Integrated X-ray crystallography, optical and computational methods in studies of structure and luminescence of new synthesized complexes of lanthanides with ligands derived from 2,6-diformylpyridine

The reaction of 2,6-diformylpyridine-bis(benzoylhydrazone) [dfpbbh] and 2,6-diformylpyridine-bis(4-phenylsemicarbazone) [dfpbpsc] with lanthanides salts yielded the new chelates complexes [Eu(dfpbpsc-H +) 2]NO 3 (1), [Dy(fbhmp) 2][Dy(dfpbbh-2H +) 2]·2EtOH·2H 2O (fbhmp = 2-formylbenzoylhydrazone-6-methoxide-pyridine; Ph = phenyl; Py = pyridine; Et = ethyl) and [Er 2(dfpbbh-2H +) 2(μ-NO 3)(H 2O) 2(OH)]·H 2O. X-ray diffraction analysis was employed for the structural characterization of the three chelate complexes. In the case of complex 1, optical, synthetic and computational methods were also exploited for ground state structure determinations and triplet energy level of the ligand and HOMO-LUMO calculations, as well as for a detailed study of its luminescence properties. © 2010 Elsevier Ltd. All rights reserved.

In vitro assessment of dentin erosion after immersion in acidic beverages: Surface profile analysis and energy-dispersive X-ray fluorescence spectrometry study

The aim of this study was to investigate the effects of some acidic drinks on dentin erosion, using methods of surface profile (SP) analysis and energy-dispersive X-ray fluorescence spectrometry (EDXRF). One hundred standardized dentin slabs obtained from bovine incisor roots were used. Dentin slabs measuring 5x5 mm were ground flat, polished and half of each specimen surface was protected with nail polish. For 60 min, the dentin surfaces were immersed in 50 mL of 5 different drinks (Gatorade®, Del Valle Mais orange juice®, Coca-Cola®, Red Bull® and white wine), 20 blocks in each drink. The pH of each beverage was measured. After the erosive challenge, the nail polish was removed and SP was analyzed. The mineral concentration of dentin surfaces was determined by means of EDXRF. Data were analyzed statistically by ANOVA and Tukey's test (α=0.05). SP analysis showed that Red-Bull had the highest erosive potential (p<0.05). EDXRF results exhibited a decrease in phosphate in the groups immersed in Red-Bull, orange juice and white wine (p<0.05), and no significant difference in calcium content between the reference surface and eroded surface. In conclusion, this study demonstrated that all studied beverages promoted erosion on root dentin and Red Bull had the highest erosive potential. There was no correlation between pH of beverages and their erosive potential and only the P content changed after erosive challenge.

Comparative in vivo study of commercially pure Ti implants with surfaces modified by laser with and without silicate deposition: Biomechanical and scanning electron microscopy analysis

The purpose of this study was to evaluate commercially pure titanium implant surfaces modified by laser beam (LS) and LS associated with sodium silicate (SS) deposition, and compare them with machined surface (MS) and dual acid-etching surfaces (AS) modified. Topographic characterization was performed by scanning electron microscopy-X-ray energy dispersive spectroscopy (SEM-EDX), and by mean roughness measurement before surgery. Thirty rabbits received 60 implants in their right and left tibias. One implant of each surface in each tibia. The implants were removed by reverse torque for vivo biomechanical analysis at 30, 60, and 90 days postoperative. In addition, the surface of the implants removed at 30 days postoperative was analyzed by SEM-EDX. The topographic characterization showed differences between the analyzed surfaces, and the mean roughness values of LS and SS were statistically higher than AS and MS. At 30 days, values removal torque LS and SS groups showed a statistically significant difference (p < 0.05) when compared with MS and AS. At 60 days, groups LS and SS showed statistically significant difference (p < 0.05) when compared with MS. At 90 days, only group SS presented statistically higher (p < 0.05) in comparison with MS. The authors can conclude that physical chemistry properties and topographical of LS and SS implants increases bone-implant interaction and provides higher degree of osseointegration when compared with MS and AS. © 2012 Wiley Periodicals, Inc.

