Thermodynamic non-ideality as an alternative source of the effect of sucrose on the thrombin-catalyzed hydrolysis of peptide p-nitroanalide substrates

The inhibitory effect of sucrose on the kinetics of thrombin-catalyzed hydrolysis of the chromogenic substrate S-2238 (D-phenylalanyl-pipecolyl-arginoyl-p-nitroanilide) is re-examined as a possible consequence of thermodynamic non-ideality-an inhibition originally attributed to the increased viscosity of reaction mixtures. However, those published results may also be rationalized in terms of the suppression of a substrate-induced isomerization of thrombin to a slightly more expanded (or more asymmetric) transition state prior to the irreversible kinetic steps that lead to substrate hydrolysis. This reinterpretation of the kinetic results solely in terms of molecular crowding does not signify the lack of an effect of viscosity on any reaction step(s) subject to diffusion control. Instead, it highlights the need for development of analytical procedures that can accommodate the concomitant operation of thermodynamic non-ideality and viscosity effects.

A high definition, finite difference time domain method

A high definition, finite difference time domain (HD-FDTD) method is presented in this paper. This new method allows the FDTD method to be efficiently applied over a very large frequency range including low frequencies, which are problematic for conventional FDTD methods. In the method, no alterations to the properties of either the source or the transmission media are required. The method is essentially frequency independent and has been verified against analytical solutions within the frequency range 50 Hz-1 GHz. As an example of the lower frequency range, the method has been applied to the problem of induced eddy currents in the human body resulting from the pulsed magnetic field gradients of an MRI system. The new method only requires approximately 0.3% of the source period to obtain an accurate solution. (C) 2003 Elsevier Science Inc. All rights reserved.

On the induced electric field gradients in the human body for magnetic stimulation by gradient coils in MRI

Prior theoretical studies indicate that the negative spatial derivative of the electric field induced by magnetic stimulation may he one of the main factors contributing to depolarization of the nerve fiber. This paper studies this parameter for peripheral nerve stimulation (PNS) induced by time.-varying gradient fields during MRI scans. The numerical calculations are based on an efficient, quasi-static, finite-difference scheme and an anatomically realistic human, full-body model. Whole-body cylindrical and planar gradient sets in MRI systems and various input signals have been explored. The spatial distributions of the induced electric field and their gradients are calculated and attempts are made to correlate these areas with reported experimental stimulation data. The induced electrical field pattern is similar for both the planar coils and cylindrical coils. This study provides some insight into the spatial characteristics of the induced field gradients for PNS in MRI, which may be used to further evaluate the sites where magnetic stimulation is likely to occur and to optimize gradient coil design.

Intramolecular electron transfer in a bacterial sulfite dehydrogenase

Sulfite dehydrogenase (SDH) from Starkeya novella, a sulfite-oxidizing molybdenum-containing enzyme, has a novel tightly bound αβ-heterodimeric structure in which the Mo cofactor and the c-type heme are located on different subunits. Flash photolysis studies of intramolecular electron transfer (IET) in SDH show that the process is first-order, independent of solution viscosity, and not inhibited by sulfate, which strongly indicates that IET in SDH proceeds directly through the protein medium and does not involve substantial movement of the two subunits relative to each other. The IET results for SDH contrast with those for chicken and human sulfite oxidase (SO) in which the molybdenum domain is linked to a b-type heme domain through a flexible loop, and IET shows a remarkable dependence on sulfate concentration and viscosity that has been ascribed to interdomain docking. The results for SDH provide additional support for the interdomain docking hypothesis in animal SO and clearly demonstrate that dependence of IET on viscosity and sulfate is not an inherent property of all sulfite-oxidizing molybdenum enzymes.

