Calculations of vibrational frequencies, Raman activities and degrees of depolarization for complexes involving water, methanol and ethanol

Raman activities and degrees of depolarization are reported for 14 complexes involving methanol, ethanol and water using the MP2/aug-cc-pVDZ model. For ethanol both trans and gauche isomers are considered. The red-shifts of the OH stretching and the blue shifts of the bending tau(CO-OH) mode were analyzed for the proton-donor molecules upon hydrogen bond. The shift of the nu(CO) stretching mode of the alcohol molecules are also analyzed and found to be specific giving characterization of the amphoteric relation, being positive for the proton-acceptor and negative for the proton-donor molecule. (c) 2008 Elsevier B.V. All rights reserved.

Spectroscopic evidences of the presence of hydrogenated species on the surface of copper during CO(2) electroreduction at low cathodic potentials

Carbon dioxide electroreduction on copper electrode was studied by surface enhanced Raman scattering (SERS) in K(2)SO(4) aqueous solutions with different pH values. CO(2) was bubbled into the solution at 0 V vs. Ag/AgCl, i.e., on an oxidized copper surface. In acidic solutions (pH around 2.5), at -0.2 V, bands indicative of the presence of ethylene on the electrode surface were detected. Although ethylene is knowledgably a product of CO(2) electroreduction on copper, it was not experimentally identified on the electrode`s surface at such a low cathodic potential in prior works. In solutions with pH around 2.5, CO bands were not observed, suggesting that hydrocarbons could be formed by a pathway that does not occur via adsorbed CO. In solutions with higher pHs, a complex spectral pattern, between 800 and 1700 cm(-1), was observed at approximately -0.4 V. The observed spectrum closely resembles those reported in the literature for adsorption of monocarboxylic acids with small chains. The spectral features indicate the presence of a structure containing a double C=C bond. a carboxyl group, and C-H bonds on the electrode`s surface. SERS spectra obtained in CO-saturated solution are also presented. However, in this case, no SERS bands were observed in the region between 800 and 1700 cm(-1) at low cathodic potentials. (c) 2009 Elsevier B.V. All rights reserved.

Comparison of SERS performances of Co and Ni ultrathin films over silver to electrochemically activated Co and Ni electrodes

In this work, the surface-enhanced Raman scattering (SERS) spectra of pyridine (py) on thin films of Co and Ni electrodeposited on an Ag electrode activated by oxidation-reduction cycles (ORC) are presented. The SERS spectra from the thin films were compared to those of py on activated bare transition metal electrodes. It was verified that the SERS spectra of py on 3 monolayers (ML)-thick films of Ni and Co presented only bands assignable to the py adsorbed on transition metal surfaces. It was also observed that even for 50 ML-thick transition metal films, the py SERS intensity was ca. 40% of the intensity from the 3 ML-thick films. The relative intensities of the SERS bands depended on the thickness of the films, and for films thicker than 7 ML for Co and 9 ML for Ni they were very similar to those of the bare transition metal electrodes. The transition metal thin films over Ag activated electrodes presented SERS intensities 3 orders of magnitude higher than the ones from bare transition metal electrodes. These films are more suitable to study the adsorption of low Raman cross-section molecules than are ORC-activated transition metal electrodes.

FT-Raman investigation of biodegradable polymers: Poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

This work presents a FT-Raman study (lambda(0) = 1064 nm) of naturally occurring polyester poly[(R)-3-hydroxybutyrate] (PHB) and its copolymer poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] (PHBV) with 5,8 and 12 mol % of HV (hydroxyvalerate). The FT-Raman spectra of films indicate that full width at half height of the band centered at 1725 cm(-1) and relative intensity of bands at 1443 and 1458 cm(-1) can be use to estimate the crystalline degree in film samples. The similarity between Raman spectra of molten PHB and PHBV and theirs CDCl(3) solutions suggested that molten polymers present similar conformation than polymers in solution. Raman data of these samples showed that bands at 1220, 1402, 1725, 2998 and 3009 cm(-1) are due to crystalline helical structure and the bands at 1453, 1740, 2881, 2938 and 2990 cm(-1) are originated from disordered domains. It is shown that composition of PHBV samples can be estimated by analyzing the ratio of the intensity of the bands at 2938 cm(-1) (nu C-H) and 1740 cm(-1) (nu C=O) in the spectra of solutions and of bands at 1354 (wCH(2)) and 1740 cm(-1) (nu C=O) in spectra of molten polymers. (C) 2010 Elsevier B.V. All rights reserved.

