Simultaneous voltammetric detection of ascorbic acid, dopamine and uric acid using a pyrolytic graphite electrode modified into dopamine solution

Pyrolytic graphite electrodes (PGE) were modified into dopamine solutions using phosphate buffer solutions, pH 10 and 6.5, as supporting electrolyte. The modification process involved a previous anodization of the working electrode at +1. 5 V into 0. 1 mol-L-1 NaOH followed by other anodization step, in the same experimental conditions, into dopamine (DA) solutions. pH of the supporting electrolyte performed an important role in the production of a superficial melanin polymeric film, which permitted the simultaneous detection of ascorbic acid (AA), (DA) and uric acid (UA), Delta EAA-DA = 222 mV-, Delta EAA-UA = 360 mV and Delta EDA-UA=138mV, avoiding the superficial poisoning effects. The calculated detection limits were: 1.4 x 10(-6) mol L-1 for uric acid, 1.3x10-(5) molL(-1) for ascorbic acid and 1.1 X 10(-7) mol L-1 for dopamine, with sensitivities of (7.7 +/- 0.5), (0.061 +/- 0.001) and (9.5 +/- 0.05)A mol(-1) cm(-2), respectively, with no mutual interference. Uric acid was determined in urine, blood and serum human samples after dilution in phosphate buffer and no additional sample pre-treatment was necessary. The concentration of uric acid in urine was higher than the values found in blood and serum and the recovery tests (92-102%) indicated that no matrix effects were observed. (C) 2008 Elsevier B.V. All rights reserved.

Square wave adsorptive cathodic stripping voltarnmetry automated by sequential injection analysis - Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L-1 Britton-Robinson buffer (pH 10) in 0.25 mol L-1 NaNO3. The homogenized mixture is injected at a flow rate of 10 mu Ls(-1) toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from -0.3 to -1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mgL(-1), with detection and quantification limits of 2 and 7 mu gL(-1), respectively. The sampling throughput is 25 h(-1) if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h(-1) if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. (C) 2007 Elsevier B.V. All rights reserved.

Synthesis, spectroscopic characterization and radiosensitizing properties of acetato-bridged copper(II) complexes with 5-nitroimidazole drugs

Three novel acetato-bridged dinuclear copper(II) complexes with 5-nitroimidazoles (CuAcNtrim) and the known copper-acetato-metronidazole have been prepared by an environment-friendly route and spectroscopically characterized. The CuAcNtrim compounds of formula [Cu(2)(mu-O(2)CCH(3))(4)Ntrim(2)], where Ntrim = metronidazole (1), secnidazole (2), tinidazole (3) or nimorazole (4), exhibit dimeric copper-acetato paddle-wheel structures with Ntrim axial ligands coordinated to copper(II) ions through the N(3) atoms of the imidazole rings. EPR data indicate antiferromagnetic behavior for this novel series of copper complexes. The constant coupling has been found to decrease along with the increasing of basicity of the Ntrim axial ligand. The CuAcNtrim complexes and the correspondent Ntrim parent drugs have shown radiosensitizer properties for Hep2 (human larynx cancer) cell line in vitro. The best enhancement of radiosensitizer activity upon coordination of the Ntrim drug to copper(II) has been found for the nimorazole compound which has the strongest Cu-Ntrim bond and exhibits the highest lipophilicity within the series of CuAcNtrim complexes. (C) 2010 Elsevier B.V. All rights reserved.

Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples

The aim of this study was to develop a fast capillary electrophoresis method for the determination of inorganic cations (Na(+), K(+), Ca(2+), Mg(2+)) in biodiesel samples, using barium (Ba(2+)) as the internal standard. The running electrolyte was optimized through effective mobility curves in order to select the co-ion and Peakmaster software was used to determine electromigration dispersion and buffer capacity. The optimum background electrolyte was composed of 10 mmol L(-1) imidazole and 40 mmol L(-1) of acetic acid. Separation was conducted in a fused-silica capillary (32 cm total length and 23.5 cm effective length, 50 mu m I.D.), with indirect UV detection at 214 nm. The migration time was only 36 s. In order to obtain the optimized conditions for extraction, a fractional factorial experimental design was used. The variables investigated were biodiesel mass, pH, extractant volume, agitation and sonication time. The optimum conditions were: biodiesel mass of 200 mg, extractant volume of 200 mu L. and agitation of 20 min. The method is characterized by good linearity in the concentration range of 0.5-20 mg kg(-1) (r > 0.999), limit of detection was equal to 0.3 mg kg(-1), inter-day precision was equal to 1.88% and recovery in the range of 88.0-120%. The developed method was successfully applied to the determination of cations in biodiesel samples. (c) 2010 Elsevier B.V. All rights reserved.

