Structure and aggregation kinetics of vinyltriethoxysilane-derived organic/silica hybrids

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

Clavulanic acid production processes in a tower bioreactor with immobilised cells

The feasibility of using Streptomyces clavuligerus ATCC 27064 bioparticles supported on alginate gel containing alumina to produce clavulanic acid (CA) was investigated. To this end, effectiveness factors for spherical bioparticles, relating respiration rates of immobilised and free cells, were experimentally determined for various dissolved oxygen (DO) levels and bioparticle radii. Monod kinetics was assumed as representative of the oxygen consuming reaction, while internal oxygen diffusion was considered the limiting step. A comparison was made of the results from a tower bioreactor operating under batch, repeated-batch and continuous conditions with immobilised bioparticles. The theoretical curve of the effectiveness factor for the zero-order reaction model, considering an inert nucleus - the dead core model - was very well fitted to the experimental data. The results of the bioprocess indicated that the batch operation was the most efficient and productive, requiring a do concentration in the reactor above 60% of the saturation value. (C) 2007 Elsevier B.V. All rights reserved.

Application of Nonisothermal Cure Kinetics to the Interaction of Poly(ethylene terephthalate) with Alkyd Resin Varnish

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Non-isothermal decomposition kinetics of the interaction of poly(ethylene terephthalate) with alkyd varnish

The recycling of soft drink bottles poly(ethylene terephthalate) (PET) has been used as an additive in varnish containing alkyd resin. The PET, called to recycled PET (PET-R), was added to the varnish in increasing amounts. Samples of varnish containing PET-R (VPET-R) were used as a film onto slides and its thermal properties were evaluated using thermogravimetry (TG). Throughout the visual analysis and thermal behavior of VPET-R it is possible to identify that the maximum amount of PET-R added to the varnish without changing in the film properties was 2%.The kinetic parameters, such as activation energy (E) and the pre-exponential factor (A) were calculated by the isoconversional Flynn-Wall-Ozawa method for the samples containing 0.5 to 2.0% PET-R. A decrease in the values of E was verified for lower amounts of PET-R for the thermal decomposition reaction. A kinetic compensation effect (KCE) represented by the lnA=-13.42+0.23E equation was observed for all samples. The most suitable kinetic model to describe this decomposition process is the autocatalytic Sestak-Berggren, being the model applied to heterogeneous systems.

Label-free DNA detection of hepatitis C virus based on modified conducting polypyrrole films at microelectrodes and atomic force microscopy tip-integrated electrodes

We present a new strategy for the label-free electrochemical detection of DNA hybridization for detecting hepatitis C virus based on electrostatic modulation of the ion-exchange kinetics of a polypyrrole film deposited at microelectrodes. Synthetic single-stranded 18-mer HCV genotype-1-specific probe DNA has been immobilized at a 2,5-bis(2-thienyl)-N-(3-phosphoryl-n-alkyl)pyrrole film established by electropolymerization at the previously formed polypyrrole layer. HCV DNA sequences (244-mer) resulting from the reverse transcriptase-linked polymerase chain reaction amplification of the original viral RNA were monitored by affecting the ion-exchange properties of the polypyrrole film. The performance of this miniaturized DNA sensor system was studied in respect to selectivity, sensitivity, and reproducibility. The limit of detection was determined at 1.82 x 10(-21) mol L-1. Control experiments were performed with cDNA from HCV genotypes 2a/c, 2b, and 3 and did not show any unspecific binding. Additionally, the influence of the spacer length of 2,5-bis(2-thienyl)-N-(3-phosphoryl-n-alkyl)pyrrole on the behavior of the DNA sensor was investigated. This biosensing scheme was finally extended to the electrochemical detection of DNA at submicrometer-sized DNA biosensors integrated into bifunctional atomic force scanning electrochemical microscopy probes. The 18-mer DNA target was again monitored by following the ion-exchange properties of the polypyrrole film. Control experiments were performed with 12-base pair mismatched sequences.

