Flow injection electrochemical determination of apomorphine

Few analytical methods are currently available for determination of apomorphine, the active substance of a new oral formulation used in the treatment of erectile dysfunction. In this way a flow injection electrochemical method (FIA-EC) was developed for its quantification and applied to pharmaceutical dosage forms. Based in previous findings regarding the stability of apomorphine in borate buffer and after optimization of several analytical parameters a single channel flow injection manifold was set up that enables the determination of this drug over the concentration range of 3 to 16 µmol L-1 with a detection limit of 0.5 µmol L-1 at a sampling rateof 90 h-1. The simplicity and rapidity of the FIA-EC method used, its reproducibility and sensitivity make it suitable for quality control of pharmaceutical preparations of apomorphine intended for clinical use and research.

Flow injection potentiometric determination of chlorpromazine

New chlorpromazine selective electrodes with a tubular arrangement and no internal reference solution are proposed. Selective membranes are of poly(vinyl chloride) (PVC) with the tetraphenylborate•chlorpromazine (TPB•CPZ) ion-exchanger dissolved in o-nitrophenyl octyl ether (oNPOE). Analytical features of the electrodes were evaluated on a single-channel flow assembly having 500 µl injection volumes and flow-rates of 4.5 ml min−1. For a carrier solution of 3.3×10−3Min sodium sulphate, Nernstian responsewas observed over the concentration range 1.0×10−5 to 1.0×10−2 M. Average slopes were about 59mVdecade−1 and squared correlation coefficients were >0.9984. Slight hiper-Nernstian behaviour was observed in buffer solutions of 4.4 pH; average slopes were of 62.06mVdecade−1. The electrode displayed a good selectivity for CPZ, with respect to, several foreign inorganic and organic species. The selective electrodes were successfully applied to the analysis of pure solutions and pharmaceutical preparations. Proposed method allows the analysis of 84 samples h−1, producing wastewaters of low toxicity. The proposed method offers the advantage of simplicity, accuracy, applicability to coloured and turbid samples, and automation feasibility.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

A survey of wireless technologies coexistence in WBAN: analysis and open research issues

Wireless Body Area Network (WBAN) is the most convenient, cost-effective, accurate, and non-invasive technology for e-health monitoring. The performance of WBAN may be disturbed when coexisting with other wireless networks. Accordingly, this paper provides a comprehensive study and in-depth analysis of coexistence issues and interference mitigation solutions in WBAN technologies. A thorough survey of state-of-the art research in WBAN coexistence issues is conducted. The survey classified, discussed, and compared the studies according to the parameters used to analyze the coexistence problem. Solutions suggested by the studies are then classified according to the followed techniques and concomitant shortcomings are identified. Moreover, the coexistence problem in WBAN technologies is mathematically analyzed and formulas are derived for the probability of successful channel access for different wireless technologies with the coexistence of an interfering network. Finally, extensive simulations are conducted using OPNET with several real-life scenarios to evaluate the impact of coexistence interference on different WBAN technologies. In particular, three main WBAN wireless technologies are considered: IEEE 802.15.6, IEEE 802.15.4, and low-power WiFi. The mathematical analysis and the simulation results are discussed and the impact of interfering network on the different wireless technologies is compared and analyzed. The results show that an interfering network (e.g., standard WiFi) has an impact on the performance of WBAN and may disrupt its operation. In addition, using low-power WiFi for WBANs is investigated and proved to be a feasible option compared to other wireless technologies.

Electric vehicle scenario simulator tool for smart grid operators

This paper presents a simulator for electric vehicles in the context of smart grids and distribution networks. It aims to support network operator´s planning and operations but can be used by other entities for related studies. The paper describes the parameters supported by the current version of the Electric Vehicle Scenario Simulator (EVeSSi) tool and its current algorithm. EVeSSi enables the definition of electric vehicles scenarios on distribution networks using a built-in movement engine. The scenarios created with EVeSSi can be used by external tools (e.g., power flow) for specific analysis, for instance grid impacts. Two scenarios are briefly presented for illustration of the simulator capabilities.

