Discrete evolution of the crystal structure during the growth of Ba-hexaferrite nanoplatelets.

An understanding of the adaptation of the crystal structure of materials confined at the nanoscale, the influences of their specific structures on the evolution of their morphologies and, finally, their functional properties is essential not only for expanding fundamental knowledge, but also for facilitating the designs of novel nanostructures for diverse technological and medical applications. Here we describe how the distinct structure of barium-hexaferrite nanoplatelets evolves in a stepwise manner in parallel with the development of their size and morphology during hydrothermal synthesis. The nanoplatelets are formed by reactions between Ba- and Fe-hydroxides in an aqueous suspension at temperatures below 80 °C. Scanning-transmission electron microscopy showed that the structure of the as-synthesized, discoid nanoplatelets (∼2.3 nm thick, ∼10 nm wide) terminates at the basal surfaces with Ba-containing planes. However, after subsequent washing of the nanoplatelets with water the top two atomic layers dissolve from the surfaces. The final structure can be represented by a SRS* sequence of the barium-hexaferrite SRS*R* unit cell, where S and R represent a hexagonal (BaFe6O11)2- and a cubic (Fe6O8)2+ structural block, respectively. Due to the stable SRS* structure, the thickness of the primary nanoplatelets remains unchanged up to approximately 150 °C, when some of the primary nanoplatelets start to grow exaggeratedly and their thicknesses increase discretely with the addition of the RS segments to their structure. The SRS* structure of the primary nanoplatelets is too thin for the complete development of magnetic ordering. However, the addition of just one RS segment (SRS*R*S structure) gives the nanoplatelets hard magnetic properties.

Novel Ba-hexaferrite structural variations stabilized on the nanoscale as building blocks for epitaxial bi-magnetic hard/soft sandwiched maghemite/hexaferrite/maghemite nanoplatelets with out-of-plane easy axis and enhanced magnetization.

Atomic-resolution scanning-transmission electron microscopy showed that barium hexaferrite (BHF) nanoplatelets display a distinct structure, which represents a novel structural variation of hexaferrites stabilized on the nanoscale. The structure can be presented in terms of two alternating structural blocks stacked across the nanoplatelet: a hexagonal (BaFe6O11)2- R block and a cubic (Fe6O8)2+ spinel S block. The structure of the BHF nanoplatelets comprises only two, or rarely three, R blocks and always terminates at the basal surfaces with the full S blocks. The structure of a vast majority of the nanoplatelets can be described with a SR*S*RS stacking order, corresponding to a BaFe15O23 composition. The nanoplatelets display a large, uniaxial magnetic anisotropy with the easy axis perpendicular to the platelet, which is a crucial property enabling different novel applications based on aligning the nanoplatelets with applied magnetic fields. However, the BHF nanoplatelets exhibit a modest saturation magnetization, MS, of just over 30 emu g-1. Given the cubic S block termination of the platelets, layers of maghemite, γ-Fe2O3, (M), with a cubic spinel structure, can be easily grown epitaxially on the surfaces of the platelets, forming a sandwiched M/BHF/M platelet structure. The exchange-coupled composite nanoplatelets exhibit a remarkably uniform structure, with an enhanced MS of more than 50 emu g-1 while essentially maintaining the out-of-plane easy axis. The enhanced MS could pave the way for their use in diverse platelet-based magnetic applications.

Proteomic analyses of early response of unicellular eukaryotic microorganism Tetrahymena thermophila exposed to TiO2 particles.

Key biological functions involved in cell survival have been studied to understand the difference between the impact of exposure to TiO2 nanoparticles (TiO2-NPs) and their bulk counterparts (bulk-TiO2). By selecting a unicellular eukaryotic model organism and applying proteomic analysis an overview of the possible impact of exposure could be obtained. In this study, we investigated the early response of unicellular eukaryotic protozoan Tetrahymena thermophila exposed to TiO2-NPs or bulk-TiO2 particles at subtoxic concentrations for this organism. The proteomic analysis based on 2DE + nLC-ESI-MS/MS revealed 930 distinct protein spots, among which 77 were differentially expressed and 18 were unambiguously identified. We identified alterations in metabolic pathways, including lipid and fatty acid metabolism, purine metabolism and energetic metabolism, as well as salt stress and protein degradation. This proteomic study is consistent with our previous findings, where the early response of T. thermophila to subtoxic concentrations of TiO2 particles included alterations in lipid and fatty acid metabolism and ion regulation. The response to the lowest TiO2-NPs concentration differed significantly from the response to higher TiO2-NPs concentration and both bulk-TiO2 concentrations. Alterations on the physiological landscape were significant after exposure to both nano- and bulk-TiO2; however, no toxic effects were evidenced even at very high exposure concentrations. This study confirms the relevance of the alteration of the lipid profile and lipid metabolism in understanding the early impact of TiO2-NPs in eukaryotic cells, for example, phagocytosing cells like macrophages and ciliated cells in the respiratory epithelium.

