Voltammetric oxidation of drugs of abuse I. Morphine and metabolites

A detailed study of the electrochemical oxidative behavior of morphine in aqueous solution is reported. Through the synthesis of several metabolites and derivatives, pseudomorphine, morphine N-oxide, normorphine, dihydromorphine and 2-(N,N-dimethylaminomethyl)morphine, and their voltammetric study it was possible to identify the oxidation peaks for morphine. The anodic waves are related with the oxidation of phenolic and tertiary amine groups. It is also possible to verify that a poorly defined peak observable during morphine oxidation is not a consequence of further oxidation of pseudomorphine but due to formation of a dimer during phenolic group oxidation. The results obtained and especially those regarding the formation of a new polymer based on a C O coupling could be useful for clarifying the discoloration phenomenon occurring during storage of morphine solutions as well as leading to a better understanding of its oxidative metabolic pathways.

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75–100 mg L−1. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9–39.5, 18.6–32.0 and 32.3–50.4 mg g−1, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

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.

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.

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.

Cloud computing sobre a plataforma Windows Azure

A utilização massiva da internet e dos serviços que oferece por parte do utilizador final potencia a evolução dos mesmos, motivando as empresas a apostarem no desenvolvimento deste tipo de soluções. Requisitos como o poder de computação, flexibilidade e escalabilidade tornam-se cada vez mais indissociáveis do desenvolvimento aplicacional, o que leva ao surgimento de paradigmas como o de Cloud Computing. É neste âmbito que surge o presente trabalho. Com o objetivo de estudar o paradigma de Cloud Computing inicia-se um estudo sobre esta temática, onde é detalhado o seu conceito, a sua evolução histórica e comparados os diferentes tipos de implementações que suporta. O estudo detalha posteriormente a plataforma Azure, sendo analisada a sua topologia e arquitetura, detalhando-se os seus componentes e a forma como esta mitiga alguns dos problemas mencionados. Com o conhecimento teórico é desenvolvido um protótipo prático sobre esta plataforma, em que se exploram algumas das particularidades da topologia e se interage com as principais redes sociais. O estudo culmina com uma análise sobre os benefícios e desvantagens do Azure e através de um levantamento das necessidades da empresa, determinam-se as oportunidades que a utilização da plataforma poderá proporcionar.

The Portuguese law on social economy

This study is a reflection on the Portuguese Framework Law on Social Economy, highlighting, from a critical point-of-view, its contribution to the explicit institutional and legal recognition of the social economy sector. It does so by defining the concept of social economy and listing the entities engaged in this sector, by defining its guiding principles and the mechanisms for its promotion and encouragement, and also by describing the creation of a tax and competition regime which will take into account its specificities. The setting up of this foundations of the social economy was based on the constitutional principle of protection of the social and cooperative sector, which substantiates the adoption of differentiating solutions in view of the positive discrimination of this sector.

Projeto e implementação de um protótipo para microprodução de energia elétrica destinado a alimentar um sistema de iluminação decorativa exterior

Com o presente trabalho é pretendido demonstrar a possibilidade de alimentação de um sistema de iluminação decorativa com recurso a soluções alternativas renováveis. O estudo é focado essencialmente na produção local de energia solar fotovoltaica e eólica. Inicialmente é efetuado o estudo técnico-económico da implementação de um sistema fotovoltaico. Posteriormente é efetuado o estudo da viabilidade técnico-económica da implementação do sistema hibrido, composto por um sistema fotovoltaico e um sistema eólico, optando pelo que mais se adequa à alimentação do sistema de iluminação decorativa exterior. Esta dissertação descreve a metodologia que procura melhorar a eficiência do sistema de led com o auxílio de ensaios em laboratório e simulação em software, com o objetivo de adaptar os sistemas de led instalados pela empresa ao sistema hibrido dimensionado. Finalmente, é efetuada a análise comparativa entre o atual sistema de iluminação decorativa e o sistema renovável dimensionado mais favorável para alimentar sistemas de iluminação decorativa. Procura-se assim com este projeto para além de apresentar um estudo teórico, proporcionar uma orientação à implementação de sistemas de microprodução destinados a alimentar sistemas de iluminação decorativa exterior.

A new MILP based approach for unit commitment in power production planning

This paper presents a complete, quadratic programming formulation of the standard thermal unit commitment problem in power generation planning, together with a novel iterative optimisation algorithm for its solution. The algorithm, based on a mixed-integer formulation of the problem, considers piecewise linear approximations of the quadratic fuel cost function that are dynamically updated in an iterative way, converging to the optimum; this avoids the requirement of resorting to quadratic programming, making the solution process much quicker. From extensive computational tests on a broad set of benchmark instances of this problem, the algorithm was found to be flexible and capable of easily incorporating different problem constraints. Indeed, it is able to tackle ramp constraints, which although very important in practice were rarely considered in previous publications. Most importantly, optimal solutions were obtained for several well-known benchmark instances, including instances of practical relevance, that are not yet known to have been solved to optimality. Computational experiments and their results showed that the method proposed is both simple and extremely effective.

