Structural XANES characterization of Ca0.99Sm0.01TiO3 perovskite and correlation with photoluminescence emission

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photoluminescence of barium titanate and barium zirconate in multilayer disordered thin films at room temperature

The emission of wide band photoluminescence showed a synergic effect on barium zirconate and barium titanate thin films in alternate multilayer system at room temperature by 488 nm exiting wavelength. The thin films obtained by spin-coating were annealed at 350, 450, and 550 degrees C for 2 h. The X-ray patterns revealed the complete separation among the BaTiO3 and BaZrO3 phases in the adjacent films. Visible and intense photoluminescence was governed by BaZrO3 thin films in the multilayer system. Quantum mechanics calculations were used in order to simulate ordered and disordered thin films structures. The disordered models, which were built by using the displacement of formers and modifier networks, showed a different symmetry in each system, which is in accordance with experimental photoluminescence emission, thus allowing to establish a correlation among the structural and optical properties of these multilayered systems.

On the photoluminescence behavior of samarium-doped strontium titanate nanostructures under UV light. A structural and electronic understanding

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Phytophthora parasitica transcriptome, a new concept in the understanding of the citrus gummosis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Drying study of siloxane-PPG nanocomposites

This is a study of the structural transformations occurring in hybrid siloxane-polypropyleneglycol (PPG) nanocomposites, with different PPG molecular weight, along the drying process. The starting materials are wet gels obtained by the sol-gel procedure using as precursor the 3-(trietoxysilyl)propylisocyanate (IsoTrEOS) and polypropylenglycol bis(2-amino-propyl-ether) (NH2-PPG-NH2). The shrinkage and mass loss measurements were performed using a temperature-controlled chamber at 50 degreesC. The nanostructural evolution of samples during drying was studied in situ by small angle x-ray scattering (SAXS). The experimental results demonstrate that the drying process is highly dependent on the molecular weight of polymer. After the initial drying stage, the progressive emptying of pores leads to the formation of a irregular drying front in gels prepared from PPG of high molecular weight, like 4000 g/mol. As a consequence, an increase of the SAXS intensity due to the increase of electronic density contrast between siloxane clusters and polymeric matrix is observed. For hybrids containing PPG of low molecular weight, the pore emptying process is fast, leading to a regular drying front, without isolated nanopockets of solvents. SAXS intensity curves exhibit a maximum, which was associated to the existence of spatial correlation of the silica clusters embedded in the polymeric matrix. The spatial correlation is preserved during drying. These results also reveal that the structural transformation during drying is governed by capillary forces and depends on the entanglement of polymer chains.

EVOLUTION OF ADENINE CLUSTERING IN 5S RIBOSOMAL-RNA

The frequency of adenine mononucleotides (A), dinucleotides (AA) and clusters, and the positions of clusters, were studied in 502 molecules of the 5S rRNA.All frequencies were reduced in the evolutive lines of vertebrates, plants and fungi, in parallel with increasing organismic complexity. No change was observed in invertebrates. All frequencies were increased in mitochondria, plastids and mycoplasmas. The presumed relatives to the ancestors of the organelles, Rhodobacteria alfa and Cyanobacteria, showed intermediate values, relative to the eubacterial averages. Firmibacterid showed very high number of cluster sites.Clusters were more frequent in single-stranded regions in all organisms. The routes of organelles and mycoplasmas accummulated clusters at faster rates in double-stranded regions. Rates of change were higher for AA and clusters than for A in plants, vertebrates and organeltes, higher for cluster sites and A in mycoplasmas, and higher for AA and A in fungi. These data indicated that selection pressures acted more strongly on adenine clustering than on adenine frequency.It is proposed that AA and clusters, as sites of lower informational content. have the property of tolerating positional variation in the sites of other molecules (or other regions of the same molecule) that interact with the adenines. This reasoning was consistent with the degrees of genic polymorphism. low in plants and vertebrates and high in invertebrates. In the eubacteria endosymbiontic or parasitic to eukaryotes, the more tolerant RNA would be better adapted to interactions with the homologous nucleus-derived ribosomal proteins: the intermediate values observed in their precursors were interpreted as preadaptive.Among other groups, only the Deinococcus-Thermus eubacteria showed excessive AA and cluster contents, possibly related to their peculiar tolerance to mutagens, and the Ciliates showed excessive AA contents, indicative of retention of primitive characters.

