration-dependent dipole-like interactions between ZnFe2O4 nanoparticles. A fraction of iron was found in the Fe2+ state, presumably substituting for Zn2+ in zinc oxide; however, the samples behave like ZnFe2O4 SPM nanoclusters/nanoparticles dispersed in a nonmagnetic ZnO particle assembly, rather than Zn(Fe)O dilute magnetic semiconductors. The relevance of the properties of the investigated material for specific applications is highlighted throughout the manuscript.

Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.

This paper describes for the first time two processing routes-the precursor method and the two-step wet chemical process-for the synthesis of magnetic cobalt ferrite using the Tamarindus indica fruit extract. These green approaches are eco-friendly, safe and efficient alternatives to classical chemical methods. The aqueous extract from tamarind fruit contains numerous metabolites (organic acids, aminoacids). All these bioactive components are able to chelate metal ions leading to the formation of the multimetallic complex (precursor of cobalt ferrite). The obtained precursor was characterized by Fourier transform infrared spectroscopy (FTIR), thermal analysis, X-ray diffraction analysis (XRD) and magnetic measurements. The structure, morphology and magnetic behavior of the cobalt ferrite samples prepared through both synthesis routes were investigated by various characterization techniques: FTIR, XRD, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), Mossbauer spectroscopy and magnetic measurements. XRD data confirmed that a cubic spinel structure was obtained for both ferrite powders with average crystallite size of 13 and 5 nm, respectively. The microstructure study by SEM revealed the formation of nanocrystallites assemblies using the precursor method and carbon-rich particles forming granulated micron-sized agglomerates, embedding ferrite nanocrystallites obtained through the two-step wet chemical process. Mossbauer spectroscopy results evidenced relaxation processes in the CoFe2O4 samples at room temperature, and the main characteristics of the involved sublattices were derived. The magnetic investigation revealed a typical magnetic behavior for a spinel, with CoFe2O4 nanoparticles ferrimagnetic at low temperature and superparamagnetic at room temperature.

Glasses from lithium-aluminum-zinc-boron-phosphorous oxide system co-doped with terbium (Tb3+) and dysprosium (Dy3+) oxides were studied for magneto-optical applications in lasers. The Fourier Transform Infrared and Raman Spectroscopy complementary analysis suggested the depolymerization of the borophosphate glass network by adding and increasing the rare-earth (RE) oxide content. Main UV-vis absorption maxima of Tb and Dy ions were identified at 348 and 1266 nm. Spectroscopic ellipsometry indicated a maximum refractive index of 1.56, at 400 nm, for the highest RE content. The Verdet constant amplified by increasing the RE content, reaching for the 9 mol% RE co-doped sample a value of -0.075 min/Oe/cm at 630 nm. The Faraday rotation angle was additionally confirmed by using a Faraday Cell Device, being also related to the specific paramagnetic behavior evidenced by Superconducting Quantum Interference Device magnetometry. The magneto-optical properties recommend such vitreous co-doped materials for magneto-optical devices.

A facile and cheap surfactant-assisted hydrothermal method was used to prepare mesoporous cobalt ferrite nanosystems with BET surface area up to 151 m(2)/g. These mesostructures with high BET surface areas and pore sizes are made from assemblies of nanoparticles (NPs) with average sizes between 7.8 and 9.6 nm depending on the initial pH conditions. The pH proved to be the key factor for controlling not only NP size, but also the phase purity and the porosity properties of the mesostructures. At pH values lower than 7, a parasite hematite phase begins to form. The sample obtained at pH = 7.3 has magnetization at saturation M-s = 38 emu/g at 300 K (54.3 emu/g at 10 K) and BET surface area S-BET = 151 m(2)/g, whereas the one obtained at pH = 8.3 has M-s = 68 emu/g at 300 K (83.6 emu/g at 10 K) and S-BET = 101 m(2)/g. The magnetic coercive field values at 10 K are high at up to 12,780 Oe, with a maximum coercive field reached for the sample obtained at pH = 8.3. Decreased magnetic performances are obtained at pH values higher than 9. The iron occupancies of the tetrahedral and octahedral sites belonging to the cobalt ferrite spinel structure were extracted through decomposition of the Mossbauer patterns in spectral components. The magnetic anisotropy constants of the investigated NPs were estimated from the temperature dependence of the hyperfine magnetic field. Taking into consideration the high values of BET surface area and the magnetic anisotropy constants as well as the significant magnetizations for saturation at ambient temperature, and the fact that all parameters can be adjusted through the initial pH conditions, these materials are very promising as recyclable anti-polluting agents, magnetically separable catalysts, and targeted drug delivery vehicles.

