Materiais bionanocompósitos a base de argilominerais e hidróxidos duplos lamelares como sistemas de liberação de fármacos

Bionanocomposites systems clay base (montmorillonite and sepiolite), layered double hidroxides and biopolymers (carboxymethylcellulose and zein) were evaluated as topical delivery systems with antibacterial activity and as oral delivery systems. For this study, neomycin, a topical antibiotic, indicated mainly for open wound infections. The drug amoxicillin, an antibiotic indicated mainly for throat infections, were also used in this study. Both antibiotics were used as model drugs. Initially, drugs were incorporated directly into the biopolymer matrix, comprising the combination of carboxymethylcellulos and zein, being conformed as movies and balls and evaluated for their antibacterial activity and controlled release simulating gastrointestinal fluids. Moreover, hybrids materials have been prepared where the neomycin drug was incorporated into the lamellar inorganic solids, such as montmorillonite by ion exchange reaction, and the fibrous type, such as sepiolite by adsorption in aqueous solution. But the drug amoxicillin was incorporated into layered double hydroxides by anion exchange and montmorillonite by cation exchange. The resulting hybrids were in turn combined with the biopolymer matrix yielding bionanocomposites shaped materials such as films were tested for their antibacterial activity, and the shaped materials beads were tested for their release in the gastrointestinal fluids. Through the analysis of various physico-chemical techniques, we observed the interactions between the studied materials, the formation of hybrids materials, obtaining the bionanocomposites materials and material efficiency when applied in controlled release of drugs both topical and use oral mainly influenced by the presence of zein, are promising as topical delivery systems and oral drugs.

Persistent localized states for a chaotically mixed bistable reaction

We describe the evolution of a bistable chemical reaction in a closed two-dimensional chaotic laminar flow, from a localized initial disturbance. When the fluid mixing is sufficiently slow, the disturbance may spread and eventually occupy the entire fluid domain. By contrast, rapid mixing tends to dilute the initial state and so extinguish the disturbance. Such a dichotomy is well known. However, we report here a hitherto apparently unremarked intermediate case, a persistent highly localized disturbance. Such a localized state arises when the Damkoehler number is great enough to sustain a "hot spot," but not so great as to lead to global spread. We show that such a disturbance is located in the neighborhood of an unstable periodic orbit of the flow, and we describe some limited aspects of its behavior using a reduced, lamellar model. Copyright American Physical Society (APS) 2006.

Chaotic mixing of a competitive-consecutive reaction

The evolution of a competitive-consecutive chemical reaction is computed numerically in a two-dimensional chaotic fluid flow with initially segregated reactants. Results from numerical simulations are used to evaluate a variety of reduced models commonly adopted to model the full advection-reaction-diffusion problem. Particular emphasis is placed upon fast reactions, where the yield varies most significantly with Peclet number (the ratio of diffusive to advective time scales). When effects of the fluid mechanical mixing are strongest, we find that the yield of the reaction is underestimated by a one-dimensional lamellar model that ignores the effects of fluid mixing, but overestimated by two other lamellar models that include fluid mixing.

Barrier distributions for weakly bound systems

We discuss the use of reduced fusion cross sections in the derivation of fusion barrier distributions. We show that the elimination of static effects associated with system sizes and optical potentials obtained by the recently introduced fusion functions can be extended to barrier distributions. This can be a useful tool for systematic studies of breakup coupling effects in fusion processes.

