989 resultados para Cu-ZnO-ZrO2 : HZSM-5


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We have demonstrated previously that the complex bis[(2-oxindol-3-ylimino)-2-(2-aminoethyl)pyridine-N,N`]copper(II), named [Cu(isaepy)(2)], induces AMPK (AMP-activated protein kinase)-dependent/p53-mediated apoptosis in tumour cells by targeting mitochondria. In the present study, we found that p38(MAPK) (p38 mitogen-activated protein kinase) is the molecular link in the phosphorylation cascade connecting AMPK to p53. Transfection of SH-SY5Y cells with a dominant-negative mutant of AMPK resulted in a decrease in apoptosis and a significant reduction in phospho-active p38(MAPK) and p53. Similarly, reverse genetics of p38(MAPK) yielded a reduction in p53 and a decrease in the extent of apoptosis, confirming an exclusive hierarchy of activation that proceeds via AMPK/p38(MAPK)/p53. Fuel supplies counteracted [Cu(isaepy)(2)]-induced apoptosis and AMPK/p38(MAPK)/p53 activation, with glucose being the most effective, suggesting a role for energetic imbalance in [Cu(isaepy)(2)] toxicity. Co-administration of 3BrPA (3-bromopyruvate), a well-known inhibitor of glycolysis, and succinate dehydrogenase, enhanced apoptosis and AMPK/p38(MAPK)/p53 signalling pathway activation. Under these conditions, no toxic effect was observed in SOD (superoxide dismutase)-overexpressing SH-SY5Y cells or in PCNs (primary cortical neurons), which are, conversely, sensitized to the combined treatment with [Cu(isaepy)(2)] and 3BrPA only if grown in low-glucose medium or incubated with the glucose-6-phosphate dehydrogenase inhibitor dehydroepiandrosterone. Overall, the results suggest that NADPH deriving from the pentose phosphate pathway contributes to PCN resistance to [Cu(isaepy)(2)] toxicity and propose its employment in combination with 3BrPA as possible tool for cancer treatment.

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Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts promoted with different quantities of Group 11 metals (Cu, Ag, Au) were characterized and tested. The presence of relatively small quantities of such metals enhanced Co reducibility and, in the cases of Ag and Au, improved the surface Co metal active site densities. EXAFS experiments with the most loaded catalyst samples show that only Co-Co and Me-Me (Me = Cu, Ag and Au) coordination could be observed. This suggests that the greater fraction of the metals form different phases. However, the reduction promoting effect of the Group 11 metal is severely hampered once the catalyst receives a mild passivation treatment following primary reduction. An explanation in terms of promoter segregation during primary reduction is proposed. At lower promoter levels (0.83%Ag and 1.51%Au) and higher Ag levels (2.76%), significant gains in Co active site densities were achieved resulting in improved CO conversion levels relative to the unpromoted catalyst. Moreover, slight decreases in light product (e.g., CH(4)) selectivity and slight increases in C(5)+ selectivity were achieved. At high Au loading (5.05%), however, too much Au was loaded which, although significantly increasing the fraction of Co reduced, blocked Co surface sites and resulted in decreased Co conversion rates. While Cu facilitated Co reduction, the increased fraction of reduced Co did not translate to improved active site densities. It appears that a fraction of Cu tended to cover the rim of Co clusters, resulting in decreases in CO conversion rates and detrimental increases in light product selectivity. (C) 2009 Elsevier B.V. All rights reserved.

