61 resultados para Electron donor strength

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


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A computer-assisted method for analysing photoacoustic spectra has been developed in the Windows(TM) environment with the use of an easy graphical interface, the computer simulation was carried out with the aim of using the entire expression of the Rosencwaig-Gersho theory, thus permitting multiple applications. The simulation was applied to a system that mimics the electron transfer process in which the concentration of octaethylporphin donor molecules was constant whereas the concentration of duroquinone and 2,3-dichloro-5,6-dicyano-1, l-benzoquinone acceptor molecules varied. The increment of the acceptor concentration influenced the photoacoustic amplitude and phase signals. In the phase signal a significant shift to smaller values was observed, denoting a faster heat generation. The analysis of the photoacoustic signal enabled the determination of the thermal diffusivity, the result obtained through the simulation was about (7 +/- 1) x 10(-7) m(2) s(-1) indicating that changes in the photoacoustic phase signals were due to the electron transfer process rather than changes in the thermal properties of the sample.

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The solvation properties of model resin and peptide-resins measured in ca. 30 solvent systems correlated better with the sum of solvent electron acceptor (AN) and electron donor (DN) numbers, in 1:1 proportion, than with other solvent polarity parameters. The high sensitivity of the (AN+DN) term to detect differentiated solvation behaviors of peptide-resins, taken as model of heterogeneous and complex solutes, seems to be in agreement with the previously proposed two-parameter model, where the sum of the Lewis acidity and Lewis basicity characters of solvent are proposed for scaling solvent effect. Besides these physicochemical aspects regarding solute-solvent interactions, important implications of this study for the solid phase peptide synthesis were also observed. Each class of peptide-resin displayed a specific salvation profile that was dependent on the amount and the nature of the resin-bound peptide sequence. Plots of resin swelling versus solvent (AN+DN) values allowed the visualization of a maximum salvation region characteristic for each class of resin. This strategy facilitates the selection of solvent systems for optimal solvation conditions of peptide chains in every step of the entire synthesis cycle. Moreover, only the AN and DN concepts allow the understanding of rules for solvation/shrinking of peptide-resins when in homogeneous or in heterogeneous mixed solvents.

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The following sequence of substitution reactions was studied spectrophotometrically in organic solvents: RNH2 + TCNQ →-HCN 7-substituted TCNQ →-HCN +RNH2 7.7-disubstituted TCNQ where R = butyl, octyl, dodecyl, and hexadecyl. The production of 7-(alkylamino)-7,7,8-tricyanoquinodimethanes proceeds via the formation of the anion radical of TCNQ (TCNQ-·) whose rate of appearance was found to be a function of the chain length of R, reaching a maximum for octylamine. The formation of TCNQ-· was sensitive to the solvent polarity and electron-donor power and was associated with a small enthalpy and a highly negative entropy of activation. Above a certain [C8H17NH2] the rate of disappearance of TCNQ-· was independent of the amine concentration, and the reaction had a much higher enthalpy and entropy of activation. The occurrence of tautomerism precluded an investigation of the conversion of 7-(octylamino)-7,8,8-tricyanoquinodimethane into 7,7-bis(octylamino)-8,8-dicyanoquinodimethane. A study of the reaction of octylamine with 7-morpholino-7,8,8-tricyanoquinodimethane (which does not exist in tautomeric forms) showed that the second substitution step proceeds with the same mechanism as the first one. The only difference between the two compounds (TCNQ and its monosubstituted morpholino derivative) is one of reactivity. © 1985 American Chemical Society.

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Fourteen complexes in the series [RuCl2(CO)(L)(PPh3)2] (where L = N-heterocycles) have been prepared and characterized by IR and NMR spectroscopies, and cyclic voltammetry. A good correlation is found between observed and calculated electrochemical potentials; E1/2 vs pKa or (Gp, σm for a series of similar ligands. It is now reported that the carbonyl stretching frequency, νCO, and the 13C and 31P NMR signals do not correlate well with any of the physico-chemical parameters used (E1/2, Taft's and Hammett's parameters). This behaviour is probably due to the characteristics of the Ru(II) species, which does not transmit the steric and electron donor/acceptor properties of the ligands to the carbonyl group, or because the measurements are not able to detect the effect induced by the changes in the ligand L. Indeed, good correlations are obtained when the measurements directly involve the metal centre, as is the case in the E1/2 measurements. Crystals of o[RuCl2(CO)(4-pic)(PPh3)2] are monoclinic, space group P21/n, a = 12.019(2), b = 13.825(3) and c = 22.253(3) . The structure was solved by the Patterson method and was refined by full-matrix least-squares procedure to R = 0.054 and Rw = 0.055, for 2114 reflections with I > 3σ(I). For L = 2-acetylpyridine and 2-methylimidazole, complexes with formulae [RuCl2(CO)(L)(PPh3)] · L and [RuCl2(CO)(L)2 (PPh3)], respectively, were obtained. © 1998 Elsevier Science Ltd. All rights reserved.

