Abordagem ao risco de crédito no âmbito do acordo de Basileia III em Portugal

Dissertação para a obtenção do Grau de Mestre em Contabilidade e Finanças Orientador: Mestre Adalmiro Álvaro Malheiro de Castro Andrade Pereira

Desenvolvimento e validação de um sistema de recolha de sinal eletromiográfico baseado em placa de aquisição

A eletromiografia é, hoje em dia, uma das técnicas mais utilizadas no estudo dos músculos, estando presente em áreas como a medicina, a biomecânica e a fisiologia, possibilitando o desenvolvimento científico e contribuindo para proporcionar melhorias na qualidade da vida humana. Sendo assim, este trabalho apresenta um protótipo de um aparelho de aquisição de sinais eletromiográficos, explicando também toda a teoria, técnicas, componentes utilizadas e softwares que estiveram presentes na sua implementação. De uma forma sucinta, para a aquisição do sinal eletromiográfico usou-se uma placa de aquisição NI-USB 6009 e para a visualização do mesmo recorreu-se ao software LabVIEW. Para validar o sinal adquirido com o equipamento desenvolvido, utilizou-se um outro equipamento, o Biopac MP36 Student Lab System, fazendo-se assim recolhas de sinais eletromiográficos com ambos os equipamentos. Os sinais recolhidos pelos dois equipamentos foram analisados no software Acknowledge 3.9.0 (Biopac Systems, Inc.), podendo observar-se os espetros de frequência correspondentes a cada sinal e retirar valores para posterior análise estatística. Feita essa análise, concluiu-se que não foram detetadas diferenças significativas entre os sinais eletromiográficos recolhidos com ambos os equipamentos, validando-se assim, o equipamento desenvolvido.

Electroanalytical determination of oxadiazon and characterization of its base-catalyzed ring-opening products

The electrochemical behavior of the hydrolysis products of oxadiazon was studied by cyclic and square-wave voltammetry using a glassy carbon electrode. Maximum currents were obtained at pH 12.8 in an aqueous electrolyte solution containing 30% ethanol and the current did not decrease with time showing that there was little adsorption of the reaction products on the electrode surface. The hydrolysis products of oxadiazon were identi®ed, after isolation and puri®cation, as 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl)-2-ethoxycarbonylhydrazine (Oxa1) and 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) with redox potentials 0.6Vand 70.1V (vs. Ag=AgCl), respectively. Based on the electrochemical behavior of 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) a simple electroanalytical procedure was developed for the determination of oxadiazon in commercial products used in the treatment of rice crops in Portugal that contain oxadiazon as the active ingredient. The detection limit was 161074 M, the mean content and relative standard deviation obtained for seven samples of two different commercial products by the electrochemical method were 28.4 0.8% (Ronstar) and 1.9 0.2% (Ronstar GR), and the recoveries were 100.3 5.4% and 101.1 5.3 %, respectively.

Development of an FIA system with amperometric detection for determination of bentazone in estuarine waters

On the basis of its electrochemical behaviour a new flow-injection analysis (FIA) method with amperometric detection has been developed for quantification of the herbicide bentazone (BTZ) in estuarine waters. Standard solutions and samples (200 µL) were injected into a water carrier stream and both pH and ionic strength were automatically adjusted inside the manifold. Optimization of critical FIA conditions indicated that the best analytical results were obtained at an oxidation potential of 1.10 V, pH 4.5, and an overall flow-rate of 2.4 mL min–1. Analysis of real samples was performed by means of calibration curves over the concentration range 2.5x10–6 to 5.0x10–5 mol L–1, and results were compared with those obtained by use of an independent method (HPLC). The accuracy of the amperometric determinations was ascertained; errors relative to the comparison method were below 4% and sampling rates were approximately 100 samples h–1. The repeatability of the proposed method was calculated by assessing the relative standard deviation (%) of ten consecutive determinations of one sample; the value obtained was 2.1%.

Adsorption behavior of α-cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of α-cypermethrin [R)-α-cyano-3-phenoxybenzyl(1S)-cis- 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α-cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α-cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (qm) (303 μg/g); followed by GAC (186 μg/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α-cypermethrin adsorption phenomena on GAC, while α-cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α-cypermethrin from water.

Citrate selective electrodes for the flow injection analysis of soft drinks, beers and pharmaceutical products

Aiming the establishment of simple and accurate readings of citric acid (CA) in complex samples, citrate (CIT) selective electrodes with tubular configuration and polymeric membranes plus a quaternary ammonium ion exchanger were constructed. Several selective membranes were prepared for this purpose, having distinct mediator solvents (with quite different polarities) and, in some cases, p-tert-octylphenol (TOP) as additive. The latter was used regarding a possible increase in selectivity. The general working characteristics of all prepared electrodes were evaluated in a low dispersion flow injection analysis (FIA) manifold by injecting 500µl of citrate standard solutions into an ionic strength (IS) adjuster carrier (10−2 mol l−1) flowing at 3ml min−1. Good potentiometric response, with an average slope and a repeatability of 61.9mV per decade and ±0.8%, respectively, resulted from selective membranes comprising additive and bis(2-ethylhexyl)sebacate (bEHS) as mediator solvent. The same membranes conducted as well to the best selectivity characteristics, assessed by the separated solutions method and for several chemical species, such as chloride, nitrate, ascorbate, glucose, fructose and sucrose. Pharmaceutical preparations, soft drinks and beers were analyzed under conditions that enabled simultaneous pH and ionic strength adjustment (pH = 3.2; ionic strength = 10−2 mol l−1), and the attained results agreed well with the used reference method (relative error < 4%). The above experimental conditions promoted a significant increase in sensitivity of the potentiometric response, with a supra-Nernstian slope of 80.2mV per decade, and allowed the analysis of about 90 samples per hour, with a relative standard deviation <1.0%.

