560 resultados para Debye shielding


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Small-angle X-ray scattering (SAXS) and nitrogen adsorption techniques were used to study the temperature and time structural evolution of the nanoporosity in silica xerogels prepared from acid- and ultrasound-catalyzed hydrolysis of tetraetboxysilane (TEOS). Silica xerogels present a structure of nanopores of fully random shape, size, and distribution, which can be described by an exponential correlation function gamma(r) = exp (-r/a), where a is the correlation distance, as predicted by the Debye, Anderson, and Brumberger (DAB) model. The mean pore size was evaluated as about 1.25 nm from SAXS and about 1.9 nm from nitrogen adsorption. The nanopore elimination in TEOS sonohydrolysis-derived silica xerogels is readily accelerated at temperatures around 900 degrees C probably by the action of a viscous flow mechanism. The nanopore elimination process takes place in such a way that the pore volume fraction and the specific surface are reduced while the mean pore size remains constant. (c) 2005 WILEY-VCH Verlag GmbH S Co. KGaA, Weinheim.

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The use of AC/DC magnetic susceptibility and impedance measurements to detect oxygen depletion effects in La0.7Ca0.3MnO3 +/-delta and NiMn2O4+delta spinel-type compounds is reported. For the NiMn2O4, for which no Mn4+ was found, three superposed Debye relaxations were observed in the range 260-180 K. Otherwise, in La0.7Ca0.3MnO3, the argon annealed has contributed to a decrease in T-C, but the amount of Mn4+ is still too high to allow the observation of a relaxation in this frequency window. (c) 2006 Elsevier B.V. All rights reserved.

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The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

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Measurements of internal friction as a function of temperature were carried out in samples of mobium containing different amounts of interstitial solutes (oxygen and nitrogen) and one sample of mobium containing initially only nitrogen as interstitial solute. The experimental spectra of internal friction as a function of temperature were obtained with a torsion pendulum of the inverted Ke-type and resolved, using the method of successive subtraction, into a series of constituent Debye peaks corresponding to different interactions. For each relaxation process it was possible to obtain the height (Q(max)(-1)) and temperature (T-p) of the peak, the activation energy (E) and the relaxation time (t(o)). The height, shape and temperature of these peaks depend on the concentration of interstitial elements. The observed peaks were associated with matrix-interstitial (Nb-O, Nb-N) and interstitial-interstitial (O-N) interaction processes. (C) 2003 Elsevier B.V. All rights reserved.

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The understanding of electrostatic interactions is an essential aspect of the complex correlation between structure and function of biological macromolecules. It is also important in protein engineering and design. Theoretical studies of such interactions are predominantly done within the framework of Debye-Huckel theory. A classical example is the Tanford-Kirkwood (TK) model. Besides other limitations, this model assumes an infinitesimally small macromolecule concentration. By comparison to Monte Carlo (MC) simulations, it is shown that TK predictions for the shifts in ion binding constants upon addition of salt become less reliable even at moderately macromolecular concentrations. A simple modification based on colloidal literature is suggested to the TK scheme. The modified TK models suggested here satisfactorily predict MC and experimental shifts in the calcium binding constant as a function of protein concentration for the calbindin D-9k mutant and calmodulin.

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Monte Carlo simulations are used to assess the adequacy of the Tanford-Kirkwood prescription for electrostatic interactions in macromolecules. Within a continuum dielectric framework, the approach accurately describes salt screening of electrostatic interactions for moderately charged systems consistent with common proteins at physiological conditions. The limitations of the Debye-Huckel theory, which forms the statistical mechanical basis for the Tanford-Kirkwood result, become apparent for highly charged systems. It is shown, both by an analysis of the Debye-Huckel theory and by numerical simulations, that the difference in dielectric permittivity between macromolecule and surrounding solvent does not play a significant role for salt effects if the macromolecule is highly charged. By comparison to experimental data, the continuum dielectric model (combined with either an approximate effective Hamiltonian as in the Tanford-Kirkwood treatment or with exact Monte Carlo simulations) satisfactorily predicts the effects of charge mutation on metal ion binding constants, but only if the macromolecule and solvent are assigned the same or similar permittivities.