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A new method is presented for spectrophotometric determination of total polyphenols content in wine. The procedure is a modified CUPRAC method based on the reduction of Cu(II), in hydroethanolic medium (pH 7.0) in the presence of neocuproine (2,9-dimethyl-1,10-phenanthroline), by polyphenols, yielding a Cu(I) complexes with maximum absorption peak at 450 nm. The absorbance values are linear (r = 0.998, n = 6) with tannic acid concentrations from 0.4 to 3.6 mu mol L(-1). The limit of detection obtained was 0.41 mu mol L(-1) and relative standard deviation 1.2% (1 mu mol L(-1); n = 8). Recoveries between 80% and 110% (mean value of 95%) were calculated for total polyphenols determination in 14 commercials and 2 synthetic wine samples (with and without sulphite). The proposed procedure is about 1.5 more sensitive than the official Folin-Ciocalteu method. The sensitivities of both methods were compared by the analytical responses of several polyphenols tested in each method. (C) 2010 Elsevier Ltd. All rights reserved.

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A flow system exploiting the multicommutation approach is proposed for spectrophotometric determination of tannin in beverages. The procedure is based on the reduction of Cu(II) in the presence of 4,4`-dicarboxy-2,2`-biquinoline, yielding a complex with maximum absorption at 558 nm. Calibration graph was linear (r=0.999) for tannic acid concentrations up to 5.00 mu mol L-1. The detection limit and coefficient of variation were estimated as 10 nmol L-1 (99.7% confidence level) and 1% (1.78 mu mol L-1 tannic acid, n=10), respectively. The sampling rate was 50 determinations per hour. The proposed procedure is more sensitive and selective than the official Folin-Denis method, also minimizing drastically waste generation. Recoveries within 91.8 and 115% were estimated for total tannin determination in tea and wine samples. (C) 2007 Elsevier B.V. All rights reserved.

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Three novel acetato-bridged dinuclear copper(II) complexes with 5-nitroimidazoles (CuAcNtrim) and the known copper-acetato-metronidazole have been prepared by an environment-friendly route and spectroscopically characterized. The CuAcNtrim compounds of formula [Cu(2)(mu-O(2)CCH(3))(4)Ntrim(2)], where Ntrim = metronidazole (1), secnidazole (2), tinidazole (3) or nimorazole (4), exhibit dimeric copper-acetato paddle-wheel structures with Ntrim axial ligands coordinated to copper(II) ions through the N(3) atoms of the imidazole rings. EPR data indicate antiferromagnetic behavior for this novel series of copper complexes. The constant coupling has been found to decrease along with the increasing of basicity of the Ntrim axial ligand. The CuAcNtrim complexes and the correspondent Ntrim parent drugs have shown radiosensitizer properties for Hep2 (human larynx cancer) cell line in vitro. The best enhancement of radiosensitizer activity upon coordination of the Ntrim drug to copper(II) has been found for the nimorazole compound which has the strongest Cu-Ntrim bond and exhibits the highest lipophilicity within the series of CuAcNtrim complexes. (C) 2010 Elsevier B.V. All rights reserved.

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In this work the effect of doping concentration and depth profile of Cu atoms on the photocatalytic and surface properties of TiO(2) films were studied. TiO(2) films of about 200 nn thickness were deposited on glass substrates on which a thin Cu layer (5 nm) was deposited. The films were annealed during 1 s to 100 degrees C and 400 degrees C, followed by chemical etching of the Cu film. The grazing incidence X-ray fluorescence measurements showed a thermal induced migration of Cu atoms to depths between 7 and 31 nm. The X-ray photoelectron spectroscopy analysis detected the presence of TiO(2), Cu(2)O and Cu(0) phases and an increasing Cu content with the annealing temperature. The change of the surface properties was monitored by the increasing red-shift and absorption of the ultraviolet-visible spectra. Contact angle measurements revealed the formation of a highly hydrophilic surface for the film having a medium Cu concentration. For this sample photocatalytic assays, performed by methylene blue discoloration, show the highest activity. The proposed mechanism of the catalytic effect, taking place on Ti/Cu sites, is supported by results obtained by theoretical calculations. (C) 2010 Elsevier B.V. All rights reserved.

