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Objectives To investigate the contribution of direct electron transfer mechanisms to electricity production in microbial fuel cells by physically retaining Shewanella oneidensis cells close to or away from the anode electrode. Results A maximum power output of 114 ± 6 mWm−2 was obtained when cells were retained close to the anode using a dialysis membrane. This was 3.5 times more than when the cells were separated away from the anode. Without the membrane the maximum power output was 129 ± 6 mWm−2. The direct mechanisms of electron transfer contributed significantly to overall electron transfer from S. oneidensis to electrodes, a result that was corroborated by another experiment where S. oneidensis cells were entrapped in alginate gels. Conclusion S. oneidensis transfers electrons primarily by direct electron transfer as opposed to mediated electron transfer.

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Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

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The reduction of luvastatin (FLV) at a hanging mercury-drop electrode (HMDE) was studied by square-wave adsorptive-stripping voltammetry (SWAdSV). FLV can be accumulated and reduced at the electrode, with a maximum peak current intensity at a potential of approximately 1.26V vs. AgCl=Ag, in an aqueous electrolyte solution of pH 5.25. The method shows linearity between peak current intensity and FLV concentration between 1.0 10 8 and 2.7 10 6 mol L 1. Limits of detection (LOD) and quantification (LOQ) were found to be 9.9 10 9 mol L 1 and 3.3 10 8 mol L 1, respectively. Furthermore, FLV oxidation at a glassy carbon electrode surface was used for its hydrodynamic monitoring by amperometric detection in a flow-injection system. The amperometric signal was linear with FLV concentration over the range 1.0 10 6 to 1.0 10 5 mol L 1, with an LOD of 2.4 10 7 mol L 1 and an LOQ of 8.0 10 7 mol L 1. A sample rate of 50 injections per hour was achieved. Both methods were validated and showed to be precise and accurate, being satisfactorily applied to the determination of FLV in a commercial pharmaceutical.

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Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1±4.3 % to 264.7±3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3±1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5±2.0 % to 118.8±1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect.

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Constrained nonlinear optimization problems are usually solved using penalty or barrier methods combined with unconstrained optimization methods. Another alternative used to solve constrained nonlinear optimization problems is the lters method. Filters method, introduced by Fletcher and Ley er in 2002, have been widely used in several areas of constrained nonlinear optimization. These methods treat optimization problem as bi-objective attempts to minimize the objective function and a continuous function that aggregates the constraint violation functions. Audet and Dennis have presented the rst lters method for derivative-free nonlinear programming, based on pattern search methods. Motivated by this work we have de- veloped a new direct search method, based on simplex methods, for general constrained optimization, that combines the features of the simplex method and lters method. This work presents a new variant of these methods which combines the lters method with other direct search methods and are proposed some alternatives to aggregate the constraint violation functions.

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In Nonlinear Optimization Penalty and Barrier Methods are normally used to solve Constrained Problems. There are several Penalty/Barrier Methods and they are used in several areas from Engineering to Economy, through Biology, Chemistry, Physics among others. In these areas it often appears Optimization Problems in which the involved functions (objective and constraints) are non-smooth and/or their derivatives are not know. In this work some Penalty/Barrier functions are tested and compared, using in the internal process, Derivative-free, namely Direct Search, methods. This work is a part of a bigger project involving the development of an Application Programming Interface, that implements several Optimization Methods, to be used in applications that need to solve constrained and/or unconstrained Nonlinear Optimization Problems. Besides the use of it in applied mathematics research it is also to be used in engineering software packages.

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Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Electrotécnica e de Computadores

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Over the past few decades there has been some discussion concerning the increase of the natural background radiation originated by coal-fired power plants, due to the uranium and thorium content present in combustion ashes. The radioactive decay products of uranium and thorium, such as radium, radon, polonium, bismuth and lead, are also released in addition to a significant amount of 40K. Since the measurement of radioactive elements released by the gaseous emissions of coal power plants is not compulsory, there is a gap of information concerning this situation. Consequently, the prediction of dispersion and mobility of these elements in the environment, after their release, is based on limited data and the radiological impact from the exposure to these radioactive elements is unknown. This paper describes the methodology that is being developed to assess the radiological impact due to the raise in the natural background radiation level originated by the release and dispersion of the emitted radionuclides. The current investigation is part of a research project that is undergoing in the vicinity of Sines coal-fired power plant (south of Portugal) until 2013. Data from preliminary stages are already available and possible of interpretation.