Composite nanoplatelets combining soft-magnetic iron oxide with hard-magnetic barium hexaferrite.

By coupling two different magnetic materials inside a single composite nanoparticle, the shape of the magnetic hysteresis can be engineered to meet the requirements of specific applications. Sandwich-like composite nanoparticles composed of a hard-magnetic Ba-hexaferrite (BaFe12O19) platelet core in between two soft-magnetic spinel iron oxide maghemite (γ-Fe2O3) layers were synthesized using a new, simple and inexpensive method based on the co-precipitation of Fe(3+)/Fe(2+) ions in an aqueous suspension of hexaferrite core nanoparticles. The required close control of the supersaturation of the precipitating species was enabled by the controlled release of the Fe(3+) ions from the nitrate complex with urea ([Fe((H2N)2C=O)6](NO3)3) and by using Mg(OH)2 as a solid precipitating agent. The platelet Ba-hexaferrite nanoparticles of different sizes were used as the cores. The controlled coating resulted in an exclusively heterogeneous nucleation and the topotactic growth of the spinel layers on both basal surfaces of the larger hexaferrite nanoplatelets. The direct magnetic coupling between the core and the shell resulted in a strong increase of the energy product |BH|max. Ultrafine core nanoparticles reacted with the precipitating species and homogeneous product nanoparticles were formed, which differ in terms of the structure and composition compared to any other compound in the BaO-Fe2O3 system.

Hydrothermal synthesis of ultrafine barium hexaferrite nanoparticles and the preparation of their stable suspensions.

The hydrothermal treatment of an appropriate suspension of Ba and Fe hydroxides in the presence of a large excess of OH(-) results in the formation of Ba hexaferrite at temperatures as low as 150 degrees C. This low formation temperature enables the synthesis of uniform, ultrafine Ba hexaferrite nanoparticles. These nanoparticles have a disc-like shape, approximately 10 nm wide, but only approximately 3 nm thick. When the temperature of the hydrothermal treatment is increased, large platelet Ba hexaferrite crystals appear as a consequence of secondary re-crystallization (Ostwald ripening). In this work, this undesired process of secondary re-crystallization has been evaluated. We show that the secondary re-crystallization can be totally suppressed with the use of an oleic acid surfactant. The addition of oleic acid enabled the synthesis of uniform, ultrafine nanoparticles at temperatures up to 240 degrees C. The nanoparticles were hydrophobic and could be suspended in nonpolar liquids to form relatively concentrated ferrofluids. Such stable suspensions of hexaferrite nanoparticles will be technologically important, especially as precursors for the preparation of new nanostructured materials, for example nanocomposites or nanostructured ceramic films.

Preparation and properties of water-based magnetic fluids.

Stable suspensions of superparamagnetic iron oxide nanoparticles in water (water-based ferrofluids) were prepared using citric acid (CA) as a surfactant. The influences of different factors on the amount of nanoparticles in a stable suspension were systematically studied. These factors, including the temperature, the pH value and the concentration of CA applied during the adsorption of the CA onto the nanoparticles and during their suspension in water, were evaluated. The highest content of nanoparticles in a stable suspension was obtained when the CA was absorbed at pH values of around 5.2, where two carboxyl groups are dissociated, and when the nanoparticles were suspended at a pH of around 10, where all three carboxyl groups of the CA are in a dissociated state.

Sonochemically assisted synthesis of zinc-doped maghemite.

Nanoparticles of zinc-doped maghemite were prepared using ultrasonic radiation. As a precursor, a suspension of maghemite in an alkaline aqueous solution of zinc nitrate at pH 9 was sonicated. The zinc-doped maghemite nanoparticles were investigated by X-ray diffraction, Mössbauer spectroscopy, high-resolution electron microscopy (HREM) and SQUID magnetometry. The Mössbauer measurements, which cover the temperature range 4.2 K to room temperature, were acquired in zero field and an applied field of 5 T. The results show that by using ultrasound radiation, zinc Zn2+ can substitute for Fe3+ up to a composition close to zinc ferrite (ZnFe2O4), which has a random distribution of Fe3+ ions over both A and B sublattices in the spinel structure with an inversity parameter of delta=0.322. This leads to a maximum saturation magnetization (Ms) of 64.1 emu/g at 300 K and 73.5 emu/g at 2 K.

[Endodontic treatment in patients at risk]. / Endodontsko lijecenje u rizicnih bolesnika.

The course of the endodontic treatment of periapical process in a patient with renal engraftment is described. Such a patient is under a constant cytostatic therapy suppressing the immune system, thus the risk of the endodontic treatment failure being higher, with the possibility of patient's health impairment. Preparation, premedication and performance of endodontic therapy applicable in patients at risk are described and explained. Consultations with respective medical professionals were necessary, pointing to the need of an interdisciplinary approach in such patients.