The size effect of BiFeO3 nanocrystals on the spatial spin modulated structure.

The spatial spin modulated structure (SSMS) of the cycloid type present in bulk BiFeO3 prevents the linear magnetoelectric effect. One way to influence this structure is to reduce the crystal size to the nanoscale. Various opinions are circulating in the literature about the effect of nanocrystal size on SSMS, and to investigate this issue, we used a number of methods, with zero-field NMR (ZF NMR) spectroscopy at the forefront. ZF NMR spectroscopy enables the direct observation of the distribution profile of local fields on iron atoms and defines the SSMS presence and its properties. We also examined the synthesized samples using XRD, TEM, and magnetometry. We conclude that SSMS persists as the nanocrystal size decreases to the cycloid period and less, becoming more harmonic. This is accompanied by the change of the anisotropy type from an "easy axis" to an "easy plane". Magnetic measurements show a significant increase in the saturation magnetization, remanent magnetization, coercivity, and exchange bias of nanocrystals with sizes close to the cycloid period, which is probably associated with incomplete spin compensation in the case of an incomplete cycloid period. Despite the fact that SSMS is retained in the samples with decreased size, the magnetic properties experience a sharp increase up to applicable values.

Mysterious long-living ultrahigh-pressure or secondary impact crisis.

High-pressure glass has attracted interest in terms of both its fundamental state under extreme conditions and its possible applications as an advanced material. In this context, natural impact glasses are of considerable interest because they are formed under ultrahigh-pressure and high-temperature (UHPHT) conditions in larger volumes than laboratory fabrication can produce. Studying the UHPHT glasses of the unique giant Kara astrobleme (Russia), we found that the specific geological position of the UHPHT melt glass veins points to an origin from a secondary ultrahigh-pressure (UHP) melt according to the characteristics of the host suevites, which suggest later bottom flow. Here, we propose a fundamentally novel model involving an upward-injected UHP melt complex with complicated multi-level and multi-process differentiation based on observations of the UHP silica glass, single-crystal coesite and related UHP smectite that crystallized from an impact-generated hydrous melt. This model proposes a secondary UHP crisis during the modification stage of the Kara crater formation. The results are very important for addressing fundamental problems in fields as diverse as condensed matter states under extreme pressure and temperature (PT) conditions, material and geological reconstructions of impact structures, water conditions in mineral substances under UHP conditions in the deep Earth, and the duration and magnitude of the catastrophic effects of large asteroid impacts.

Effect of exfoliating agent on rheological behavior of ß-chitin fibrils in aqueous suspensions and on mechanical properties of poly(acrylic acid)/ß-chitin composites.

Chitin whiskers are promising reinforcing filler for composites due to their mechanical properties, renewable nature and low cost. A new method for preparation of ß-chitin fibrils from squid pens in ascorbic acid aqueous solutions (AscA) was developed. Stirring of the solution with 2 g/l AscA for 2 h disperses the swollen chitin to individualized fibrils with an aspect ratio > 250. The optimal conditions of ß-chitin exfoliation in acrylic acid (AcrA) aqueous solution were found (0.75-2 g/l, 3-4 h). TEMPO-oxidized ß-chitin fibrils were chosen as a reference sample for comparison of different methods. 0.1% chitin suspensions exfoliated in AscA and AcrA solutions show similar gel-like behavior with a storage modulus (G') of 98 ±â€¯23 and 34 ±â€¯12 Pa, respectively, whereas G' of 0.1% dispersion of the TEMPO-oxidized ß-chitin fibrils was 0.015 ±â€¯0.005 Pa only. Composites based on poly(acrylic acid) comprising 1-3 wt% of ß-chitin fibrils were fabricated by polymerization filling. Mechanical properties of the composites were investigated in dry state in the temperature range of 25-250 °C and at controlled relative humidity in the range from 53.6% to 100%. It was revealed that the maximum reinforcing effect is achieved at high temperature (>120 °C) and high relative humidity (≥75.3%RH).

Grazing-incidence small-angle X-ray scattering study of correlated lateral density fluctuations in W/Si multilayers.