Small-angle X-ray scattering study of gelation and aging of Eu3+-doped sol-gel-derived siloxane-poly(oxyethylene) nanocomposites

The aggregation, gelation, and aging of urea-cross-linked siloxane-poly(oxyethylene) nanohybrids [(U600)-n] containing two different amounts of europium triflate initially dissolved in an ethanol-water mixture were investigated by in situ small-angle X-ray scattering (SAXS). For both low (n = [O]/[Eu] = 80) and high (n = 25) europium contents, the SAXS intensity was attributed to the formation of siloxane clusters of about 8-11 Angstrom in size. Siloxane cluster formation and growth is a rapid process in hybrids with low Eu contents and slow in Eu-rich hybrids. An additional contribution to the scattering intensity at very low angles was attributed to the formation of a coarse structure level. At this secondary level, the structure can be described as a set of dense domains containing siloxane clusters embedded in a depleted matrix composed of unfolded polymer chains and solvent. By fitting a theoretical function for this model to the experimental SAXS curves, relevant structural parameters were determined as functions of time during the sol-gel transition and gel aging. For hybrids with low europium contents (n = 80), the size of the siloxane clusters remains essentially invariant, whereas the dense segregation domains progressively grow. In hybrids with high doping contents (n = 25), the preponderant structure variation during the first stages of the sol-gel transformation is the slow growth of siloxane clusters. For these hybrids, the segregation of siloxane clusters forming dense domains occurs only during advanced stages of the process.

Use of strontium for bovine oocyte activation

Strontium efficiently activates mouse oocytes, however, there is limited information on its use in cattle. Thus, the objective of this study was to establish a suitable protocol for activating bovine oocyte with strontium. For pronuclear development, the absence of calcium and magnesium in the activation medium (TALP) with 10 and 50mM strontium (34.4 and 53.1%, respectively) was superior to the complete TALP (6.5 and 19.4%, respectively). In all activation media, better results were observed with 25 and 50 mM strontium (21.9-53.1 and 19.4-53.1%, respectively). Incubation for 4 h promoted similar results in all strontium concentrations. However, strontium at 15, 20, and 25 mM for 6 and 8 h (40.7, 46.7, and 48.3%, and 29.3, 48.3, and 40.7%, respectively) were superior to control (15.5 and 10%, respectively). After in vitro maturation for 26 h, strontium (S; 20 mM in Ca2+ and Mg2+-free TALP for 6 h), ionomycin + strontium (IS), and strontium + ionomycin (SI) (60, 63.3, and 65%, respectively) were similar in pronuclear development and superior to ionomycin (I; 5 mu M for 5 min; 36.7%). In treatments S and I, only 1 PN zygotes were observed. In treatment S, most of them had 1 and 2 PB (35.7 and 60.7%, respectively), and in treatment I, 0, 1, and 2 PB (14.3, 57.1, and 28.6%, respectively). Most of the zygotes in treatment IS and SI were 1 PN 2 PB (77.4 and 61.6%, respectively). The number of oocytes with clusters of cortical granules was similar in all treated groups (11-29%). Cortical granule exocytosis in treatment IS (68%) was similar to S (54%) and superior to 1, SI, and control (27, 45, and 5.0%, respectively). Cleavage and blastocyst rates were similar for S, I, IS, and SI treatments (61.7-76.7, and 8.3-13.3%, respectively) and the same was observed for ICM, TE, and total cell number, and ICM/total cell ratio (22-25, 64-69, and 86-95, and 0.26-0.27). In conclusion, strontium may be efficiently applied for bovine oocyte activation at 20 mM in Ca2+-and Mg2+-free TALP medium for 6 h.

Apoptosis in the epithelial cells of the rests of Malassez of the periodontium of rat molars

Background and Objectives: Epithelial rests of Malassez are clusters of cells derived from Hertwig's root sheath that remain in the periodontal ligament throughout life. Although it is known that the cells of Malassez proliferate, there are no studies showing that they undergo programmed cell death, i.e. apoptosis. In most tissues, proliferation is balanced by apoptosis. Thus we examined regions of the periodontium of young and adult rat molars in the hope of detecting apoptosis.Methods: Wistar rats aged 29, 45 and 120 days were killed with chloral hydrate (600 mg/kg). Fragments containing maxillary molars were removed and fixed in formaldehyde, decalcified, and embedded in paraffin and glycol methacrylate. Sections were stained with hematoxylin/eosin and the Terminal deoxynucleotidyl transferase-mediated dUTP Nick End Labeling (TUNEL) method for detection of apoptosis. Specimens were also fixed in glutaraldehyde-formaldehyde, decalcified and processed for transmission electron microscopy.Results: Epithelial rests of Malassez containing round/ovoid basophilic dense bodies and TUNEL-positive structures were found in all specimens examined. Ultrastructural examination revealed that some cells of Malassez contained masses of condensed peripheral chromatin and a shrunken cytoplasm exhibiting intact organelles - images typical of apoptosis. Moreover, round/ovoid electron-opaque structures appeared to be in the process of being engulfed by neighboring epithelial cells of Malassez.Conclusions: Our results demonstrate that epithelial cells of Malassez's rests undergo apoptosis in the developing and adult periodontium. Apoptosis may, together with proliferation, be part of the mechanism of turnover/remodelling of the cells of Malassez.

