9 resultados para Substitution reactions

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


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The cation substitutions in the crystal lattice of binary potassium-holmium vanadate (V) K3Ho(VO4)2 by magnesium have been studied using various types of chemical solid state reactions. It was shown that in the presence of the quasi-ternary system K3VO4-Mg3(VO4)2-HoVO 4 at 700°C there a compound defined as K3Ho(VO4)2 with a narrow homogeneity range where K and Ho are partially substituted by Mg in accordance with various schemes. © 1998 Published by Elsevier Science S.A.

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The power flow problem, in transmission networks, has been well solved, for most cases, using Newton-Raphson method (NR) and its decoupled versions. Generally speaking, the solution of a non-linear system of equations refers to two methods: NR and Successive Substitution. The proposal of this paper is to evaluate the potential of the Substitution-Newton-Raphson Method (SNR), which combines both methods, on the solution of the power flow problem. Simulations were performed using a two-bus test network in order to observe the characteristics of these methods. It was verified that the NR is faster than SNR, in terms of convergence, considering non-stressed scenarios. For those cases where the power flow in the network is closed to the limits (stressed system), the SNR converges faster. This paper presents the power flow formulation of the SNR and describes its potential for its application in special cases such as stressed scenarios. © 2006 IEEE.

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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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0.7125ZrF4-0.2375(1 - xLaF3 • xLnF3)-0.05AIF3 with x = 0.01, 0.02 and 0.03 for Ln = Er and x = 0.03 for Ln = Pr, Nd glasses were studied by differential thermal analysis (DTA), X-ray diffraction and optical spectroscopy. Avrami parameters (Ec and n) were obtained from DTA curves. With La3+ substitution a decrease in the stability against crystallization was observed. This decrease follows the order Er3+ > Nd3+ ≈ Pr3+ for 3% molar substitution. n values suggest an interface controlled growth mechanism with grain edge nucleation abler saturation. Two crystalline polymorphs of the LaZr3F15 phase were identified. With the substitution of 3 mol% of Pr3+, Nd3+ or Er3+ for La3+ only the crystallization of the rhombohedral α-LnZr3F15 phase was observed. An increase in Ω6 Judd's intensity parameter occurs with crystallization and also an increase in the 1.04 μm peak emission cross-section for Nd3+ 4I3/2 state suggesting the potential application of these glass ceramics in optical amplification devices. © 1997 Elsevier Science B.V.

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Recently, was proposed a chemical method for preparation of ferroelectric thin films based on oxide precursors. In this work, PZT thin films were prepared to attest the viability of this method for cation-substitution. In this study, a small concentration of Nb (5 mol%) was selected as substitute of B-site in ABO 3 structure of PZT. Dielectric and ferroelectric properties of PZT films were studied as a function of cation-substitution. Results for Nb-PZT were compared with PZT films undoped. The values of dielectric constant, at typical 100 kHz frequency, were 358 and 137, for PZT and Nb-PZT films respectively. Remanent polarizations of these films were respectively 7.33 μ C/cm 2 and 13.3 μ C/cm 2 , while the measured coercive fields were 101 kV/cm and 93 kV/cm. As a result, changes on observed dielectric and ferroelectric values confirm the Nb substitution in PZT thin film produced by oxide precursor method. © 2002 Taylor & Francis.

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Room-temperature photoluminescence (PL) was observed in undoped and 2 mol% Cr-, Al- and Y-doped amorphous SrTiO3 thin films. Doping increased the PL, and in the case of Cr significantly reduced the associated PL wavelength. The optical bandgaps, calculated by means of UV-vis absorption spectra, increased with crystallinity and decreased with the doping level. It was considered that yttrium and aluminum substituted Sr2+, whereas chromium replaced Ti4+. It is believed that luminescence centers are oxygen-deficient BO6 complexes, or the same centers with some other defects, such as oxygen or strontium vacancies, or BO6 complexes with some other defects placed in their neighborhood. The character of excitation and the competition for negatively charged non-bridging oxygen (NBO) among numerous types of BO6 defect complexes in doped SrTiO3 results in various broadband luminescence peak positions. The results herein reported are an indicative that amorphous titanates are sensitive to doping, which is important for the control of the electro-optic properties of these materials. The probable incorporation of Cr into the Ti site suggests that the existence of a double network former can lead to materials displaying a more intense photoluminescence.

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Postbloom fruit drop (PFD) of citrus, caused by Colletotrichum acutatum, produces orange-brown lesions on petals and results in premature fruit drop and the retention of calyces. C. gloeosporioides is common in groves and causes postharvest anthracnose on fruit. Both diseases are controlled effectively by the fungicide benomyl in research fields and commercial orchards. Highly sensitive and resistant isolates of C. gloeosporioides were found, whereas all isolates of C. acutatum tested were moderately resistant. In preliminary studies conducted in vitro with three isolates of each, mycelial growth of sensitive isolates of C. gloeosporioides was inhibited completely by benomyl (Benlate 50 WP) at 1.0 μg/ml, whereas resistant isolates grew well at 10 μg/ml. Growth of all isolates of C. acutatum was inhibited by about 55% at 0.1 μg/ml and by 80% at 1.0 μg/ml. Spore germination of C. acutatum was inhibited more at 0.1 μg/ml than at 1.0 μg/ml or higher concentrations. In all, 20 isolates of C. acutatum from 17 groves and 20 isolates of C. gloeosporioides from 7 groves were collected from locations with different histories of benomyl usage in São Paulo, Brazil, and Florida, United States. Benomyl at 1.0 μ.g/ml completely inhibited growth of 133 isolates of C. gloeosporioides, with the exception of 7 isolates that were highly resistant to the fungicide, whereas all isolates of C. acutatum were only partially inhibited at 0.1 and 1.0 μg/ml. Analysis of variance indicated that the sensitivity of the isolates of C. acutatum was not affected by benomyl usage or grove of origin, and country of origin had only minor effects. No highly resistant or sensitive isolate of C. acutatum was recovered. Partial sequencing of the β-tubulin gene did not reveal nucleotide substitutions in codons 198 or 200 in C. acutatum that usually are associated with benomyl resistance in other fungi.

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We study aperiodic and periodic tilings induced by the Rauzy fractal and its subtiles associated with beta-substitutions related to the polynomial x3-ax2-bx-1 for a≥b≥1. In particular, we compute the corresponding boundary graphs, describing the adjacencies in the tilings. These graphs are a valuable tool for more advanced studies of the topological properties of the Rauzy fractals. As an example, we show that the Rauzy fractals are not homeomorphic to a closed disc as soon as a≤2b-4. The methods presented in this paper may be used to obtain similar results for other classes of substitutions.© 2012 Elsevier B.V. All rights reserved.

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The effect of substitution of [Pd(PPh3)(4)], which is unstable in air, by complexes of the type [MCl2L2] (M = Pd, Pt; L = AsPh3, SbPh3), [PdL4](L = PPh3, AsPh3, SbPh3) and [NiX2(PPh3)(2)] on the syntheses of thioethers, acetylenes and ketones is described.