A structural characterization of W/Si multilayers using X-ray reflectivity (XRR), scanning transmission electron microscopy (STEM) and grazing-incidence small-angle X-ray scattering (GISAXS) is presented. STEM images revealed lateral, periodic density fluctuations in the Si layers, which were further analysed using GISAXS. Characteristic parameters of the fluctuations such as average distance between neighbouring fluctuations, average size and lateral distribution of their position were obtained by fitting numerical simulations to the measured scattering images, and these parameters are in good agreement with the STEM observations. For the numerical simulations the density fluctuations were approximated as a set of spheroids distributed inside the Si layers as a 3D paracrystal (a lattice of spheroids with short-range ordering but lacking any long-range order). From GISAXS, the density of the material inside the density fluctuations is calculated to be 2.07 g cm-3 which is 89% of the bulk value of the deposited layer (2.33 g cm-3).

Three-Dimensional Structure of Cytochrome c Nitrite Reductase As Determined by Cryo-Electron Microscopy.

The structure of cytochrome c nitrite reductase from the bacterium Thioalkalivibrio nitratireducens was determined by cryo-electron microscopy (cryo-EM) at a 2.56 Å resolution. Possible structural heterogeneity of the enzyme was assessed. The backbone and side-chain orientations in the cryo-EM-based model are, in general, similar to those in the high-resolution X-ray diffraction structure of this enzyme.

Magnetism of Bi2Se3 thin films with Eu-rich flat inclusions.

We report the results of experimental and theoretical studies of Eu-doped Bi2Se3 thin films with extremely inhomogeneous distribution of magnetic component. The obtained electron microscopy images suggest that Eu atoms are concentrated within platelet-like nanoinclusions. The number of inclusions grows with the increase in Eu content, x. Moreover, at relatively high x values, the stacks of platelets (inclusions located one under another) become rather frequent. A comparative analysis of magnetic properties of the films under study reveals no pronounced changes of their temperature dependence with the increase in x, which, however, leads to the decrease in the average magnetic moment [Formula: see text] per Eu atom. A theoretical analysis of different mechanisms contributing to a possible magnetic ordering in the Eu-doped films demonstrates that at small distances (i.e. within a platelet) a dominant contribution is related to the RKKY interaction via electrons in the bulk, while the ordering at inter-platelet distances is governed by magnetic dipole-dipole interaction. The latter implies the antiferromagnetic ordering within the stacks of platelets explaining a drop of [Formula: see text] per Eu atom. We employ the model of a metallic spin glass to estimate the transition temperature, characterising the interaction within the ensemble of randomly distributed magnetic platelets. This estimate gives satisfactory agreement with the experiment, even if we take into account a finite film thickness, thus, neglecting the interaction anisotropy and including only the antiferromagnetism related to the stacking. While the overall contribution of interface Dirac electrons is damped in the systems under study, we argue that the obtained results can be used for the investigation of ultrathin films with analogous impurity profile, where this contribution should be clearly pronounced.

[Isolation of extracellular micro-vesicles from cell culture medium: comparative evaluation of methods]. / Sravnitel'nyi analiz metodov vydeleniia vnekletochnykh mikrovezikul iz kul'tural'noi sredy.

Extracellular vesicles (EV) are secreted by cells of multicellular organisms. EV mediate specific mode of intercellular communication by "horizontal" exchange of substances and information. This phenomenon seems to have an essential biological significance and became a subject of intensive research. Biogenesis, structural and functional features of the EV is being commonly studies in in vitro condition. Several methods of EV isolation from cell culture medium are established, however selection of method might influence on obtained results. The choice of the optimal method depends usually from the amount of medium and the aims of the research while is still challenging issue. We performed a comparative analysis of four different methods of EV isolation from cell culture medium: differential ultracentrifugation, ultracentrifugation with a 30% sucrose/D2O "cushion", precipitation with plant proteins and immune-affinity capturing. EV isolated by different approaches were compared in terms of following parameters: size, concentration, morphology of EV, contamination by non-vesicular particles, content of exosomal tetraspanins on the EV surface, content of total proteins, RNA, and several glioma-associated miRNAs. Applied methods included nano-patricle tracking analysis (NTA), dynamic light scattering (DLS), cryo-electron microscopy, flow cytometry and RT-qPCR. On the base of obtained results, we developed practical recommendations that may help researchers to make a best choice of EV isolation method.

