Voltammetric quantification of fluoxetine: application to quality control and quality assurance processes

The oxidative behaviour of fluoxetine was studied at a glassy carbon electrode in various buffer systems and at different pH using cyclic, differential pulse and square wave voltammetry. A new square wave voltammetric method suitable for the quality control of fluoxetine in commercial formulations has been developed using a borate pH 9 buffer solution as supporting electrolyte. Under optimized conditions, a linear response was obtained in the range 10 to 16 μM with a detection limit of 1.0 μM. Validation parameters such as sensitivity, precision and accuracy were evaluated. The proposed method was successfully applied to the determination of fluoxetine in pharmaceutical formulations. The results were statistically compared with those obtained by the reference high-performance liquid chromatographic method. No significant differences were found between the methods.

Role of abrasive material on micro-abrasion wear tests

Micro-abrasion wear tests with ball-cratering configuration are widely used. Sources of variability are already studied by different authors and conditions for testing are parameterized by BS EN 1071-6: 2007 standard which refers silicon carbide as abrasive. However, the use of other abrasives is possible and allowed. In this work, ball-cratering wear tests were performed using four different abrasive particles of three dissimilar materials: diamond, alumina and silicon carbide. Tests were carried out under the same conditions on a steel plate provided with TiB2 hard coating. For each abrasive, five different test durations were used allowing understanding the initial wear phenomena. Composition and shape of abrasive particles were investigated by SEM and EDS. Scar areas were observed by optical and electronic microscopy in order to understand the wear effects caused by each of them. Scar geometry and grooves were analyzed and compared. Wear coefficient was calculated for each situation. It was observed that diamond particles produce well-defined and circular wear scars. Different silicon carbide particles presented dissimilar results as consequence of distinct particle shape and size distribution.

Influence of the abrasive particles size in the micro-abrasion wear tests of TiAlSiN thin coatings

Ball rotating micro-abrasion tribometers are commonly used to carry out wear tests on thin hard coatings. In these tests, different kinds of abrasives were used, as alumina (Al2O3), silicon carbide (SiC) or diamond. In each kind of abrasive, several particle sizes can be used. Some studies were developed in order to evaluate the influence of the abrasive particle shape in the micro-abrasion process. Nevertheless, the particle size was not well correlated with the material removed amount and wear mechanisms. In this work, slurry of SiC abrasive in distilled water was used, with three different particles size. Initial surface topography was accessed by atomic force microscopy (AFM). Coating hardness measurements were performed with a micro-hardness tester. In order to evaluate the wear behaviour, a TiAlSiN thin hard film was used. The micro-abrasion tests were carried out with some different durations. The abrasive effect of the SiC particles was observed by scanning electron microscopy (SEM) both in the films (hard material) as in the substrate (soft material), after coating perforation. Wear grooves and removed material rate were compared and discussed.

Análise estocástica com recurso a ferramentas informáticas no planeamento de empreitadas de construção

O presente trabalho, desenvolvido sob a orientação do Prof. Jaime Gabriel Silva, centra-se na procura e aplicação de metodologias de planeamento com apoio de ferramentas informáticas de análise de risco, que permitem realizar, em tempo útil, o cálculo dos prazos resultantes de inúmeras combinações possíveis associadas à incerteza das durações das atividades, recorrendo a modelos estocásticos. O trabalho aborda inicialmente o contexto da Gestão na Construção, com particular enfase na Gestão do Risco. Nessa fase inicial, fez-se também um pequeno inquérito a profissionais com diferentes níveis de responsabilidade organizacional e empresas do setor. A parte fundamental do trabalho, incide nos procedimentos a adotar na elaboração do planeamento de empreitadas. Nesta parte do trabalho, introduzem-se os conceitos da análise de risco com recurso a uma ferramenta informática de apoio, o @Risk, que permite a utilização do Método de Monte Carlo, para obtenção de resultados num contexto de uma tomada de decisão baseada no risco. Refira-se que houve vários contactos com o fornecedor do programa, que permitiram tirar partido de outro programa da Palisade, Evolver, direcionado para otimização matemática, podendo ser utilizado, por exemplo, na perspetiva da minimização dos custos, o que pode interessar pela relação destes com as opções adotadas na elaboração do planeamento de empreendimentos. Finalmente, toma-se um exemplo real do planeamento de uma empreitada em execução à data da realização deste trabalho, onde se aplicaram os conceitos desenvolvidos no trabalho, confrontando os resultados com o andamento da obra.