A complex investigation of the morpho-structural, magnetic, magneto-optical and magneto-transport properties of amorphous Fe-Gd thin films crossing the magnetization compensation point is reported and the unexpected observed magneto-functionalities are discussed. A tendency of magnetic domain formation with increasing the Fe content over the compensation concentration is observed. The switch from a reversed Magneto-optical Kerr Effect loop to a direct loop when increasing the Fe content over the compensation point is explained via the specific contribution to the rotation of the polarization vector from each magnetic sublattice, belonging to Fe and Gd, respectively. Local atomic configurations and magnetic interactions ascertained the amorphous character and revealed an out-ofplane orientation of the magnetic moment of Fe above the compensation point. The thermomagnetic curves prove a concentration dependent behavior, explained by weakly coupled magnetization relaxation processes of the two magnetic sub-lattices. On the other hand, the magnetic hysteresis loops gave evidence of two exchange coupled magnetic phases with different coercive fields. According to structural and Fe-57 Mossbauer Spectroscopy results, the two phases correspond to definite nanosized volumes of two different average concentrations (one of them closer to the compensation point) which are randomly distributed in the film. The unexpected single step-like behavior of the magneto-resistivity curves was explained by dissimilar switching of the spins in these two magnetic phases distributed in nano-sized volumes.

This work investigates the structural, magnetic and magneto-optical properties of a new zinc phosphate-tellurite glass belonging to the 45ZnO-10Al(2)O(3)-40P(2)O(5)-5TeO(2)system. The glass was prepared by a wet method of processing the starting reagents followed by suitable melting-stirring-quenching-annealing steps. Specific parameters such as density, average molecular mass, molar volume, oxygen packaging density, refractive index, molar refractivity, electronic polarizability, reflection loss, optical transmission, band gap and optical basicity have been reported together with thermal, magnetic and magneto-optical characteristics. Absorption bands appear in the blue and red visible region, while over 600 nm the glass becomes more transparent. FTIR and Raman spectra evidenced phosphate-tellurite vibration modes proving the P(2)O(5)and TeO(2)network forming role. Magnetic measurements reveal the diamagnetic character of the Te-doped glass with an additional weak ferromagnetic signal, specific to diluted ferromagnetic oxides. Positive Faraday rotation angle with monotonous decreasing value at increasing wavelength was evidenced from magneto-optical measurements. The final product is a composite material comprising of a non-crystalline vitreous phase and Te-based nanoclusters accompanied by oxygen vacancies. The metallic-like Te colloids are responsible for the dark reddish color of the glass whereas the accompanying oxygen vacancies might be responsible for the weak ferromagnetic signal persisting up to room temperature.

Issues related to the optimization of heat transfer mechanisms dominated by superparamagnetic relaxation are considered in the case of AC (alternating current) magnetic field hyperthermia procedures. The key role in the conversion of electromagnetic energy to the thermal one via the superparamagnetic relaxation mechanism is played by the magnetic anisotropy of nanoparticles, easily to be controlled via the shape anisotropy component. The optimization process has been discussed in the case of magnetite (Fe3O4) ellipsoidal nanoparticles with dominant shape anisotropy dispersed in different media. Nanoparticles of different sizes and aspect ratios have been considered in correlation with those specific parameters of the actuating AC magnetic field which respect an established biological safely criterion. It has been proven that the dissipated power can be maximized for a given set of biological compatible RF (radiofrequency) field parameters (frequency and field amplitude at the sample space) only for specific pairs of particle sizes and aspect ratios. For instance, it has been shown that ellipsoidal magnetite nanoparticles with 10 nm equatorial size and aspect ratio of 2 are optimal for a maximum transferred power under radiofrequency excitations of 250 kHz and field amplitude of 20 kA/m, if high viscosity dispersion media are used. The methodology for deriving the optimal shape (geometrical) parameters of a specific type of nanoparticles in conditions of using available radiofrequency excitations, or vice versa, for deriving the optimal radiofrequency working parameters in the case of ferrofluids with specific nanoparticles (type and geometry) is described and discussed in detail.