(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Determination of fluoxetine in plasma by gas chromatography-mass spectrometry using stir bar sorptive extraction

This article presents a method employing stir bar sorptive extraction (SBSE) with in situ derivatization, in combination with either thermal or liquid desorption on-line coupled to gas chromatography-mass spectrometry for the analysis of fluoxetine in plasma samples. Ethyl chloroformate was employed as derivatizing agent producing symmetrical peaks. Parameters such as solvent polarity, time for analyte desorption, and extraction time, were evaluated. During the validation process, the developed method presented specificity, linearity (R-2 > 0.99), precision (R.S.D. < 15%), and limits of quantification (LOQ) of 30 and 1.37 pg mL(-1), when liquid and thermal desorption were employed, respectively. This simple and highly sensitive method showed to be adequate for the measurement-of fluoxetine in typical and trace concentration levels. (c) 2008 Elsevier B.V. All rights reserved.

Polydimethylsiloxane/polypyrrole stir bar sorptive extraction and liquid chromatography (SBSE/LC-UV) analysis of antidepressants in plasma samples

A new polymeric coating consisting of a dual-phase, polydimethylsiloxane (PDMS) and polypyrrole (PPY) was developed for the stir bar sorptive extraction (SBSE) of antidepressants (mirtazapine, citalopram, paroxetine, duloxetine, fluoxetine and sertraline) from plasma samples, followed by liquid chromatography analysis (SBSE/LC-UV). The extractions were based on both adsorption (PPY) and sorption (PDMS) mechanisms. SBSE variables, such as extraction time, temperature, pH of the matrix, and desorption time were optimized, in order to achieve suitable analytical sensitivity in a short time period. The PDMS/PPY coated stir bar showed high extraction efficiency (sensitivity and selectivity) toward the target analytes. The quantification limits (LOQ) of the SBSE/LC-UV method ranged from 20 ng mL(-1) to 50 ng mL(-1), and the linear range was from LOQ to 500 ng mL(-1), with a determination coefficient higher than 0.99. The inter-day precision of the SBSE/LC-UV method presented a variation coefficient lower than 15%. The efficiency of the SBSE/LC-UV method was proved by analysis of plasma samples from elderly depressed patients. (C) 2008 Elsevier B.V. All rights reserved.

Performance evaluation of ventilation radiators

A ventilation radiator is a combined ventilation and heat emission unit currently of interest due to its potential for increasing energy efficiency in exhaust ventilated buildings with warm water heating. This paper presents results of performance tests of several ventilation radiator models conducted under controlled laboratory conditions.   The purpose of the study was to validate results achieved by Computational Fluid Dynamics (CFD) in an earlier study and indentify possible improvements in the performance of such systems. The main focus was on heat transfer from internal convection fins, but comfort and health aspects related to ventilation rates and air temperatures were also considered.   The general results from the CFD simulations were confirmed; the heat output of ventilation radiators may be improved by at least 20 % without sacrificing ventilation efficiency or thermal comfort.   Improved thermal efficiency of ventilation radiators allows a lower supply water temperature and energy savings both for heating up and distribution of warm water in heat pumps or district heating systems. A secondary benefit is that a high ventilation rate can be maintained all year around without risk for cold draught.

