Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.

Approximate solution of the autocatalytic hydrolysis of cellulose

Depolymerization of cellulose in homogeneous acidic medium is analyzed on the basis of autocatalytic model of hydrolysis with a positive feedback of acid production from the degraded biopolymer. The normalized number of scissions per cellulose chain, S(t)/nA degrees A = 1 - C(t)/C(0), follows a sigmoid behavior with reaction time t, and the cellulose concentration C(t) decreases exponentially with a linear and cubic time dependence, C(t) = C(0)exp[-at - bt (3)], where a and b are model parameters easier determined from data analysis.

Default mercado de crédito parcelado para bens duráveis : veículos automotores

The present work aims to study the macroeconomic factors influence in credit risk for installment autoloans operations. The study is based on 4.887 credit operations surveyed in the Credit Risk Information System (SCR) hold by the Brazilian Central Bank. Using Survival Analysis applied to interval censured data, we achieved a model to estimate the hazard function and we propose a method for calculating the probability of default in a twelve month period. Our results indicate a strong time dependence for the hazard function by a polynomial approximation in all estimated models. The model with the best Akaike Information Criteria estimate a positive effect of 0,07% for males over de basic hazard function, and 0,011% for the increasing of ten base points on the operation annual interest rate, toward, for each R$ 1.000,00 on the installment, the hazard function suffer a negative effect of 0,28% , and an estimated elevation of 0,0069% for the same amount added to operation contracted value. For de macroeconomics factors, we find statistically significant effects for the unemployment rate (-0,12%) , for the one lag of the unemployment rate (0,12%), for the first difference of the industrial product index(-0,008%), for one lag of inflation rate (-0,13%) and for the exchange rate (-0,23%). We do not find statistic significant results for all other tested variables.

Criação da matéria em cosmologias com velocidade da luz variável e eletrônico não-linear

In this work we obtain the cosmological solutions and investigate the thermodynamics of matter creation in two diferent contexts. In the first we propose a cosmological model with a time varying speed of light c. We consider two diferent time dependence of c for a at Friedmann-Robertson- Walker (FRW) universe. We write the energy conservation law arising from Einstein equations and study how particles are created as c decreases with cosmic epoch. The variation of c is coupled to a cosmological Λ term and both singular and non-singular solutions are possible. We calculate the "adiabatic" particle creation rate and the total number of particles as a function of time and find the constrains imposed by the second law of thermodynamics upon the models. In the second scenario, we study the nonlinearity of the electrodynamics as a source of matter creation in the cosmological models with at FRW geometry. We write the energy conservation law arising from Einstein field equations with cosmological term Λ, solve the field equations and study how particles are created as the magnetic field B changes with cosmic epoch. We obtain solutions for the adiabatic particle creation rate, the total number of particles and the scale factor as a function of time in three cases: Λ = 0, Λ = constant and Λ α H2 (cosmological term proportional to the Hubble parameter). In all cases, the second law of thermodynamics demands that the universe is not contracting (H ≥ 0). The first two solutions are non-singular and exhibit in ationary periods. The third case studied allows an always in ationary universe for a suficiently large cosmological term

Alkaloids extracted from Pterogyne nitens induce apoptosis in malignant breast cell line

In the present study, two alkaloids isolated from Pterogyne nitens, a plant native to Brazil, have been shown to induce apoptosis in human breast cancer cells. These compounds, pterogynine (PGN) and pterogynidine (PGD), were tested for their effect on a human infiltrating ductal carcinoma cell line (ZR-7531). The cell line was treated with each alkaloid at several concentrations. Time-dependence (with or without recuperation time) and concentration-dependence (in the range 0.25-10 mM) were investigated in cytotoxicity and apoptosis assays. The annexin assay indicated an apparently higher percentage of death by necrosis of malignant cells after 24 h exposure to both P. nitens extracts than the Hoechst assay. Thus, our results in the two tests demonstrated that the Hoechst assay can discriminate between late apoptotic cells and necrosis, whereas the flow cytometry-based annexin V assay cannot. We concluded that PGN and PGD have effective antineoplastic activity against human breast cancer cells in vitro, by inducing programmed cell death.

Studying nonlinear effects on the early stage of phase ordering using a decomposition method

Nonlinear effects on the early stage of phase ordering are studied using Adomian's decomposition method for the Ginzburg-Landau equation for a nonconserved order parameter. While the long-time regime and the linear behavior at short times of the theory are well understood, the onset of nonlinearities at short times and the breaking of the linear theory at different length scales are less understood. In the Adomians decomposition method, the solution is systematically calculated in the form of a polynomial expansion for the order parameter, with a time dependence given as a series expansion. The method is very accurate for short times, which allows to incorporate the short-time dynamics of the nonlinear terms in a analytical and controllable way. (c) 2005 Elsevier B.V. All rights reserved.

