mer-[RuCl3(P-P)H2O] (P-P=dppb or diop) as a starting material for the synthesis of binuclear complexes. Crystallographic structures of [(dppb)ClRu-mu(Cl)(3)-RuCl(dppb)] and [(eta(6)-C6H6)Ru-mu(Cl)(3)-RuCl(dppb)]. Imine hydrogenation using mono- and binuclear ruthenium complexes

The reactivity of the mer-[RuCl3(dppb)H2O] complex (1) with di-hydrogen shows that the products formed depend on the conditions of the reaction, i.e., solvents and presence or absence of a base. The new mixed-valence complexes [(diop)ClRu-(h-Cl)(3)-RuCl(dppb)] (3), [(binap)CIRu-(p-Cl)(3)-RuCl(dppb)] (4), [(PPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (6), [(dppn)ClRu-(mu-Cl)(3)-RuCl(dppb)] (7), [(P-ptol(3))(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (8), [(SbPh3)(2)ClRu-(mu-Cl)(3)-RuCl(dppb)] (9), [(eta(6)-C6H6)Ru-(mu-Cl)(3)-RuCl(dppb)] (11) and the known mixed-valence [(dppb)CIRu-(mu-Cl)(3)-RuCl(dppb)] (5) and [(diop)ClRu-(mu-Cl)(3)-RuCl(diop)] (10) were synthesized from complexes (1) or (2) using a methodology developed in our research group. The known complexes [(dppb)ClRu-(mu-Cl)(2)-RuCl(dppb)] (12), [(dppb)(CO)Ru-(mu-Cl)(3)-RuCl(dppb)] (13) and [H2NEt2][(dppb)ClRu-(mu-Cl)(3)-RuCl(dppb)] (14) were synthesized by changing the reaction conditions between mer-[RuCl3(dppb)H2O] (1) and dihydrogen. The crystal structures of (5) and (11) were determined by single-crystal X-ray diffraction. Some of the complexes described here are effective pre-catalysts for the hydrogenation of imines. Preliminary results on the homogeneous hydrogenation of the imines Ph-CH2-N=CH-Ph and Ph-N=CH-Ph are presented. (C) 2004 Elsevier Ltd. All rights reserved.

Micro-Raman analysis of cubic GaN layers grown by MBE on (001) GaAs substrate

Cubic GaN layers are grown by molecular beam epitaxy on (001) GaAs substrates. Optical micrographs of the GaN epilayers intentionally grown at Ga excess reveal the existence of surface irregularities such as bright rectangular structures, dark dots surrounded by rectangles and dark dots without rectangles. Micro-Raman spectroscopy is used to study the structural properties of these inclusions and of the epilayers in greater detail. We conclude that the observed irregularities are the result of a melting process due to the existence of a liquid Ga phase on the growing surface.

Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)(2)

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

Photoreflectance studies of optical transitions in cubic GaN grown on GaAs(001) substrates

The optical properties of cubic GaN epitaxial layers were investigated by modulated photoreflectance (PR) and photoluminescence in the temperature interval from 5 to 300 K. The epilayers were grown on GaAs(001) substrates by molecular beam epitaxy using a nitrogen RIF-activated plasma source. The PR spectra show a transition which is well fitted using the third-derivative functional form of the unperturbed dielectric function, which we interpret as band-to-band transition. Our results allow determination of the temperature dependence of the main gap of c-GaN and give insights into the residual strain in the film, as well as allow us to estimate the binding energy of the complex formed by an exciton bound to a neutral acceptor. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Electronic and structural properties of the (001) SrZrO3 surface

The structural and electronic properties of SrZrO3 selected surfaces were investigated by means of density functional theory applied to periodic calculations at B3LYP level. The relaxation effects for two symmetric and asymmetric terminations are analyzed. The electronic and energy band properties are discussed on the basis of band structure as well density of states. There is a more significant rumpling in the SrO as compared to the ZrO2 terminated surfaces. The calculated indirect gap is 4.856, 4.562, 4.637 eV for bulk, ZrO2 and asymmetric terminations, respectively. The gap becomes direct; 4.536 eV; for SrO termination. The contour in the (110) diagonal plane indicates a partial covalent character between Zr and 0 atoms for the SrO terminated surface. (c) 2007 Elsevier B.V. All rights reserved.