Magnetic iron oxides have been used in biomedical applications, such as contrast agents for magnetic resonance imaging, carriers for controlled drug delivery and immunoassays, or magnetic hyperthermia for the past 40 years. Our aim is to investigate the effect of pressure and temperature on the structural, thermal, and magnetic properties of iron oxides prepared by hydrothermal synthesis at temperatures of 100-200 degrees C and pressures of 20-1000 bar. It has been found that pressure influences the type of iron oxide crystalline phase. Thus, the results obtained by Mossbauer characterization are in excellent agreement with X-ray diffraction and optical microscopy characterization, showing that, for lower pressure values (100 bar, the major crystalline phase is goethite. In addition, thermal analysis results are consistent with particle size analysis by X-ray diffraction, confirming the crystallization of the synthesized iron oxides. One order of magnitude higher magnetization has been obtained for sample synthesized at 1000 bar. The same sample provides after annealing treatment, the highest amount of good quality magnetite leading to a magnetization at saturation of 30 emu/g and a coercive field of 1000 Oe at 10 K and 450 Oe at 300 K, convenient for various applications.

A critical discussion on the presently available models for the relaxation time of magnetic nanoparticles approaching the superparamagnetic regime in the presence of interparticle dipolar interactions is considered. The direct implications of such interactions for magnetic fluid hyperthermia therapy through susceptibility loss mechanisms give rise to an indirect method for their study via specific absorption rate measurements performed on ferrofluids of different volume fractions. The theoretical support for the specific evolution of the relaxation time constant and the anisotropy energy barrier versus the interparticle interactions in a perturbation approach of the simple Neel expression for the relaxation time is provided via static and time-dependent micromagnetic simulations.

A quantitative treatment of the effects of magnetic mutual interactions on the specific absorption rate of a superparamagnetic system of iron oxide nanoparticles coated with oleic acid is reported. The nanoparticle concentration of the considered ferrofluid samples varied from a very low (0.005) to a medium (0.16) value of the volume fraction, whereas the amplitude of the exciting AC magnetic field ranged from 14-35 kA m(-1). It was proved that a direct effect of the interparticle interactions resides in the regime of the modified superparamagnetism, dealing, besides the usual increase in the anisotropy energy barrier per nanoparticle, with the decrease in the specific time constant tau(0) of the relaxation law, usually considered as a material constant. Consequently, the increase in the specific absorption rate versus the volume fraction is significantly diminished in the presence of the interparticle interactions compared to the case of non-interacting superparamagnetic nanoparticles, with direct influence on the magnetic hyperthermia efficiency.

A new methodology for the accurate determination of the specific absorption rate of ferrofluids with magnetite nanoparticles of average size of about 10 nm subjected to alternative current magnetic fields is proposed. A simple numerical compensation of the heating rates by the cooling rates obtained at similar temperatures is employed. Comparisons of the as-obtained adiabatic heating curves with theoretical evaluations are discussed.

The aim of this paper is to present a reliable procedure for the experimental determination of the specific absorption rate (SAR) in case of superparamagnetic Fe oxide nanoparticles dispersed in liquid environments. It is based on the acquisition of consecutive steps of time-temperature dependences along of both heating and cooling processes. Linear fitting of these recorded steps provides the heating and cooling speeds at different temperatures, which finally allow the determination of the heating profile in adiabatic-like conditions over a broad temperature range. The presented methodology represents on one hand, a useful alternative tool for the experimental evaluation of the heating capability of nanoparticulate systems for magnetic hyperthermia applications and on the other hand, gives support for a more accurate modeling of bio-heat transfer phenomena.

Ferrofluid samples consisting of magnetite nanoparticles (NPs) coated with oleic acid and dispersed in a non-polar organic solvent have been synthesized by chemical routes. Different volume fractions, phi, of magnetic NPs were considered. The overall structural characterization of NPs has been performed by x-ray diffractometry, with lattice parameters and average coherence lengths evaluated via Rietveld refinements. The magnetic properties of different samples have been analysed by SQUID magnetometry and temperature-dependent Mossbauer spectroscopy and finally explained by adequate magnetic relaxation mechanisms. Zero field cooling-field cooling protocols provided useful information about specific volume fraction dependent magnetic relaxation and de-freezing processes, the lack of the Verwey transition and stronger dipolar interactions at higher volume fractions. Anisotropy energies as obtained by both temperature dependent Mossbauer spectroscopy and magnetometry data are compared and a new procedure for a quantitative characterization of the dipolar interactions is proposed.

Exchange coupling in a SrFe12O19 - Fe3O4 nanocomposite magnet was explored in this study. The composition, microstructure, local structure and magnetic properties were investigated by XRD, SEM, Mossbauer spectroscopy, and SQUID magnetometry. The magnetoplumbite SrFe12O19 and spinel Fe3O4 structures were verified by X-ray diffraction. The morphology of the composite reveals the characteristics of the two components. The hyperfine parameters allowed the identification of the Wyckoff positions of the iron ions corresponding to the involved phases. The magnetic measurements of the composite, showing a single-phase-like magnetic hysteresis loop, confirmed the exchange coupling between the hard and soft magnetic phases.