Salting kinetics and salt diffusivities in farmed Pantanal caiman muscle

A criação de jacaré do Pantanal (Caiman crocodilus yacare) em cativeiro tem sido estimulada, e entre as técnicas de processamento de sua carne, a salga é um processo de conservação relativamente simples e de baixo custo. O objetivo deste trabalho foi estudar a cinética de difusão de cloreto de sódio em carne de jacaré do Pantanal criado em cativeiro, durante a salga úmida. Foram utilizados volumes limitados de salmoura e os experimentos foram realizados com relações salmoura/músculo de 3, 4 e 5, com concentrações de salmoura de 15%, 20% e 25% em peso e temperaturas de 10, 15 e 20ºC. A solução analítica da segunda lei de Fick, considerando difusão unidimensional em uma placa infinita em contato com uma solução bem agitada de volume limitado, foi utilizada para calcular os coeficientes de difusão efetivos de sal e estimar o conteúdo de cloreto de sódio nos filés. Obteve-se boa concordância entre o modelo analítico considerado e os dados experimentais. As difusividades do sal nos filés ocorreram na faixa de 0,47x10-10 a 9,62x10-10 m²/s.

Growth kinetics of tin oxide nanocrystals in colloidal suspensions under hydrothermal conditions

Colloidal suspensions of tin oxide nanocrystals were synthesized at room temperature by the hydrolysis reaction of tin chloride (II), in an ethanolic solution. The coarsening kinetics of such nanocrystals was studied by submitting the as-prepared suspensions to hydrothermal treatments at temperatures of 100, 150 and 200 degrees C for periods between 60 and 12,000 min. Transmission electron microscopy (TEM) was used to characterize the samples (i.e. distribution of nanocrystal size, average particle radius and morphology). The results show that the usual Ostwald ripening coarsening mechanism does not fit well the experimental data, which is an indicative that this process is not significant for SnO2 nanocrystals, in the studied experimental conditions. The morphology evolution of the nanocrystals upon hydrothermal treatment indicates that growth by oriented attachment (OA) should be significant. A kinetic model that describes OA growth is successfully applied to fit the data. (c) 2006 Elsevier B.V. All rights reserved.

The energy landscape for solvent dynamics in electron transfer reactions: A minimalist model

Energy fluctuations of a solute molecule embedded in a polar solvent are investigated to depict the energy landscape for solvation dynamics. The system is modeled by a charged molecule surrounded by two layers of solvent dipolar molecules with simple rotational dynamics. Individual solvent molecules are treated as simple dipoles that can point toward or away from the central charge (Ising spins). Single-spin-flip Monte Carlo kinetics simulations are carried out in a two-dimensional lattice for different central charges, radii of outer shell, and temperatures. By analyzing the density of states as a function of energy and temperatures, we have determined the existence of multiple freezing transitions. Each of them can be associated with the freezing of a different layer of the solvent. (C) 2002 American Institute of Physics.

HIGHER-DERIVATIVE SCHWINGER MODEL

Using the operator formalism, we obtain the bosonic representation for the free fermion field satisfying an equation of motion with higher-order derivatives. Then, we consider the operator solution of a generalized Schwinger model with higher-derivative coupling. Since the increasing of the derivative order implies the introduction of an equivalent number of extra fermionic degrees of freedom, the mass acquired by the gauge field is bigger than the one for the standard two-dimensional QED. An analysis of the problem from the functional integration point of view corroborates the findings of canonical quantization, and corrects certain results previously announced in the literature on the basis of Fujikawa's technique.

REDUCTION OF TODA LATTICE HIERARCHY TO GENERALIZED KDV HIERARCHIES AND THE 2-MATRIX MODEL

Toda lattice hierarchy and the associated matrix formulation of the 2M-boson KP hierarchies provide a framework for the Drinfeld-Sokolov reduction scheme realized through Hamiltonian action within the second KP Poisson bracket. By working with free currents, which Abelianize the second KP Hamiltonian structure, we are able to obtain a unified formalism for the reduced SL(M + 1, M - k) KdV hierarchies interpolating between the ordinary KP and KdV hierarchies. The corresponding Lax operators are given as superdeterminants of graded SL(M + 1, M - k) matrices in the diagonal gauge and we describe their bracket structure and field content. In particular, we provide explicit free field representations of the associated W(M, M - k) Poisson bracket algebras generalising the familiar nonlinear W-M+1 algebra. Discrete Backlund transformations for SL(M + 1, M - k) KdV are generated naturally from lattice translations in the underlying Toda-like hierarchy. As an application we demonstrate the equivalence of the two-matrix string model to the SL(M + 1, 1) KdV hierarchy.