Properties and one-step synthesis of (2-acetylpyridine)tetraammineruthenium(II), [Ru-II(2-acpy)(NH3)(4)](2+) and tetraammine(2-benzoylpyridine)ruthenium(II), [Ru-II(NH3)(4)(2-bzpy)](2+) Redox potentials, UV-Vis and NMR spectra

A more direct and efficient route to the syntheses of [Ru(NH3)(4)(X-Y)](BF4)(2), where X-Y can be 2-acetylpyridine (2-acpy) or 2-benzoylpyridine (2-bzpy), based on the reactions of [RuCl(NH3)(5)]Cl-2 with these ortho-substituted azines is described. The [Ru(2-acpy)(NH3)(4)](BF4)(2) and [Ru(NH3)(5)(2-bzpy)](BF4)(2) complexes have a molar conductance of 328 and 292 Ohm(-1) cm(2) mol(-1), respectively, corresponding to a 1:2 species in solution. These complexes showed two intense absorption bands around 620-650 and 380 nm, the energies of which are solvent dependent, decreasing with the increase of the Gutman's donor number of the solvent, and were assigned as metal-to-ligand charge transfer (MLCT). The complexes have oxidation potentials (Ru-II/III) of +0.380 V vs. Ag/AgCl (2-acpy) and +0.400 V vs. Ag/AgCl (2-bzpy), and reduction potentials (X-Y0/-) of -1.10 V vs. Ag/AgCl (2-acpy) and -0.950 V vs. Ag/AgCl (2-bzpy) on CF3COOH/NaCF3COO at pH=3.0, scan rate 100 mV s(-1), [Ru]=1.0x10(-3) mol l(-1). Both processes show a coupled chemical reaction. Upon oxidation of the metal center, the MLCT absorption bands are bleached and restored upon subsequent reduction. In order to confirm the structure of the complexes a detailed LH NMR investigation was performed in d(6)-acetone. Further confirmation of the structure was obtained by recording the N-15 NMR spectrum of [Ru(NH3)(4)(2-bzpy)](2+) in d(6)-DMSO using the INEPT pulse sequence improving the sensitivity of N-15 by polarization transfer from the protons to the N-15. The Nuclear Overhauser Effect (NOE) experiments were made qualitatively for [Ru(NH3)(4)(2-acpy)](2+), and showed that H-6 of the pyridine is close to a NH3 proton, which should then be in a cis position, and, hence, confirming that acpy is acting as a bidentate ligand. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

Hybrid reflections in InGaP/GaAs(001) by synchrotron radiation multiple diffraction

Hybrid reflections (HRs) involving substrate and layer planes (SL type) [Morelhao et al., Appl. Phys. Len. 73 (15), 2194 (1998)] observed in Chemical Beam Epitaxy (CBE) grown InGaP/GaAs(001) structures were used as a three-dimensional probe to analyze structural properties of epitaxial layers. A set of (002) rocking curves (omega-scan) measured for each 15 degrees in the azimuthal plane was arranged in a pole diagram in phi for two samples with different layer thicknesses (#A -58 nm and #B - 370 nm) and this allowed us to infer the azimuthal epilayer homogeneity in both samples. Also, it was shown the occurrence of (1 (1) over bar3) HR detected even in the thinner layer sample. Mappings of the HR diffraction condition (omega:phi) allowed to observe the crystal truncation rod through the elongation of HR shape along the substrate secondary reflection streak which can indicate in-plane match of layer/substrate lattice parameters. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Kinetic studies on the reactions of Ru(II) tetraammines with CS2N- 3

The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

Phochemical behavior of trans-[Ru(NH3)4P(OEt)3L]2+ complex ions (L = P(OEt)3, CO, H2O)

trans-[Ru(NH3)4P(OEt)3H2O] 2+, trans-[Ru(NH3)4(P(OEt)3)]2+, and trans-[Ru(NH3)4P(OEt)3CO]2+ were photolyzed with light of 313 nm on the lowest energy ligand field excited state. Photoaquation of the thermally substitution inert ammonia is observed for all three complexes with φ ≅ 0.30 mol/einstein. trans-[Ru(NH3)4(P(OEt)3)2] 2+ undergoes P(OEt)3 photoaquation with φ ≅ 0.12 mol/einstein, while trans-[Ru(NH3)4P(OEt)3CO]2+ displays CO photoaquation with φ = 0.07 mol/einstein. The results suggest that the electronic configuration of the lowest energy excited state of these complexes have contributions from E and A2 states. Furthermore, in trans-[Ru(NH3)4P(OEt)3CO]2+ the photoaquation of CO is explained by depopulation of a bonding dπ orbital and population of a σ* orbital. © 1992 American Chemical Society.

