Approaches for multicopper oxidases in the design of electrochemical sensors for analytical applications

We report an effective approach for the construction of a biomimetic sensor of multicopper oxidases by immobilizing a cyclic-tetrameric copper(II) species, containing the ligand (4-imidazolyl)ethylene-2-amino-1-ethylpyridine (apyhist), in the Nafion (R) membrane on a vitreous carbon electrode surface. This complex provides a tetranuclear arrangement of copper ions that allows an effective reduction of oxygen to water, in a catalytic cycle involving four electrons. The electrochemical reduction of oxygen was studied at pH 9.0 buffer solution by using cyclic voltammetry, chronoamperometry, rotating disk electrode voltammetry and scanning electrochemical microscopy techniques. The mediator shows good electrocatalytic ability for the reduction of O(2) at pH 9.0, with reduction of overpotential (350 mV) and increased current response in comparison with results obtained with a bare glassy carbon electrode. The heterogeneous rate constant (k(ME)`) for the reduction of O(2) at the modified electrode was determined by using a Koutecky-Levich plot. In addition, the charge transport rate through the coating and the apparent diffusion coefficient of O(2) into the modifier film were also evaluated. The overall process was found to be governed by the charge transport through the coating, occurring at the interface or at a finite layer at the electrode/coating interface. The proposed study opens up the way for the development of bioelectronic devices based on molecular recognition and self-organization. (C) 2010 Elsevier Ltd. All rights reserved.

The shoving model for the glass-former LiCl center dot 6H(2)O: A molecular dynamics simulation study

Molecular dynamics (MD) simulations of LiCl center dot 6H(2)O Showed that the diffusion coefficient D, and also I lie structural relaxation time , follow a power law at high temperatures, D(-1) proportional to (T - T(0))(-mu), with the same experimental parameters for viscosity (T(0) = 207 K, mu = 2.08). Decoupling between D and occurs at T(x) similar to 1.1 T(0). High frequency acoustic excitations for the LiCl center dot 6H(2)O model were obtained by the calculation of time correlation functions of mass current fluctuations. The temperature dependence of the instantaneous shear modulus, G,(T), was considered in the shoving model for supercooled liquids [J.C. Dyre, T. Christensen, N.B. Olsen, J. Non-Cryst. Solids 352 (2006) 4635] resulting in a linear relationship log (D(-1)) vs. G root T. (C) 2009 Elsevier B.V. All rights reserved.

Biobased composites from tannin-phenolic polymers reinforced with coir fibers

Tannin-phenolic polymers prepared using tannin, a macromolecule obtained from natural sources, were used in the preparation of composites reinforced with coir fibers. The composites based on tannin-phenolic polymers (50% (w/w) of tannin as substitute of the phenol) were prepared using the coir fibers as reinforcement (30-70% (w/w), 3.0-6.0 cm, randomly distributed). The Izod impact strength of the composites showed an improvement in this property due to the incorporation of coir fibers in the tannin-phenolic matrices. The SEM images showed excellent adhesion at the fiber/matrix interface. The coir fiber had bundles regularly spaced, which enhanced the diffusion of the resin into the fiber. In addition, the high lignin content of this fiber results in a high concentration of aromatic rings, which increased the compatibility with the matrix. The values of the diffusion coefficient of water, determined using Fick`s laws, show that there was no correlation between the fiber percentage and the water diffusion. The DMTA curves showed that the storage moduli of the composites reinforced with coir fibers were considerably higher than that of the thermoset, and the increase in the proportion of fibers led to a proportional increase in the storage moduli of these materials. The biobased composites obtained have potential for non-structural applications, such as in the internal parts of automotives vehicles. To our knowledge, this is the first study on this kind of biobased composites. (C) 2010 Elsevier B.V. All rights reserved.

