Cholesterol Hydroperoxides Generate Singlet Molecular Oxygen [O(2) ((1)Delta(g))]: Near-IR Emission, (18)O-Labeled Hydroperoxides, and Mass Spectrometry

In mammalian membranes, cholesterol is concentrated in lipid rafts. The generation of cholesterol hydroperoxides (ChOOHs) and their decomposition products induces various types of cell damage. The decomposition of some organic hydroperoxides into peroxyl radicals is known to be a potential source of singlet molecular oxygen [O(2) ((1)Delta(g))] in biological systems. We report herein on evidence of the generation of O(2) ((1)Delta(g)) from ChOOH isomers in solution or in liposomes containing ChOOHs, which involves a cyclic mechanism from a linear tetraoxide intermediate originally proposed by Russell. Characteristic light emission at 1270 nm, corresponding to O(2) ((1)Delta(g)) monomolecular decay, was observed for each ChOOH isomer or in liposomes containing ChOOHs. Moreover, the presence of O(2) ((1)Delta(g)) was unequivocally demonstrated using the direct spectral characterization of near-infrared light emission. Using (18)O-labeled cholesterol hydroperoxide (Ch(18)O(18)OH), we observed the formation of (18)O-labeled O(2) ((1)Delta(g)) [(18)O(2) ((1)Delta(g))] by the chemical trapping of (18)O(2) ((1)Delta(g)) with 9,10-diphenylanthracene (DPA) and detected the corresponding (18)O-labeled DPA endoperoxide (DPA(18)O(18)O) and the (18)O-labeled products of the Russell mechanism using high-performance liquid chromatography coupled to tandem mass spectrometry. Photoemission properties and chemical trapping clearly demonstrate that the decomposition of Ch(18)O(18)OH generates (18)O(2) ((1)Delta(g)), which is consistent with the Russell mechanism and points to the involvement of O(2) ((1)Delta(g)) in cholesterol hydroperoxide-mediated cytotoxicity.

Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

The anionic complexes [Cu(L(1-))(3)](1-), L(-) = dopasemiquinone or L-dopasemiqui none, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the vCC + vCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g= 2.0005 and g = 2.0923, and for Cu(II) with g = 2.008 and g = 2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease. (c) 2008 Elsevier B.V. All rights reserved.

Studies on the resonance Raman spectra of polyaniline obtained with near-IR excitation

The effects of near-IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANIES) and base (PANI-EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm-1 in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm-` were associated to vC-N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm-1 in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to vC=N modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 run causes the deprotonation of PANI-ES and the formation of cross-linking segments having phenazine and/or oxazine rings. For PANI-EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright (c) 2007 John Wiley & Sons, Ltd.

Effect of the catalyst composition in the Pt-x(Ru-Ir)(1-x)/C system on the electro-oxidation of methanol in acid media

The effect of variations in the composition for ternary catalysts of the type Pt-x(Ru-Ir)(1-x)/C on the methanol oxidation reaction in acid media for x values of 0.25, 0.50 and 0.75 is reported. The catalysts were prepared by the sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic absorption spectroscopy (AAS) and energy dispersive X-ray (EDX) analyses. The nanometric character (2.8-3.2 nm) of the sol-gel deposits was demonstrated by XRD and TEM while EDX and AAS analyses showed that the metallic ratio in the compounds was very near to the expected one. Cyclic voltammograms for methanol oxidation revealed that the reaction onset occur at less positive potentials in all the ternary catalysts tested here when compared to a Pt-0.75-Ru-0.25/C (E-Tek) commercial composite. Steady-state polarization experiments (Tafel plots) showed that the Pt-0.25(Ru-Ir)(0.75)/C catalyst is the more active one for methanol oxidation as revealed by the shift of the reaction onset towards lower potentials. In addition, constant potential electrolyses suggest that the addition of Ru and Ir to Pt decreases the poisoning effect of the strongly adsorbed species generated during methanol oxidation. Consequently, the Pt-0.25 (Ru-Ir)(0.75)/C Composite catalyst is a very promising one for practical applications. (c) 2007 Elsevier B.V. All rights reserved.

