Morphotropic phase boundary and electrical properties of 1-x[Bi 0.5Na0.5]TiO3 -xBa[Zr0.25Ti 0.75]O3 lead-free piezoelectric ceramics

Lead-free solid solutions (1-x)Bi0.5Na0.5TiO 3 (BNT)-xBaZr0.25Ti0.75O3 (BZT) (x=0, 0.01, 0.03, 0.05, and 0.07) were prepared by the solid state reaction method. X-ray diffraction (XRD) and Rietveld refinement analyses of 1-x(BNT)-x(BZT) solid solution ceramic were employed to study the structure of these systems. A morphotropic phase boundary (MPB) between rhombohedral and cubic structures occured at the composition x=0.05. Raman spectroscopy exhibited a splitting of the (TO3) mode at x=0.05 and confirmed the presence of MPB region. Scanning electron microcopy (SEM) images showed a change in the grain shape with the increase of BZT into the BNT matrix lattice. The temperature dependent dielectric study showed a gradual increase in dielectric constant up to x=0.05 and then decrease with further increase in BZT content. Maximum coercive field, remanent polarization and high piezoelectric constant were observed at x=0.05. Both the structural and electrical properties show that the solid solution has an MPB around x=0.05. © 2012 Elsevier Ltd and Techna Group S.r.l.

Synthesis, characterization, x-ray structure, DNA cleavage, and cytotoxic activities of palladium(ii) complexes of 4-phenyl-3-thiosemicarbazide and triphenylphosphane

Complexes of the type [PdX(PPh3)(1)]X [1 = 4-phenyl-3- thiosemicarbazide; X = Cl- (2), Br- (3), I- (4), and SCN- (5)] have been synthesized and characterized by elemental analyses and IR, UV/Vis, and 1H and 13C NMR spectroscopy. The molecular structure of complex 4 was determined by single-crystal X-ray diffraction. The binding of the complexes with a purine base (guanosine) was investigated by 1H NMR spectroscopy and mass spectrometry, which showed the complexes to coordinate to guanosine through N7. A gel electrophoresis assay demonstrated the ability of 2-5 to cleave DNA plasmid. All the complexes were tested in vitro by means of the MTT assay for their cytotoxicity against two murine cell lines, LM3 (mammary adenocarcinoma) and LP07 (lung adenocarcinoma), and compared with cisplatin. Complexes 2-5 exhibited good cytotoxicity that surpasses that of cisplatin in the case of LM3. A series of thiosemicarbazide/phosphane palladium(II) complexes have been synthesized and fully characterized. These complexes are able to cleave DNA plasmid and show cytotoxicity against adenocarcinoma (mammary LM3 and lung LP07), surpassing the cytotoxicity of cisplatin in the case of LM3. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, structural characterization and photophysical properties of highly photoluminescent crystals of Eu(III), Tb(III) and Dy(III) with 2,5-thiophenedicarboxylate

Lanthanide compounds of general formula [Ln2(2,5-tdc) 3(dmf)2(H2O)2] ·2dmf·H2O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc2- = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T1) of 2,5-tdc2- ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc2- ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω2 for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the 5D0 emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs). © 2013 Elsevier B.V. All rights reserved.

Sodium dodecyl sulfate (SDS) effect on the thermal stability of oxy-HbGp: Dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) studies

Glossoscolex paulistus (HbGp) hemoglobin is an oligomeric protein, presenting a quaternary structure constituted by 144 globin and 36 non-globin chains (named linkers) with a total molecular mass of 3.6MDa. SDS effects on the oxy-HbGp thermal stability were studied, by DLS and SAXS, at pH 5.0, 7.0 and 9.0. DLS and SAXS data show that the SDS-oxy-HbGp interactions induce a significant decrease of the protein thermal stability, with the formation of larger aggregates, at pH 5.0. At pH 7.0, oxy-HbGp undergoes complete oligomeric dissociation, with increase of temperature, in the presence of SDS. Besides, oxy-HbGp 3.0mg/mL, pH 7.0, in the presence of SDS, has the oligomeric dissociation process reduced as compared to 0.5mg/mL of protein. At pH 9.0, oxy-HbGp starts to dissociate at 20°C, and the protein is totally dissociated at 50°C. The thermal dissociation kinetic data show that oxy-HbGp oligomeric dissociation at pH 7.0, in the presence of SDS, is strongly dependent on the protein concentration. At 0.5mg/mL of protein, the oligomeric dissociation is complete and fast at 40 and 42°C, with kinetic constants of (2.1±0.2)×10-4 and (5.5±0.4)×10-4s-1, respectively, at 0.6mmol/L SDS. However, at 3.0mg/mL, the oligomeric dissociation process starts at 46°C, and only partial dissociation, accompanied by aggregates formation is observed. Moreover, our data show, for the first time, that, for 3.0mg/mL of protein, the oligomeric dissociation, denaturation and aggregation phenomena occur simultaneously, in the presence of SDS. Our present results on the surfactant-HbGp interactions and the protein thermal unfolding process correspond to a step forward in the understanding of SDS effects. © 2013 Elsevier B.V.