Laws of large numbers for non-additive probabilities

We apply the concept of exchangeable random variables to the case of non-additive robability distributions exhibiting ncertainty aversion, and in the lass generated bya convex core convex non-additive probabilities, ith a convex core). We are able to rove two versions of the law of arge numbers (de Finetti's heorems). By making use of two efinitions. of independence we rove two versions of the strong law f large numbers. It turns out that e cannot assure the convergence of he sample averages to a constant. e then modal the case there is a true" probability distribution ehind the successive realizations of the uncertain random variable. In this case convergence occurs. This result is important because it renders true the intuition that it is possible "to learn" the "true" additive distribution behind an uncertain event if one repeatedly observes it (a sufficiently large number of times). We also provide a conjecture regarding the "Iearning" (or updating) process above, and prove a partia I result for the case of Dempster-Shafer updating rule and binomial trials.

Caracterização para o beneficiamento do carvão de Candiota

O presente trabalho apresenta estudos sistemãticos da caracterização do carvão de Candiota em termos do seu beneficiamento. O carvão de Candiota possui caracteristicas de moabilidade que o indicam como bastantefriável. A geração de finos (-28 malhas) atinge valores superiores a 20% independente do grau de britagem . As distribuições granulométricas resultantes da britagem do carvão obedecem a equação de ROSIN-RAIIMLER-BENNETT, dentro do intervalo previsto (frações menores do ue -4 malhas e maiores do que 100 malhas). Os valores de n e d ' não variam significativamente com a abertura do britador o, que evidencia sua friabiliade. foram estabelecidas equações que relacionam aberturado britador, coeficientes de distribuição e diâmetro médio.Estudos rni croscópicos demonstraram que, o grau de d i-s seminação da matéria inorgânica é muitointenso , e sua liberação atinge malhas muito pequenas (provavelmente menores do que 400 malhas). O teor de cinzas, como por exemplo do grau de disseminação, não variou significativamente com a diminuição de tamanho, como acontece com outros carvões. Foram estabelecidos dois critérios de liberação das particulas em função da quantidade de matéria carbonosa presente nas unidades mistas (20 - 80% e 5 - 95%, respectivamente). Estes indices de partyculas mistas (5 - 95% de matéria carbonosa) mantiveram-se constantes até tamanhos aproximados de 115 malhas, para logo diminuirem nas frações menores. Ainda assim, para frações menores do que 53 micrômetro a quantidade de mistos ( 5 - 95%) foi de 34%. As curvas de lavabilidade deste carvão (tanto da fração grossa quanto afina), reflexo das caracteristicas anteriores, indicam-no como de muito dificil beneficiamento (lavagem). Isto basicamente é devido ao alto grau de "near gravity matterial" presente e de seu grau de liberação. 0s testes de jigagem por bateladas, bem como outros processos de beneficiamento, demonstraram a dificuldade do beneficiamento deste carvão. O melhor teste de jigagem por bateladas, obteve uma recuperação de materia carbonosa de 73, 21 com um teor de cinzas de 45,51 no concretado (alimentação contendo 50% de cinzas). de 37,59% de cinzas (alimentação de 50% de cinzas). Propõe-se, finalmente, um circuito de beneficiamento convencional do carvão de Candiota, incluindo uma classificação do carvão ROM com o objetivo de separar a alimentação em duas frações (+28 e -28 malhas), seguido de um processo de beneficiamento das frações grosseiras por meios densos (tanques), e um tratamento das frações finas por hidrociclonagem. Os resultados obtidos concluem que o carvão de Candiota é o mais dificil de ser lavado dentre os carvões sul-brasileiros devido ao alto teor de cinzas e ao grau de disseminação, sendo que este teor de cinzas não varia muito com a granulometria, o que implica em um grau de liberação muito baixo. Sugere- se como outra alternativa no seu beneficiamento, o estudo de processos não convencionais que incluem um alto grau de cominuiçáo ate completa liberação.

Studies in non-Gaussian analysis

This thesis presents general methods in non-Gaussian analysis in infinite dimensional spaces. As main applications we study Poisson and compound Poisson spaces. Given a probability measure μ on a co-nuclear space, we develop an abstract theory based on the generalized Appell systems which are bi-orthogonal. We study its properties as well as the generated Gelfand triples. As an example we consider the important case of Poisson measures. The product and Wick calculus are developed on this context. We provide formulas for the change of the generalized Appell system under a transformation of the measure. The L² structure for the Poisson measure, compound Poisson and Gamma measures are elaborated. We exhibit the chaos decomposition using the Fock isomorphism. We obtain the representation of the creation, annihilation operators. We construct two types of differential geometry on the configuration space over a differentiable manifold. These two geometries are related through the Dirichlet forms for Poisson measures as well as for its perturbations. Finally, we construct the internal geometry on the compound configurations space. In particular, the intrinsic gradient, the divergence and the Laplace-Beltrami operator. As a result, we may define the Dirichlet forms which are associated to a diffusion process. Consequently, we obtain the representation of the Lie algebra of vector fields with compact support. All these results extends directly for the marked Poisson spaces.