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We investigate the analytic properties of finite-temperature self-energies of bosons interacting with fermions at one-loop order. A simple boson-fermion model was chosen due to its interesting features of having two distinct couplings of bosons with fermions. This leads to a quite different analytic behavior of the bosons self-energies as the external momentum K-mu=(k(0),k) approaches zero in the two possible limits. It is shown that the plasmon and Debye masses are consistently obtained at the pole of the corrected propagator even when the self-energy is analytic at the origin in the frequency-momentum space.

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Fractal dimensions of grain boundary region in doped SnO2 ceramics were determined based on previously derived fractal model. This model considers fractal dimension as a measure of homogeneity of distribution of charge carriers. Application of the derived fractal model enables calculation of fractal dimension using results of impedance spectroscopy. The model was verified by experimentally determined temperature dependence of the fractal dimension of SnO2 ceramics. Obtained results confirm that the non-Debye response of the grain boundary region is connected with distribution of defects and consequently with a homogeneity of a distribution of the charge carriers. Also, it was found that C-T-1 function has maximum at temperature at which the change in dominant type of defects takes place. This effect could be considered as a third-order transition.

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In the last 50 years several studies have been made to understand the relaxation mechanisms of the heavy interstitial atoms present in transition metals and their alloys. Internal friction measurements have been carried out in a Nb-Ti alloy containing 3.1 at.% of Ti produced by the Materials Department of Chemical Engineering Faculty of Lorena (Brazil), with several quantities of oxygen in solid solution using a torsion pendulum. These measurements have been performed by a torsion pendulum in the temperature range from 300 to 700 K with an oscillation frequency between 0.5 and 10 Hz. The experimental results show complex internal friction spectra that have been resolved, into a series of Debye peaks corresponding to different interactions. For each relaxation process it was possible to obtain the height and temperature of the peak, the activation energy and the relaxation time of the process. (C) 2003 Elsevier B.V. All rights reserved.

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

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Triplet carbonyls can be generated not only from the thermal cleavage of dioxetanes, but also enzymatically from appropriate substrates. The excited species can phosphoresce with an intensity depending upon the extent of shielding from deactivating oxygen collisions, react and also transfer energy, thus promoting sensitized emission and sensitized photochemistry. © 1994.

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A novel fractal model for grain boundary regions of ceramic materials was developed. The model considers laterally inhomogeneous distribution of charge carriers in the vicinity of grain boundaries as the main cause of the non-Debye behaviour and distribution of relaxation times in ceramic materials. Considering the equivalent circuit the impedance of the grain boundary region was expressed. It was shown that the impedance of the grain boundary region has the form of the Davidson-Cole equation. The fractal dimension of the inhomogeneous distribution of charge carriers in the region close to the grain boundaries could be calculated based on the relation ds = 1 + β, where β is the constant from the Davidson-Cole equation.

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Mn(II) doped SnO2 thin films used for shielding fluoride glasses against corrosion were investigated by x-ray absorption spectroscopy (EXAFS and XANE)S at the Sn and Mn K-edges. The effect of firing treatment on the densification of the films was studied. It has been evidenced a partial change of Mn valence from 2.3 to 2.6 upon heating which is attributed to a change of ratios of two Mn sites: grafted divalent Mn ions at the surface of SnO 2 nanocrystallites and trivalent Mn ions embedded into a substitutional solid solution with Sn. © Physica Scripta 2005.

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We study the running of the QCD coupling with the momentum squared (Q 2) and the temperature scales in the high temperature limit (T > Tc), using a mass dependent renormalization scheme to build the Renormalization Group Equations. The approach used guaranty gauge invariance, through the use of the Hard Thermal Loop approximation, and independence of the vertex chosen to renormalize the coupling. In general, the dependence of the coupling with the temperature is not logarithmical, although in the region Q2 ∼ T2 the logarithm approximation is reasonable. Finally, as known from Debye screening, color charge is screened in the coupling. The number of flavors, however, is anti-screened.