Structure, characterization and near-infrared emission of a novel 6-connected uninodal 3D network of Nd(III) containing 2,5-thiophenedicarboxylate anion

The novel coordination polymer with the formula {[Nd2(2,5-tdc)3(dmf)2(H2O)2].dmf.H2O}n (2,5-tdc2-=2,5-thiophedicarboxylate anion and dmf=dimethylformamide) has been synthesized and characterized by thermal analysis (TG/DTA), vibrational spectroscopy (FTIR) and single crystal X-ray diffraction analysis (XRD). Structure analysis reveals that Nd(III) ions show dicapped trigonal prism coordination geometry. The 2,5-tdc2- ligands connect four Nd(III) centers, adopting (κ1 - κ1) - (κ1 - κ1) - μ4 coordination mode, generating an interesting 6-connected uninodal 3D network. Photophysical properties were studied using diffuse reflectance spectroscopy (DR) and excitation/emission spectra. The photoluminescence data show the near infrared emission (NIR) with the characteristic 4F3/2→4IJ (J=9/2, 11/2 and 13/2) transitions of Nd(III) ion, indicating that 2,5-tdc2- is able to act as a sensitizer for emission in NIR region. © 2013 Elsevier B.V.

Caracterização dielétrica de partículas nanométricas e nanoestruturadas de óxido de niobato da família tetragonal tungstênio bronze com estequiometria K'Sr IND. 2' N'b IND. 5' 'O IND. 15'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese e aplicação de catalisadores à base de óxidos de cério, tungstênio e HZSM-5 para a produção do biodiesel

This work presents a study on the production of biodiesel by esterification reaction of oleic acid with methanol using batch reactor and different catalysts based on CeO2 and WO3 and HZSM-5. Acid treatment was performed in order to increase the catalytic activity. Different characterization techniques were performed, among them X-ray diffraction (XRD), Thermogravimetric analysis TGA/DTA, Spectroscopy in the Region in Fourier Transform Infrared (FTIR) and X-ray fluorescence (XRF). The effects of independent variables: temperature, molar ratio of oil: alcohol and the amount of catalyst and their interactions on the dependent variable (conversion of oleic acid to the corresponding ester). Overall, through the results obtained in the characterization was observed that the applied treatments were efficient, however the XRF technique, indicated that tungsten oxide leaching could occur during the preparation of the materials. The treatments performed on HZSM-5 caused no significant changes in the structure indicating that the zeolite was quite resistant to the treatments used. It was evaluated using complete 23 factorial design. For the catalysts investigated, the best reaction conditions were obtained when using higher levels of the independent variables temperature and amount of catalyst. However, for the variable molar ratio the lowest level showed significant yields for most of the synthesized catalyst, obtaining maximum conversion to the OC (67.97%), OW (74.37%), HZSM-5 (61.16%) OC-OW 1 (75.93%), OC-OW 2 (82.57%), OC-OW 3 (79.15%), S/OC-OW 1 (86.90%), S/OC-OW 2 (91.04%), S/OC-OW 3 (88.60%), S/OC-OW/H 1 (92.34%), S/OC-OW/H 2 (100%) and S/OC-OW/H 3 (98.16%). According to the experimental design, the temperature has the biggest influence on the reaction variable for all the synthesized catalysts. Among the catalysts investigated S/OC-OW/H 2 e S/OC-OW/H 3 were more effective. Reuse tests showed that the catalyst activity decreased after each cycle, indicating that the regeneration process was effective. The leaching test indicated that the catalysts are heterogeneous in the evaluated operating range. The catalysts investigated showed themselves promising for the production of biodiesel.

