Electroanalytical study of fluvoxamine

Fluvoxamine (FVX) can be reduced at a mercury- drop electrode, with a maximum peak current intensity being obtained at a potential of -0.7 V vs. Ag/ AgCl, in an aqueous electrolyte solution of pH 2. The compound was determined in a pharmaceutical product and in spiked human serum by square-wave adsorptivestripping voltammetry (SWAdSV) after accumulation at the electrode surface, under batch conditions. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was also possible to determine FVX in the pharmaceutical product by use of a flow-injection analysis (FIA) system with SWAdSV detection. The methods developed were validated and successfully applied to the quantification of FVX in a pharmaceutical product. Recoveries between 76 and 89% were obtained in serum analysis. The FIA– SWAdSV method enabled analysis of up to 120 samples per hour at reduced cost, implying the possibility of competing with the chromatographic methods usually used for this analysis.

Electroanalytical determination of paroxetine in pharmaceuticals

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with SWAdSV detection (FIA-SWAdSV) were developed for the determination of paroxetine (PRX). The methods were based on the reduction of PRX at a mercury drop electrode at −1.55V versus Ag/AgCl, in a borate buffer of pH 8.8, and the possibility of accumulating the compound at the electrode surface. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was also possible to determine PRX using FIASWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs. Both methods developed were validated and successfully applied to the quantification of PRX in pharmaceutical products.

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%.

Electrochemical determination of dihydrocodeine in pharmaceuticals

Two analytical methods for the quality control of dihydrocodeine in commercial pharmaceutical formulations have been developed and compared with reference methods: a square wave voltammetric (SWV) method and a flow injection analysis system with electrochemical detection (FIA-EC). The electrochemical methods proposed were successfully applied to the determination of dihydrocodeine in pharmaceutical tablets and in oral solutions. These methods do not require any pretreatment of the samples, the formulation only being dissolved in a suitable electrolyte. Validation of the methods showed it to be precise, accurate and linear over the concentration range of analysis. The automatic procedure based on a flow injection analysis manifold allows a sampling rate of 115 determinations per hour.

Electroanalytical study of the antidepressant sertraline

Aflowinjection squarewave cathodic stripping voltammetric method has been developed for the determination of sertraline in a pharmaceutical preparation. The method shows linearity between peak current intensity and sertraline concentration for the interval between 0.20×10−6 and 1.20×10−6 mol L−1. Limits of detection and quantification were found to be 1.5×10−7 and 5.0×10−7 mol L−1, respectively. Up to 70 samples per hour can be analysed with a good precision (R.S.D. = 2.5%). The proposed method was successfully applied to the determination of sertraline in a commercial product. In the voltammetric determination of sertraline in flow, a high sample rate is obtained at reduced costs, opening the possibility to compete with the chromatographic methods generally used for this analysis.

Custeio baseado em atividades: concepção e implementação numa empresa de serviços

Trabalho de Projeto apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Contabilidade e Finanças, sob orientação de Paulino Manuel Leite da Silva

Saving energy in the GFRP pultrusion process

This study addresses to the optimization of pultrusion manufacturing process from the energy-consumption point of view. The die heating system of external platen heaters commonly used in the pultrusion machines is one of the components that contribute the most to the high consumption of energy of pultrusion process. Hence, instead of the conventional multi-planar heaters, a new internal die heating system that leads to minor heat losses is proposed. The effect of the number and relative position of the embedded heaters along the die is also analysed towards the setting up of the optimum arrangement that minimizes both the energy rate and consumption. Simulation and optimization processes were greatly supported by Finite Element Analysis (FEA) and calibrated with basis on the temperature profile computed through thermography imaging techniques. The main outputs of this study allow to conclude that the use of embedded cylindrical resistances instead of external planar heaters leads to drastic reductions of both the power consumption and the warm-up periods of the die heating system. For the analysed die tool and process, savings on energy consumption up to 60% and warm-up period stages less than an half hour were attained with the new internal heating system. The improvements achieved allow reducing the power requirements on pultrusion process, and thus minimize industrial costs and contribute to a more sustainable pultrusion manufacturing industry.

