Light-Induced Structural Change in Iridium Complexes Studied by Electron Spin Resonance

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural, electronic structure and magnetic studies of GdFe1-xNixO3 (x <= 0.5)

The structural, electronic structure and magnetic properties of Ni doped GdFeO3 perovskite materials have been studied. A decreasing trend in volume with the increasing Ni concentration without any structural change is confirmed from X-ray diffraction studies. The electronic structural studies show that the competing ions within the ensemble have +3 oxidation states, which includes the Gd, Fe and Ni ions, and also confirms the octahedral symmetry of the Fe/Ni ions. The magnetic properties clearly depict that the Ni doping can tailor the phase transitions arising due to temperature/field dependence having a heavy impact on spin dynamics. (C) 2012 Elsevier B.V. All rights reserved.

Structural Health Monitoring in Smart Structures Through Time Series Analysis

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

Photoinduced structural changes in antimony polyphosphate based glasses

A photocontraction effect in amorphous films of the binary glass system 0.20 [Sb(PO3)(3)](n)-0.80 Sb2O3 has been observed after UV irradiation using the 350.7 nm Kr+ ion laser line with 5.0 W/cm(2). Good optical quality films up to 4.0 mum were deposited on silica substrates at room temperature in vacuum by electron beam physical vapor deposition (EB-PVD) and characterized using WDX, XRD, optical absorption, infrared reflectance, profilometry and atomic force microscopy (AFM) techniques. Very stable glasses were prepared by the melt quenching technique and used as evaporation source for the production of films. The photoinduced structural change (PSC) was observed as a variation of about 6% in the film thickness and this effect is accompanied by a photobleaching of the irradiated area with a blue shift of the optical absorption edge. Otherwise this photoinduced change in the film thickness is very sensitive to the variations in the shape and intensity of the laser beam; therefore several possibilities in optical recording arise from these results. (C) 2003 Published by Elsevier B.V.

Low-temperature structural effects in the (TMTSF)2PF6 and AsF6 Bechgaard salts

We present a detailed low-temperature investigation of the statics and dynamics of the anions and methyl groups in the organic conductors (TMTSF) 2PF6 and (TMTSF)2AsF6 (TMTSF: tetramethyl-tetraselenafulvalene). The 4 K neutron-scattering structure refinement of the fully deuterated (TMTSF)2PF6-D12 salt allows locating precisely the methyl groups at 4 K. This structure is compared to the one of the fully hydrogenated (TMTSF)2PF6-H12 salt previously determined at the same temperature. Surprisingly, it is found that deuteration corresponds to the application of a negative pressure of 5×102 MPa to the H12 salt. Accurate measurements of the Bragg intensity show anomalous thermal variations at low temperature both in the deuterated PF 6 and AsF6 salts. Two different thermal behaviors have been distinguished. Small Bragg-angle measurements reflect the presence of low-frequency modes at characteristic energies θE = 8.3 K and θE = 6.7 K for the PF6-D12 and AsF6-D12 salts, respectively. These modes correspond to the low-temperature methyl group motion. Large Bragg-angle measurements evidence an unexpected structural change around 55 K, which probably corresponds to the linkage of the anions to the methyl groups via the formation of F...D-CD2 bonds observed in the 4 K structural refinement. Finally we show that the thermal expansion coefficient of (TMTSF)2PF6 is dominated by the librational motion of the PF6 units. We quantitatively analyze the low-temperature variation of the lattice expansion via the contribution of Einstein oscillators, which allows us to determine for the first time the characteristic frequency of the PF6 librations: θE ≈ 50 K and θE = 76 K for the PF6-D12 and PF6-H12 salts, respectively. © 2013 American Physical Society.

Relation among optical, thermal and thermo-optical properties and niobium concentration in tellurite glasses

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Cooperação técnica internacional: aportes teóricos

Induzidos por uma mudança estrutural na dinâmica da sociedade internacional, muitos municípios, por meio do exercício da chamada paradiplomacia ou diplomacia federativa, vêm elaborando instrumentos de gestão municipal para captar recursos via experiências de Cooperação Técnica Internacional (CTI). Nesse contexto, o objetivo deste artigo é mapear conceitualmente o fenômeno de CTI, visando a facilitar sua compreensão e suas consequências práticas para a sociedade brasileira.

Ensino Fundamental de 9 anos: estamos preparados para implantá-lo?

