14 resultados para hot electron contribution

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.

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This work discusses on the preparation of Ni-45Ti-5Mo, Ni-40Ti-10Mo and Ni-46Ti-2Mo-2Zr (at-%) alloys by high-energy ball milling and hot pressing, which are potentially attractive for dental and medical applications. The milling process was performed in stainless steel balls (19mm diameter) and vials (225 mL) using a rotary speed of 300rpm and a ball-to-powder weight ratio of 10:1. Hot pressing under vacuum was performed in a BN-coated graphite crucible at 900 degrees C for 1 h using a load of 20 MPa. The milled and hot-pressed materials were characterized by X-ray diffraction, electron scanning microscopy, and electron dispersive spectrometry. Peaks of B2-NiTi and Ni4Ti3 were identified in XRD patterns of Ni-45Ti-5Mo, Ni-40Ti-10Mo and Ni-46Ti-2Mo-2Zr powders milled for 1h. The NiTi compound dissolved small Mo amounts lower than 4 at%, which were measured by EDS analysis. Moreover, it was identified the existence of an unknown Mo-rich phase in microstructures of the hot-pressed Ni-Ti-Mo alloys.

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The possibility of setting constraints on the Couplings of a scalar (pseudoscalar) Higgs boson to the tau lepton and the b quark in the reactions e(+)e(-)-->v (v) over bar tau(+)tau(-) and e(+)e(-)-->v (v) over barb (b) over bar at a future linear electron-positron collider of total energy roots = 500 GeV is studied. The admixture of a new hypothetical pseudoscalar state of the Higgs boson in the Hf (f) over bar vertex is parametrized in the form (mf/v)(a+igamma(5)b). on the basis of an analysis of differential distributions for the processes under study, it is shown that data from the future linear collider TESLA will make it possible to constrain the parameters a and b as -0.32 less than or equal to Deltaa less than or equal to 0.24 and -0.73 less than or equal to b less than or equal to 0.73 in the case of the reaction e(+)e(-)-->v (v) over bar tau(+)tau(-) and as -0.026 less than or equal to Deltaa less than or equal to 0.027 and -0.23 less than or equal to b less than or equal to 0.23 in the case of the reaction e(+)e(-) --> v (v) over barb (b) over bar. It is emphasized that the contribution of the fusion Subprocess WW --> H in the channel involving an electron neutrino is of particular importance, since this contribution enhances the sensitivity of data to the parameters being analyzed. (C) 2004 MAIK Nauka/Inierperiodica.

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Field emission properties of hot filament chemical vapor deposited boron doped polycrystalline diamond have been studied. Doping level (N-B) of different samples has been varied by the B/C concentration in the gas feed during the growth process and doping saturation has been observed for high B/C ratios. Threshold field (E-th) for electron emission as function of B/C concentration has been measured, and the influences of grain boundaries, doping level and surface morphology on field emission properties have been investigated. Carrier transport through conductive grains and local emission properties of surface sites have been figured out to be two independent limiting effects in respect of field emission. Emitter current densities of 500 nA cm(-2) were obtained using electric fields less than 8 V/mu m. (c) 2007 Elsevier B.V. All rights reserved.

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Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.

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Solvent effects play a major role in controlling electron-transfer reactions. The solvent dynamics happens on a very high-dimensional surface, and this complex landscape is populated by a large number of minima. A critical problem is to understand the conditions under which the solvent dynamics can be represented by a single collective reaction coordinate. When this unidimensional representation is valid, one recovers the successful Marcus theory. In this study the approach used in a previous work [V. B. P. Leite and J. N. Onuchic; J. Phys. Chem. 100, 7680 (1996)] is extended to treat a more realistic solvent model, which includes energy correlation. The dynamics takes place in a smooth and well behaved landscape. The single shell of solvent molecules around a cavity is described by a two-dimensional system with periodic boundary conditions with nearest neighbor interaction. It is shown how the polarization-dependent effects can be inferred. The existence of phase transitions depends on a factor y proportional to the contribution from the two parameters of the model. For the present model, γ suggests the existence of weak kinetic phase transitions, which are used in the analysis of solvent effects in charge-transfer reactions. © 1999 American Institute of Physics.