Sanções ao Irã: como elas vêm impactando a sociedade civil iraniana?

O presente trabalho visa analisar quais os efeitos das sanções impostas pelos Estados Unidos da América, União Europeia e Conselho de Segurança das Nações Unidas contra a sociedade civil da República Islâmica do Irã. Inicialmente será abordado o histórico da construção das sanções, observando como se deu a relação entre os EUA e o Irã após 1979 até a imposição das mais recentes sanções, com ênfase no período pós-2009, época que apresenta uma mudança no comportamento das entidades sancionadoras. Vê-se que a política norte-americana para o Irã sempre foi baseada na dualidade entre diálogo e pressões econômicas, sendo este ultimo utilizado como ferramenta para desenvolvimento do primeiro. Em seguida se analisará todo o arcabouço jurídico construído com vistas a restringir a capacidade econômica iraniana e consequentemente sua capacidade de desenvolver seu programa nuclear. Neste capitulo é observada a amplitude que alcançaram as sanções e como estas buscam apesar de tudo gerar mecanismos de alivio a sociedade civil, deixando transparecer um discurso humanitário. O ultimo capitulo terá como ênfase os impactos das sanções na sociedade civil, nele será demonstrado que apesar das exceções legislativas, a população iraniana tem sido amplamente afetada. Através da analise de depoimentos e de noticias de periódicos serão vistas quais foram esses impactos e sua extensão. Por fim faremos um breve balanço do que fora apresentado, refletindo se quais os resultados alcançados pelas sanções e se eles superam os custos sociais impostos a população iraniana.

Contributo da Academia Sénior: a força de ir mais além! Um estudo descritivo simples e longitudinal da qualidade de vida do idoso

O aumento do número de idosos com necessidades de ocupação, implica a necessidade de respostas por parte da sociedade, de forma a melhorarem a qualidade de vida da população idosa. O presente estudo, teve como objetivo conhecer os níveis de perceção da qualidade de vida e bem-estar, em indivíduos de terceira idade. Trata-se de um estudo descritivo longitudinal, que resulta da avaliação em dois momentos. Foi estudada uma população com 26 idosos, com idades iguais ou superiores a 64 anos de idade, participantes num projeto educativo de uma academia sénior, com a duração de quatro meses. Foi utilizada a escala EASY-care, para avaliação da qualidade de vida percecionada pelos idosos. Para análise dos dados, utilizou-se o programa estatístico SPSS 19.0. Através dos resultados obtidos, verificou-se que a maioria da população estudada foi do sexo feminino, cerca de 92.3%, e 7.7% do sexo masculino. No que se referiu às idades, 26,9% apresentaram idades compreendidas entre 65-69 anos, 42.3%, entre 70-74 anos, e por fim 30.8% entre 75-80 anos. Sendo na sua maioria, viúva, reformada, pensionista e com fraca escolaridade, entendendo-se que, apenas 57.7% da população apresentou o primeiro ciclo de escolaridade. Os resultados obtidos revelaram-se positivos, uma vez que, os scores médios para cada domínio foram indicadores de independência e elevada qualidade de vida, em ambos os momentos de análise, com valores médios mais elevados no segundo momento. Para os resultados de “(in) dependência”, no primeiro momento, o score médio foi de 2.8. Para o “risco e falha de cuidados”, o score médio foi 3.7, para o “risco de quedas”, o score médio de 0.9. No segundo momento, para “pontuação (in) dependência”, o score médio foi 1.8, para o “risco de falha de cuidados,” de 0.88 e para o “risco de quedas”, de 0.6. No domínio “Visão, Audição e Comunicação”, no primeiro momento, o score médio foi de 0.55. No segundo momento, para o mesmo domínio, o score médio foi de 0.3. No domínio “Saúde Mental e Bem-estar”, no primeiro momento, o score médio foi de 10.7, e no segundo momento de 5.6. Concluiu-se que a perceção da qualidade de vida e bemestar dos idosos, foi elevada nos dois momentos, verificando-se um aumento dos valores absolutos do primeiro para o segundo momento. Ressalvamos a importância da monitorização da qualidade de vida e bem-estar dos idosos, como forma de promoção de uma intervenção adequada às necessidades da população.