Breakup coupling effects on near-barrier quasi-elastic scattering of (6,7)Li on (144)Sm

Excitation functions of quasi-elastic scattering at backward angles have been measured for the (6,7)Li + (144)Sm systems at near-barrier energies, and fusion barrier distributions have been extracted from the first derivatives of the experimental cross sections with respect to the bombarding energies. The data have been analyzed in the framework of continuum discretized coupled-channel calculations, and the results have been obtained in terms of the influence exerted by the inclusion of different reaction channels, with emphasis on the role played by the projectile breakup.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Analysis of multiple gas solid reactions

Multiple gas solid reactions involving one solid and N gaseous reactants are investigated in this study by using a matched asymptotic expansion technique. Two cases are particularly studied. In the first case all N chemical reaction rates are faster than the diffusion rate. While in the second case only M (M < N) chemical reaction rates are faster than the diffusion rate and the rates of the remaining (N-M) chemical reactions are comparable to that of diffusion. For these two cases the solid concentration profile behaves like a travelling wave. In the first case the wave front velocity is contributed linearly by all gaseous reactants (additive law) while in the second case this law does not hold.

Approximate analytical solutions for porous catalysts with nonuniform activity

Using a novel finite integral transform technique, the problem of diffusion and chemical reaction in a porous catalyst with general activity profile is investigated theoretically. Analytical expressions for the effectiveness factor are obtained for pth order and Michaelis-Menten kinetics. Perturbation methods are employed to provide useful asymptotic solutions for large or small values of Thiele modulus and Biot number.

Oxidation mechanism of Si3N4-bonded SiC ceramics by CO, CO2 and steam

This paper presents a theoretical and experimental investigation into the oxidation reactions of Si3N4-bonded SiC ceramics. Such ceramics which contain a small amount of silicon offer increased oxidation and wear resistance and are widely used as lining refractories in blast furnaces. The thermodynamics of oxidation reactions were studied using the JANAF tables. The weight gain was measured using a thermogravimetric analysis technique to study the kinetics. The temperature range of oxidation measurements is from 1073 to 1573 K and the oxidation atmosphere is water vapour, pure CO and CO-CO2 gas mixtures with various CO-to-CO2 ratios. Thermodynamic simulations showed that the oxidation mechanism of Si3N4-bonded SiC ceramics is passive oxidation and all components contribute to the formation of a silica film. The activated energies of the reactions follow the sequence Si3N4>SiC>Si. The kinetic study revealed that the oxidation of Si3N4-bonded SiC ceramics occurred in a mixed regime controlled by both interface reaction and diffusion through the silica film. Under the atmosphere conditions prevailing in the blast furnace, this ceramic is predicted to be passively oxidized with the chemical reaction rate becoming more dominant as the CO concentration increases. (C) 1998 Chapman & Hall.

Finite element modelling of reactive mass transport problems in fluid-saturated porous media

We use the finite element method to solve reactive mass transport problems in fluid-saturated porous media. In particular, we discuss the mathematical expression of the chemical reaction terms involved in the mass transport equations for an isothermal, non-equilibrium chemical reaction. It has turned out that the Arrhenius law in chemistry is a good mathematical expression for such non-equilibrium chemical reactions especially from the computational point of view. Using the finite element method and the Arrhenius law, we investigate the distributions of PH (i.e. the concentration of H+) and the relevant reactive species in a groundwater system. Although the main focus of this study is on the contaminant transport problems in groundwater systems, the related numerical techniques and principles are equally applicable to the orebody formation problems in the geosciences. Copyright (C) 1999 John Wiley & Sons, Ltd.

Finite element modelling of rock alteration and metamorphic process in hydrothermal systems

We use the finite element method to simulate the rock alteration and metamorphic process in hydrothermal systems. In particular, we consider the fluid-rock interaction problems in pore-fluid saturated porous rocks. Since the fluid rock interaction takes place at the contact interface between the pore-fluid and solid minerals, it is governed by the chemical reaction which usually takes place very slowly at this contact interface, from the geochemical point of view. Due to the relative slowness of the rate of the chemical reaction to the velocity of the pore-fluid flow in the hydrothermal system to be considered, there exists a retardation zone, in which the conventional static theory in geochemistry does not hold true. Since this issue is often overlooked by some purely numerical modellers, it is emphasized in this paper. The related results from a typical rock alteration and metamorphic problem in a hydrothermal system have shown not only the detailed rock alteration and metamorphic process, but also the size of the retardation zone in the hydrothermal system. Copyright (C) 2001 John Wiley & Sons, Ltd.