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Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

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This paper reports our initial research to obtain SrWO4 microcrystals by the injection of ions into a hot aqueous solution and their photocatalytic (PC) properties. These microcrystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The shape and average size of these SrWO 4 microcrystals were observed by field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). In addition, we have investigated the PC activity of microcrystals for the degradation of rhodamine B (RhB) and rhodamine 6G (Rh6G) dyes. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy confirmed that SrWO4 microcrystals have a scheelite-type tetragonal structure without deleterious phases. FT-Raman spectra exhibited 12 Raman-active modes in a range from 50 to 1000 cm-1. FE-SEM and TEM images suggested that the SrWO4 microcrystals (rice-like - 95%; star-, flower-, and urchin-like - 5%) were formed by means of primary/secondary nucleation events and self-assembly processes. Based on these FE-SEM/TEM images, a crystal growth mechanism was proposed and discussed in details in this work. Finally, a good PC activity was first discovered of the SrWO4 microcrystals for the degradation of RhB after 80 min and Rh6G after 50 min dyes under ultraviolet-light, respectively. © 2012 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder.

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This study was conducted to evaluate the morphologic modifications in tissues of the fruit and seed of the crambe (Crambe abyssinica Hochst. Ex R.E. Fr.) after drying at different temperatures. Fruits with a water content of 0.38 kg water/kg dry matter were harvested and manually homogenized. Drying was accomplished at 35, 45, 60, 75, and 90°C and at 21,9,7,5, and 2% relative humidity, respectively. After drying, the structure of the pericarp and tegument of the seed were evaluated and the embryo was removed from the fruit/seed for morphological analysis (structural and ultrastructural and the histolocalization of reserve substances). Drying at different temperatures did not affect the cellular structure of the tissues composing the pericarp of the fruits, but it disorganized the structure of the seed tegument. The cells of the tegument and cotyledons presented a contraction in their volumes. The lowest contractions in the cellular volumes of both the tegument and cotyledons occurred after drying at 35 and 45°C. The cytoplasm of the cotyledon cells contains oil drops and the protein bodies contain protein granules and starch grains. There were no changes in the cellular walls of the embryos of the fruits dried at different temperatures; however, ungluing of the medium lamella occurred. This damage occurred with greater intensity after drying at temperatures above 60°C. The form of the oil drops in the cytoplasm of the cotyledon cells was altered after drying. At temperatures above 60°C, the drops broke up and coalesced. After drying at 45 and 60°C, the form of some protein bodies was altered, whereas at 75 and 90°C coalescence of the protein bodies occurred in some cells. It was concluded that the identified alterations can affect the physiologic quality of crambe seeds. © 2013 Copyright Taylor and Francis Group, LLC.

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The objective of this work was the obtaining in situ of alpha-SiAlON-SiC composite, using an alternative rare-earth oxide mixture, RE2O3, as sintering additive, by two different sintering processes. As sintering additive, 20 vol.% of AlN-RE2O3 in a molar ratio of 90: 10 was mixed to the alpha-Si3N4 powder. In the Si3N4-AlN-RE2O3 powder mixture, 0, 10, 15 and 20wt.% of SiC were added. The powder batches were milled, dried and compacted by cold isostatic pressing. Two different sintering processes were used: gas-pressure sintering at 1950 degrees C for 1 h under 1.5 MPa of N-2 atmosphere, or uniaxial hot-pressing at 1750 degrees C, for 30 min under pressure of 20 MPa. The sintered samples were characterized by X-ray diffraction, scanning electron microscopy and mechanical properties. XRD patterns indicate only alpha-SiAlON (alpha') and beta-SiC as crystalline phases. It was observed that the SiC addition did not influence the alpha-SiAlON formation, although the growth of elongated alpha'-grains is substantially decreased. The hot-pressed composites presented better mechanical properties, exhibiting fracture toughness of 5 MPa m(1/2) and hardness around 21.5 GPa. (c) 2007 Elsevier B.V. All rights reserved.

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Alumina/alumina wear couple can lower the wear rates and thus metallic ion releasing on load bearing metallic implant materials. However, the low fracture toughness of ceramics is still a major concern. Therefore, the present study aims to process and to triboelectrochemically characterise the 5 and 10 vol.-%Al2O3 reinforced CoCrMo matrix composites. Corrosion and tribocorrosion behaviour of the composites were investigated in 8 g L−1 NaCl solution at body temperature. Corroded and worn surfaces were investigated by a field emission gun scanning electron microscope equipped with energy dispersive X-ray spectroscopy. After tribocorrosion experiments, wear rates were calculated using a profilometer. Results suggest that Al2O3 particle addition decreased the tendency of CoCrMo alloy to corrosion under both static and tribocorrosion conditions. However, no significant influence on the corrosion and wear rates was observed in composites mainly due to increased porosity and insufficient matrix/reinforcement bonding.