Construção de um variador de frequência

A dificuldade de controlo de um motor de indução, bem como o armazenamento de energia CC e posterior utilização como energia alternada promoveram o desenvolvimento de variadores de frequência e inversores. Assim, como projeto de tese de mestrado em Automação e Sistemas surge o desenvolvimento de um variador de frequência. Para elaboração do variador de frequência efetuou-se um estudo sobre as técnicas de modulação utilizadas nos inversores. A técnica escolhida e utilizada é a Sinusoidal Pulse Width Modulation (SPWM). Esta técnica baseia-se na modelação por largura de impulso (PWM), o qual é formado por comparação de um sinal de referência com um sinal de portadora de elevada frequência. Por sua vez, a topologia escolhida para o inversor corresponde a um Voltage Source Inverter (VSI) de ponte trifásica completa a três terminais. O desenvolvimento da técnica de modulação SPWM levou ao desenvolvimento de um modelo de simulação em SIMULINK, o qual permitiu retirar conclusões sobre os resultados obtidos. Na fase de implementação, foram desenvolvidas placas para o funcionamento do variador de frequência. Assim, numa fase inicial foi desenvolvida a placa de controlo, a qual contém a unidade de processamento e que é responsável pela atuação de Insulated Gate Bipolar Transistors (IGBTs). Para além disso, foi desenvolvida uma placa para proteção dos IGBTs (evitando condução simultânea no mesmo terminal) e uma placa de fontes isoladas para alimentação dos circuitos e para atuação dos IGBTs. Ainda, foi desenvolvida a técnica de SPWM em software para a unidade de controlo e finalmente foi desenvolvida uma interface gráfica para interação com o utilizador. A validação do projeto foi conseguida através da variação da velocidade do motor de indução trifásico. Para isso, este foi colocado a funcionar a diversas frequências de funcionamento e a diferentes amplitudes. Para além disso, o seu funcionamento foi também validado utilizando uma carga trifásica equilibrada de 3 lâmpadas de forma a ser visualizada a variação de frequência e variação de amplitude.

A New Approach in the Design of Air Stripping Columns for the Treatment of Groundwater Contaminated With Volatile Organic Compounds

Volatile organic compounds are a common source of groundwater contamination that can be easily removed by air stripping in columns with random packing and using a counter-current flow between the phases. This work proposes a new methodology for column design for any type of packing and contaminant which avoids the necessity of an arbitrary chosen diameter. It also avoids the employment of the usual graphical Eckert correlations for pressure drop. The hydraulic features are previously chosen as a project criterion. The design procedure was translated into a convenient algorithm in C++ language. A column was built in order to test the design, the theoretical steady-state and dynamic behaviour. The experiments were conducted using a solution of chloroform in distilled water. The results allowed for a correction in the theoretical global mass transfer coefficient previously estimated by the Onda correlations, which depend on several parameters that are not easy to control in experiments. For best describe the column behaviour in stationary and dynamic conditions, an original mathematical model was developed. It consists in a system of two partial non linear differential equations (distributed parameters). Nevertheless, when flows are steady, the system became linear, although there is not an evident solution in analytical terms. In steady state the resulting ODE can be solved by analytical methods, and in dynamic state the discretization of the PDE by finite differences allows for the overcoming of this difficulty. To estimate the contaminant concentrations in both phases in the column, a numerical algorithm was used. The high number of resulting algebraic equations and the impossibility of generating a recursive procedure did not allow the construction of a generalized programme. But an iterative procedure developed in an electronic worksheet allowed for the simulation. The solution is stable only for similar discretizations values. If different values for time/space discretization parameters are used, the solution easily becomes unstable. The system dynamic behaviour was simulated for the common liquid phase perturbations: step, impulse, rectangular pulse and sinusoidal. The final results do not configure strange or non-predictable behaviours.

Performance evaluation of a cooperative reputation system for vehicular delay-tolerant networks

In the last decade, both scientific community and automotive industry enabled communications among vehicles in different kinds of scenarios proposing different vehicular architectures. Vehicular delay-tolerant networks (VDTNs) were proposed as a solution to overcome some of the issues found in other vehicular architectures, namely, in dispersed regions and emergency scenarios. Most of these issues arise from the unique characteristics of vehicular networks. Contrary to delay-tolerant networks (DTNs), VDTNs place the bundle layer under the network layer in order to simplify the layered architecture and enable communications in sparse regions characterized by long propagation delays, high error rates, and short contact durations. However, such characteristics turn contacts very important in order to exchange as much information as possible between nodes at every contact opportunity. One way to accomplish this goal is to enforce cooperation between network nodes. To promote cooperation among nodes, it is important that nodes share their own resources to deliver messages from others. This can be a very difficult task, if selfish nodes affect the performance of cooperative nodes. This paper studies the performance of a cooperative reputation system that detects, identify, and avoid communications with selfish nodes. Two scenarios were considered across all the experiments enforcing three different routing protocols (First Contact, Spray and Wait, and GeoSpray). For both scenarios, it was shown that reputation mechanisms that punish aggressively selfish nodes contribute to increase the overall network performance.

Controlo da velocidade e posição de um tapete rolante

A utilização eficiente da energia é essencial para a competitividade económica de um país. Sendo a intensidade energética de Portugal elevada, onde a utilização de motores elétricos, absorve cerca de metade da energia elétrica consumida na indústria, a utilização de conversores eletrónicos de potência permite obter economias de energia. Nesta tese pretende-se controlar a velocidade e o posicionamento de um tapete rolante através da utilização de um conversor eletrónico de potência. Na fundamentação teórica são referidos os conceitos de variação da tensão e frequência, controle escalar e vetorial, modelação por largura de pulso (PWM) assim como a retificação e ondulação da tensão de um variador de velocidades. Na parte prática será utilizado um servo motor, controlado por um variador eletrónico de velocidades, para efetuar o referido projeto. É ainda objeto desta tese o estudo dos parâmetros fundamentais assim como a pesquisa dos parâmetros a utilizar para o desempenho pretendido.