The force, power, and energy of the 100 meter sprint

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

Transition to complete synchronization in phase-coupled oscillators with nearest neighbor coupling

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Escape and transport for an open bouncer: Stretched exponential decays

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Dynamical scaling in fractal structures in the aggregation of tetraethoxysilane-derived sonogels

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

Waveguides and gratings fabrication in zirconium-based organic/inorganic hybrids

Sol-gel derived poly(oxyethylene)/siloxane organic/inorganic di-ureasil hybrids containing different amounts of methacrylic acid (McOH, CH(2)=C(CH(3))COOH)) modified zirconium oxo-clusters (Zr-OMc) were processed as thin films deposited in glassy substrates via spin coating and as transparent and shape controlled monoliths. Channel monomode waveguides and diffraction gratings were UV patterned using the Talbot interferometer and the Lloyd mirror interferometer experimental setups. The time dependence of the diffraction gratings efficiency was studied for hybrids containing different amounts of Zr-OMc. Finally, the number of propagating modes and the refractive index gradient within the waveguide region, determined as a Gaussian section located below the patterned channel, was evaluated and modeled, a maximum index contrast of 2.43 X 10(-5) being estimated.

Dynamical scaling properties of nanoporous undoped and Sb-doped SnO2 supported thin films during tri- and bidimensional structure coarsening

The coarsening of the nanoporous structure developed in undoped and 3% Sb-doped SnO2 sol-gel dip-coated films deposited on a mica substrate was studied by time-resolved small-angle x-ray scattering (SAXS) during in situ isothermal treatments at 450 and 650 degrees C. The time dependence of the structure function derived from the experimental SAXS data is in reasonable agreement with the predictions of the statistical theory of dynamical scaling, thus suggesting that the coarsening process in the studied nanoporous structures exhibits dynamical self-similar properties. The kinetic exponents of the power time dependence of the characteristic scaling length of undoped SnO2 and 3% Sb-doped SnO2 films are similar (alpha approximate to 0.09), this value being invariant with respect to the firing temperature. In the case of undoped SnO2 films, another kinetic exponent, alpha('), corresponding to the maximum of the structure function was determined to be approximately equal to three times the value of the exponent alpha, as expected for the random tridimensional coarsening process in the dynamical scaling regime. Instead, for 3% Sb-doped SnO2 films fired at 650 degrees C, we have determined that alpha(')approximate to 2 alpha, thus suggesting a bidimensional coarsening of the porous structure. The analyses of the dynamical scaling functions and their asymptotic behavior at high q (q being the modulus of the scattering vector) provided additional evidence for the two-dimensional features of the pore structure of 3% Sb-doped SnO2 films. The presented experimental results support the hypotheses of the validity of the dynamic scaling concept to describe the coarsening process in anisotropic nanoporous systems.

Unilamellar vesicles obtained by simply mixing dioctadecyldimethylammonium chloride and bromide with water

Optically clear dispersions of dioctadecyldimethylammonium bromide and chloride (DODAX, X = Br-, Cl-) in water can be obtained by simply mixing the amphiphiles at low concentrations (I mM) and at a temperature safely above the gel to liquid crystalline phase transition temperature (T-m approximate to 45-48 degrees C) of DODAX in water. Under these conditions, dynamic light scattering shows that, at room temperature, the dispersions contain two well-defined populations of large vesicles with average hydrodynamic radii (RH) of 80 and 337 nm for DODAB and of 69 and 247 nm for DODAC. Cryo-transmission electron microscopy (cryo-TEM) micrographs show that DODAX vesicles are unilamellar and polydisperse with apparent radius up to 800 nm. The vesicles are stable for at least I month according to the ageing time-dependence of the turbidity and molar absorption coefficient. (c) 2006 Elsevier B.V.. All rights reserved.

FRACTAL CHARACTERISTICS OF THE HORIZONTAL MOVEMENT OF WATER IN SOILS

Observed deviations from traditional concepts of soil-water movement are considered in terms of fractals. A connection is made between this movement and a Brownian motion, a random and self-affine type of fractal, to account for the soil-water diffusivity function having auxiliary time dependence for unsaturated soils. The position of a given water content is directly proportional to t(n), where t is time, and exponent n for distinctly unsaturated soil is less than the traditional 0.50. As water saturation is approached, n approaches 0.50. Macroscopic fractional Brownian motion is associated with n < 0.50, but shifts to regular Brownian motion for n = 0.50.