Simulated annealing metaheuristic to solve the optimal power flow

The optimal power flow problem has been widely studied in order to improve power systems operation and planning. For real power systems, the problem is formulated as a non-linear and as a large combinatorial problem. The first approaches used to solve this problem were based on mathematical methods which required huge computational efforts. Lately, artificial intelligence techniques, such as metaheuristics based on biological processes, were adopted. Metaheuristics require lower computational resources, which is a clear advantage for addressing the problem in large power systems. This paper proposes a methodology to solve optimal power flow on economic dispatch context using a Simulated Annealing algorithm inspired on the cooling temperature process seen in metallurgy. The main contribution of the proposed method is the specific neighborhood generation according to the optimal power flow problem characteristics. The proposed methodology has been tested with IEEE 6 bus and 30 bus networks. The obtained results are compared with other wellknown methodologies presented in the literature, showing the effectiveness of the proposed method.

Ant colony search algorithm for the optimal power flow problem

To maintain a power system within operation limits, a level ahead planning it is necessary to apply competitive techniques to solve the optimal power flow (OPF). OPF is a non-linear and a large combinatorial problem. The Ant Colony Search (ACS) optimization algorithm is inspired by the organized natural movement of real ants and has been successfully applied to different large combinatorial optimization problems. This paper presents an implementation of Ant Colony optimization to solve the OPF in an economic dispatch context. The proposed methodology has been developed to be used for maintenance and repairing planning with 48 to 24 hours antecipation. The main advantage of this method is its low execution time that allows the use of OPF when a large set of scenarios has to be analyzed. The paper includes a case study using the IEEE 30 bus network. The results are compared with other well-known methodologies presented in the literature.

Gestão e monitorização de uma rede departamental: um caso de estudo

Mestrado em Engenharia Electrotécnica e de Computadores

Avaliação da qualidade do ar interior e estudos CFD em espaços do ISEP

Mestrado em Engenharia Química. Ramo Tecnologias de Protecção Ambiental.

Cooperative framework for open real-time systems

Actualmente, os sistemas embebidos estão presentes em toda a parte. Embora grande parte da população que os utiliza não tenha a noção da sua presença, na realidade, se repentinamente estes sistemas deixassem de existir, a sociedade iria sentir a sua falta. A sua utilização massiva deve-se ao facto de estarem practicamente incorporados em quase os todos dispositivos electrónicos de consumo, telecomunicações, automação industrial e automóvel. Influenciada por este crescimento, a comunidade científica foi confrontada com novos problemas distribuídos por vários domínios científicos, dos quais são destacados a gestão da qualidade de serviço e gestão de recursos - domínio encarregue de resolver problemas relacionados com a alocação óptima de recursos físicos, tais como rede, memória e CPU. Existe na literatura um vasto conjunto de modelos que propõem soluções para vários problemas apresentados no contexto destes domínios científicos. No entanto, não é possível encontrar modelos que lidem com a gestão de recursos em ambientes de execução cooperativos e abertos com restrições temporais utilizando coligações entre diferentes nós, de forma a satisfazer os requisitos não funcionais das aplicações. Devido ao facto de estes sistemas serem dinâmicos por natureza, apresentam a característica de não ser possível conhecer, a priori, a quantidade de recursos necessários que uma aplicação irá requerer do sistema no qual irá ser executada. Este conhecimento só é adquirido aquando da execução da aplicação. De modo a garantir uma gestão eficiente dos recursos disponíveis, em sistemas que apresentam um grande dinamismo na execução de tarefas com e sem restrições temporais, é necessário garantir dois aspectos fundamentais. O primeiro está relacionado com a obtenção de garantias na execução de tarefas de tempo-real. Estas devem sempre ser executadas dentro da janela temporal requirida. O segundo aspecto refere a necessidade de garantir que todos os recursos necessários à execução das tarefas são fornecidos, com o objectivo de manter os níveis de performance quer das aplicações, quer do próprio sistema. Tendo em conta os dois aspectos acima mencionados, o projecto CooperatES foi especificado com o objectivo de permitir a dispositivos com poucos recursos uma execução colectiva de serviços com os seus vizinhos, de modo a cumprir com as complexas restrições de qualidade de serviço impostas pelos utilizadores ou pelas aplicações. Decorrendo no contexto do projecto CooperatES, o trabalho resultante desta tese tem como principal objectivo avaliar a practicabilidade dos conceitos principais propostos no âmbito do projecto. O trabalho em causa implicou a escolha e análise de uma plataforma, a análise de requisitos, a implementação e avaliação de uma framework que permite a execução cooperativa de aplicações e serviços que apresentem requisitos de qualidade de serviço. Do trabalho desenvolvido resultaram as seguintes contribuições: Análise das plataformas de código aberto que possam ser utilizadas na implementação dos conceitos relacionados com o projecto CooperatES; Critérios que influenciaram a escolha da plataforma Android e um estudo focado na análise da plataforma sob uma perspectiva de sistemas de tempo-real; Experiências na implementação dos conceitos do projecto na plataforma Android; Avaliação da practicabilidade dos conceitos propostos no projecto CooperatES; Proposta de extensões que permitam incorporar características de sistemas de tempo real abertos na plataforma Android.