A comprehensive insight into floc characteristics and their impact on compressibility and settleability of activated sludge

This paper presents a comprehensive study of sludge floc characteristics and their impact on compressibility and settleability of activated sludge in full scale wastewater treatment processes. The sludge flocs were characterised by morphological (floc size distribution, fractal dimension, filament index), physical (flocculating ability, viscosity, hydrophobicity and surface charge) and chemical (polymeric constituents and metal content) parameters. Compressibility and settleability were defined in terms of the sludge volume index (SVI) and zone settling velocity (ZSV). The floc morphological and physical properties had important influence on the sludge compressibility and settleability. Sludges containing large flocs and high quantities of filaments, corresponding to lower values of fractal dimension (D-f), demonstrated poor compressibility and settleability. Sludge flocs with high flocculating ability had lower SVI and higher ZSV, whereas high values of hydrophobicity, negative surface charge and viscosity of the sludge flocs correlated to high SVI and low ZSV. The quantity of the polymeric compounds protein. humic substances and carbohydrate in the sludge and the extracted extracellular polymeric substances (EPS) had significant positive correlations with SVI. The ZSV was quantitatively independent of the polymeric constituents. High concentrations of the extracted EPS were related to poor compressibility and settleability. The cationic ions Ca, Mg, Al and Fe in the sludge improved significantly the sludge compressibility and settleability. (C) 2003 Elsevier Science B.V. All rights reserved.

Amylases in enzyme detergents and their effects on a simulated long-life dairy dessert

Enzyme detergents used in the food industry contain proteinase as the major enzyme but amylase may be present, either by design or inadvertently. Three commercial enzyme detergents and 3 enzyme preparations used in detergents were assayed for alpha-amylase activity by the Ceralpha method using the Megazyme kits. The amylase activities of the detergents varied from 3.2x 10(-6) to 32x 10(-6) mumoles ml(-1) h(-1) while the enzyme preparations had much higher activities ranging from 0.05 to 8.06 mumoles ml(-1) h(-1). When added aseptically to a simulated dairy dessert (2% starch solution) and stored for 42 days, the enzyme detergents caused an increase in viscosity; enzyme preparations at low concentrations caused an initial increase in viscosity followed by a decrease; and enzyme preparations at high concentrations caused an immediate decrease in viscosity. The increase in viscosity corresponded to formation of a distinct network of starch granules while the decrease in viscosity was characterised by a marked decrease in size of the granules and little or no network of granules. Decreases in viscosity corresponded to increases in reducing sugars but samples which increased in viscosity showed no measurable reducing sugars. The amylase activity in all sources was destroyed by heating at 75degreesC for 15 min at pH 1.8.

Diagnosing the cause of proteolysis in UHT milk

Proteolysis of UHT milk during storage at room temperature is a major factor limiting its shelf-life through changes in its flavour and texture. The latter is characterised by increases in viscosity leading in some cases to gel formation. The enzymes responsible for the proteolysis are the native milk alkaline proteinase, plasmin, and heat-stable, extracellular bacterial proteinases produced by psychrotrophic bacterial contaminants in the milk prior to heat processing. These proteinases react differently with the milk proteins and produce different peptides in the UHT milk. In order to differentiate these peptide products, reversed-phase HPLC and the fluorescamine method were used to analyse the peptides soluble in 12% trichloroacetic acid (TCA) and those soluble at pH 4.6. The TCA filtrate showed substantial peptide peaks only if the milk was contaminated by bacterial proteinase, while the pH 4.6 filtrate showed peptide peaks when either or both bacterial and native milk proteinases caused the proteolysis. Results from the fluorescamine test were in accordance with the HPLC results whereby the TCA filtrate exhibited significant proteolysis values only when bacterial proteinases were present, but the pH 4.6 filtrates showed significant values when the milk contained either or both types of proteinase. A procedure based on these analyses is proposed as a diagnostic test for determining which type of proteinase-milk plasmin, bacterial proteinase, or both-is responsible for proteolysis in UHT milk. (C) 2003 Swiss Society of Food Science and Technology. Published by Elsevier Science Ltd. All rights reserved.

Yogurt from UHT milk: a review

Continuous heat treatment by UHT processing has attracted interest as an alternative to the batch-heating method conventionally used in the production of yogurt. Several studies have been conducted on the manufacture of yogurt from milk heated by UHT processes and have compared it with the conventional method. This paper reviews the characteristics of yogurt made from UHT milk, including its apparent viscosity, gel strength, microstructure, syneresis (water-holding capacity) and flavour, as well as the behaviour of yogurt cultures in the UHT-treated pre-mix.