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This paper describes an investigation on CuO and CuO-ZnO catalysts supported on CeO(2) and CeO(2)-La(2)O(3) oxides, which were designed for the low temperature water-gas shift reaction (WGSR). Bulk catalysts were prepared by co-precipitation of metal nitrates and characterized by energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), surface area (by the BET method), X-ray photoelectron spectroscopy (XPS), and in situ X-ray absorption near edge structure (XANES). The catalysts` activities were tested in the forward WGSR, and the CuO/CeO(2) catalyst presented the best catalytic performance. The reasons for this are twofold: (1) the presence of Zn inhibits the interaction between Cu and Ce ions, and (2) lanthanum oxide forms a solid solution with cerium oxide, which will cause a decrease in the surface area of the catalysts. Also the CuO/CeO(2) catalyst presented the highest Cu content on the surface, which could influence its catalytic behavior. Additionally, the Cu and Cu(1+) species could influence the catalytic activity via a reduction-oxidation mechanism, corroborating to the best catalytic performance of the Cu/Ce catalyst. (c) 2010 Elsevier B.V. All rights reserved.

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Este trabalho revisa a geologia e apresenta dados inéditos do Depósito de Cobre Cerro dos Martins (DCM), incluindo geocronologia Pb-Pb em zircão, inclusões fluidas, isótopos estáveis (C, O e S), composição isotópica do Sr e geoquímica de elementos maiores e traços das rochas vulcânicas encaixantes. O depósito está hospedado na seqüência vulcano-sedimentar do Grupo Bom Jardim, da Bacia do Camaquã, do Neoproterozóico do Escudo Sul Rio-grandense, e possui reservas calculadas de 1.450.000 t, com teor médio de 0,83% Cu. O depósito consiste de um conjunto de veios sulfetados que preenchem fraturas de direção N40º-60ºW em rochas andesíticas e sedimentares clásticas, com disseminações confinadas em níveis de siltito, arenito, andesito e conglomerado, da Formação Hilário do Grupo Bom Jardim. Os minerais do minério filoneano são a calcosina e bornita com calcopirita, pirita, galena e esfalerita subordinadas. Digenita, covelita, malaquita cuprita e azurita ocorrem como minério secundário em ganga constituída de carbonatos, quartzo, minerais argilosos, barita e rara hematita. A composição química das vulcânicas (elementos maiores e traços, incluindo ETR) indicam uma afinidade alcalina para o vulcanismo relacionado à Formação Hilário na região do Cerro dos Martins. Um corpo de quartzo-diorito, intrusivo nas rochas vulcânicas e sedimentares, mostrou idade de 550 ±5 Ma (Pb-Pb em zircões) indicando um valor mínimo para a geração do minério do DCM. Esta idade confirma a posição estratigráfica desta rocha na Formação Acampamento Velho e também fornece uma idade mínima para a deposição da seqüência vulcano-sedimentar encaixante do DCM. Os sulfetos do DCM mostram δS34 CDT com valores relativamente homogêneos entre - 6.2 e + 0.9‰ (n= 7). O valor de δS34 CDT da calcopirita, levemente positivo (+0.9‰), indica uma origem magmática para o S, mas os valores negativos encontrados nestes sulfetos, poderiam indicar o envolvimento de outras fontes com enxofre reduzido. Entretanto, a presença de hematita nas paragêneses minerais indica que o minério foi formado sob condições oxidantes, modificando a composição isotópica original do enxofre magmático (δS34 CDT ~ 0‰) para valores negativos. As baritas analisadas apresentam valores com δS34 CDT entre +9.25 e +10.65‰ (n=4) indicando deposição em condições oxidantes, originadas pela mistura de um fluido magmático-hidrotermal com água meteórica. A composição isotópica do C das calcitas do DCM varia com δC13 PDB entre - 1,90 a -4,45‰, interpretada como resultante da mistura entre carbono de fonte magmática com mármores do embasamento. Inclusões fluidas em quartzo do minério indicam temperaturas de deposição entre 157 e 273 °C com mediana de 215 °C (n = 45). A composição isotópica do oxigênio da água em equilibrio com a calcita do fluido hidrotermal (T= 215 °C) mostra valores de δ O18 SMOW entre 3 e 14, indicando H2O de origem magmática, com contribuição de água meteórica. A razão Sr87/Sr86 das mesmas calcitas mostram valores entre 0,7068 – 0,7087, de crosta superior. Rochas plutônicas e vulcânicas do escudo com idades próximas de 550 Ma possuem razões iniciais Sr87/Sr86 entre 0,704 – 0,710, compatíveis com aquelas encontradas nas calcitas da mineralização. Os fluidos hidrotermais do magmatismo shoshonítico-alcalino com idade de 595 Ma e Sr87/Sr86 entre 0,7041 a 0,7053, também são candidatos a fonte do Sr dos carbonatos hidrotermais, mas necessitariam de um componente mais radiogênico. Assim, a fonte de C-O e Sr das calcitas do minério pode ter sido originada diretamente de um fluido magmático-hidrotermal ou de uma mistura entre este fluido e mármores do embasamento. Portanto, o depósito Cerro dos Martins é interpretado como de origem magmática-hidrotermal, relacionado ao evento magmático alcalinoshoshonítico, pós-colisional da Orogênese Dom Feliciano, com idade entre 595-550 Ma. Novos modelos exploratórios para depósitos de cobre no Escudo do Rio Grande do Sul devem considerar o magmatismo alcalino na gênese dos depósitos.