Fe K-edge X-ray absorption spectroscopy study of Pb(Fe2/3W 1/3)O3-PbTiO3 multiferroic ceramics

The present paper is a comprehensive study concerning Fe K-edge X-ray absorption spectroscopy (XAS) measurements, which were performed to characterize the local structure of (1 - x)Pb(Fe2/3W1/3)O 3-xPbTiO3 samples as a function of temperature and PbTiO3 content. Results obtained by the fits of extended X-ray absorption fine structure consist with rhombohedral symmetry for Pb(Fe 2/3W1/3)O3 composition at temperatures lower than room temperature. This result is in apparent disagreement with X-ray and neutron diffraction characterization which have been reported. This apparent disagreement is related to the fact that XAS probes the short-range order, whereas X-ray diffraction provides structural information about the average structure. Moreover, as the PbTiO3 content increases, a disorder has been detected at local structure of the FeO6 octahedron. Analysis of X-ray absorption near edge structure spectra did not show modifications in intensity nor energy of transitions. © 2013 American Institute of Physics.

Monte Carlo simulation applied in total reflection X-ray fluorescence: Preliminary results

The X-ray Fluorescence (XRF) analysis is a technique for the qualitative and quantitative determination of chemical constituents in a sample. This method is based on detection of the characteristic radiation intensities emitted by the elements of the sample, when properly excited. A variant of this technique is the Total Reflection X-ray Fluorescence (TXRF) that utilizes electromagnetic radiation as excitation source. In total reflection of X-ray, the angle of refraction of the incident beam tends to zero and the refracted beam is tangent to the sample support interface. Thus, there is a minimum angle of incidence at which no refracted beam exists and all incident radiation undergoes total reflection. In this study, we evaluated the influence of the energy variation of the beam of incident x-rays, using the MCNPX code (Monte Carlo NParticle) based on Monte Carlo method. © 2013 AIP Publishing LLC.

Role of Ca, Fe, Cu and Zn in breast cancer: Study by X-ray fluorescence techniques and immunohistochemical analysis

In recent years, several studies have shown that concentrations of trace elements are altered in neoplastic breast tissues. However, the microenvironment and metabolic changes caused by tumors are complex and still not completely understood. Under this aspect, the combination of different techniques to investigate the role of trace elements in promoting and/or maintaining a tumor is interesting once the combination of information obtained by analytical techniques and immunohistochemical assays, associated with clinicopathological data, may allow a better metabolic understanding of trace elements in breast cancer. In this work, the role of the trace elements Ca, Fe, Cu and Zn in neoplastic breast tissues was investigated by X-ray fluorescence (XRF) techniques and immunohistochemical assays. We determined concentrations of Ca, Fe, Cu and Zn in normal and neoplastic breast tissues using energy dispersive XRF, and these values were used to set the positive or negative expression of elements in normal and neoplastic tissues. These expressions were correlated with the spatial distributions of trace elements (evaluated by micro-XRF) and with immunoexpression of matrix metalloproteinases (MMPs), tissue inhibitors of MMPs and vascular endothelial growth factor. The results revealed that the expression of the trace elements Fe, Cu and vascular endothelial growth factor are related, indicating that higher levels of these elements can be associated with the angiogenic process in breast cancer. Also, associations between Ca, Zn and MMPs expression have been observed, possibly because of the fact that both metals are present in these proteins. © 2013 John Wiley & Sons, Ltd.

Simple procedure for nutrient analysis of coffee plant with energy dispersive X-ray fluorescence spectrometry (EDXRF)

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

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.