Simulação de fluxo de fluidos em meios porosos desordenados uma análise de efeito de escala na estimativa da permeabilidade e do coeficiente de arrasto

The present study provides a methodology that gives a predictive character the computer simulations based on detailed models of the geometry of a porous medium. We using the software FLUENT to investigate the flow of a viscous Newtonian fluid through a random fractal medium which simplifies a two-dimensional disordered porous medium representing a petroleum reservoir. This fractal model is formed by obstacles of various sizes, whose size distribution function follows a power law where exponent is defined as the fractal dimension of fractionation Dff of the model characterizing the process of fragmentation these obstacles. They are randomly disposed in a rectangular channel. The modeling process incorporates modern concepts, scaling laws, to analyze the influence of heterogeneity found in the fields of the porosity and of the permeability in such a way as to characterize the medium in terms of their fractal properties. This procedure allows numerically analyze the measurements of permeability k and the drag coefficient Cd proposed relationships, like power law, for these properties on various modeling schemes. The purpose of this research is to study the variability provided by these heterogeneities where the velocity field and other details of viscous fluid dynamics are obtained by solving numerically the continuity and Navier-Stokes equations at pore level and observe how the fractal dimension of fractionation of the model can affect their hydrodynamic properties. This study were considered two classes of models, models with constant porosity, MPC, and models with varying porosity, MPV. The results have allowed us to find numerical relationship between the permeability, drag coefficient and the fractal dimension of fractionation of the medium. Based on these numerical results we have proposed scaling relations and algebraic expressions involving the relevant parameters of the phenomenon. In this study analytical equations were determined for Dff depending on the geometrical parameters of the models. We also found a relation between the permeability and the drag coefficient which is inversely proportional to one another. As for the difference in behavior it is most striking in the classes of models MPV. That is, the fact that the porosity vary in these models is an additional factor that plays a significant role in flow analysis. Finally, the results proved satisfactory and consistent, which demonstrates the effectiveness of the referred methodology for all applications analyzed in this study.

Short-term temporal changes of soil carbon losses after tillage described by a first-order decay model

Tillage stimulates soil carbon (C) losses by increasing aeration, changing temperature and moisture conditions, and thus favoring microbial decomposition. In addition, soil aggregate disruption by tillage exposes once protected organic matter to decomposition. We propose a model to explain carbon dioxide (CO2) emission after tillage as a function of the no-till emission plus a correction due to the tillage disturbance. The model assumes that C in the readily decomposable organic matter follows a first-order reaction kinetics equation as: dC(sail)(t)/dt = -kC(soil)(t) and that soil C-CO2 emission is proportional to the C decay rate in soil, where C-soil(t) is the available labile soil C (g m(-2)) at any time (t). Emissions are modeled in terms soil C available to decomposition in the tilled and non-tilled plots, and a relationship is derived between no-till (F-NT) and tilled (F-Gamma) fluxes, which is: F-T = a1F(NT)e(-a2t), where t is time after tillage. Predicted and observed fluxes showed good agreement based on determination coefficient (R-2), index of agreement and model efficiency, with R-2 as high as 0.97. The two parameters included in the model are related to the difference between the decay constant (k factor) of tilled and no-till plots (a(2)) and also to the amount of labile carbon added to the readily decomposable soil organic matter due to tillage (a,). These two parameters were estimated in the model ranging from 1.27 and 2.60 (a(1)) and - 1.52 x 10(-2) and 2.2 x 10(-2) day(-1) (a(2)). The advantage is that temporal variability of tillage-induced emissions can be described by only one analytical function that includes the no-till emission plus an exponential term modulated by tillage and environmentally dependent parameters. (C) 2008 Elsevier B.V. All rights reserved.