Changeover during in situ compositional modulation of hexacyanoferrate (Prussian Blue) material

This paper describes the importance of (H2O)(6) clusters in controlling the properties of hexacyanoferrate (Prussian Blue) materials. A careful in situ study of compositional changes by using electrogravimetric techniques (in ac and dc modes) in hexacyanoferrates containing K+ alkali metals reveals the existence of a changeover in the properties of these films in a narrow potential range. Control of the compositional variation of the changeover is dependent on the K+ stoichiometric number in the compound structure. However, a specific K+ occupation in the compound structure activates the occupation of the (H2O)(6) cluster by H3O+ and/or H+, causing the changeover in the properties of hexacyanoferrate film. Thus, the information thus obtained is very useful for understanding the mechanisms involved in the electrochemical reversible switch between ferrimagnetism/paramagnetism, semiconductor/metal and electroluminescence/nonelectroluminescence properties of molecular cyanide materials.

A comparative study of the corrosion of high copper dental amalgams

Metallographic studies carried out for Tytin-Plus and Dispersalloy amalgams show a porous multiphase material, whose surface phases are: gamma-(Ag3Sn), gamma(1)-(Ag2Hg3), eta'-(Cu6Sn5) and epsilon-(Cu3Sn). Additionally, Dispersalloy is present in the Ag-Cu eutectic. The application of surface analysis by SEM reveal a heterogeneous distribution of the above mentioned phases. Microstructures consisting of colonies or clusters were not observed. The corrosion testing of these materials was done in 0.9% NaCl aerated solution at 25 degrees C using potentiodynamic polarization curves and ac impedance measurements. The corrosion process in these multiphase systems can be interpreted as the sum of more than one electrodissolution process and the posterior formation of corrosion films. on each electrode, the corrosion film is formed by different mechanisms. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Electro-precipitation of Fe(3)O(4) nanoparticles in ethanol

The preparation of superparamagnetic magnetite (Fe(3)O(4)) nanoparticles by electro-precipitation in ethanol is proposed. Particle average size can be set from 4.4 to 9 nm with a standard deviation around 20%. Combination of wide-angle X-ray scattering (WAXS), Electron energy loss spectroscopy (EELS) and Mossbauer spectroscopy characterizations clearly identifies the particles as magnetite single-crystals (Fe(3)O(4)). (C) 2008 Elsevier B.V. All rights reserved.

Factors that cause genotype by environment interaction and use of a multiple-trait herd-cluster model for milk yield of Holstein cattle from Brazil and Colombia

Descriptive herd variables (DVHE) were used to explain genotype by environment interactions (G x E) for milk yield (MY) in Brazilian and Colombian production environments and to develop a herd-cluster model to estimate covariance components and genetic parameters for each herd environment group. Data consisted of 180,522 lactation records of 94,558 Holstein cows from 937 Brazilian and 400 Colombian herds. Herds in both countries were jointly grouped in thirds according to 8 DVHE: production level, phenotypic variability, age at first calving, calving interval, percentage of imported semen, lactation length, and herd size. For each DVHE, REML bivariate animal model analyses were used to estimate genetic correlations for MY between upper and lower thirds of the data. Based on estimates of genetic correlations, weights were assigned to each DVHE to group herds in a cluster analysis using the FASTCLUS procedure in SAS. Three clusters were defined, and genetic and residual variance components were heterogeneous among herd clusters. Estimates of heritability in clusters 1 and 3 were 0.28 and 0.29, respectively, but the estimate was larger (0.39) in Cluster 2. The genetic correlations of MY from different clusters ranged from 0.89 to 0.97. The herd-cluster model based on DVHE properly takes into account G x E by grouping similar environments accordingly and seems to be an alternative to simply considering country borders to distinguish between environments.