Radiation properties of coil-coated steel in building envelope surfaces and the influence on building thermal performance

Recent studies have shown that the optical properties of building exterior surfaces are important in terms of energy use and thermal comfort. While the majority of the studies are related to exterior surfaces, the radiation properties of interior surfaces are less thoroughly investigated. Development in the coil-coating industries has now made it possible to allocate different optical properties for both exterior and interior surfaces of steel-clad buildings. The aim of this thesis is to investigate the influence of surface radiation properties with the focus on the thermal emittance of the interior surfaces, the modeling approaches and their consequences in the context of the building energy performance and indoor thermal environment. The study consists of both numerical and experimental investigations. The experimental investigations include parallel field measurements on three similar test cabins with different interior and exterior surface radiation properties in Borlänge, Sweden, and two ice rink arenas with normal and low emissive ceiling in Luleå, Sweden. The numerical methods include comparative simulations by the use of dynamic heat flux models, Building Energy Simulation (BES), Computational Fluid Dynamics (CFD) and a coupled model for BES and CFD. Several parametric studies and thermal performance analyses were carried out in combination with the different numerical methods. The parallel field measurements on the test cabins include the air, surface and radiation temperatures and energy use during passive and active (heating and cooling) measurements. Both measurement and comparative simulation results indicate an improvement in the indoor thermal environment when the interior surfaces have low emittance. In the ice rink arenas, surface and radiation temperature measurements indicate a considerable reduction in the ceiling-to-ice radiation by the use of low emittance surfaces, in agreement with a ceiling-toice radiation model using schematic dynamic heat flux calculations. The measurements in the test cabins indicate that the use of low emittance surfaces can increase the vertical indoor air temperature gradients depending on the time of day and outdoor conditions. This is in agreement with the transient CFD simulations having the boundary condition assigned on the exterior surfaces. The sensitivity analyses have been performed under different outdoor conditions and surface thermal radiation properties. The spatially resolved simulations indicate an increase in the air and surface temperature gradients by the use of low emittance coatings. This can allow for lower air temperature at the occupied zone during the summer. The combined effect of interior and exterior reflective coatings in terms of energy use has been investigated by the use of building energy simulation for different climates and internal heat loads. The results indicate possible energy savings by the smart choice of optical properties on interior and exterior surfaces of the building. Overall, it is concluded that the interior reflective coatings can contribute to building energy savings and improvement of the indoor thermal environment. This can be numerically investigated by the choice of appropriate models with respect to the level of detail and computational load. This thesis includes comparative simulations at different levels of detail.

Numerical Simulation Of Sediment Transport And Bedmorphology Around A Hydraulic Structure On A River

Scour around hydraulic structures is a critical problem in hydraulic engineering. Under prediction of scour depth may lead to costly failures of the structure, while over prediction might result in unnecessary costs. Unfortunately, up-to-date empirical scour prediction formulas are based on laboratory experiments that are not always able to reproduce field conditions due to complicated geometry of rivers and temporal and spatial scales of a physical model. However, computational fluid dynamics (CFD) tools can perform using real field dimensions and operating conditions to predict sediment scour around hydraulic structures. In Korea, after completing the Four Major Rivers Restoration Project, several new weirs have been built across Han, Nakdong, Geum and Yeongsan Rivers. Consequently, sediment deposition and bed erosion around such structures have became a major issue in these four rivers. In this study, an application of an open source CFD software package, the TELEMAC-MASCARET, to simulate sediment transport and bed morphology around Gangjeong weir, which is the largest multipurpose weir built on Nakdong River. A real bathymetry of the river and a geometry of the weir have been implemented into the numerical model. The numerical simulation is carried out with a real hydrograph at the upstream boundary. The bedmorphology obtained from the numerical results has been validated against field observation data, and a maximum of simulated scour depth is compared with the results obtained by empirical formulas of Hoffmans. Agreement between numerical computations, observed data and empirical formulas is judged to be satisfactory on all major comparisons. The outcome of this study does not only point out the locations where deposition and erosion might take place depending on the weir gate operation, but also analyzes the mechanism of formation and evolution of scour holes after the weir gates.

Temperature Dynamics Investigation At Small And Shallow Lakes Using Hydrodynamic Model