A generalised dynamic model for char particle gasification with structure evolution and peripheral fragmentation

A generalised model for the prediction of single char particle gasification dynamics, accounting for multi-component mass transfer with chemical reaction, heat transfer, as well as structure evolution and peripheral fragmentation is developed in this paper. Maxwell-Stefan analysis is uniquely applied to both micro and macropores within the framework of the dusty-gas model to account for the bidisperse nature of the char, which differs significantly from the conventional models that are based on a single pore type. The peripheral fragmentation and random-pore correlation incorporated into the model enable prediction of structure/reactivity relationships. The occurrence of chemical reaction within the boundary layer reported by Biggs and Agarwal (Chem. Eng. Sci. 52 (1997) 941) has been confirmed through an analysis of CO/CO2 product ratio obtained from model simulations. However, it is also quantitatively observed that the significance of boundary layer reaction reduces notably with the reduction of oxygen concentration in the flue gas, operational pressure and film thickness. Computations have also shown that in the presence of diffusional gradients peripheral fragmentation occurs in the early stages on the surface, after which conversion quickens significantly due to small particle size. Results of the early commencement of peripheral fragmentation at relatively low overall conversion obtained from a large number of simulations agree well with experimental observations reported by Feng and Bhatia (Energy & Fuels 14 (2000) 297). Comprehensive analysis of simulation results is carried out based on well accepted physical principles to rationalise model prediction. (C) 2001 Elsevier Science Ltd. AH rights reserved.

Percolation of colloids with distinct interaction sites

We generalize the Flory-Stockmayer theory of percolation to a model of associating (patchy) colloids, which consists of hard spherical particles, having on their surfaces f short-ranged-attractive sites of m different types. These sites can form bonds between particles and thus promote self-assembly. It is shown that the percolation threshold is given in terms of the eigenvalues of a m x m matrix, which describes the recursive relations for the number of bonded particles on the ith level of a cluster with no loops; percolation occurs when the largest of these eigenvalues equals unity. Expressions for the probability that a particle is not bonded to the giant cluster, for the average cluster size and the average size of a cluster to which a randomly chosen particle belongs, are also derived. Explicit results for these quantities are computed for the case f = 3 and m = 2. We show how these structural properties are related to the thermodynamics of the associating system by regarding bond formation as a (equilibrium) chemical reaction. This solution of the percolation problem, combined with Wertheim's thermodynamic first-order perturbation theory, allows the investigation of the interplay between phase behavior and cluster formation for general models of patchy colloids.

Processamento de imagem para determinação de distribuições granulométricas de gotas numa suspensão

Mestrado em Engenharia Electrotécnica e de Computadores

Heterogeneous kinetics of the reduction of chromium (VI) by elemental iron

Zero valent iron (ZVI) has been extensively used as a reactive medium for the reduction of Cr(VI) to Cr(III) in reactive permeable barriers. The kinetic rate depends strongly on the superficial oxidation of the iron particles used and the preliminary washing of ZVI increases the rate. The reaction has been primarily modelled using a pseudo-first-order kinetics which is inappropriate for a heterogeneous reaction. We assumed a shrinking particle type model where the kinetic rate is proportional to the available iron surface area, to the initial volume of solution and to the chromium concentration raised to a power ˛ which is the order of the chemical reaction occurring at surface. We assumed α= 2/3 based on the likeness to the shrinking particle models with spherical symmetry. Kinetics studies were performed in order to evaluate the suitability of this approach. The influence of the following parameters was experimentally studied: initial available surface area, chromium concentration, temperature and pH. The assumed order for the reaction was confirmed. In addition, the rate constant was calculated from data obtained in different operating conditions. Digital pictures of iron balls were periodically taken and the image treatment allowed for establishing the time evolution of their size distribution.