A revisão da história do desenvolvimento da educação brasileira ao longo do séc. XX permite-nos observar que grande parte das alternativas implantadas com o intuito de resolver os problemas de democratização, acesso e permanência do aluno em uma escola de qualidade foram suplantadas por políticas de caráter econômico e financeiro que acabavam preterindo os aspectos pedagógicos. Com base nesta constatação, entendemos que a atual proposição de ampliação do Ensino Fundamental de 8 para 9 anos representa uma nova oportunidade para a revisão deste procedimento histórico no âmbito da sociedade brasileira. Tendo em vista que o prazo proposto para adequação de todas as escolas à lei é 2010, realizou-se uma investigação junto a 2 (dois) Núcleos Regionais de Ensino, 8 (oito) Secretarias Municipais de Educação e 12 (doze) escolas vinculadas a estes órgãos, localizadas em diferentes cidades e regiões do estado do Paraná-Brasil, com o objetivo de investigar como a referida proposta chegou às escolas, bem como de que forma as mesmas estão se preparando para este processo. Para tanto, foram realizadas entrevistas junto a representantes dos núcleos e secretarias e também, junto aos diretores e professores das escolas. Pode-se constatar que muito pouco se sabe acerca da proposta de Implantação do Ensino Fundamental de 9 anos e que pairam muitas dúvidas e preocupações sobre se a proposta não consiste somente em mais uma mudança política e estrutural, se não significa, apenas, uma antecipação da alfabetização que poderá prejudicar as crianças. Assim sendo, parece ficar evidente a precocidade da implantação de forma ampla e generalizada, antes que sejam garantidas as condições de preparação das respectivas escolas e professores.

Crystallographic and spectroscopic characterization of a molecular hinge: Conformational changes in bothropstoxin I, a dimeric Lys49 phospholipase A2 homologue

Bothropstoxin I(BthTX-I) from the venom of Bothrops jararacussu is a myotoxic phospholipase A2 (PLA2) homologue which, although catalytically inactive due to an Asp49-->Lys substitution, disrupts the integrity of lipid membranes by a Ca2+-independent mechanism, the crystal structures of two dimeric farms of BthLTX-I which diffract X-rays eo resolutions of 3.1 and 2.1 Angstrom have been determined, the monomers in both structures are related by an almost perfect twofold axis of rotation and the dimer interfaces are defined by contacts between the N-terminal alpha-helical regions and the tips of the beta-wings of partner monomers. Significant differences in the relative orientation of the monomers in the two crystal forms results in open and closed dimer conformations, Spectroscopic Investigations of BthTX-I in solution have correlated these conformational differences with changes in the intrinsic fluorescence emission of the single tryptophan residues located at the dimer interface, the possible relevance of this structural transition in the Ca2+-independent membrane damaging activity is discussed. (C) 1998 Wiley-Liss, Inc.

Characterization of BaTi1-xZrxO3 thin films obtained by a soft chemical spin-coating technique

Single-phase perovskite structure BaZrxTi1-xO3 (BZT) (0.05less than or equal toxless than or equal to0.25) thin films were deposited on Pt-Ti-SiO2-Si substrates by the spin-coating technique. The structural modifications in the thin films were studied using x-ray diffraction and micro-Raman scattering techniques. Lattice parameters calculated from x-ray data indicate an increase in lattice (a axis) with the increasing content of zirconium in these films. Such Zr substitution also result in variations of the phonon mode wave numbers, especially those of lower wave numbers, for BaZrxTi1-xO3 thin films, corroborate to the structural change caused by the zirconium doping. on the other hand, Raman modes persist above structural phase transition, although all optical modes should be Raman inactive in the cubic phase. The origin of these modes must be interpreted as a function of a local breakdown of the cubic symmetry, which could be a result of some kind of disorder. The BZT thin films exhibited a satisfactory dielectric constant close to 181-138, and low dielectric loss tan delta<0.03 at the frequency of 1 kHz. The leakage current density of the BZT thin films was studied at elevated temperatures and the data obey the Schottky emission model. Through this analysis the Schottky barrier height values 0.68, 1.39, and 1.24 eV were estimated to the BZT5, BZT15, and BZT25 thin films, respectively. (C) 2004 American Institute of Physics.