Logic-based schedulability analysis for compositional hard real-time embedded systems

Over the past decades several approaches for schedulability analysis have been proposed for both uni-processor and multi-processor real-time systems. Although different techniques are employed, very little has been put forward in using formal specifications, with the consequent possibility for mis-interpretations or ambiguities in the problem statement. Using a logic based approach to schedulability analysis in the design of hard real-time systems eases the synthesis of correct-by-construction procedures for both static and dynamic verification processes. In this paper we propose a novel approach to schedulability analysis based on a timed temporal logic with time durations. Our approach subsumes classical methods for uni-processor scheduling analysis over compositional resource models by providing the developer with counter-examples, and by ruling out schedules that cause unsafe violations on the system. We also provide an example showing the effectiveness of our proposal.

Influence of dual-task on sit-to-stand-to-sit postural control in Parkinson's disease

Postural control deficits are the most disabling aspects of Parkinson's disease (PD), resulting in decreased mobility and functional independence. The aim of this study was to assess the postural control stability, revealed by variables based on the centre of pressure (CoP), in individuals with PD while performing a sit-to-stand-to-sit sequence under single- and dual-task conditions. An observational, analytical and cross-sectional study was performed. The sample consisted of 9 individuals with PD and 9 healthy controls. A force platform was used to measure the CoP displacement and velocity during the sit-to-stand-to-sit sequence. The results were statistically analysed. Individuals with PD required greater durations for the sit-to-stand-to-sit sequence than the controls (p < 0.05). The anteroposterior and mediolateral CoP displacement were higher in the individuals with PD (p < 0.05). However, only the anteroposterior CoP velocity in the stand-to-sit phase (p = 0.006) was lower in the same individuals. Comparing the single- and dual-task conditions in both groups, the duration, the anteroposterior CoP displacement and velocity were higher in the dual-task condition (p < 0.05). The individuals with PD presented reduced postural control stability during the sit-to-stand-to-sit sequence, especially when under the dual-task condition. These individuals have deficits not only in motor performance, but also in cognitive performance when performing the sit-to-stand-to-sit sequence in their daily life tasks. Moreover, both deficits tend to be intensified when two tasks are performed simultaneously.

Effects of Soil Compaction and Organic Carbon Content on Preferential Flow in Loamy Field Soils

Abstract: Preferential flow and transport through macropores affect plant water use efficiency and enhance leaching of agrochemicals and the transport of colloids, thereby increasing the risk for contamination of groundwater resources. The effects of soil compaction, expressed in terms of bulk density (BD), and organic carbon (OC) content on preferential flow and transport were investigated using 150 undisturbed soil cores sampled from 15 × 15–m grids on two field sites. Both fields had loamy textures, but one site had significantly higher OC content. Leaching experiments were conducted in each core by applying a constant irrigation rate of 10 mm h−1 with a pulse application of tritium tracer. Five percent tritium mass arrival times and apparent dispersivities were derived from each of the tracer breakthrough curves and correlated with texture, OC content, and BD to assess the spatial distribution of preferential flow and transport across the investigated fields. Soils from both fields showed strong positive correlations between BD and preferential flow. Interestingly, the relationships between BD and tracer transport characteristics were markedly different for the two fields, although the relationship between BD and macroporosity was nearly identical. The difference was likely caused by the higher contents of fines and OC at one of the fields leading to stronger aggregation, smaller matrix permeability, and a more pronounced pipe-like pore system with well-aligned macropores.

Molecularly imprinted electrochemical sensor for ochratoxin A detection in food samples

A novel electrochemical sensor for ochratoxin A (OTA) detection was fabricated through the modification of a glassy carbon electrode (GCE) with multiwalled carbon nanotubes (MWCNTs) and a molecularly imprinted polymer (MIP). The MWCNTs dramatically promoted the sensitivity of the developed sensor, while polypyrrole (PPy) imprinted with OTA served as the selective recognition element. The imprinted PPy film was prepared by electropolymerization of pyrrole in the presence of OTA as a template molecule via cyclic voltammetry (CV). The electrochemical oxidation of OTA at the developed sensor was investigated by CV and differential pulse voltammetry (DPV). The developed MIP/MWCNT/GCE sensor showed a linear relationship, when using DPV, between peak current intensity and OTA concentration in the range between 0.050 and 1.0 μM, with limits of detection (LOD) and quantification of 0.0041 μM (1.7 μg/L) and 0.014 μM (5.7 μg/L) respectively. With the developed sensor precise results were obtained; relative standard deviations of 4.2% and 7.5% in the evaluation of the repeatability and reproducibility, respectively. The MIP/MWCNT/GCE sensor is simple to fabricate and easy to use and was successfully applied to the determination of OTA in spiked beer and wine samples, with recoveries between 84 and 104%, without the need of a sample pre-treatment step.