Carriers escape mechanisms in shallow InGaAs/GaAs quantum wells grown on vicinal (001) GaAs substrates

We used photoluminescence spectroscopy in order to investigate the carriers escape mechanisms in In0.15Ga0.85As/GaAs quantum wells grown on top of nominal (001) and 2°-, 4°-and 6°-off (001) towards (111)A GaAs substrates. We described the escape processes using two models that fit the Arrhenius plot of the integrated PL intensity as a function of the inverse of the sample temperature. In the first model, we considered equal escape probability for electrons and holes. In the second one, we assumed that a single type of carrier can escape from the well. At high temperature, the first model fits the experimental data well, whereas, between 50 K and 100 K, the second model has to be taken into account to describe the data. We observed that the escape activation energy depends on the misorientation angle. An unusual behavior was noted when the full width at half maximum of the photoluminescence main emission was plotted as a function of the sample temperature. We showed that the escape process of the less-confined carriers drives this behavior. © 1999 Academic Press.

Effects of heat treatments on the electrocatalytic activity of Pt-Ru/C for methanol oxidation

The Pt-Ru/C materials of this study were prepared by a microemulsion method with fixed water to surfactant molar ratio and heat treated at low temperatures, to avoid changes in the average particle size, in different atmospheres. All samples were characterized by X-ray diffraction (XRD) and the mean crystallite size was estimated by using Scherrer's equation. Catalysts morphology was characterized by transmission electron microscopy (TEM). Average composition was obtained by energydispersive X-ray analysis (EDX). The general electrochemical behavior was evaluated by cyclic voltammetry in 0.5 M sulfuric acid and the electrocatalytic activity towards the oxidation of methanol was studied in 0.5 M methanol acid solutions by potential sweeps and chronoamperometry. Oxidation of adsorbed CO was used to estimate the electrochemical active area and to infer the surface properties. ©The Electrochemical Society.

Hydrostatic and [001] uniaxial pressure on anatase TiO2 by periodic B3LYP-D* calculations

The effect of high hydrostatic and [001] uniaxial pressures on TiO 2 anatase was studied under the framework of periodic calculations with the inclusion of DFT-D2 dispersion potential adjusted for this system (B3LYP-D*). The role of dispersion in distorted unit cells was evaluated in terms of lattice parameters, elastic constants, equation of state, vibrational properties, and electronic properties (band structure and density of states). A more reliable description at high pressures was achieved because the B3LYP-D* presented an improvement in all properties for undistorted bulk over conventional B3LYP and B3LYP-D. From density of states analysis, we observed that the contribution of crystalline orbitals to the edge of valence and conduction bands changed within applied pressure. The studied distortions can give some insight into behavior of electronic and structural properties due to local stress in anatase bulk from doping, defects, and physical tensions in nanometric forms. © 2013 American Chemical Society.

Structural and electrical properties of LaNiO3 thin films grown on (100) and (001) oriented SrLaAlO4 substrates by chemical solution deposition method

LaNiO3 thin films were deposited on SrLaAlO4 (1 0 0) and SrLaAlO4 (0 0 1) single crystal substrates by a chemical solution deposition method and heat-treated in oxygen atmosphere at 700° C in tube oven. Structural, morphological, and electrical properties of the LaNiO 3 thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and electrical resistivity as temperature function (Hall measurements). The X-ray diffraction data indicated good crystallinity and a structural preferential orientation. The LaNiO3 thin films have a very flat surface and no droplet was found on their surfaces. Samples of LaNiO3 grown onto (1 0 0) and (0 0 1) oriented SrLaAlO4 single crystal substrates reveled average grain size by AFM approximately 15-30 nm and 20-35 nm, respectively. Transport characteristics observed were clearly dependent upon the substrate orientation which exhibited a metal-to-insulator transition. The underlying mechanism is a result of competition between the mobility edge and the Fermi energy through the occupation of electron states which in turn is controlled by the disorder level induced by different growth surfaces. © 2013 Elsevier Ltd and Techna Group S.r.l.

Participação do endotélio e das espécies reativas de oxigênio no efeito hipotensor e na resposta vasodilatadora do novo doador de Óxido Nítrico [Ru(terpy)(bdq)NO+]3+ (TERPY) em ratos espontaneamente hipertensos (SHR)

Pós-graduação em Ciências Fisiológicas - FOA

Estudo das propriedades de eletrocatalisadores de Pt-Ru nanoparticulados preparados via microemulsão para oxidação de metanol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)