Síntese de derivados de ácidos fenólicos e estudo da sua actividade antioxidante

A peroxidação lipídica, além de causar sérios danos no corpo humano, é a principal causa da deterioração dos alimentos afectando a sua cor, aroma e valor nutricional, o que conduz a uma diminuição do seu ciclo de vida. O fenómeno de oxidação pode ser retardado com recurso a antioxidantes, de origem natural ou sintética, que inibam a formação de espécies reactivas, ou que reajam com estas, formando posteriormente radicais com menor grau de reactividade. Nesta dissertação procedeu-se à síntese e elucidação estrutural de novos antioxidantes, derivados dos ácidos 3,4-diidroxibenzóico (PCA) e 3,4-diidroxifenilacético (DOPAC), e à avaliação da sua actividade anti-radicalar e antioxidante. Os novos antioxidantes sintetizados foram caracterizados usando RMN de 1H e de 13C, FTIR e EM-IE. A avaliação da actividade antioxidante foi realizada com base no método do radical 2,2- difenil-1-picrilhidrazilo (DPPH·) e por técnicas electroquímicas (voltametria de impulso diferencial e voltametria cíclica). Os resultados obtidos permitiram concluir que a eficácia anti-radicalar (AE) é determinada por aspectos da estrutura molecular dos compostos, nomeadamente pela presença de grupos hidroxilo no anel aromático e também de grupos extensores relativamente à posição do grupo carboxílico. Os resultados permitiram verificar que o DOPAC apresenta a mais elevada eficiência anti-radicalar dos compostos em estudo, incluindo o trolox e o ácido gálhico (compostos de referência). Com base nos resultados obtidos concluiu-se que, um menor potencial de oxidação conduz a uma melhor actividade anti-radicalar dos compostos. De facto, verificou-se para o PCA e respectivos ésteres o maior potencial de oxidação e também a menor eficiência anti-radicalar. Em contrapartida, os antioxidantes com maior eficiência anti-radicalar, DOPAC, trolox e ácido gálhico, apresentaram menor potencial de oxidação.

Voltammetric oxidation of drugs of abuse II. Codeine and metabolites

The oxidation of codeine on glassy carbon electrodes has been studied in detail using differential pulse voltammetry. The results obtained using a glassy carbon electrode clearly show a much more complex oxidation mechanism than that previously reported when platinum and gold electrodes were used. To clarify the codeine oxidative profile, several metabolites and analogues of this alkaloid, codeine N-oxide, norcodeine, dihydrocodeine, acetylcodeine and 6- chlorodesoxycodeine, were synthesized and studied. It was deduced that the anodic waves observed in codeine oxidation are related to the presence of methoxy, hydroxy and tertiary amine groups. Due to the similarity of potentials at which these oxidative processes take place, at some pHs an overlap of peaks occurs and only one anodic wave is observed.

Voltammetric oxidation of drugs of abuse III. Heroin and metabolites

The oxidative behavior of heroin in aqueous solution is reported. In order to identify its oxidation peaks, several metabolites, 6-monoacetylmorphine, 3-monoacetylmorphine and norheroin, were synthesized and their electrochemical behavior studied using differential pulse voltammetry. The anodic waves observed for heroin correspond to the oxidation of the tertiary amine group and its follow-up product (secondary amine), and to the oxidation of the phenolic group obtained from hydrolysis, at alkaline pHs, of the 3-acetyl group. The results enabled a new oxidative mechanism for heroin to be proposed in which a secondary amine, norheroin, and an aldehyde are obtained. The voltammetric behavior of 6-monoacetylmorphine and morphine was found to be similar demonstrating that the presence of an acetyl substituent on the 6-hydroxy group does not have a relevant influence on the peak potential of the wave resulting from oxidation of the 3-phenolic group.

DNA-based biosensor for the electrocatalytic determination of antioxidant capacity in beverages

Reactive oxygen species (ROS) are produced as a consequence of normal aerobic metabolism and are able to induce DNA oxidative damage. At the cellular level, the evaluation of the protective effect of antioxidants can be achieved by examining the integrity of the DNA nucleobases using electrochemical techniques. Herein, the use of an adenine-rich oligonucleotide (dA21) adsorbed on carbon paste electrodes for the assessment of the antioxidant capacity is proposed. The method was based on the partial damage of a DNA layer adsorbed on the electrode surface by OH• radicals generated by Fenton reaction and the subsequent electrochemical oxidation of the intact adenine bases to generate an oxidation product that was able to catalyze the oxidation of NADH. The presence of antioxidant compounds scavenged hydroxyl radicals leaving more adenines unoxidized, and thus, increasing the electrocatalytic current of NADHmeasured by differential pulse voltammetry (DPV). Using ascorbic acid (AA) as a model antioxidant species, the detection of as low as 50nMof AA in aqueous solution was possible. The protection efficiency was evaluated for several antioxidant compounds. The biosensor was applied to the determination of the total antioxidant capacity (TAC) in beverages.