Otimização da Amostragem e Estudo de Viabilidade da Monitorização de Sondas na ETAR de Rabada

Mestrado em Engenharia Química - Tecnologias de Protecção Ambiental

Virtual Power Player Using Demand Response to Deal with Unexpected Low Wind Power Generation

Demand response is assumed as an essential resource to fully achieve the smart grids operating benefits, namely in the context of competitive markets and of the increasing use of renewable-based energy sources. Some advantages of Demand Response (DR) programs and of smart grids can only be achieved through the implementation of Real Time Pricing (RTP). The integration of the expected increasing amounts of distributed energy resources, as well as new players, requires new approaches for the changing operation of power systems. The methodology proposed in this paper aims the minimization of the operation costs in a distribution network operated by a virtual power player that manages the available energy resources focusing on hour ahead re-scheduling. When facing lower wind power generation than expected from day ahead forecast, demand response is used in order to minimize the impacts of such wind availability change. In this way, consumers actively participate in regulation up and spinning reserve ancillary services through demand response programs. Real time pricing is also applied. The proposed model is especially useful when actual and day ahead wind forecast differ significantly. Its application is illustrated in this paper implementing the characteristics of a real resources conditions scenario in a 33 bus distribution network with 32 consumers and 66 distributed generators.

Energy resources management in three distinct time horizons considering a large variation in wind power

The intensive use of distributed generation based on renewable resources increases the complexity of power systems management, particularly the short-term scheduling. Demand response, storage units and electric and plug-in hybrid vehicles also pose new challenges to the short-term scheduling. However, these distributed energy resources can contribute significantly to turn the shortterm scheduling more efficient and effective improving the power system reliability. This paper proposes a short-term scheduling methodology based on two distinct time horizons: hour-ahead scheduling, and real-time scheduling considering the point of view of one aggregator agent. In each scheduling process, it is necessary to update the generation and consumption operation, and the storage and electric vehicles status. Besides the new operation condition, more accurate forecast values of wind generation and consumption are available, for the resulting of short-term and very short-term methods. In this paper, the aggregator has the main goal of maximizing his profits while, fulfilling the established contracts with the aggregated and external players.

Distributed energy resources scheduling considering real-time resources forecast

Energy resource scheduling is becoming increasingly important, such as the use of more distributed generators and electric vehicles connected to the distribution network. This paper proposes a methodology to be used by Virtual Power Players (VPPs), regarding the energy resource scheduling in smart grids and considering day-ahead, hour-ahead and realtime time horizons. This method considers that energy resources are managed by a VPP which establishes contracts with their owners. The full AC power flow calculation included in the model takes into account network constraints. In this paper, distribution function errors are used to simulate variations between time horizons, and to measure the performance of the proposed methodology. A 33-bus distribution network with large number of distributed resources is used.

Real-time Energy Resource Scheduling considering a Real Portuguese Scenario

The development in power systems and the introduction of decentralized generation and Electric Vehicles (EVs), both connected to distribution networks, represents a major challenge in the planning and operation issues. This new paradigm requires a new energy resources management approach which considers not only the generation, but also the management of loads through demand response programs, energy storage units, EVs and other players in a liberalized electricity markets environment. This paper proposes a methodology to be used by Virtual Power Players (VPPs), concerning the energy resource scheduling in smart grids, considering day-ahead, hour-ahead and real-time scheduling. The case study considers a 33-bus distribution network with high penetration of distributed energy resources. The wind generation profile is based on a real Portuguese wind farm. Four scenarios are presented taking into account 0, 1, 2 and 5 periods (hours or minutes) ahead of the scheduling period in the hour-ahead and realtime scheduling.

Análise estatística do preço da energia elétrica em mercado livre - Uma aplicação ao caso português

Neste relatório apresentam-se resultados de um estudo estatístico que procura contribuir para um melhor entendimento da problemática inerente à liberalização do setor elétrico em Portugal e dos desafios que esta liberalização, existente desde meados de 2007, trás aos seus intervenientes. Iniciam-se os trabalhos com um estudo que pretende avaliar a existência de relação entre o Preço de Mercado da eletricidade e um conjunto de variáveis potencialmente explicativas/condicionantes do Preço de Mercado. Neste estudo consideram-se duas abordagens. A primeira usa a função de correlação cruzada para avaliar a existência de relação do tipo linear entre pares de variáveis. A segunda considera o teste causalidade de Granger na avaliação de uma relação de causa e efeito entre esses pares. Este estudo avaliou a relação entre o Preço de Mercado da eletricidade e 19 variáveis ditas condicionantes distribuídas por três categorias distintas (consumo e produção de eletricidade; indicadores climáticos; e energias primárias). O intervalo de tempo em estudo cinge-se ao biénio 2012-2103. Durante este período avaliam-se as relações entre as variáveis em diversos sub-períodos de tempo em ciclos de consumo representativos do consumo em baixa (fim de semana) e de consumo mais elevado (fora de vazio) com os valores observados de cada uma das variáveis tratados com uma base horária e diária (média). Os resultados obtidos mostram a existência relação linear entre algumas das variáveis em estudo e o preço da eletricidade em regime de mercado liberalizado, mas raramente é possível identificar precedência temporal entre as variáveis. Considerando os resultados da análise de correlação e causalidade, apresenta-se ainda um modelo de previsão do Preço de Mercado para o curto e médio prazo em horas de período fora de vazio.