Ethanol electro-oxidation in an alkaline medium using Pd/C, Au/C and PdAu/C electrocatalysts prepared by electron beam irradiation

Carbon-supported Pd, Au and bimetallic PdAu (Pd:Au 90:10, 50:50 and 30:70 atomic ratios) electrocatalysts were prepared using electron beam irradiation. The obtained materials were characterized by energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their catalytic activities toward ethanol electro-oxidation were evaluated in an alkaline medium using electrochemical techniques, in situ attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) analysis and a single alkaline direct ethanol fuel cell (ADEFC). EDX analyses showed that the actual Pd: Au atomic ratios were very similar to the nominal ones. X-ray diffractograms of PdAu/C electrocatalysts evidenced the presence of Pd-rich (fcc) and Au-rich (fcc) phases. TEM analysis showed a homogeneous dispersion of nanoparticles on the carbon support, with an average size in the range of 3-5 nm and broad size distributions. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments revealed the superior ambient activity toward ethanol electro-oxidation of PdAu/C electrocatalysts with Pd: Au ratios of 90:10 and 50:50. In situ ATR-FTIR spectroscopy measurements have shown that the mechanism for ethanol electro-oxidation is dependent on catalyst composition, leading to different reaction products, such as acetaldehyde and acetate, depending on the number of electrons transferred. Experiments on a single ADEFC were conducted between 50 and 900 C, and the best performance of 44 mW cm-2 in 2.0molL-1 ethanol was obtained at 850C for the Pd:Au 90:10 catalysts. This superior performance is most likely associated with enhancement of ethanol adsorption on Pd, oxidation of the intermediates, the presence of gold oxide-hydroxyl species, low mean particle diameters and better distribution of particles on the support. © 2013 Elsevier Ltd. 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.

Estudo eletroquímico e termoanalítico dos sistemas Ir/Hg e Pt - (30%) Ir/Hg

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Multivariate curve resolution analysis applied to time-resolved synchrotron X-ray Absorption Spectroscopy monitoring of the activation of copper alumina catalyst

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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.

A Quality Assessment of Titanium Castings Produced in an Experimental Short-Heating-Cycle Investment

The aim of this study was to evaluate the quality of casting produced in an experimental short-term heating-cycle investment. Thus, reaction layer and castability of titanium casting using an experimental spinel-based investment (VR) with short heating cycle were compared with the commercial short-heating-cycle spinel-based investment Trinell (TR), the silica-phosphate-based investment Rematitan Plus ( RP), and the conventional spinel-based investment Rematitan Ultra (RU). VR has polymeric fibers added to inorganic particles. Reaction layer assessments were carried out using Vickers hardness and elemental analysis using dispersive X-ray microanalysis (EDX). Mesh patterns were used for castability test, and powder characterization was made by scanning electron microscopy (SEM). Hardness evaluation showed no difference among the investments between 100 and 200 mu m. The most important contaminant element for VR, TR, and RU was oxygen. Higher levels of mold filling were found for TR, VR, and RU compared with that obtained with RP. The quality of castings, characterized by means of the assessments of reaction layer and castability, made from the VR was similar to the commercial investments TR and RU but superior to the RP.

Thermal study of the solid-state reactions on Pt-15%Rh/Hg system

Thermogravimetry (TG), energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface and X-ray diffraction (XRD) were used for the study of solid-state reaction on Pt-15%Rh with electrodeposited mercury. The results suggest when heated the mercury film react with the Pt-15%Rh alloy to form intermetallics having different thermal stabilities indicated by three mass loss steps. The first mass loss step occurs between room temperature and 184 degrees C only the bulk Hg is removed and PtHg4, PtHg2 and RhHg2 were characterized by XRD. The second step, between 184 and 271 degrees C, was attributed to PtHg4 decomposition with formation of PtHg2 stabilized by RhHg2. The third step, between 271 and 340 degrees C, was attributed to decomposition of a solid-solution of PtHg2/RhHg2. The fourth step, between 340 and 600 degrees C, was ascribed to: (1) a thermal decomposition of PtHg2, formed by a PtHg eutectoid reaction (similar to 340 degrees C) on the surface and (2) Hg removal from a solid solution of Pt-15%Rh(Hg). (C) 2013 Elsevier B.V. All rights reserved.