Adsorption of 4-aminopyridine on Co and Ag electrodes probed by SERS

The adsorption of 4-aminopyridine (4-AP) on Co and Ag electrodes in acid or alkaline solutions of KCl and KI electrolyte salts were monitored by the Surface-enhanced Raman Spectroscopy (SERS) technique. The SERS intensity for the Ag electrode was in 2 orders of magnitude higher than for the Co electrode, due to the enhancement of the Raman cross-section on Ag by the surface-plasmon excitation. In acidic chloride medium (pH 4), the SERS results for Ag electrodes indicate that the protonated form of 4-AP (4-APH(+)) adsorbs in the potential range of -0.1 to -0.6 V (Ag broken vertical bar AgCl broken vertical bar KCl sat) through hydrogen-bonding between 4-APH(+) and Cl(-) adsorbed on the electrode surface: at more negative potentials the neutral form 4-AP is the predominant adsorbed species. For Co electrode in the same medium, only bands due to neutral 4-AP were observed in the spectra at -0.8 and -0.9 V. For more negative potentials bands assigned to both 4-AP and 4-AP surface complex are observed, with the lasts being enhanced, as the potentials are turned more negative. In alkaline chloride medium (pH 13), for less negative potentials the bands assigned to free 4-AP were observed in the spectra of both Ag and Co surfaces. For more negative potentials, only bands assigned to the 4-AP surface complex were observed. For 0.1 mol L(-1) KI acidic or alkaline solutions, bands assigned to 4-AP and 4-APH(+) were observed in a wider potential range than in chloride solutions. An adsorption scheme of 4-AP on Ag and Co is proposed for acidic and alkaline solutions. (C) 2010 Elsevier B.V. All rights reserved.

Cation size effects-modified phase and PTCR development in Er3+ and Ca2+ co-doped BaTiO3 ceramics during sintering

Development of the positive temperature coefficient of resistivity (PTCR) in Er3+ and Ca2+ co-doped ferroelectric BaTiO3 was studied in this work, with Er3+ being used to act as a donor doping. Irrespective of all the materials showing high densities after sintering at 1200 to 1300 ºC, these revealed insulator at the lowest sintering temperature, changing to semiconducting and PTCR-type materials only when the sintering temperature was further increased. Observations from X-ray diffraction help correlating this effect with phase development in this formulated (Ba,Ca,Er)TiO3 system, considering the formation of initially two separated major (Ba,Ca)TiO3- and minor (Ca,Er)TiO3-based compounds, as a consequence of cation size-induced stress energy effects. Thus, appearance and enhancement here of the semiconducting and PTCR responses towards higher sintering temperatures particularly involve the incorporation of Er3+ into the major phase, rendering finally possible the generation and "percolative-like" migration of electrons throughout the whole material.

Óxidos do tipo perovskita para reação de redução de no com CO

In this work, the perovskite-type oxides LaNiO3, LaMnO3, La0,7Sr0,3NiO3 and La0,7Sr0,3MnO3 were prepared by co-precipitation and tested in the NO reduction with CO at 400 and 500 ºC for 10 h. The catalysts were characterized by X-ray diffraction, temperature programmed reduction with hydrogen, nitrogen adsorption and chemical analysis. The nonstoichiometric oxygen was quantified by temperature programmed reduction, and the catalytic tests showed that the La0,7Sr0,3MnO3 catalyst presented the higher performance for the reduction reaction of NO with CO. The partial substitution of lanthanum by strontium increased the NO conversion and the N2 yield.

Co-eletrodeposição oscilatória de cobre e estanho

It is investigated in the present contribution the oscillatory co-electrodeposition of CuSn on a polycrystalline gold surface in the presence of Triton X-100 surfactant and citric acid as additive, in acidic media. The experiments were conducted under potentiostatic control and the system dynamics characterized in terms of the morphology and stability of the current oscillations. Besides modulations in the frequency and amplitude of the current oscillations, several patterned states were observed, including relaxation-like and mixed mode oscillations. The oscillations were found to be very robust and some time series presented regular motions up to about two hours.

Áreas de vulnerabilidade para co-infecção HIV-aids/TB em Ribeirão Preto, SP

OBJETIVO: Identificar áreas de vulnerabilidade para os casos novos de co-infecção HIV/tuberculose (TB). MÉTODOS: Estudo descritivo ecológico realizado por meio do georreferenciamento dos casos novos de HIV/TB notificados em Ribeirão Preto, SP, em 2006. Os dados foram obtidos do sistema de informação estadual paulista de notificação de TB. Os casos novos de co-infecção HIV/TB foram analisados conforme características sociodemográficas e clínicas e, posteriormente, georreferenciados na base cartográfica do município segundo endereço residencial. Os setores do município foram categorizados em três níveis socioeconômicos: inferior, intermediário e superior, com base na análise de componentes principais das variáveis do censo demográfico de 2000 (renda, instrução e percentagem de domicílios com cinco ou mais moradores). Foi calculada a incidência da co-infecção HIV/TB para cada nível socioeconômico. RESULTADOS: A co-infecção HIV/TB acometeu mais adultos do sexo masculino em idade economicamente ativa e a forma pulmonar da TB foi a mais comum. A distribuição espacial mostrou que as incidências nas áreas com níveis socioeconômicos intermediários e inferiores (8,3 e 11,5 casos por 100 mil habitantes, respectivamente) foram superiores àquela (4,8 casos por 100 mil habitantes) de nível socioeconômico superior. CONCLUSÕES: A taxa de incidência de co-infecção HIV/TB analisada por níveis socioeconômicos mostrou padraÞo espacial de distribuiçaÞo não homogêneo e apresentou valores mais altos em áreas de maior vulnerabilidade social. O estudo diagnosticou aìreas geograìficas prioritaìrias para o controle da co-infecção e a tecnologia do sistema de informação geográfica pode ser empregada no planejamento das ações em saúde pelos gestores municipais.