Drying of persimmon: Mathematical model for diffusivity as a simultaneous function of moisture content and shrinkage

Fresh persimmon has a high moisture content (about 85% wet basis) making it highly perishable and requiring adequate drying conditions to obtain an acceptable dehydrated product. Drying kinetics of persimmon cv. Rama Forte was studied in a fixed bed dryer at temperatures ranging from 50 to 80 degreesC and air velocity of 0.8 m/s. Shrinkage during drying was described by a linear correlation with respect to water content. Evaluation of effective diffusivity as a function of moisture content, with undergoing shrinkage during drying was based on Fourier series solution of Fick's diffusion equation. Effective diffusivity values at moisture contents between 0.09 - 4.23 kg water/kg dry matter were found to be in the range of 2.6 x 10(-10) m(2)/s to 5.4 x 10(-10) m(2)/s, and its dependence on air drying temperature was represented by an Arrhenius type equation. Activation energy increased with decreasing water content in persimmons.

Crystal nucleation kinetics of a metastable phase on cordierite glass surfaces

The crystal nucleation rates of a metastable phase (chi) on the surface of a near stoichiometric cordierite glass were determined for temperatures between 839 and 910 degrees C (T-g similar to 800 degrees C). The surface nucleation kinetics of that phase on our glass, as well as on a stoichiometric glass (2 MgO-2Al(2)O(3)-5SiO(2)) studied by other authors, were analysed in terms of the classical nucleation theory; for the first time. It was shown that the effective interfacial energy for surface nucleation is substantially lower than that for homogeneous volume nucleation in silicate glasses, vindicating the assumption of heterogeneous nucleation on free glass surfaces. The average wetting angle between the nucleating crystals and the active solid particles was estimated to be around 46 degrees C. The pre-exponential constant was several orders of magnitude higher than the theoretical values as found for volume homogeneous nucleation in oxide glasses.

Composting of urban solid residues (USR) by different dispositions - Kinetics of thermal decomposition

The thermal behavior and non-isothermal kinetics of thermal decomposition of three different kinds of composting of the USR like: stack with drilled PVC tubes (ST), revolved stack (SR) and stack with material of structure (SM), from the usine of composing of Araraquara city, São Paulo state, Brazil, within a period of 132 days of composting were studied.Results from TG, DTG and DSC curves obtained on inert atmosphere indicated that the cellulosic fraction present, despite the slow degradation during the composting process, is thermally less stable than other substances originated from that process. Due to that behavior, the cellulosic fraction decomposition could be kinetically evaluated through non-isothermal methods of analysis.The values obtained were: average activation energy, E-a=248, 257 and 259 kJ mol(-1) and pre-exponential factor, logA=21.4, 22.5, 22.7 min(-1), to the ST, SR and SM, respectively.From E-a and logA values and DSC curves, Malek procedure could be applied, suggesting that the SB (Sestak-Berggren) kinetic model is the appropriated one to the first thermal decomposition step.

Influence from the free volume on the photoinduced birefringence in azocompound-containing polymers

The photoinduced birefringence is analyzed in a guest-host azobenzene-containing polymer in the temperature range from 20 to 330 K. An anomalous behavior arises in the low-temperature range, suggesting strong influence from the free volume for the chromophores in the polymer. This influence is so strong that quenched samples have a photoinduced signal ca. 5 times greater than the annealed ones at room temperature. An extended free volume model is presented based on two assumptions about thermal fluctuations in the cavities and their size distribution. This model, which is an extension of the model by Mita et al., can explain the main features of the photoinduced birefringence as a function of time, temperature, and initial free volume state. To account for the influence of free volume on the photoorientation, the detailed reorientation model by Sekkat's was used. We show that Sekkat's model leads to an exponential behavior at small orientation regimes, which simplifies the mathematical treatment and allows the mean free volume to be obtained from the data fitting.

The dead core model applied to beads with immobilized cells in a fed-batch cephalosporin C production bioprocess

Viable cells immobilized in inert supports are currently studied for a wide range of bioprocesses. The intrinsic advantages of such systems over suspended cultures incite new research, including studies on fundamental aspects as well as on the industrial viability of these non-conventional processes. In aerobic culture of filamentous fungi, scale-up is hindered by oxygen mass transfer limitation through the support material and bioprocess kinetics must be studied together with mass transfer limitation. In this work, experimental and simulated data of cephalosporin C production were compared. Concentrations in the bulk fermentation medium and cellular mass profiles inside the bioparticles are focused. Immobilized cells were used in a tower bioreactor, operated in fed-batch mode. To describe the radial variation of oxygen concentration within the pellet, a dead core model was used. Despite the extremely low sugar concentrations, bioreaction rates in the pellets were limited by the dissolved oxygen concentration. Cell growth occurs only in the outer layers, a result also confirmed by scanning electron microscopy. (C) 2001 Elsevier B.V. Ltd. All rights reserved.