Um estudo da formação de disponibilidade de piromorfita (Pb 5(PO4)3OH) em solos contaminados com Pb e remediados com NH4H2PO4

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Migração (2,5-D) com amplitudes verdadeiras em meios com gradiente constante de velocidade

A migração com amplitudes verdadeiras de dados de reflexão sísmica, em profundidade ou em tempo, possibilita que seja obtida uma medida dos coeficientes de reflexão dos chamados eventos de reflexão primária. Estes eventos são constituídos, por exemplo, pelas reflexões de ondas longitudinais P-P em refletores de curvaturas arbitrárias e suaves. Um dos métodos mais conhecido é o chamado migração de Kirchhoff, através do qual a imagem sísmica é produzida pela integração do campo de ondas sísmicas, utilizando-se superfícies de difrações, denominadas de Superfícies de Huygens. A fim de se obter uma estimativa dos coeficientes de reflexão durante a migração, isto é a correção do efeito do espalhamento geométrico, utiliza-se uma função peso no operador integral de migração. A obtenção desta função peso é feita pela solução assintótica da integral em pontos estacionários. Tanto no cálculo dos tempos de trânsito como na determinação da função peso, necessita-se do traçamento de raios, o que torna a migração em situações de forte heterogeneidade da propriedade física um processo com alto custo computacional. Neste trabalho é apresentado um algoritmo de migração em profundidade com amplitudes verdadeiras, para o caso em que se tem uma fonte sísmica pontual, sendo o modelo de velocidades em subsuperfície representado por uma função que varia em duas dimensões, e constante na terceira dimensão. Esta situação, conhecida como modelo dois-e-meio dimensional (2,5-D), possui características típicas de muitas situações de interesse na exploração do petróleo, como é o caso da aquisição de dados sísmicos 2-D com receptores ao longo de uma linha sísmica e fonte sísmica 3-D. Em particular, é dada ênfase ao caso em que a velocidade de propagação da onda sísmica varia linearmente com a profundidade. Outro tópico de grande importância abordado nesse trabalho diz respeito ao método de inversão sísmica denominado empilhamento duplo de difrações. Através do quociente de dois empilhamentos com pesos apropriados, pode-se determinar propriedades físicas e parâmetros geométricos relacionados com a trajetória do raio refletido, os quais podem ser utilizados a posteriori no processamento dos dados sísmicos, visando por exemplo, a análise de amplitudes.

Migração com amplitude verdadeira em meios bidimensionais (2-D) e introdução ao caso 2,5-D

Nos últimos anos tem-se verificado através de várias publicações um interesse crescente em métodos de migração com amplitude verdadeira, com o objetivo de obter mais informações sobre as propriedades de refletividade da subsuperfície da terra. A maior parte desses trabalhos tem tratado deste tema baseando-se na aproximação de Born, como em Bleistein (1987) e Bleistein et al. (1987), ou na aproximação do campo de ondas pela teoria do raio como Hubral et al. (1991), Schleicher et al. (1993) e Martins et al. (1997). Considerando configurações arbitrárias de fontes e receptores, as reflexões primárias compressionais podem ser imageadas em reflexões migradas no domínio do tempo ou profundidade de tal modo que as amplitudes do campo de ondas migrado são uma medida do coeficiente de reflexão dependente do ângulo de incidência. Para realizar esta tarefa, vários algoritmos têm sido propostos nos últimos anos baseados nas aproximações de Kirchhoff e Born. Essas duas abordagens utilizam um operador integral de empilhamento de difrações ponderado que é aplicado aos dados da seção sísmica de entrada. Como resultado obtém-se uma seção migrada onde, em cada ponto refletor, tem-se o pulso da fonte com amplitude proporcional ao coeficiente de reflexão naquele ponto. Baseando-se na aproximação de Kirchhoff e na aproximação da teoria do raio do campo de ondas, neste trabalho é obtida a função peso para modelos bidimensionais (2-D) e dois e meio dimensionais (2,5-D) que é aplicada a dados sintéticos com e sem ruído. O resultado mostra a precisão e estabilidade do método de migração em 2-D e 2,5-D como uma ferramenta para a obtenção de informações importantes da subsuperfície da terra, que é de grande interesse para a análise da variação da amplitude com o afastamento (ângulo). Em suma, este trabalho apresenta expressões para as funções peso 2-D e 2,5-D em função de parâmetros ao longo de cada ramo do raio. São mostrados exemplos da aplicação do algoritmo de migração em profundidade a dados sintéticos 2-D e 2,5-D obtidos por modelamento sísmico através da teoria do raio usando o pacote Seis88 (Cervený e Psencík, 1988) e os resultados confirmaram a remoção do espalhamento geométrico dos dados migrados mesmo na presença de ruído. Testes adicionais foram realizados para a análise do efeito de alongamento do pulso na migração em profundidade (Tygel et al., 1994) e a aplicação do empilhamento múltiplo (Tygel et al., 1993) para a estimativa de atributos dos pontos de reflexão - no caso o ângulo de reflexão e a posição do receptor.