Comparison of non-linear growth models to describe the growth curve in West African Dwarf sheep

The objectives of this study were to compare the goodness of fit of four non-linear growth models, i.e. Brody, Gompertz, Logistic and Von Bertalanffy, in West African Dwarf (WAD) sheep. A total of 5274 monthly weight records from birth up to 180 days of age from 889 lambs, collected during 2001 to 2004 in Betecoucou breeding farm in Benin were used. In the preliminary analysis, the General Linear Model Procedure of the Statistical Analysis Systems Institute was applied to the dataset to identify the significant effects of the sex of lamb (male and female), type of birth (single and twin), season of birth (rainy season and dry season), parity of dam (1, 2 and 3) and year of birth (2001, 2002, 2003 and 2004) on the observed birth weight and monthly weight up to 6 months of age. The models parameters (A, B and k), coefficient of determination (112), mean square error (MSE) were calculated using language of technical computing package Matlab(R), 2006. The mean values of A, B and k were substituted into each model to calculate the corresponding Akaike's Information Criterion (AIC). Among the four growth functions, the Brody model has been selected for its accuracy of fit according to the higher R(2), lower MSE and A/C Finally, the parameters A, B and k were adjusted in Matlab(R) 2006 for the sex of lamb, year of birth, season of birth, birth type and the parity of ewe, providing a specific slope of the Brody growth curve. The results of this study suggest that Brody model can be useful for WAD sheep breeding in Betecoucou farm conditions through growth monitoring.

Análise da magnetohidrodinâmica com transferência de calor em canais de placas paralelas via transformação integral

The main goal of the present work is related to the dynamics of the steady state, incompressible, laminar flow with heat transfer, of an electrically conducting and Newtonian fluid inside a flat parallel-plate channel under the action of an external and uniform magnetic field. For solution of the governing equations, written in the parabolic boundary layer and stream-function formulation, it was employed the hybrid, numericalanalytical, approach known as Generalized Integral Transform Technique (GITT). The flow is sustained by a pressure gradient and the magnetic field is applied in the direction normal to the flow and is assumed that normal magnetic field is kept uniform, remaining larger than any other fields generated in other directions. In order to evaluate the influence of the applied magnetic field on both entrance regions, thermal and hydrodynamic, for this forced convection problem, as well as for validating purposes of the adopted solution methodology, two kinds of channel entry conditions for the velocity field were used: an uniform and an non-MHD parabolic profile. On the other hand, for the thermal problem only an uniform temperature profile at the channel inlet was employed as boundary condition. Along the channel wall, plates are maintained at constant temperature, either equal to or different from each other. Results for the velocity and temperature fields as well as for the main related potentials are produced and compared, for validation purposes, to results reported on literature as function of the main dimensionless governing parameters as Reynolds and Hartman numbers, for typical situations. Finally, in order to illustrate the consistency of the integral transform method, convergence analyses are also effectuated and presented

Modelagem numérica de escoamento em padrão anular com transferência de calor e massa

Annular flow is the prevailing pattern in transport and energy conversion systems and therefore, one of the most important patterns in multiphase flow in ducts. The correct prediction of the pressure gradient and heat transfer coefficient is essential for optimizing the system s capacity. The objective of this work is to develop and implement a numerical algorithm capable of predicting hydrodynamic and thermal characteristics for upflow, vertical, annular flow. The numerical algorithm is then complemented with the physical modeling of phenomena that occurs in this flow pattern. These are, turbulence, entrainment and deposition and phase change. For the development of the numerical model, axial diffusion of heat and momentum is neglected. In this way the time-averaged equations are solved in their parabolic form obtaining the velocity and temperature profiles for each axial step at a time, together with the global parameters, namely, pressure gradient, mean film thickness and heat transfer coefficient, as well as their variation in the axial direction. The model is validated for the following conditions: fully-developed laminar flow with no entrainment; fully developed laminar flow with heat transfer, fully-developed turbulent flow with entrained drops, developing turbulent annular flow with entrained drops, and turbulent flow with heat transfer and phase change

Método não destrutivo de estimativa da área foliar de plantas daninhas de ambiente aquático: tanner-grass e capim-fino