A study of the radiation degradation of styrene/alkane and α-methylstyrene/alkane copolymers

The effects of copolymer composition and microstructure on the radiation chemistry of styrene/alkane and alpha-methylstyrene/alkane copolymers have been studied. The primary radical species formed on radiolysis of the copolymers at 77 K, and identified by ESR spectroscopy, are the same as those formed during radiolysis of the homopolymers. The yields of radicals for the copolymer are as predicted assuming that the cross-section is proportional to the electron density of each component; however, there is some evidence of radical migration to aromatic groups at 77 K. Changes in molecular structure on irradiation were detected by using C-13 NMR spectroscopy. Evidence of the consumption of terminal double bonds, and chain scission in alpha-methylstyrene/alkane copolymers was found. Measurements of viscosity supported the mechanism of cross-linking predominating in styrene/alkane copolymers, while in alpha-methylstyrene/alkane copolymers chain scission was the major result of irradiation. (C) 2003 Society of Chemical Industry.

Crystallisation and moisture sorption properties of selected Australian unifloral honeys

The sorption properties of yapunyah (Eucalyptus ochropholia) and yellow box (Eucalyptus melliodora) honeys (Australian unifloral honeys) were investigated in a controlled relative humidity (RH) environment at 30degreesC for 71 days. The original water activity of the honeys affected the sorption properties. These two honeys absorbed moisture at and above 67.9% RH and desorbed moisture at and below 51.4% RH. The crystallisation behaviour of tea tree (Melaleuca quinquenervia) and yapunyah honeys was studied during storage at 13 and 23 degreesC. The degree of crystallisation was monitored by measuring the absorbance at 660 and 665 nm using a spectrophotometer. The heat-treated honeys did not show any sign of crystallisation after S months, whereas a seeding with precrystallised honey induced crystallisation of the same honeys. This crystallisation was more rapid at 13 than at 23degreesC. (C) 2003 Society of Chemical Industry.

Modelagem da dispersão de odores em ambientes urbanos

O presente trabalho investigou o problema da modelagem da dispersão de compostos odorantes em presença de obstáculos (cúbicos e com forma complexa) sob condição de estabilidade atmosférica neutra. Foi empregada modelagem numérica baseada nas equações de transporte (CFD1) bem como em modelos algébricos baseados na pluma Gausseana (AERMOD2, CALPUFF3 e FPM4). Para a validação dos resultados dos modelos e a avaliação do seu desempenho foram empregados dados de experimentos em túnel de vento e em campo. A fim de incluir os efeitos da turbulência atmosférica na dispersão, dois diferentes modelos de sub-malha associados à Simulação das Grandes Escalas (LES5) foram investigados (Smagorinsky dinâmico e WALE6) e, para a inclusão dos efeitos de obstáculos na dispersão nos modelos Gausseanos, foi empregado o modelo PRIME7. O uso do PRIME também foi proposto para o FPM como uma inovação. De forma geral, os resultados indicam que o uso de CFD/LES é uma ferramenta útil para a investigação da dispersão e o impacto de compostos odorantes em presença de obstáculos e também para desenvolvimento dos modelos Gausseanos. Os resultados também indicam que o modelo FPM proposto, com a inclusão dos efeitos do obstáculo baseado no PRIME também é uma ferramenta muito útil em modelagem da dispersão de odores devido à sua simplicidade e fácil configuração quando comparado a modelos mais complexos como CFD e mesmo os modelos regulatórios AERMOD e CALPUFF. A grande vantagem do FPM é a possibilidade de estimar-se o fator de intermitência e a relação pico-média (P/M), parâmetros úteis para a avaliação do impacto de odores. Os resultados obtidos no presente trabalho indicam que a determinação dos parâmetros de dispersão para os segmentos de pluma, bem como os parâmetros de tempo longo nas proximidades da fonte e do obstáculo no modelo FPM pode ser melhorada e simulações CFD podem ser usadas como uma ferramenta de desenvolvimento para este propósito. Palavras chave: controle de odor, dispersão, fluidodinâmica computacional, modelagem matemática, modelagem gaussiana de pluma flutuante, simulação de grandes vórtices (LES).