A three-dimensional time-dependent hydrodynamic and heat transport model of Lake Binaba, a shallow and small dam reservoir in Ghana, emphasizing the simulation of dynamics and thermal structure has been developed. Most numerical studies of temperature dynamics in reservoirs are based on one- or two-dimensional models. These models are not applicable for reservoirs characterized with complex flow pattern and unsteady heat exchange between the atmosphere and water surface. Continuity, momentum and temperature transport equations have been solved. Proper assignment of boundary conditions, especially surface heat fluxes, has been found crucial in simulating the lake’s hydrothermal dynamics. This model is based on the Reynolds Average Navier-Stokes equations, using a Boussinesq approach, with a standard k − ε turbulence closure to solve the flow field. The thermal model includes a heat source term, which takes into account the short wave radiation and also heat convection at the free surface, which is function of air temperatures, wind velocity and stability conditions of atmospheric boundary layer over the water surface. The governing equations of the model have been solved by OpenFOAM; an open source, freely available CFD toolbox. As its core, OpenFOAM has a set of efficient C++ modules that are used to build solvers. It uses collocated, polyhedral numerics that can be applied on unstructured meshes and can be easily extended to run in parallel. A new solver has been developed to solve the hydrothermal model of lake. The simulated temperature was compared against a 15 days field data set. Simulated and measured temperature profiles in the probe locations show reasonable agreement. The model might be able to compute total heat storage of water bodies to estimate evaporation from water surface.

Análise das políticas de suprimento praticadas pelas grandes empresas industriais brasileiras

O objetivo principal deste estudo é contribuir para o entendimento das relações de suprimento estabelecidas entre as grandes empresas industriais do Brasil e seus fornecedores. A pesquisa parte do princípio que existem algumas variáveis que afetam as políticas de suprimento e procura verificar as correlações existentes entre estas variáveis e as políticas. Baseia-se em um conjunto de teorias, entre as quais, a teoria geral das organizações, a teoria dos jogos, a economia dos custos das transações, os estudos sobre a importância da confiança nas relações de negócios teoria da confiança e a teoria de compras. Através de um questionário, construído com baseado em escalas de Likert e de diferenc ial semântico, procurou-se validar um modelo de relacionamento que coloca em extremos as relações chamadas de CFD (Contratos de fornecimento discretos) e CFP (Contratos de fornecimento de parcerias). Foram remetidos questionários a 300 empresas e se obteve o retorno de 238. A amostra contém empresas de 14 estados brasileiros e 11 setores. O estudo em sua parte descritiva concluiu que existem diferenças significativas nas ações das empresas de acordo com o ramo no qual atuam. Não existem, no entanto, diferenças significativas entre os diversos estados brasileiros nos quais se situam suas matrizes, o que indica uma homogeneização de práticas em todo o território nacional, ao menos entre as grandes empresas. Foram encontradas correlações significativas entre algumas variáveis independentes e as estratégias de suprimento. Isto pode fornecer subsídios tanto para a definição de posturas para as empresas fornecedores de insumos industriais, quanto para as empresas que estão montando estratégias de suprimento e querem utilizar o estudo como “benchmark” dos seus processos em relação às maiores empresas brasileiras.

Modelagem mecânica e aproximação por métodos estabilizados de escoamentos multicomponentes

Este estudo foi motivado pela possibilidade de se empregar os conhecimentos da engenharia mecânica na solução de problemas de engenharia de alimentos por métodos numéricos, assim como pela utilização da dinâmica dos fluidos computacional (CFD) em mais um campo de pesquisa. A idéia básica foi a aplicação do método de elementos finitos na solução de problemas de escoamentos envolvendo mistura de diferentes componentes. Muitos alimentos apresentam-se como fluidos, e seu comportamento material pode ser newtoniano ou não newtoniano, às vezes descrito por relações constitutivas bastante complexas. Utilizou-se uma teoria de misturas apoiada nos conceitos de mecânica do contínuo para a modelagem mecânica do que se passou a considerar como um sistema multicomponente. Necessitou-se de uma detalhada revisão sobre os postulados clássicos da mecânica para que se pudesse recolocá-los, com alguma segurança e embasamento teórico, para sistemas multicomponentes. Tendo em mãos a modelagem do balanço de momentum e massa em sistemas multicomponentes, pôde-se aproximar estas equações através do método de elementos finitos. A literatura aponta que o método clássico de Galerkin não possui a eficiência necessária para a solução das equações de escoamento, que envolvem uma formulação mista onde se faz necessário tomar compatíveis os subespaços de velocidade e pressão, e também devido à natureza assimétrica da aceleração advectiva, o que também aparece como uma dificuldade na solução de problemas de advecçãodifusão, nos casos de advecção dominante. Assim, fez-se uso do método estabilizado tipo GLS, o qual supera as dificuldades enftentadas pelo método de Galerkin clássico em altos números de Reynolds, adicionando termos dependentes da malha, construídos de forma a aumentar a estabilidade da formulação de Galerkin original sem prejudicar sua consistência. Os resultados numéricos dividem-se em três categorias: problemas de transferência de quantidade de movimento para fluidos newtonianos, problemas de transferência de quantidade de movimento para fluidos com não linearidade material e problemas de advecção e difusão de massa em misturas. A comparação de algumas aproximações obtidas com as de outros autores se mostraram concordantes. A aproximação de problemas de fluidos segundo os modelos Carreau e Casson geraram os resultados esperados. A aproximação de um problema de injeção axial com mistura de dois fluidos produziu resultados coerentes, motivando a aplicação prática da aproximação por métodos estabilizados de problemas de misturas.