Avaliação do desempenho energético e da qualidade do ar de uma piscina coberta

Este trabalho teve como propósito fazer uma avaliação do desempenho energético e da qualidade do ar no interior das instalações de uma Piscina Municipal Coberta, localizada na zona norte de Portugal, sendo estabelecidos os seguintes objetivos: caracterização geral da piscina, no que respeita aos seus diferentes espaços e equipamentos, cálculo dos consumos térmicos e elétricos bem como o registo das concentrações de elementos poluentes para controlo da qualidade do ar no interior da piscina, tendo como base a legislação atualmente em vigor. A caracterização geral da piscina permitiu verificar algumas inconformidades como a temperatura da água nos tanques de natação que tem valores superiores aos recomendados e a sala de primeiros socorros que não possui acesso direto ao exterior. Acrescente-se que o pavimento nos chuveiros da casa de banho feminina e os valores de pH para água do tanque grande e pequeno não estão sempre dentro da gama de recomendação. O caudal da renovação de ar está a ser operado manualmente e quando está a funcionar a 50% da sua capacidade máxima, que acontece numa parte do dia, apenas consegue renovar 77,5% do caudal recomendado pelo RSECE. Para se obter o valor recomendado é necessário ter pelo menos 7 horas com o caudal a 100% da capacidade máxima. A avaria na UTA2 originou que 40% dos registos diários da humidade relativa interior estivessem fora da gama de valores recomendados e que esta é fortemente dependente da humidade no exterior e pode ser agravada quando as portas dos envidraçados da nave são abertas. Analisando ainda a quantidade de água removida na desumidificação do ar com a água evaporada em condições de Outono-Inverno ou Primavera-Verão, este estudo permitiu concluir que todas as combinações demonstraram a necessidade de desumidificação salvo a combinação Outono-Inverno e UTA2 a funcionar a 100% da sua capacidade máxima. Os isolamentos das tubagens na sala das caldeiras foram observados e comparados com as soluções recomendadas pelas empresas especialistas e verificou-se que alguns estão mal colocados com parcial ou total degradação, promovendo perdas térmicas. No caso das perdas calorificas por evaporação, estas representaram cerca de 67,78% das perdas totais. Como tal, estudou-se a aplicação de uma cobertura sobre o plano de água durante o período de inatividade da piscina (8 horas) e verificou-se que o resultado seria uma poupança de 654,8 kWh/dia, na ausência de evaporação da água, mais 88,00 kWh/dia do período da UTA2 a funcionar a 50% da sua capacidade, perfazendo um total de 742,8 kWh/dia. A aplicação da cobertura permite obter um VAL de valor positivo, uma TIR de 22,77% e sendo este valor superior ao WACC (Weight Average Cost of Capital), o projeto torna-se viável com um Pay-Back de 3,17 anos. Caracterizou-se também o consumo total diário em eletricidade, e verificou-se que as unidades de climatização, as bombas de circulação de água, a iluminação, e outros equipamentos representam, respetivamente, cerca de 67,81, 25,26, 2,68 e 3,91% da energia elétrica total consumida. Por fim, a análise à qualidade do ar no interior da nave em Maio e Setembro identificou que as concentrações de ozono apresentavam valores no limite do aceitável em Maio e superiores ao valor de emissão em Setembro. Os compostos orgânicos voláteis também apresentavam valores em Maio 4,98 vezes superior e em Setembro 6,87 vezes superior aos valores máximos exigidos pelo D.L. nº 79/2006. Houve ainda altas concentrações de radão registadas na casa dos filtros, em Maio com um valor 11,49 vezes superior, no entanto esse valor desceu em Setembro para 1,08 vezes, mesmo assim superior ao exigido pelo D.L. nº 79/2006.