Reabilitação de um edifício – Rua Azevedo Coutinho

Este trabalho teve como objectivo o estudo de uma acção de conservação/reabilitação de um edifício, localizado na rua Azevedo Coutinho na zona do Porto. Trata-se, portanto, de um trabalho académico que visa efectuar uma proposta de acções correctivas a implementar num edifício habitacional, onde foram detectadas anomalias. Esta monografia encontra-se dividida em dois capítulos, onde, o primeiro faz uma abordagem teórica, muito breve e sucinta, às matérias correntemente utilizadas no segundo capitulo. Dando também algumas noções e definições de alguns termos utilizados neste ramo da construção. A segunda parte do trabalho consiste no estudo do caso prático do edifício onde serão implementados processos metodológicos definidos no primeiro capítulo. De forma a implementar esta metodologia, apresenta-se, então, um edifício construído em meados de 1975, que apresenta ligeiros sinais de degradação que sugerem a uma possível acção de intervenção em alguns dos seus componentes. Sumariamente, pretendeu-se identificar as várias manifestações anómalas do interior e exterior do edifício, procurando associar as mesmas. Neste sentido, esta metodologia fundamenta-se num estudo de documentação técnica, fotográfica e histórica do edifício onde se procurou recolher o mais detalhadamente possível todas as informações essenciais para o estudo, incluindo informações por parte dos seus residentes. Com base neste conjunto de informação foi possível realizar um diagnóstico credível, apesar de não ser completamente conclusivo. Procurou-se listar as possíveis causas que desencadearam o aparecimento das anomalias, propondo finalmente um conjunto de soluções para a conservação/reabilitação do edifício. Esta proposta de intervenção contempla um conjunto de recomendações, que norteiam a definição de soluções para a conservação/reabilitação do interior do edifício e da sua fachada, de forma a se garantir que as mesmas assegurem resultados satisfatórios a longo prazo.

Levantamento, reparação e beneficiação do simulador TERCO PST 2200 do Laboratório de Sistemas de Energia do ISEP

Este trabalho é baseado no simulador de redes PST2200 do Laboratório de Sistemas de Energia (LSE) pois está avariado com vários problemas conhecidos, designadamente: - Defeito de isolamento (disparo de diferencial), - Desregulação da velocidade da máquina primária (motor DC), - Circuito de excitação da máquina síncrona inoperacional, - Inexistência de esquemas elétricos dos circuitos do simulador, - Medidas desreguladas e com canais de medida com circuito impresso queimado. O trabalho executado foi: - O levantamento e desenho de raiz (não existe qualquer manual) dos esquemas dos 10 módulos do simulador, designadamente naqueles com avaria ou com desempenho problemático a fim de que se possa ter uma visão mais pormenorizada dos circuitos e seus problemas, por forma a intervir para os minimizar e resolver, - Foi realizado o diagnóstico de avaria do simulador e foram propostas soluções para os mesmos, - Realizaram-se as intervenções propostas e aprovadas. Nas intervenções realizadas, os princípios orientadores foram: - Aumentar a robustez do equipamento por forma a garantir a sua integridade a utilizações menos apropriados e manobras 'exóticas' próprias de alunos, que pela sua condição, estão em fase de aprendizagem, - Atualizar o equipamento, colocando-o em sintonia com o 'estado da arte', - Como fator de valorização suplementar, foi concebida e aplicada a supervisão remota do funcionamento do simulador através da rede informática. Foram detetados inúmeros erros: - Má ligação do motor de corrente continua ao variador, resultando a falta de controlo da frequência da rede do sistema, - Ligações entre painéis trocadas resultando em avarias diversas das fontes de alimentação, - Cartas eletrónicas de medidas avariadas e que além de se reparar, foram também calibradas. Devido ao mecenato da empresa Schnitt + Sohn participando monetariamente, fez-se o projeto de alteração e respetiva execução de grande parte do simulador aumentando a fiabilidade do mesmo, diminuindo assim a frequência das avarias naturais mais as que acontecem involuntariamente devido a este ser um instrumento didático. Além do trabalho elétrico, foi feito muito trabalho de chaparia para alteração de estrutura e suporte do material com diferenças de posicionamento. Neste trabalho dá-se também alguns exemplos de cálculo e simulação das redes de transporte que se pode efetuar no simulador como estudo e simulação de avarias num sistema produtivo real. Realizou-se a monitorização de dois aparelhos indicadores de parâmetros de energia (Janitza UMG96S) através duma rede com dois protocolos ethernet e profibus utilizando o plc (Omron CJ2M) como valorização do trabalho.