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

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Chromium electrodeposition is a technique for the production of functional coatings on engineering components. These coatings are extensively micro-cracked and present high level of hardness, resistance to corrosion and wear and low coefficient of friction. In this paper the shot peening influence on the fatigue strength of aluminum 7050-T7451 alloy chromium electroplated, was investigated.The shot peening process was carried out to create residual stresses using ceramic and glass shots. A hard chromium electroplated coating of 100 mu m thickness was performed on the base material and the shot peened base material surfaces. S-N curves were obtained in axial and bending fatigue tests and compared with the 7050-T7451 aluminum alloy. In order to study the influence of residual stresses on fatigue life, the behavior of compressive residual stress field was measured by an X-ray tensometry.An increase in the axial fatigue strength of 25% and 50% of ceramic and glass shots, respectively, was observed. The lower performance in fatigue life for ceramic-shot peening may be attributed to higher surface damage, as a consequence of the overpeening intensity performed. However, in bending fatigue the behavior was practically equivalent for both processes. Fracture surface analysis by scanning electron microscopy was used to observe crack origin sites from shot peened and chromium electroplated samples. (C) 2006 Elsevier Ltd. All rights reserved.

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It is known that chromium electroplating is related to the reduction in the fatigue strength of base metal. However, chromium results in protection against wear and corrosion combined with chemical resistance and good lubricity. Environmental requirements are an important point to be considered in the search for possible alternatives to hard chrome plating. Aircraft landing gear manufactures are considering WC thermal spray coating applied by the high-velocity oxygen-fuel (HVOF) process an alternative candidate, which shows performance at least comparable to results, obtained for hard chrome plating. The aim of this study is to compare the influence of WC-17Co and WC-10Co-4Cr coatings applied by HVOF process and hard chromium electroplating on the fatigue strength of AISI 4340 steel, with and without shot peening. S-N curves were obtained in axial fatigue test for base material, chromium plated and tungsten carbide coated specimens. Tungsten carbide thermal spray coating results in higher fatigue strength when compared to hard chromium electroplated. Shot peening prior to thermal spraying showed to be an excellent alternative to increase fatigue strength of AISI 4340 steel. Experimental data showed higher axial fatigue and corrosion resistance in salt fog exposure for samples WC-10Co-4Cr HVOF coated when compared with WC-17Co. Fracture surface analysis by scanning electron microscopy (SEM) indicated the existence of a uniform coverage of nearly all substrates. (C) 2004 Elsevier B.V. All rights reserved.

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Recovered substrates have been extensively used in the aerospace field. Cadmium electroplating has been widely applied to promote protective coatings in aeronautical components, resulting in excellent corrosion protection combined with a good performance in cyclic loading. Ecological considerations allied to the increasing demands for corrosion resistance have resulted in the search for possible alternatives. Zinc-nickel (Zn-Ni) alloys have received considerable interest recently, because these coatings show advantages such as a good resistance to white and red rust, high plating rates, and acceptance in the market. In this study, the effect of electroplated Zn-Ni coatings on AISI 4340 high-strength steel was analyzed for rotating bending fatigue strength, corrosion, and adhesion resistance. The compressive residual stress field was measured by x-ray diffraction prior to fatigue tests. Optical microscopy documented coating thickness, adhesion characteristics, and coverage extent for nearly all substrates. Fractured fatigue specimens were investigated using scanning electron microscopy (SEM). Three different Zn-Ni coating thicknesses were tested, and comparisons with the rotating bending fatigue data from electroplated Cd specimens were performed. Experimental results differentiated the effects of the various coatings on the AISI 4340 steel behaviour when submitted to fatigue testing and the influence of coating thickness on the fatigue strength.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Objectives. This study was undertaken to evaluate the shear bond strength of four materials used as aesthetic material bonded to Ni-Cr alloy.Methods. Sixty-eight alloy discs were prepared and divided equally into four groups, and received four treatments for veneering: conventional feldspathic porcelain (Noritake EX-3) and three light-cured prosthodontic composite resins (Artglass, Solidex and Targis). The aesthetic materials were applied after metal structure conditioning in accordance with the manufacturers' recommendations. The specimens were stored in distilled water at 37 degreesC for 7 days. A universal testing machine was used to measure the shear bond strength of the specimens at a cross head speed of 0.5 mm/min. Fractured specimens were examined by using both optical and scanning electron microscope.Results. The analysis of variance and Tukey's test showed that the strongest mean shear bond was obtained with Noritake EX-3 (mean shear bond strength 42.90 +/- 7.82 MPa). For composites, the highest mean shear bond strength was observed for Targis (12.30 +/- 1.57 MPa); followed by Solidex (11.94 +/- 1.04 MPa) and Artglass (10.04 +/- 0.75 MPa). Optical analysis of the fractured surf aces indicated that for Targis and Noritake EX-3 all failures were a mixture of both cohesive and adhesive patterns. As for Artglass and Solidex, the fractures were mainly adhesive in nature.Conclusions. The Solidex system was equivalent to the Targis system in bond strength and exhibited greater strength than the Artglass system. The porcelain fused-to-metal showed considerably higher shear bond strength than the three metal-resin bonding techniques. (C) 2003 Elsevier B.V. Ltd. Ali rights reserved.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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

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