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Este trabalho apresenta o estudo da efetividade de barreiras de amortecimento para atenuar a vibração causada pela propagação de ondas sísmicas oriundas de detonações. A barreira consta de uma porção do terreno cujas características de propagação são modificadas artificialmente pela detonação de uma linha de furos com parâmetros idênticos aos dos furos de produção. Os resultados obtidos demonstram a efetividade deste recurso, evidenciado pelo coeficiente de redução entre os valores de vibração gerados em situações com e sem o uso de barreira (0,41) e também através da mudança dos coeficientes da equação de previsão via Distância Escalonada, possibilitando em escala de produção o aumento na carga máxima por tempo de retardo ( 4,9 % à 118,9% ), com redução de custos devido ao menor consumo de retardos por furo ( -5,7 % à - 40,7 % ).

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In Chapter 1, rhodium nanoparticles were supported on multiwalled carbon nanotubes (MWCNTs) and bound to the magnetic core-shell system Fe3O4@TiO2. The composite Fe3O4@TiO2-Rh-MWCNT and the intermediates were characterized by SEM, EDS and TEM. Their catalytic activity was studied using i) the hydrogenation transfer of nitroarenes and cyclohexene in the presence of hydrazine hydrate; ii) the reduction of 2-nitrophenol with NaBH4; and iii) the decoloration of pigments in the presence of hydrogen peroxide. The results were monitored by gas chromatography (i) and UV Visible (ii and iii). In the second chapter, the catalytic activity of six oxidovanadium(V) aroylhydrazone complexes, viz. [VOL1(OEt)][VOL1(OEt)(EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(H2L2)]2·EtOH (4), [VOL1(µ -O)VOL1] (5) and [VOL2(µ -O)VOL2] (6) (H2L1 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2hydroxybenzohydrazide and H2L2 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2 aminobenzohydrazide), anchored on nanodiamonds with different treatments, was studied towards the microwave-assisted partial oxidation of 1-phenylethanol to acetophenone in the presence of tert-butyl hydroperoxide (TBHP) as oxidant. A high selectivity for acetophenone was achieved for the optimized conditions. The possibility of recycling and reuse the heterogeneous catalysts was also investigated. In chapter 3, the catalytic activity of gold nanoparticles supported at different metal oxides, such as Fe2O3, Al2O3 ZnO or TiO2, was studied for the above reaction. The effect of the support, quantity of the catalyst and temperature was investigated. The recyclability of the gold catalysts was also studied. In the last chapter, a new copper nanocomposite with functionalized mutiwalled carbon nanotubes (Cu-MWCNT) was synthesized using a microwave assisted polyol method. The characterization was performed using XRD and SEM. The catalytic activity of Cu-MWCNT was studied through the degradation of pigments, such as amaranth, brilliant blue, indigo, tartrazine and methylene blue.