Elaboração e análise de extrato hidrossolúvel de gergelim (Sesamum indicum)

O objetivo do presente estudo foi elaborar e caracterizar um extrato hidrossolúvel à base de gergelim para ser usado como possível substituto do leite de vaca e extrato de soja. Foi proposto um modelo de cinética de absorção de água durante a etapa de maceração no qual estimou o tempo ideal de batimento do gergelim macerado e se essa etapa influencia no rendimento do produto. Posteriormente com o objetivo de saber a influência do tempo de batimento (0,45 min a 14,55 min) e a concentração do extrato (1,925% a 23,07%) foram avaliadas através de um delineamento composto central rotacional (DCCR), ou seja, um delineamento 22 incluindo 4 ensaios nas condições axiais e 5 repetições no ponto central, totalizando 13 experimentos. Para todos os ensaios do delineamento realizou-se análises de viscosidade, cor, sólidos solúveis totais e rendimento. As mesmas análises foram realizadas em amostras comerciais de leite de vaca e extrato hidrossolúvel de soja com o intuito de comparação. Após a realização dessa etapa foi possível à seleção de algumas amostras para elaboração do extrato hidrossolúvel de gergelim e então realizou-se análises físico-químicas (proteína, cinzas, lipídios, carboidratos) e determinou-se a capacidade antioxidante por ABTS e teor de compostos fenólicos de tais amostras. Quanto à análise de rendimento não houve diferença significativa da quantidade de extrato obtido em diferentes temperaturas de maceração pelo teste de Tukey (p> 0,05). O DCCR foi realizado no programa Statistica e selecionaram-se os ensaios 1, 2, 6, 7, PC (ponto central) que foram as amostras que mais se assemelharam com as amostras comerciais estudadas. Nessas amostras realizou-se as análises físico-químicas além de capacidade antioxidante e compostos fenólicos. O conteúdo de sólidos totais na amostra 6 foi superior as demais amostras, diferindo estatisticamente das demais amostras (p> 0,05). Já para o teor de lipídios, cinzas e proteínas encontrados nas amostras 6 e PC foram maiores que as demais amostras, enquanto a amostra 7 exibiu o menor teor de lipídios e proteínas, considerando que o teor de cinzas das amostras 1, 2 e 7 foram estatisticamente iguais. O teor de carboidratos calculado por diferença foi superior nas amostras 1, 2 e 7 e com o menor valor na amostra 6. Os valores de capacidade antioxidante e compostos fenólicos não se diferenciaram estatisticamente entre si ao nível de 5% de probabilidade. Concluiu-se portanto que a etapa de maceração não influenciou no rendimento do produto final. A partir das análises físico-químicas pode-se concluir que o extrato hidrossolúvel de gergelim em determinadas amostras apresentou um melhor desempenho quanto ao valor nutricional comparado ao extrato de soja.

Estudo do efeito da adição de gás condensado sobre o ponto de fluidez e a viscosidade de petróleos pesados