Tramas da (ir)racionalidade contemporânea para a composição do mito-tecno-lógico

The plot myth-techno-logic, contemporary, was developed starting from the dualism myth-reason. In this study, we deepened the alluded dualism taking as reference the historical contexts of the Renaissance and of the Enlightenment, emphasizing the discussion of the economical rationalization as conductive thread of the western development, in which we identified the game of the rational and of the irrational, for assure the superiority of the reason. In the context of that game, we analyzed the implications of the modernization, for the education, in function of the instrumental rationality, responsible for the environment of adaptation of the technological instruments to the scenery of the contemporary modernization. The new context is constituted by points of union and of ruptures among the technique, the science and the myth. Through our analysis, we noticed that the basic needs for the contemporary society were linked to the changes in the production means, for which the machine determine the rhythm of the work and the quality of the product. However, the changes in the productive processes promoted the appearance of the commercial marks that, as we see it, they represented the synthesis of the perfect harmony of the myth, of the technique, of the science and of the technology, in the conduction of the economical rationalization to the contemporary modernization. Thus, the contemporary modernization it arrives us for the economical rationalization, developed with the support of the technician-scientific knowledge and communicated by the articulations of the myth-techno-logical

Estudo de coprólito da bacia sedimentar do Araripe por meios de espectroscopia FT-IR e difração de Raios-X

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Detecção de áreas degradadas na sub-bacia hidrográfica do rio taperoá/pb, utilizando parâmetros físicos dos sensores modis/terra e tm/landsat

This study includes the results of the analysis of areas susceptible to degradation by remote sensing in semi-arid region, which is a matter of concern and affects the whole population and the catalyst of this process occurs by the deforestation of the savanna and improper practices by the use of soil. The objective of this research is to use biophysical parameters of the MODIS / Terra and images TM/Landsat-5 to determine areas susceptible to degradation in semi-arid Paraiba. The study area is located in the central interior of Paraíba, in the sub-basin of the River Taperoá, with average annual rainfall below 400 mm and average annual temperature of 28 ° C. To draw up the map of vegetation were used TM/Landsat-5 images, specifically, the composition 5R4G3B colored, commonly used for mapping land use. This map was produced by unsupervised classification by maximum likelihood. The legend corresponds to the following targets: savanna vegetation sparse and dense, riparian vegetation and exposed soil. The biophysical parameters used in the MODIS were emissivity, albedo and vegetation index for NDVI (NDVI). The GIS computer programs used were Modis Reprojections Tools and System Information Processing Georeferenced (SPRING), which was set up and worked the bank of information from sensors MODIS and TM and ArcGIS software for making maps more customizable. Initially, we evaluated the behavior of the vegetation emissivity by adapting equation Bastiaanssen on NDVI for spatialize emissivity and observe changes during the year 2006. The albedo was used to view your percentage of increase in the periods December 2003 and 2004. The image sensor of Landsat TM were used for the month of December 2005, according to the availability of images and in periods of low emissivity. For these applications were made in language programs for GIS Algebraic Space (LEGAL), which is a routine programming SPRING, which allows you to perform various types of algebras of spatial data and maps. For the detection of areas susceptible to environmental degradation took into account the behavior of the emissivity of the savanna that showed seasonal coinciding with the rainy season, reaching a maximum emissivity in the months April to July and in the remaining months of a low emissivity . With the images of the albedo of December 2003 and 2004, it was verified the percentage increase, which allowed the generation of two distinct classes: areas with increased variation percentage of 1 to 11.6% and the percentage change in areas with less than 1 % albedo. It was then possible to generate the map of susceptibility to environmental degradation, with the intersection of the class of exposed soil with varying percentage of the albedo, resulting in classes susceptibility to environmental degradation