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

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Metal/ceramic interfaces using zirconia have dominated the industrial applications in the last decade, due to the high mechanical strength and fracture toughness of zirconia, especially at temperatures below 300 ºC. Also noteworthy is the good ionic conductivity in high temperatures of this component. In this work joining between ZrO2 Y-TZP and ZrO2 Mg-PSZ with austenitic stainless steel was studied. These joints were brazed at high-vacuum after mechanical metallization with Ti using filler alloys composed by Ag-Cu and Ag-Cu-Ni. The influence of the metallization, and the affinity between the different groups (ceramic / filler alloys) was evaluated, in order to achieve strong metal/ceramic joints. Evaluation of joints and interfaces, also the characterization of base materials was implemented using various techniques, such as: x-ray diffraction, leak test, three-point flexural test and scanning electron microscopy with chemical analysis. The microstructural analysis revealed physical and chemical bonds in the metal/ceramic interfaces, providing superior leak proof joints and stress cracking, in order to a good joint in all brazed samples. Precipitation zones and reaction layers with eutetic characteristics were observed between the steel and the filler metal

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Literature has demonstrated to the narrow relation between deleterious habits and the occurrence of malocclusion in minors of 5 years. The existence of these habits, however, already considered as risk factors, having also, its determinative ones, which present cultural dimensions and economic social, many of them related to the parents of the child, having in account that such habits if develop in phases in which the child establish a narrow relation of dependence. This study it had an objective to investigate the prevalence of deleterious buccal habits in children and its relation with the economic social and characteristics of the parents. It was developed an epidemiologist study of transversal character with interview, through daily pay-tested form, with 218 parents in the day of the National Campaign of Vaccination. In the cast of the variable that had composed the study, they had been used, as changeable dependents, the use of the baby's bottle, bottle and the digital suction, being considered as outcomes of the research. Amongst the independent variable, the economic social factors (type of occupation, number of children, civil state, sort, schooling and age) and staffs of the parents (self perception in oral health) had entered as the variable to be analyzed in the problems of the infantile odontology. The collected data had been submitted to the analysis descriptive and inferential statistics, being used the test qui-square and the analysis of the possibility reasons. As main results, it was found that breast feeding before the six months if presents as one of the main factors of risk for the use of baby's bottle (p< 0.001, OR= 2.8, I.C= 1.589 4.906), bottle (p< 0.001, OR= 3.7, I.C.= 2.076 6.624) and digital suction (p< 0.014, OR= 3.5, I.C.= 1.225 10.181). From the data found, one concludes that breast-feeding is considered a primordial factor for not the installation of deleterious oral habits and that the economic social and cultural factors can reflect in central way in the performance of this act

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The degradation behaviour of SnO(2)-based varistors (SCNCr) due to current pulses (8/20 mu s) is reported here for the first time in comparison with the ZnO-based commercial varistors (ZnO). Puncturing and/or cracking failures were observed in ZnO-based varistors possessing inferior thermo-mechanical properties in comparison with that found in a SCNCr system free of failures. Both systems presented electric degradation related to the increase in the leakage current and decrease in the electric breakdown field, non-linear coefficient and average value of the potential barrier height. However, it was found that a more severe degradation occurred in the ZnO-based varistors concerning their non-ohmic behaviour, while in the SCNCr system, a strong non-ohmic behaviour remained after the degradation. These results indicate that the degradation in the metal oxide varistors is controlled by a defect diffusion process whose rate depends on the mobility, the concentration of meta-stable defects and the amount of electrically active interfaces. The improved behaviour of the SCNCr system is then inferred to be associated with the higher amount of electrically active interfaces (85%) and to a higher energy necessary to activate the diffusion of the specific defects.