Molinate quantification in environmental water by a glutathione-S-transferase based biosensor

A glutathione-S-transferase (GST)based biosensor was developed to quantify the thiocarbamate herbicide molinate in environmental water.The biosensor construction was based on GST immobilization onto a glassy carbon electrode via aminosilane–glutaraldehyde covalent attachment. The principle supporting the use of this biosensor consists of the GST inhibition process promoted by molinate. Differential pulse voltammetry was used to obtain a calibration curve for molinate concentration, ranging from 0.19 to 7.9 mgL -1 and presenting a detection limit of 0.064 mgL- 1. The developed biosensor is stable,and reusable during 15 days.The GST-based biosensor was successfully applied to quantify molinate in rice paddy field floodwater samples. The results achieved with the developed biosensor were in accordance with those obtained by high performance liquid chromatography. The proposed device is suitable for screening environmental water analysis and, since no sample preparation is required, it can be used in situ and in real-time measurements.

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.

Simulation of offshore wind system with two-level converters: HVDC power transmission

A new integrated mathematical model for the simulation of offshore wind energy conversion system performance is presented in this paper. The mathematical model considers an offshore variable-speed turbine in deep water equipped with a permanent magnet synchronous generator using full-power two-level converter, converting the energy of a variable frequency source in injected energy into the electric network with constant frequency, through a high voltage DC transmission submarine cable. The mathematical model for the drive train is a concentrate two mass model which incorporates the dynamic for the structure and tower due to the need to emulate the effects of the moving surface. Controller strategy considered is a proportional integral one. Also, pulse width modulation using space vector modulation supplemented with sliding mode is used for trigger the transistor of the converter. Finally, a case study is presented to access the system performance. © 2014 IEEE.

Electrochemical studies on small electron transfer proteins using membrane electrodes

Journal of Electroanalytical Chemistry 541 (2003) 153-162

A simulation of integrated photovoltaic conversion into electric grid

This paper presents a systemic modeling for a PV system integrated into an electric grid. The modeling includes models for a DC-DC boost converter and a DC-AC two-level inverter. Classical or fuzzy PI controllers with pulse width modulation by space vector modulation associated with sliding mode control is used for controlling the PV system and power factor control is introduced at the output of the system. Comprehensive performance simulation studies are carried out with the modeling of the DC-DC boost converter followed by a two-level power inverter in order to compare the performance with the experimental results obtained during in situ operation with three commercial inverters. Also, studies are carried out to assess the quality of the energy injected into the electric grid in terms of harmonic distortion. Finally, conclusions regarding the integration of the PV system into the electric grid are presented. (C) 2014 Elsevier Ltd. All rights reserved.

Simulation of offshore wind system with two levels converters: HVDC power transmission

A new integrated mathematical model for the simulation of offshore wind energy conversion system performance is presented in this paper. The mathematical model considers an offshore variable-speed turbine in deep water equipped with a permanent magnet synchronous generator using full-power two-level converter, converting the energy of a variable frequency source in injected energy into the electric network with constant frequency, through a high voltage DC transmission submarine cable. The mathematical model for the drive train is a concentrate two mass model which incorporates the dynamic for the structure and tower due to the need to emulate the effects of the moving surface. Controller strategy considered is a proportional integral one. Also, pulse width modulation using space vector modulation supplemented with sliding mode is used for trigger the transistor of the converter. Finally, a case study is presented to access the system performance. © 2014 IEEE.

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.

The comb signal and its Fourier transform

SignalProcessing, Vol. 81, nº 3

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.

Simulation of a-Si PV system grid connected by boost and inverter

This paper is about a PV system connected to the electric grid by power electronic converters, using classical PI controller. The modelling for the converters emulates the association of a DC-DC boost with a two-level power inverter (TwLI) or three-level power inverter (ThLI) in order to follow the performance of a testing experimental system. Pulse width modulation (PWMo) by sliding mode control (SMCo) associated with space vector modulation (SVMo) is applied to the boost and the inverter. The PV system is described by the five parameters equivalent circuit. Parameter identification and simulation studies are performed for comparison with the testing experimental system.

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.