The continuous inputs from agriculture areas and human or industrial sewer have been provided a widely demographic explosion of tropical tanner-grass and para grasss plants in the rivers and water reservoirs of Brazil. Considering the importance of these noxious weeds there is a vast necessity of basic studies on aspects related to reproduction, growing, development, nutritional requirements, responses to control systems and others. In most studies, leaf area knowledge is crucial and it is one of the most difficult characteristics to be measured because it usually requires expensive equipments or it uses a destructive technique. The objective of this work was to develop equations for leaf blade dimensional parameters to allow determination of the leaf area of African tanner-grass (Brachiaria subquadripara (Trin.) Hitchc) and para grass (Brachiaria mutica (Forsk.) Stapf.). Correlations between real leaf area and dimensional parameters of leaf blade such as length along the main vein (L) and maximum width (W) perpendicular to the main axis were studied. Only the linear equations allowed a good leaf area estimate. It is suggested to opt for a simple linear equation involving respective products of length times maximum width considering linear coefficient equal to zero. Thus, B. subquadripara (SS) and B. mutica (SM) non destructive leaf blade area estimates may be performed by the following formulas: SS = 0.7719 (L x W) and SM = 0.7479 (L x W), with coefficients of determination (R(2)) of 0.9594 and 0.9408, respectively.

Sistema de secagem solar para frutos tropicais e modelagem da secagem de banana em um secador de coluna estática

In this study were projected, built and tested an electric solar dryer consisting of a solar collector, a drying chamber, an exhaust fan and a fan to promote forced hot air convection. Banana drying experiments were also carried out in a static column dryer to model the drying and to obtain parameters that can be used as a first approximation in the modeling of an electric solar dryer, depending on the similarity of the experimental conditions between the two drying systems. From the banana drying experiments conducted in the static column dryer, we obtained food weight data as a function of aqueous concentration and temperature. Simplified mathematical models of the banana drying were made, based on Fick s and Fourier s second equations, which were tested with the experimental data. We determined and/or modeled parameters such as banana moisture content, density, thin layer drying curves, equilibrium moisture content, molecular diffusivity of the water in banana DAB, external mass transfer coefficient kM, specific heat Cp, thermal conductivity k, latent heat of water evaporation in the food Lfood, time to heat food, and minimum energy and power required to heat the food and evaporate the water. When we considered the shrinkage of radius R of a banana, the calculated values of DAB and kM generally better represent the phenomenon of water diffusion in a solid. The latent heat of water evaporation in the food Lfood calculated by modeling is higher than the latent heat of pure water evaporation Lwater. The values calculated for DAB and KM that best represent the drying were obtained with the analytical model of the present paper. These values had good agreement with those assessed with a numeric model described in the literature, in which convective boundary condition and food shrinkage are considered. Using parameters such as Cp, DAB, k, kM and Lfood, one can elaborate the preliminary dryer project and calculate the economy using only solar energy rather than using solar energy along with electrical energy

On the incorporation of the non-steroidal anti-inflammatory naproxen into cationic O/W microemulsions

Microemulsions (ME) containing hexadecyltrimethylammonium bromide (HTAB)/ethanol as surfactant, isopropylmyristate (IM) or butylstearate (BS) as oil phase and aqueous buffer were studied. Pseudo-ternary phase diagrams of the investigated systems were obtained at constant surfactant/cosurfactant molar ratio (1:5) by titration in order to characterize the proportions between the components to obtain clear systems. Oil in water microemulsions were prepared in a wide range of phase volume (phi). UV-vis absorption spectra of naproxen at pH 5.5 showed that the solubility of Np increases significantly in the presence of O/W ME in high phase volumes. For both, IM and BS microemulsions, the dynamic light scattering experiments showed that the size of the oil droplets remains constant in low values of phi, increasing abruptly in high phi values. Phase solubility study revealed that for both IM and BS microemulsions, the drug incorporation followed a straight-line profile in all range of phi. The data could be analyzed through the phase-separation model and the association constants (K) calculated varied from 27 to 90 M-1, depending on the pH and on the microemulsion oil phase. (c) 2005 Elsevier B.V. All rights reserved.

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