Determination of ametryn in soils via microwave-assisted solvent extraction coupled to anodic stripping voltammetry with a gold ultramicroelectrode

An extraction-anodic adsorptive stripping voltammetric procedure using microwave-assisted solvent extraction and a gold ultramicroelectrode was developed for determining the pesticide ametryn in soil samples. The method is based on the use of acetonitrile as extraction solvent and on controlled adsorptive accumulation of the herbicide at the potential of 0.50 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 3.3). Soil sample extracts were analysed directly after drying and redissolution with the supporting electrolyte but without other pre-treatment. The limit of detection obtained for a 10 s collection time was 0.021 µg g-1. Recovery experiments for the global procedure, at the 0.500 µg g-1 level, gave satisfactory mean and standard deviation results which were comparable to those obtained by HPLC with UV detection.

Electroanalytical study of the pesticide asulam

The electrochemical behaviour of the herbicide Asulam was studied by cyclic and square wave voltammetry. Asulam may be irreversibly oxidised at a glassy carbon electrode. Maximum currents were obtained at pH=1.9 in aqueous electrolyte solution. Based on the electrochemical behaviour of Asulam, two analytical methodologies were developed for its determination in water samples, using square wave voltammetry (SWV) and flow injection analysis (FIA) coupled with an amperometric detector. Limits of detection of 7.1x10-6 mol L-1 and 1.2x10-8 mol L-1 for SWV and FIA respectively, were achieved. Repeatability was calculated by assessing the relative standard deviation (%) for 10 consecutive determinations of one sample. The found values were 2.1% for SWV and 5.0% for FIA. Validation of the results provided by SWV and FIA methodologies was performed by comparison with results from an HPLC-DAD technique. Good relative deviations were found (<5%). Recovery trials were performed to assess the accuracy of the results and the obtained values were between 84% and 107% for both methods.

A sensitivity study of the WRF model in wind simulation for an area of high wind energy

The performance of the Weather Research and Forecast (WRF) model in wind simulation was evaluated under different numerical and physical options for an area of Portugal, located in complex terrain and characterized by its significant wind energy resource. The grid nudging and integration time of the simulations were the tested numerical options. Since the goal is to simulate the near-surface wind, the physical parameterization schemes regarding the boundary layer were the ones under evaluation. Also, the influences of the local terrain complexity and simulation domain resolution on the model results were also studied. Data from three wind measuring stations located within the chosen area were compared with the model results, in terms of Root Mean Square Error, Standard Deviation Error and Bias. Wind speed histograms, occurrences and energy wind roses were also used for model evaluation. Globally, the model accurately reproduced the local wind regime, despite a significant underestimation of the wind speed. The wind direction is reasonably simulated by the model especially in wind regimes where there is a clear dominant sector, but in the presence of low wind speeds the characterization of the wind direction (observed and simulated) is very subjective and led to higher deviations between simulations and observations. Within the tested options, results show that the use of grid nudging in simulations that should not exceed an integration time of 2 days is the best numerical configuration, and the parameterization set composed by the physical schemes MM5–Yonsei University–Noah are the most suitable for this site. Results were poorer in sites with higher terrain complexity, mainly due to limitations of the terrain data supplied to the model. The increase of the simulation domain resolution alone is not enough to significantly improve the model performance. Results suggest that error minimization in the wind simulation can be achieved by testing and choosing a suitable numerical and physical configuration for the region of interest together with the use of high resolution terrain data, if available.

O impacto de um programa de exercícios com o Inspirómetro de Incentivo na função pulmonar em doentes com Escoliose Idiopática