Prótese total articulada de joelho utilizada no tratamento de osteossarcoma apendicular em cão

O objetivo do trabalho foi reportar o planejamento cirúrgico, a técnica operatória, a instrumentação e os resultados da substituição completa do terço médio distal do fêmur, do platô tibial e da articulação do joelho por prótese em um cão acometido por osteossarcoma no fêmur esquerdo. A prótese foi confeccionada em aço, apresentando três componentes articulados, mantendo o movimento semelhante à articulação do joelho. As porções femorais e tibiais da prótese foram cimentadas aos respectivos ossos, após ostectomia do fêmur e do platô tibial. O animal foi submetido a seis sessões de quimioterapia, com doxorrubicina e carboplatina, intercaladas mensalmente, objetivando inibir o crescimento de possíveis metástases pulmonares. Durante os seis primeiros dias, o animal apresentou neuropraxia e impotência funcional do membro. Aos 10 dias, o cão iniciou leve apoio e aos 30 dias já utilizava o membro pélvico de forma mais efetiva, porém, o ângulo de extensão da articulação foi reduzido de 150° a 100° devido à contratura muscular e à fibrose na região da fossa poplítea. Após um ano de observação, não houve melhora do ângulo de extensão do joelho, porém, o animal fazia uso do membro com claudicação. Aos 425 dias de pós-operatório, o animal veio a óbito por insuficiência renal. Nesse tempo não ocorreram metástases pulmonares ou locais visíveis radiograficamente, mas o proprietário não permitiu a realização da necropsia do paciente, sendo impossível confirmar outros dados que pudessem esclarecer melhor a causa morte. Conclui-se que a substituição total do joelho de cão é uma cirurgia factível, que permite a preservação e a utilização do membro após ressecção da neoplasia, embora outras pesquisas devam ser conduzidas para obtenção de melhores resultados pós-cirúrgicos.

Meningoencefalite necrotizante de cão Maltês

A Meningoencefalite Necrotizante (MEN) é uma encefalopatia causada por uma disfunção inflamatória de característica necrotizante. O objetivo deste relato é descrever os aspectos clínicos e anatomopatológicos da Meningoencefalite Necrotizante (MEN) em um cão Maltês. A doença tem um caráter necrótico único e está relacionada intimamente à Encefalite do Cão Pug (ECP) devido a suas semelhanças, bem como à Leucoencefalite Necrotizante (LEN). Embora o primeiro relato de caso de ECP tenha mais de 15 anos e o primeiro relato de caso de MEN em Maltês tenha 11 anos, há muito a ser revelado sobre a etiologia e os mecanismos imunopatológicos da doença. Neste trabalho, relata-se o caso de um cão Maltês com sinais que foram compatíveis com a MEN. Foram detectadas nas imagens macroscópicas, cavitação cerebral, e na microscopia, perda de células do parênquima em certas regiões do córtex cerebral. A partir dessas descobertas descreve-se o primeiro caso de MEN em cão Maltês no Brasil.

Microstructural Evidence of beta Co(2)Si- phase Stability in the Co-Si System

The aim of this work was to verify the stability of the beta Co(2)Si phase in the Co-Si system. The samples were produced via arc-melting and characterized through Scanning Electron Microscopy (SEM) and Differential Thermal Analysis (DTA). The results have confirmed the stability of the beta Co(2)Si phase, however, a modification of the shape of beta CoSi phase field is proposed in order to fully explain the results.