Flow amperometric determination of carbofuran and fenobucarb

A simple, rapid, and precise amperometric method for quantification of N-methylcarbamate pesticides in water samples and phytopharmaceuticals is presented. Carbofuran and fenobucarb are the target analytes. The method is developed in flow conditions providing the anodic oxidation of phenolic-based compounds formed after alkaline hydrolysis. Optimization of instrumental and chemical variables is presented. Under the optimal conditions, the amperometric signal is linear for carbofuran and fenobucarb concentrations over the range of 1.0*10-7 to 1.0*10-5 molL-1, with a detection limit of about 2 ngmL-1. The amperometric method is successfully applied to the analysis of spiked environmental waters and commercial formulations. The proposed method allows 90 samples to be analysed per hour, using 500 mL of sample, and producing wastewaters of low toxicity. The proposed method permits determinations at the mgL 1 level and offers advantages of simplicity, accuracy, precision, and applicability to coloured and turbid samples, and automation feasibility.

Sulfadiazine-potentiometric sensors for flow and batch determinations of sulfadiazine in drugs and biological fluids

New PVC membrane electrodes for the determination of sulfadiazine (SDZ) are presented. The electrodes are fabricated with conventional and tubular configurations with a graphite-based electrical contact, and no internal reference solution. The selective membranes consist of bis(triphenylphosphoranilidene)ammonium·SDZ (electrode A), tetraoctylammonium bromide (electrode B), or iron(II)-phthalocyanine (FePC) (electrode C) electroactive materials dispersed in a PVC matrix of o-nitrophenyl octyl ether (o-NPOE) plasticizer. The sensors A, B, and C displayed linear responses over the concentration ranges 1.0*10-2 – 1.0*10–5, 1.0*10–2 – 7.5*10–6, and 3.2*10–2 – 7.0* 10–6 mol l–1 (detection limits of 1.09, 2.04 and 0.87 mg ml–1) with anionic slopes of –57.3 ± 0.1, –46.7 ± 0.5, and –65.1 ± 0.2 mV decade–1, respectively. No effect from pH was observed within 4.0 – 5.5, 4.8 – 10, and 4.5 – 8, respectively, and good selectivity was found. The sensors were applied to the analysis of pharmaceuticals and biological fluids in steady state and in flow conditions.

New biomimetic sensors for the determination of tetracycline in biological samples: batch and flow mode operations

New potentiometric membrane sensors with cylindrical configuration for tetracycline (TC) are described based on the use of a newly designed molecularly imprinted polymer (MIP) material consisting of 2-vinylpyridine as a functional monomer in a plasticized PVC membrane. The sensor exhibited significantly enhanced response towards TC over the concentration range 1.59 10 5–1.0 10 3 mol L 1 at pH 3–5 with a lower detection limit of 1.29 10 5 mol L 1. The response was near-Nernstian, with average slopes of 63.9 mV decade 1. The effect of lipophilic salts and various foreign common ions were tested and were found to be negligible. The possibility of applying the proposed sensor to TC determination in spiked biological fluid samples was demonstrated.

Direct electroanalytical determination of fluvastatin in a pharmaceutical dosage form: batch and flow analysis

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.