Laser weld: microstructure and corrosion study of Ag-Pd-Au-Cu alloy of the dental application

The laser Welding process was introduced into dentistry by the end of the 1980s, resulting on a great impulse to that area with the development of cheaper and smaller equipment, using simpler technique. This allowed greater use of that process on the confection of prostheses compared to the brazing process since the heat source for that process is a concentrated light beam of high power, which minimizes distortion problems on the prosthetic pieces. Ag-Pd-Au-Cu alloy used on the confection of dental implant prostheses was observed before and after subjection to the laser welding process. The microstructure was analyzed with the. use of optic microscopy and the corrosion resistance was studied by the traditional electrochemical techniques and by electrochemical impedance, under environmental conditions simulating the aggressiveness found in the mouth cavity. A structural change was detected on the weld area, which presented a refined microstructure deriving from the high-speed cooling. The base metal out of the weld area presented a fusion coarse microstructure. The electrochemical essays showed differences on the potentiodynamic polarization behavior in both weld and metal base areas, indicating superior corrosion resistance in the weld area. The impedance spectra were characterized by capacitive distorted components, presenting linear impedance in the low frequencies area. (C) 2002 Elsevier B.V. B.V. All rights reserved.

The role of hydration on the mechanism of allosteric regulation: In situ measurements of the oxygen-linked kinetics of water binding to hemoglobin

We report here the first direct measurements of changes in protein hydration triggered by a functional binding. This task is achieved by weighing hemoglobin (Hb) and myoglobin films exposed to an atmosphere of 98%, relative humidity during oxygenation. The binding of the first oxygen molecules to Hb tetramer triggers a change in protein conformation, which increases binding affinity to the remaining empty sites giving rise to the appearance of cooperative phenomena. Although crystallographic data have evidenced that this structural change increases the protein water-accessible surface area, isobaric osmotic stress experiments in aqueous cosolutions have shown that water binding is linked to Hb oxygenation. Now we show that the differential hydration between fully oxygenated and fully deoxygenated states of these proteins, determined by weighing protein films with a quartz crystal microbalance, agree with the ones determined by osmotic stress in aqueous cosolutions, from the linkage between protein oxygen affinity and water activity. The agreements prove that the changes in water activity brought about by adding osmolytes to the buffer solution shift biochemical equilibrium in proportion to the number of water molecules associated with the reaction. The concomitant kinetics of oxygen and of water binding to Hb have been also determined. The data show that the binding of water molecules to the extra protein surface exposed on the transition from the low-affinity T to the high-affinity R conformations of hemoglobin is the rate-limiting step of Hb cooperative reaction. This evidences that water binding is a crucial step on the allosteric mechanism regulating cooperative interactions, and suggests the possibility that environmental water activity might be engaged in the kinetic control of some important reactions in vivo.

On the interaction of small molecules with hemoproteins: Sperm whale myoglobin

The spin label TEMPO does not show a binding to myoglobin molecule in solution. This is probably due to the fact that this protein does not have a hydrophobic pocket large enough to accommodate the TEMPO molecule. In the crystal the spin label is bound and two kinds of spectra are observed: one isotropic and the other anisotropic. The anisotropic site is probably an intermolecular one. The correlation time for the label in the crystal is very sensitive to temperature showing a transition near 30 °C. This change can be explained as a result of the conformational change observed for myoglobin near this temperature: the motion of the spin label becomes more restricted below this temperature. Change in hydration is the probable cause of this structural change. The changes in the EPR spectra of the anisotropic label suggest that it is bound near the first layers of protein in the crystal. © 1985 Societá Italiana di Fisica.

Evolution of the fractal structure during sintering of SnO2 compacted sol-gel powder

The structural evolution during sintering of compacted SnO2 sol-gel powder was investigated using nitrogen adsorption isotherm analysis. Results show that for sintering temperatures up to 400°C the samples have a fractal pore size distribution. As the sintering temperature increases, a structural rearragement occurs, allowing an increase of the efficiency of particle packing and the reduction of fractality. Above 400°C, the pore size growth associated with grain coalescence is the main structural change observed as the sintering temperature increases. © 1995.

Preparation and characterization of glass-ceramic materials in the BaO-Li2O-ZrO2-SiO2 system and their dependence on treatment temperatures

The preparation and characterization of transparent glass-ceramics in the composition of 30Li2O:5ZrO2:xBaO:(100-x) SiO2 with x = 0, 5, 10, 15, and 20 mol% are described. Glasses were melted in a platinum crucible at 1100°C for 2 h and then heat-treated at 900°C for 3 h. The characterizations were performed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman and infrared spectroscopy, and scanning electron microscopy (SEM). The experimental results indicate that there was a structural change in the glass-ceramics as the BaO concentration in the mixture increased. In the XRD patterns of samples without heat treatment, only the halo was observed. After heat treatment, the appearance of the materials was verified by X-ray diffraction peaks. The reorganization of the amorphous solid was confirmed by Raman and IR spectroscopy along with XPS and SEM, with a more homogeneous phase formation being observed.