High temperature magnetism and microstructure of ferromagnetic alloy Si1-x Mn x.

The results of a detailed study of magnetic properties and of the microstructure of SiMn films with a small deviation from stoichiometry are presented. The aim was to reveal the origin of the high temperature ferromagnetic ordering in such compounds. Unlike SiMn single crystals with the Curie temperature ~30 K, considered Si1-x Mn x compounds with x = 0.5 +Δx and Δx in the range of 0.01-0.02 demonstrate a ferromagnetic state above room temperature. Such a ferromagnetic state can be explained by the existence of highly defective B20 SiMn nanocrystallites. These defects are Si vacancies, which are suggested to possess magnetic moments. The nanocrystallites interact with each other through paramagnons (magnetic fluctuations) inside a weakly magnetic manganese silicide matrix giving rise to a long range ferromagnetic percolation cluster. The studied structures with a higher value of Δx ≈ 0.05 contained three different magnetic phases: (a)-the low temperature ferromagnetic phase related to SiMn; (b)-the above mentioned high temperature phase with Curie temperature in the range of 200-300 K depending on the growth history and

Topotactic synthesis of the overlooked multilayer silicene intercalation compound SrSi2.

Silicene, a 2D honeycomb lattice of Si atoms similar to graphene, is expected to be a platform for nanoelectronics and home to novel quantum phenomena. Unlike graphene, free-standing silicene is notoriously difficult to stabilize, while strong hybridization of silicene with substrates destroys its desirable properties. On the other hand, Dirac cones of silicene are effectively realized in a bulk - stoichiometric ionic multilayer silicene intercalation compound CaSi2. Besides, a number of new 2D silicene-based materials are synthesized employing CaSi2 as a precursor. However, the rather complex atomic structure of CaSi2 and fresh opportunities of physical and chemical breakthroughs drive the search for alternative compounds with silicene networks. Here, a new polymorph of SrSi2 is synthesized, enjoying both the structure of intercalated multilayer silicene and the simplest possible stacking of silicene sheets. The MBE-quality synthesis accomplished on Si(001) and Si(111) surfaces leads to epitaxial films of SrSi2 with orientation controlled by the substrate, as revealed by XRD, RHEED and electron microscopy studies. The structural SrSi2/Si relation is mirrored in the transport properties of the films.

The structure and continuous stoichiometry change of 1DTbBrx@SWCNTs.

HRTEM and HAADF STEM of 1DTbBrx@SWCNT meta-nanotubes reveal three structural modifications of 1D nanocrystals within single wall carbon nanotube channels attributed to a different stoichiometry of the guest crystal. For SWCNTs with diameters Dm > 1.4 nm a most complete tetragonal unit cell is observed. When crystallization occurs inside SWCNT with Dm < 1.4 nm 1D TbBrx crystal deforms a nanotube to elliptical shape in cross section. In this case the 1D crystal unit cell becomes monoclinic, with possible loss of a part of bromine atoms. Two modifications of a monoclinic unit cell appear. One of them is characterized by single or pair vacancies in the structure of the 1D crystal. Another structure is explained by peripheral and central bromine atoms loss. An appearance of such modifications can be stimulated by electron irradiation. The loss of bromine atoms is in agreement with chemical analysis data. Electronic properties of obtained meta-nanotubes are investigated using optical absorption and Raman spectroscopy. It is shown that intercalation of terbium bromide into SWCNTs leads to acceptor doping of SWCNTs. According to local EDX analysis and elemental mapping this doping can arise from significant stoichiometry change in 1D nanocrystal indicating an average Tb:Br atomic ratio of 1:2.8 ± 0.1.

In situ synthesis and characterization of magnetic nanoparticles in shells of biodegradable polyelectrolyte microcapsules.