Determinação dos campos de velocidade e temperatura em ambientes ventilados

No presente trabalho apresenta-se um estudo numérico do escoamento de ar em um ambiente interno tridimensional típico, sujeito a um sistema de ventilação por deslocamento. O estudo numérico consiste na obtenção dos campos de velocidade e temperatura presentes no interior deste ambiente. A determinação dos campos de velocidade e temperatura é necessária na avaliação precisa das condições de conforto térmico, produzidas por um determinado sistema de climatização. Este tipo de estudo não serve somente para determinar a viabilidade da aplicação de um determinado sistema de distribuição de ar, mas através dele também se pode determinar as condições ótimas de uso deste sistema. De forma crescente observa-se o interesse dos projetistas de ar condicionado em aperfeiçoar as suas técnicas de cálculo, de modo que a simulação numérica poderá tornar-se uma técnica usual em pouco tempo. Atualmente duas técnicas estão disponíveis para o estudo do escoamento de ar em ambientes internos: investigação experimental e simulação numérica. Em princípio, medidas diretas dão informações mais realísticas relativas ao escoamento do ar interno, contudo, medições experimentais são muito caras e consomem muito tempo, inviabilizando a sua aplicação caso a caso. Devido às limitações da investigação experimental e à disponibilidade de computadores cada vez mais rápidos, o uso da simulação numérica surge como uma opção considerável nos dias de hoje O método de solução numérica, utilizado no presente trabalho, baseia-se na resolução das equações de conservação de massa, de quantidade de movimento e de energia, em um domínio de cálculo discretizado com o uso do Método dos Volumes Finitos. Os efeitos da turbulência são levados em conta através da utilização do modelo de turbulência K- ε e de um modelo de turbulência simplificado. Resultados bem convergidos para o problema abordado somente são obtidos com a utilização do modelo de turbulência simplificado. As simulações numéricas apresentadas no presente trabalho foram realizadas com o uso do código Fluent. Com base na comparação dos resultados numéricos obtidos no presente trabalho e os resultados experimentais de Yuan et al., 1999a, pode-se concluir que o modelo simplificado é adequado, ao menos provisoriamente, para determinar a distribuição de velocidade e de temperatura no escoamento de ar em ambientes internos.

Análise numérica de uma torre de resfriamento de grande porte

Este trabalho tem como objetivo principal determinar a troca de calor em uma torre de resfriamento de grande porte, do tipo seca. A força motriz deste sistema é o empuxo resultante da diferença de temperatura entre o ar interior e exterior da torre. A partir de uma certa velocidade o vento externo também desempenha um papel importante. A convecção natural ocorre em regime turbulento, devido às grandes dimensões. A modelagem numérica é feita pelo Método dos Volumes Finitos com malhas criadas sobre Elementos Finitos, através dos softwares comerciais Fluent e CFX. Os resultados são obtidos para diferentes potências dissipadas no trocador de calor. A partir dos resultados são realizados estudos sobre a viabilidade de mudanças na geometria da torre, a fim de se obter melhorias no escoamento, bem como uma troca de calor mais eficiente. Faz-se ainda uma regressão a fim de obter correlações entre a potência dissipada no trocador de calor e a vazão mássica de ar necessária para a troca. Estas correlaçõoes são de utilidade, para aplicações posteriores, na implantação de um simulador para o processo de troca de calor nesta torre. O trocador de calor também é enfocado a fim de se determinar o coeficiente global de troca térmica, a fim de disponibilizá-lo para aplicação em outros trabalhos