A distributed system for learning programming on-line

Several Web-based on-line judges or on-line programming trainers have been developed in order to allow students to train their programming skills. However, their pedagogical functionalities in the learning of programming have not been clearly defined. EduJudge is a project which aims to integrate the “UVA On-line Judge”, an existing on-line programming trainer with an important number of problems and users, into an effective educational environment consisting of the e-learning platform Moodle and the competitive learning tool QUESTOURnament. The result is the EduJudge system which allows teachers to apply different pedagogical approaches using a proven e-learning platform, makes problems easy to search through an effective search engine, and provides an automated evaluation of the solutions submitted to these problems. The final objective is to provide new learning strategies to motivate students and present programming as an easy and attractive challenge. EduJudge has been tried and tested in three algorithms and programming courses in three different Engineering degrees. The students’ motivation and satisfaction levels were analysed alongside the effects of the EduJudge system on students’ academic outcomes. Results indicate that both students and teachers found that among other multiple benefits the EduJudge system facilitates the learning process. Furthermore, the experi- ment also showed an improvement in students’ academic outcomes. It must be noted that the students’ level of satisfaction did not depend on their computer skills or their gender.

Electrochemical and spectroscopic studies of the oxidation mechanism of the herbicide propanil

Electrochemical oxidation of propanil in deuterated solutions was studied by cyclic, differential pulse, and square wave voltammetry using a glassy carbon microelectrode. The oxidation of propanil in deuterated acid solutions occurs at the nitrogen atom of the amide at a potential of +1.15 V vs Ag/ AgCl. It was also found that, under the experimental conditions used, protonation at the oxygen atom of propanil occurs, leading to the appearance of another species in solution which oxidizes at +0.60 V. The anodic peak found at +0.79 V vs Ag/AgCl in deuterated basic solutions is related to the presence of an anionic species in which a negative charge is on the nitrogen atom. The electrochemical data were confirmed by the identification of all the species formed in acidic and basic deuterated solutions by means of NMR spectroscopy. The results are supported by electrochemical and spectroscopic studies of acetanilide in deuterated solutions.

Lower protocol layers for wireless sensor networks: a survey

Wireless Sensor Networks (WSNs) have been attracting increasing interests in the development of a new generation of embedded systems with great potential for many applications such as surveillance, environment monitoring, emergency medical response and home automation. However, the communication paradigms in Wireless Sensor Networks differ from the ones attributed to traditional wireless networks, triggering the need for new communication protocols and mechanisms. In this Technical Report, we present a survey on communication protocols for WSNs with a particular emphasis on the lower protocol layers. We give a particular focus to the MAC (Medium Access Control) sub-layer, since it has a prominent influence on some relevant requirements that must be satisfied by WSN protocols, such as energy consumption, time performance and scalability. We overview some relevant MAC protocol solutions and discuss how they tackle the trade-off between the referred requirements.

Friction losses of Newtonian and non-Newtonian fluids flowing in laminar regime in a helical coil

This study aimed to carry out experimental work to determine, for Newtonian and non-Newtonian fluids, the friction factor (fc) with simultaneous heat transfer, at constant wall temperature as boundary condition, in fully developed laminar flow inside a vertical helical coil. The Newtonian fluids studied were aqueous solutions of glycerol, 25%, 36%, 43%, 59% and 78% (w/w). The non-Newtonian fluids were aqueous solutions of carboxymethylcellulose (CMC), a polymer, with concentrations of 0.2%, 0.3%, 0.4% and 0.6% (w/w) and aqueous solutions of xanthan gum (XG), another polymer, with concentrations of 0.1% and 0.2% (w/w). According to the rheological study done, the polymer solutions had shear-thinning behavior and different values of viscoelasticity. The helical coil used has an internal diameter, curvature ratio, length and pitch, respectively: 0.00483 m, 0.0263, 5.0 m and 11.34 mm. It was concluded that the friction factors, with simultaneous heat transfer, for Newtonian fluids can be calculated using expressions from literature for isothermal flows. The friction factors for CMC and XG solutions are similar to those for Newtonian fluids when the Dean number, based in a generalized Reynolds number, is less than 80. For Dean numbers higher than 80, the friction factors of the CMC solutions are lower those of the XG solutions and of the Newtonian fluids. In this range the friction factors decrease with the increase of the viscometric component of the solution and increase for increasing elastic component. The change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, is in accordance with the study of Ali [4]. There is a change of behavior at Dean number 80, for Newtonian and non-Newtonian fluids, which is in according to previous studies. The data also showed that the use of the bulk temperature or of the film temperature to calculate the physical properties of the fluid has a residual effect in the friction factor values.