Give some to get some - Analysing the relationship between worker satisfaction with human resources management and perceived individual performance in a Portuguese hospital

The purpose of this study is to investigate the association between the satisfaction with HRM practices in an organization and the workers' perceived performance. We are interested in learning if indeed workers that are more satisfied with the organization’s practices will also perceive themselves as more hardworking than others, thus confirming the happy-productive worker hypothesis, from an individual perception standpoint. Data originates from a large Portuguese hospital, with a sample of 952 clinical and nonclinical hospital workers. Data was originally explored using SPSS software and later tested in AMOS software where a multiple regression model was constructed and tested. Results indicate that overall satisfaction with HRM practices are related with the workers’ perceived performance; most of the HRM satisfaction subscales also relate, except for pay and performance appraisal, that do not seem to be good predictors of the workers perceived performance. The present study is based on a single large public hospital, and thus, these findings need to be further tested in other settings. This study offers some clues regarding the areas of HRM that seem to be more related with the workers’ perceived performance, and hence provide an interesting framework for managers dealing with healthcare teams. This study contributes to the happy-productive worker hypothesis research, by including seldom used variables in the equation and taking a different perspective. Results provide new clues for investigation and practice regarding the areas of action in HRM that seem to be more prone to elicit perceived effort from the workers.

Bases de Dados NoSQL

Com o advento da invenção do modelo relacional em 1970 por E.F.Codd, a forma como a informação era gerida numa base de dados foi totalmente revolucionada. Migrou‐se de sistemas hierárquicos baseados em ficheiros para uma base de dados relacional com tabelas relações e registos que simplificou em muito a gestão da informação e levou muitas empresas a adotarem este modelo. O que E.F.Codd não previu foi o facto de que cada vez mais a informação que uma base de dados teria de armazenar fosse de proporções gigantescas, nem que as solicitações às bases de dados fossem da mesma ordem. Tudo isto veio a acontecer com a difusão da internet que veio ligar todas as pessoas de qualquer parte do mundo que tivessem um computador. Com o número de adesões à internet a crescer, o número de sites que nela eram criados também cresceu (e ainda cresce exponencialmente). Os motores de busca que antigamente indexavam alguns sites por dia, atualmente indexam uns milhões de sites por segundo e, mais recentemente as redes sociais também estão a lidar com quantidades gigantescas de informação. Tanto os motores de busca como as redes sociais chegaram à conclusão que uma base de dados relacional não chega para gerir a enorme quantidade de informação que ambos produzem e como tal, foi necessário encontrar uma solução. Essa solução é NoSQL e é o assunto que esta tese vai tratar. O presente documento visa definir e apresentar o problema que as bases de dados relacionais têm quando lidam com grandes volumes de dados, introduzir os limites do modelo relacional que só até há bem pouco tempo começaram a ser evidenciados com o surgimento de movimentos, como o BigData, com o crescente número de sites que surgem por dia e com o elevado número de utilizadores das redes sociais. Será também ilustrada a solução adotada até ao momento pelos grandes consumidores de dados de elevado volume, como o Google e o Facebook, enunciando as suas características vantagens, desvantagens e os demais conceitos ligados ao modelo NoSQL. A presente tese tenciona ainda demonstrar que o modelo NoSQL é uma realidade usada em algumas empresas e quais as principias mudanças a nível programático e as boas práticas delas resultantes que o modelo NoSQL traz. Por fim esta tese termina com a explicação de que NoSQL é uma forma de implementar a persistência de uma aplicação que se inclui no novo modelo de persistência da informação.