Introdução: A escoliose é uma deformidade vertebral muito comum e de grande importância social. A etiologia da escoliose idiopática da adolescência é desconhecida e descrita como multifatorial. Segundo a literatura existe uma forte correlação entre a função pulmonar anormal e a gravidade da deformidade da coluna vertebral. Tem sido proposto como abordagem terapêutica o uso de Inspirómetro de Incentivo, contudo, ainda se encontra incerto a sua eficácia nesta patologia. Objetivo: Analisar o impacto de um programa de exercícios domiciliários com o Inspirómetro de Incentivo em doentes com Escoliose Idiopática nos volumes pulmonares e na força muscular dos músculos respiratórios. Metodologia: Foram avaliados, por meio de um estudo experimental, 12 indivíduos do sexo feminino (com média e desvio padrão correspondentes a 15,1 e 1,6 respetivamente) com diagnóstico de Escoliose Idiopática antes e 3meses após a cirurgia corretiva e 12 indivíduos saudáveis também do sexo feminino (com média e desvio padrão correspondentes a 15,2 e 1,4 respetivamente). A função pulmonar foi avaliada através do espirómetro computorizado Spinolab®, a força dos músculos respiratórios avaliou-se através da mensuração da PImáx e PEmáx com o Microrpm®. Para finalizar a avaliação o participante foi sujeito a aplicação do THRESHOLD® com 30% da PImáx obtida. O protocolo domiciliário, referente à parte experimental, baseou-se no uso bi-diário do Inspirómetro de Incentivo Respiflo FS®, que foi fornecido aos participantes no dia da alta hospitalar. Resultados: Foram encontrados valores menores da função respiratória e força muscular (p<0,05) no grupo de doentes com Escoliose em relação ao grupo dos Saudáveis, excepto em relação ao Índice de Tiffeneau (p=0,17). No entanto, quando se comparou o grupo Controlo e o Grupo Experimental não severificaram diferenças estatisticamente significativas em relação às variáveis estudadas. Por fim, na análise dos parâmetros nos dois momentos de avaliação (inicial e final) entre o grupo dos Saudáveis e grupo Experimental verificou-se que existiam diferenças estatisticamente significativas ao nível da CFV (pi=0,02; pf=0,00), FEV1 (pi=0,01; pf=0,00) e PImáx inicial (p=0,02) e PImáx th inicial (p=0,03). Conclusão: A função pulmonar e a força dos músculos respiratórios em indivíduos com diagnóstico de Escoliose Idiopática encontra-se diminuída quando comparada com uma população saudável. Dentro das condições propostas no presente estudo, verificou-se que a aplicação de um programa de exercícios com o Inspirómetro de Incentivo com duração de 3 meses não revela resultados significativos ao nível da função pulmonar e da força dos músculos respiratórios.

QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solven and matrix-matched) over the established concentration range (5 500 mg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n D 4) at 167 mg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 mg/kg respectively.

Simuladores Fisiológicos na avaliação metrológica de esfigmomanómetros

Este documento apresenta uma avaliação sobre o uso dos simuladores fisiológicos como padrão para avaliação metrológica dos esfigmomanómetros automáticos na estimação da pressão sanguínea pelo método não invasivo (PNI). O presente estudo procurou avaliar o enquadramento destes equipamentos com os procedimentos das normas e recomendações usadas para apreciação metrológica dos esfigmomanómetros digitais. No contexto da prática metrológica existente determinou-se a existência de uma oportunidade de melhoria nos processos relacionados. O trabalho procurou obter resposta a diversas questões, relacionando a medição da pressão pelo método não invasivo, com o uso dos simuladores fisiológicos, o contexto em que estes podem ser usados, as formas de simulação, as medições e os resultados, procurando a perspetiva metrológica como enquadramento. As recomendações existentes [1] [2] [3] [4] [5] [6] [7] [8], são muito claras nos procedimentos, validação e nos desvios permitidos para os monitores da tensão arterial (MTA), equipamento que permite a avaliação dos parâmetros fisiológicos do paciente, no entanto, quando se pretende avançar para outro domínio, como o do uso dos simuladores, em particular para a simulação da PNI, não existem recomendações ou normas tão claras, e não existe sobretudo um padrão de referência que imite a natureza dinâmica que caracteriza a pressão sanguínea. O trabalho procurou ainda estabelecer a ligação entre o método clássico de auscultação (o principio de determinação da PS), a técnica digital de medição e os simuladores, para uma melhor compreensão do que é a pressão sanguínea, e como relacionar a problemática da simulação e a de um padrão de referência. Neste trabalho estão ainda presentes abordagens a diversos tópicos, como as validações clínicas, acessórios, ou a metrologia e que influenciam no final os equipamentos e o contexto que se pretende avaliar. Os diversos equipamentos testados procuraram conter amostras diversificadas, quer para os MTA de uso profissional ou doméstico, assim como para os simuladores. A avaliação dos simuladores foi realizada contra um grupo de MTAs. Foi testada a influência na medição, causada pela mudança de acessórios, ou seja, nos resultados, merecendo consideração pela perspetiva metrológica. No resumo dos testes e do estudo sobre este tema, verificou-se que esta tipologia de equipamentos pode contribuir como complemento do processo de calibração típico (estático). Não constitui por si só um método alternativo, mas permitiu estimar possíveis limites de erro e desvio padrão a partir da observação dos resultados práticos, limites esses inferiores aos processos de validação clínica. Atendendo às particularidades, estimou-se como desvio aceitável um erro mais desvio padrão de 5 + 3 mmHg para o processo de simulação. Contudo considera-se ainda importante os testes adicionais em que o simulador permite, ao verificar as medidas de segurança implementadas no equipamento e a condição dos acessórios, que como verificado afetam os resultados. No entanto nem todos os simuladores se mostram adequados a este processo pelo que a qualidade da seleção do equipamento para este fim pode eventualmente reduzir ainda mais os possíveis limites.