Hollow microcapsules with the shell composed of biodegradable polyelectrolytes modified with the maghemite nanoparticles were fabricated by in situ synthesis. The nanoparticles were synthesized from the iron salt and the base directly on the capsule shells prepared by "layer by layer" technique. An average diameter of the capsule was about 6.7 µm while the average thickness of the capsule shell was 0.9 µm. XRD, HRTEM, Raman and Mössbauer spectroscopy data revealed that the iron oxide nanoparticles have the crystal structure of maghemite γ-Fe2O3. The nanoparticles were highly monodisperse with medium size of 7.5 nm. The Mössbauer spectroscopy data revealed that the nanoparticles have marked superparamagnetic behavior which was retained up to room temperature due to slow spin relaxation. Because of that, the microcapsules can be handled by an external magnetic field. Both these properties are important for target drug delivery. Based on the Mössbauer spectroscopy data, the spin blocking temperatures TB of about 90K was found for the particles with size D≤5 nm and TB≈250 K for particles with D≥6 nm. The anisotropy constants K were determined using the superparamagnetic approximation and in the low temperature approximation of collective magnetic excitation.

Reconstruction of the polar interface between hexagonal LuFeO3 and intergrown Fe3O4 nanolayers.

We report the observation of an unusual phase assembly behavior during the growth of hexagonal LuFeO(3) thin films which resulted in the formation of epitaxial Fe(3)O(4) nanolayers. The magnetite layers were up to 5 nm thick and grew under the conditions at which Fe(2)O(3) is thermodynamically stable. These Fe(3)O(4) nanolayers act as buffer layers promoting a highly epitaxial growth of the hexagonal LuFeO(3) thin film up to 150 nm thick. Using scanning transmission electron microscopy, we show that the interface between (001) LuFeO(3) and (111) Fe(3)O(4) can be reconstructed in two ways depending on the sequence in which these compounds grow on each other. We suggest the polarity of the interface is the reason behind the observed interface reconstruction and epitaxial stabilization of magnetite.

The structure of nanocomposite 1D cationic conductor crystal@SWNT.

Nanocomposites consisting of one-dimensional (1D) crystals of the cationic conductors CuI, CuBr and AgBr inside single-walled carbon nanotubes, mainly (n, 0), were obtained using the capillary technique. 1D crystal structure models were proposed based on the high resolution transmission electron microscopy performed on a FEI Titan 80-300 at 80 kV with aberration correction. According to the models and image simulations there are two modifications of 1D crystal: hexagonal close-packed bromine (iodine) anion sublattice (growth direction <001>) and 1D crystal cubic structure (growth direction <112>) compressed transversely to the nanotube (D(m) ∼1.33 nm) axis. Tentatively this kind of 1D crystal can be considered as monoclinic. One modification of the anion sublattice reversibly transforms into the other inside the nanotube, probably initiated by electron beam heating. As demonstrated by micrographs, copper or silver cations can occupy octahedral positions or are statistically distributed across two tetrahedral positions. A 1DAgBr@SWNT (18, 0; 19, 0) pseudoperiodic 'lattice distortion' is revealed resulting from convolution of the nanotube wall function image with 1D cubic crystal function image.

Incorporation of fluorine ions into hydroxyapatite by a pH cycling method.

Fluorine ions were incorporated into hydroxyapatite (HA) using a pH cycling method and the resulting materials were studied using transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical analysis. TEM observations showed that fluoridated hydroxyapatite (FHA) nanoparticles with a narrow particle size distribution were obtained at several different levels of fluorine incorporation. Significant particle growth was observed following calcining at 1200 degrees C. The TEM data revealed that, instead of forming laminated structures, a mixture of HA and FA was obtained, and that this mixture transformed into a single homogeneous FHA phase upon heating. It was found that the efficiency of fluorine incorporation did not vary significantly with the initial HA particle size, but increased as the fluorine content of the initial solution was increased. A relatively low fluorine incorporation efficiency, approximately 60%, was attained for most of the FHA samples and this was attributed to the short holding time at each pH cycle and the limited number of pH cycles employed in the current study.