High levels of T lymphocyte activation in Leishmania-HIV-1 co-infected individuals despite low HIV viral load

Background: Concomitant infections may influence HIV progression by causing chronic activation leading to decline in T-cell function. In the Americas, visceral (AVL) and tegumentary leishmaniasis (ATL) have emerged as important opportunistic infections in HIV-AIDS patients and both of those diseases have been implicated as potentially important co-factors in disease progression. We investigated whether leishmaniasis increases lymphocyte activation in HIV-1 co-infected patients. This might contribute to impaired cellular immune function. Methods: To address this issue we analyzed CD4(+) T absolute counts and the proportion of CD8(+) T cells expressing CD38 in Leishmania/HIV co-infected patients that recovered after anti-leishmanial therapy. Results: We found that, despite clinical remission of leishmaniasis, AVL co-infected patients presented a more severe immunossupression as suggested by CD4(+) T cell counts under 200 cells/mm(3), differing from ATL/HIV-AIDS cases that tends to show higher lymphocytes levels (over 350 cells/mm(3)). Furthermore, five out of nine, AVL/HIV-AIDS presented low CD4(+) T cell counts in spite of low or undetectable viral load. Expression of CD38 on CD8(+) T lymphocytes was significantly higher in AVL or ATL/HIV-AIDS cases compared to HIV/AIDS patients without leishmaniasis or healthy subjects. Conclusions: Leishmania infection can increase the degree of immune system activation in individuals concomitantly infected with HIV. In addition, AVL/HIV-AIDS patients can present low CD4(+) T cell counts and higher proportion of activated T lymphocytes even when HIV viral load is suppressed under HAART. This fact can cause a misinterpretation of these laboratorial markers in co-infected patients.

Ultra-Structural Changes at the Apical Stop Irradiated with CO(2) Laser

Objective: This study evaluated ultra-structural dentine changes at the apical stop after CO(2) laser irradiation used during biomechanical preparation. Background: Most studies evaluating the sealing efficiency of CO(2) lasers have been carried out after apical root canal resections and retro-filling procedures. Methods: Sixty human canines were prepared with #1 to #6 Largo burs. The apical stops were established at 1 mm (n = 30) and 2 mm (n = 30) from the apex. Final irrigation was performed with 1% NaOCl and 15% EDTA followed by 20 ml of distilled and deionized water. Specimens were subdivided into three subgroups (n = 10 for each stop distance): GI-no radiation (n = 20); GII-3W potency (n = 20), GIII-5W potency (n = 20). After preparation, specimens were evaluated by scanning electron microscopy, with ultra-structural changes classified according to a scoring system based on six qualitatively different outcomes. Results: Statistical analysis using the Mann-Whitney test confirmed more intense results for the specimens irradiated at 5 W potency than at 3 W (p<0.0001). The Kruskal-Wallis test indicated that when using the same potencies (3 or 5 W) at 1 and 2 mm from the apex, there were no statistically significant differences in ultra-structural changes. Conclusions: Our results showed that ultra-structural changes ranged from smear layer removal to dentine fusion. As laser potency was increased from 3 to 5 W, ultra-structural changes included extensive fused lava-like areas sealing the apical foramen.

First stars XI. Chemical composition of the extremely metal-poor dwarfs in the binary CS 22876-032

Context. Unevolved metal-poor stars constitute a fossil record of the early Galaxy, and can provide invaluable information on the properties of the first generations of stars. Binary systems also provide direct information on the stellar masses of their member stars. Aims. The purpose of this investigation is a detailed abundance study of the double-lined spectroscopic binary CS 22876-032, which comprises the two most metal-poor dwarfs known. Methods. We used high-resolution, high-S/N ratio spectra from the UVES spectrograph at the ESO VLT telescope. Long-term radial-velocity measurements and broad-band photometry allowed us to determine improved orbital elements and stellar parameters for both components. We used OSMARCS 1D models and the TURBOSPECTRUM spectral synthesis code to determine the abundances of Li, O, Na, Mg, Al, Si, Ca, Sc, Ti, Cr, Mn, Fe, Co and Ni. We also used the (COBOLD)-B-5 model atmosphere code to compute the 3D abundance corrections, notably for Li and O. Results. We find a metallicity of [Fe/H] similar to -3.6 for both stars, using 1D models with 3D corrections of similar to -0.1 dex from averaged 3D models. We determine the oxygen abundance from the near-UV OH bands; the 3D corrections are large, -1 and -1.5 dex for the secondary and primary respectively, and yield [O/Fe] similar to 0.8, close to the high-quality results obtained from the [OI] 630 nm line in metal-poor giants. Other [alpha/Fe] ratios are consistent with those measured in other dwarfs and giants with similar [Fe/H], although Ca and Si are somewhat low ([X/Fe] less than or similar to 0). Other element ratios follow those of other halo stars. The Li abundance of the primary star is consistent with the Spite plateau, but the secondary shows a lower abundance; 3D corrections are small. Conclusions. The Li abundance in the primary star supports the extension of the Spite Plateau value at the lowest metallicities, without any decrease. The low abundance in the secondary star could be explained by endogenic Li depletion, due to its cooler temperature. If this is not the case, another, yet unknown mechanism may be causing increased scatter in A( Li) at the lowest metallicities.