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RESUMO - A 8 de Maio de 2008 surgiu o centro de atendimento “Linha Saúde24” (S24) no sentido de modernizar o SNS, aproximando-o do cidadão. O serviço surge baseado no modelo inglês – o NHS Direct – que pode ser encarado como um serviço de informação telefónico apoiado por enfermeiros, disponível 24h por dia, concebido para expandir os serviços púbicos de acesso à rede prestadora de cuidados com intuito de aliviar a pressão da procura na rede de urgências hospitalares e médicos de família, assim como diluir as iniquidades regionais na prestação de serviços. A S24 assenta na perspectiva de ser um ponto de contacto inicial do utente com a rede de prestação de cuidados de saúde com capacidade de orientação. O objectivo da linha está na tentativa mais eficiente no uso dos recursos disponíveis, ao mesmo tempo que delega responsabilidade no cidadão na forma como este utiliza os recursos disponíveis, com melhor racionalização financeira na área da saúde aliada a uma melhor qualidade de serviço prestada e adequada, colocando os cidadãos no mesmo patamar, diluindo as dificuldades de acesso a aqueles que necessitam na tentativa de harmonizar e racionalizar o consumo de serviços de saúde. Esta estrutura permite ao cidadão conhecer melhor o seu estado de saúde e decidir mais acertadamente quanto à decisão a tomar. Com este estudo, e com base na literatura nacional e internacional, pretende-se descrever o perfil de utilizador que acede à S24 – definir o tipo de utilizador, disposição geográfica, motivos pelo qual acede ao serviço e qual o seu destino final, fazendo comparação com o perfil do NHS Direct. Assim, e com os dados obtidos, far-se-á uma avaliação preliminar em termos do contributo da linha S24 no que concerne à sua eficiência, equidade e empowerment dado ao utilizador. --- ------------------------------ABSTRACT - Saúde 24 (S24) is a national 24-hour health line initiated in May 2008 aiming at modernizing the Portuguese NHS by bringing it closer to the citizen. Indeed, S24 be seen as an initial contact point between the patient and the healthcare network, facilitating a better a management of health care demand. The service is inspired on the UK NHS Direct – a nurse-led telephone line to provide easier and faster advice information to people about health, illness and NHS services. It is expected to provide information so that people can deal with their health problems or their families´ on their own, with the purpose of reducing demand to A&E department and out-of-hours GP services. Additionally it can contribute to a reduction in regional inequities in healthcare provision through bringing health care advice to remote areas. The purpose of S24 is to handle more efficiently the available resources by enabling responsibilities in citizens. By doing so, S24 encourages a more appropriate use of available resources, with better financial outcomes and a better quality of care. It is meant, in terms of empowerment, to help people to be in control of their health and healthcare interactions by participating in the final decision. Based on quantitative data, this study defines the S24 caller user profile in terms of type, geographical reference, reasons for calling and outcome. This analysis allows us to perform a preliminary evaluation of the S24 in terms of its contribution to efficiency, equity and empowerment. Then the S24 is compared to

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In this study, the concentration probability distributions of 82 pharmaceutical compounds detected in the effluents of 179 European wastewater treatment plants were computed and inserted into a multimedia fate model. The comparative ecotoxicological impact of the direct emission of these compounds from wastewater treatment plants on freshwater ecosystems, based on a potentially affected fraction (PAF) of species approach, was assessed to rank compounds based on priority. As many pharmaceuticals are acids or bases, the multimedia fate model accounts for regressions to estimate pH-dependent fate parameters. An uncertainty analysis was performed by means of Monte Carlo analysis, which included the uncertainty of fate and ecotoxicity model input variables, as well as the spatial variability of landscape characteristics on the European continental scale. Several pharmaceutical compounds were identified as being of greatest concern, including 7 analgesics/anti-inflammatories, 3 β-blockers, 3 psychiatric drugs, and 1 each of 6 other therapeutic classes. The fate and impact modelling relied extensively on estimated data, given that most of these compounds have little or no experimental fate or ecotoxicity data available, as well as a limited reported occurrence in effluents. The contribution of estimated model input variables to the variance of freshwater ecotoxicity impact, as well as the lack of experimental abiotic degradation data for most compounds, helped in establishing priorities for further testing. Generally, the effluent concentration and the ecotoxicity effect factor were the model input variables with the most significant effect on the uncertainty of output results.