Partículas magnéticas: ferrita de ítrio 'Y IND. 3''FE IND. 5''O IND. 12' (YIG) recoberta com sílica ('SIO IND. 2')

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

Influência da queima da palha de cana de açúcar na constituição do material particulado atmosférico (MP2,5 e MP10) e as suas implicações potenciais sobre a saúde humana

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Síntese, caracterização estrutural e análise do potencial catalítico do SrTiO3 e das Perovskitas duplas de Sr1-xKxTiCux/2O3, onde x = 0,2; 0,3 e 0,5, na preparação de biodiesel

Pós-graduação em Química - IBILCE

Study of K beta X-ray emission spectroscopy applied to Mn((2-x))V((1+x))O4 (x=0 and 1/3) oxyspinel and comparison with XANES

Oxidation state and coordination of transition metal cations seems to be hard to assess when considering multiple cations, each one with different possible oxidation states. In fact, this is the case of the spineltype double oxides family. High resolution K beta X-ray fluorescence spectra were measured in Mn(2-x)V(1+4)O4 (x=0 and 1/3) spinels-type double oxides in order to determine the oxidation state and coordination of V and Mn cations. The relative intensity of radiative Auger effect KM2,3M4,5 to the total intensity and the integral absolute difference value were used as reference parameters for the characterization of Mn oxidation states. The coordination of Mn ions was inferred by the intensity of the K beta(5) line. In the case of V compounds, it was used as the intensity of the line K beta' relative to the total area of K beta region. The obtained results were further compared with X-ray absorption spectra analysis, showing good agreements regarding the oxidation state characterization. However, there were found some discrepancies in coordination, due to customary oversimplifications in the K beta(5) line origin. The obtained results might represent valuable and useful data for chemical scopes of characterizing spineltype oxides family. (C) 2013 Elsevier Ltd. All rights reserved.

Low-temperature degradation of a Y-TZP ceramic after surface treatments

The purpose of this study was to evaluate the influence of zirconia surface treatments on low-temperature degradation (LTD). Disc-shaped specimens were subjected to one of four surface treatments, denoted as C (controlno surface treatment), Si (air abrasion with 30 mu m silica-modified alumina particles), Al (air abrasion with 30 mu m alumina particles), and Gr (grinding with 120 grit diamond discs). Half of the samples were submitted to autoclave treatment for 12 h (127 degrees C, 1.5 bar). Samples were characterized by x-ray diffraction and profilometer analysis and were subjected to biaxial flexural strength test. All of the groups exhibited an increase in the amount of monoclinic phase (m-phase) after LTD. The tm transformation was remarkable for the specimens from the C group, which also exhibited a significant increase in strength. The Gr group also exhibited an increase in strength but lower initial roughness, which probably suppressed LTD on the zirconia surface. The specimens subjected to air abrasion exhibited higher initial amounts of m-phase and a small increase in m-phase after LTD; the strength was not affected in these groups. The effects of LTD were different with each surface treatment applied. Apparently, LTD may be suppressed by smoother surfaces or the presence of an initial amount of m-phase on zirconia surface. (c) 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 101B: 1387-1392, 2013.