Neste trabalho foi estudado o comportamento de quatro óleos pesados, com densidade API variando de 13,7 a 21,6, frente à adição de gás condensado, com o objetivo de se obter informações relevantes para o processo de escoamento destes óleos. Assim, foi analisado o comportamento da densidade à 20 °C, pontos de fluidez máximo e mínimo, e viscosidade dinâmica à 50 °C dos óleos contendo diferentes concentrações de gás condensado. Também foi analisado o efeito da variação da temperatura sobre a viscosidade dos óleos crus, e, adicionalmente, após o estudo do efeito do gás condensado sobre os óleos, foi avaliado o comportamento da viscosidade dinâmica dos mesmos com a adição de diferentes solventes orgânicos (querosene, aguarrás e tolueno). Os resultados obtidos indicaram que o gás condensado foi eficiente para a redução da densidade, dos pontos de fluidez máximo e mínimo e da viscosidade dos quatros óleos analisados. O óleo A apresentou uma taxa de decaimento da densidade mais baixa do que os outros óleos e foi o que apresentou o comportamento mais próximo de mistura ideal. A amostra de óleo mais pesada (óleo D) foi a que apresentou as maiores variações nos valores dos pontos de fluidez máximo e mínimo com a adição de condensado, chegando a reduzir um total de 19 °C no ponto de fluidez máximo e um total de 21 °C no ponto de fluidez mínimo com a adição de apenas 10,7% v/v de gás condensado. Nos resultados obtidos nas análises da viscosidade dinâmica observou-se que a grande maioria das misturas preparadas apresentou um comportamento de fluido newtoniano. Todas as amostras apresentaram uma notável diminuição da sua viscosidade, chegando a atingir valores percentuais de redução de viscosidade que variaram entre 75 e 91%, na concentração de 14% v/v de gás condensado. A partir desta concentração a viscosidade continua a decair, porém de forma mais atenuada, e o uso do condensado acima desta concentração pode significar gastos desnecessários com o solvente com a finalidade de se reduzir a viscosidade de óleos pesados. O óleo D foi o que apresentou os maiores percentuais de redução da viscosidade enquanto o óleo B foi o que apresentou os mais baixos valores. Comparando o gás condensado aos outros três solventes orgânicos testados, o condensado apresentou um comportamento bem semelhante ao tolueno quando analisadas as suas capacidades de redução da viscosidade dos óleos estudados.

Correlation between grain nutritional content and pasting properties of pre-gelatinized red rice flour

As with any variety of rice, red rice characteristics are subject to varietal differences, growing conditions, types of processing, and nutritional and rheological properties. This study determined the nutritional characteristics (centesimal composition and minerals) and paste viscosity properties of raw grains of four red rice genotypes (Tradicional MNAPB0405, MNACE0501 and MNACH0501) and the paste viscosity properties of pre-gelatinized flours obtained at different cooking times (20, 30 and 40 min). The main nutritional properties were correlated with the pasting properties of the pre-gelatinized flours. The samples showed differences in nutritional properties and paste viscosity. MNAPB0405 and MNACE0501 showed higher levels of fiber and fat and provided higher caloric energy than Tradicional and MNACH0501, which, in turn, showed higher levels of amylose. MNACH0501 showed higher peak viscosity (2402 cP), higher breakdown viscosity (696 cP) and a greater tendency to retrogradation (1510 cP), while Tradicional, MNAPB0405 and MNACE0501 had pasting profiles with peak viscosities varying between 855 and 1093 cP, breaking viscosity below 85 cP and retrogradation tendency between 376 and 1206 cP. The factors genotype and cooking time influenced the rheological behavior of pre-gelatinized flours, decreasing their pasting properties. The protein and amylose levels are correlated with the pasting properties and can be used as indicators of these properties in different genotypes of red rice, whether raw or processed into pre-gelatinized flours.

Chemical, morphological, rheological and thermal properties of Solanum lycocarpum phosphorylated starches

The increasing need for starches with specific characteristics makes it important to study unconventional starches and their modifications in order to meet consumer demands. The aim of this work was to study physicochemical characteristics of native starch and phosphate starch of S. lycocarpum. Native starch was phosphated with sodium tripolyphosphate (5-11%) added with stirring. Chemical composition, morphology, density, binding ability to cold water, swelling power and solubility index, turbidity and syneresis, rheological and calorimetric properties were determined. Phosphorus was not detected in the native sample, but the phosphating process produced modified starches with phosphorus contents of 0.015, 0.092 and 0.397%, with the capacity of absorbing more water, either cold or hot. Rheological data showed the strong influence of phosphorus content on viscosity of phosphate starch, with lower pasting temperature and peak viscosity higher than those of native starch. Enthalpy was negatively correlated with the phosphorus content, requiring 9.7; 8.5; 8.1 and 6.4 kJ g-1 of energy for the transition from the amorphous to the crystalline state for the starch granules with phosphorus contents of 0; 0.015; 0.092 and 0.397%, respectively. Cluster analysis and principal component analysis showed that starches with 0.015 and 0.092% phosphorus have similar characteristics and are different from the others. Our results show that the characteristics of phosphate modified S. lycocarpum starch have optimal conditions to meet the demands of raw materials, which require greater consistency in stickiness, combined with low rates of retrogradation and syneresis.