Maltol determination in food by microwave assisted extraction and electrochemical detection

An electrochemical method is proposed for the determination of maltol in food. Microwave-assisted extraction procedures were developed to assist sample pre-treating steps. Experiments carried out in cyclic voltammetry showed an irreversible and adsorption controlled reduction of maltol. A cathodic peak was observed at -1.0 V for a Hanging Mercury Drop Electrode versus an AgCl/Ag (in saturated KCl), and the peak potential was pH independent. Square wave voltammetric procedures were selected to plot calibration curves. These procedures were carried out with the optimum conditions: pH 6.5; frequency 50 Hz; deposition potential 0.6 V; and deposition time 10 s. A linear behaviour was observed within 5.0 × 10-8 and 3.5 × 10-7 M. The proposed method was applied to the analysis of cakes, and results were compared with those obtained by an independent method. The voltammetric procedure was proven suitable for the analysis of cakes and provided environmental and economical advantages, including reduced toxicity and volume of effluents and decreased consumption of reagents.

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.

Structural modification of TiO2 nanorod films with an influence on the photovoltaic efficiency of a dye-sensitized solar cell (DSSC).

TiO2 nanorod films have been deposited on ITO substrates by dc reactive magnetron sputtering technique. The structures of these nanorod films were modified by the variation of the oxygen pressure during the sputtering process. Although all these TiO2 nanorod films deposited at different oxygen pressures show an anatase structure, the orientation of the nanorod films varies with the oxygen pressure. Only a very weak (101) diffraction peak can be observed for the TiO2 nanorod film prepared at low oxygen pressure. However, as the oxygen pressure is increased, the (220) diffraction peak appears and the intensity of this diffraction peak is increased with the oxygen pressure. The results of the SEM show that these TiO2 nanorods are perpendicular to the ITO substrate. At low oxygen pressure, these sputtered TiO2 nanorods stick together and have a dense structure. As the oxygen pressure is increased, these sputtered TiO2 nanorods get separated gradually and have a porous structure. The optical transmittance of these TiO2 nanorod films has been measured and then fitted by OJL model. The porosities of the TiO2 nanorod films have been calculated. The TiO2 nanorod film prepared at high oxygen pressure shows a high porosity. The dye-sensitized solar cells (DSSCs) have been assembled using these TiO2 nanorod films prepared at different oxygen pressures as photoelectrode. The optimum performance was achieved for the DSSC using the TiO2 nanorod film with the highest (220) diffraction peak and the highest porosity.

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.

Biosensor based on multi-walled carbon nanotubes paste electrode modified with laccase for pirimicarb pesticide quantification

This study focused on the development of a sensitive enzymatic biosensor for the determination of pirimicarb pesticide based on the immobilization of laccase on composite carbon paste electrodes. Multi- walled carbon nanotubes(MWCNTs)paste electrode modified by dispersion of laccase(3%,w/w) within the optimum composite matrix(60:40%,w/w,MWCNTs and paraffin binder)showed the best performance, with excellent electron transfer kinetic and catalytic effects related to the redox process of the substrate4- aminophenol. No metal or anti-interference membrane was added. Based on the inhibition of laccase activity, pirimicarb can be determined in the range 9.90 ×10- 7 to 1.15 ×10- 5 molL 1 using 4- aminophenol as substrate at the optimum pH of 5.0, with acceptable repeatability and reproducibility (relative standard deviations lower than 5%).The limit of detection obtained was 1.8 × 10-7 molL 1 (0.04 mgkg 1 on a fresh weight vegetable basis).The high activity and catalytic properties of the laccase- based biosensor are retained during ca. one month. The optimized electroanalytical protocol coupled to the QuEChERS methodology were applied to tomato and lettuce samples spiked at three levels; recoveries ranging from 91.0±0.1% to 101.0 ± 0.3% were attained. No significant effects in the pirimicarb electro- analysis were observed by the presence of pro-vitamin A, vitamins B1 and C,and glucose in the vegetable extracts. The proposed biosensor- based pesticide residue methodology fulfills all requisites to be used in implementation of food safety programs.

Dependência entre a performance de baterias VRLA e as características físico-químicas da matéria activa positiva

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Avaliação da função diastólica no ventrículo esquerdo em mulheres hipertensas com excesso de peso ou obesidade

Mestrado em Tecnologia de Diagnóstico e Intervenção Cardiovascular - Ramo de especialização: Ultrassonografia Cardiovascular

Aplicação de filmes de suberina na produção de materiais bio-funcionais

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Quantifying the channel quality for interference-aware wireless sensor networks

Reliability of communications is key to expand application domains for sensor networks. SinceWireless Sensor Networks (WSN) operate in the license-free Industrial Scientific and Medical (ISM) bands and hence share the spectrum with other wireless technologies, addressing interference is an important challenge. In order to minimize its effect, nodes can dynamically adapt radio resources provided information about current spectrum usage is available. We present a new channel quality metric, based on availability of the channel over time, which meaningfully quantifies spectrum usage. We discuss the optimum scanning time for capturing the channel condition while maintaining energy-efficiency. Using data collected from a number of Wi-Fi networks operating in a library building, we show that our metric has strong correlation with the Packet Reception Rate (PRR). This suggests that quantifying interference in the channel can help in adapting resources for better reliability. We present a discussion of the usage of our metric for various resource allocation and adaptation strategies.

Introducing the fractional-order Darwinian PSO

One of the most well-known bio-inspired algorithms used in optimization problems is the particle swarm optimization (PSO), which basically consists on a machinelearning technique loosely inspired by birds flocking in search of food. More specifically, it consists of a number of particles that collectively move on the search space in search of the global optimum. The Darwinian particle swarm optimization (DPSO) is an evolutionary algorithm that extends the PSO using natural selection, or survival of the fittest, to enhance the ability to escape from local optima. This paper firstly presents a survey on PSO algorithms mainly focusing on the DPSO. Afterward, a method for controlling the convergence rate of the DPSO using fractional calculus (FC) concepts is proposed. The fractional-order optimization algorithm, denoted as FO-DPSO, is tested using several well-known functions, and the relationship between the fractional-order velocity and the convergence of the algorithm is observed. Moreover, experimental results show that the FO-DPSO significantly outperforms the previously presented FO-PSO.

A multi-objective approach for the motion planning of redundant manipulators

Kinematic redundancy occurs when a manipulator possesses more degrees of freedom than those required to execute a given task. Several kinematic techniques for redundant manipulators control the gripper through the pseudo-inverse of the Jacobian, but lead to a kind of chaotic inner motion with unpredictable arm configurations. Such algorithms are not easy to adapt to optimization schemes and, moreover, often there are multiple optimization objectives that can conflict between them. Unlike single optimization, where one attempts to find the best solution, in multi-objective optimization there is no single solution that is optimum with respect to all indices. Therefore, trajectory planning of redundant robots remains an important area of research and more efficient optimization algorithms are needed. This paper presents a new technique to solve the inverse kinematics of redundant manipulators, using a multi-objective genetic algorithm. This scheme combines the closed-loop pseudo-inverse method with a multi-objective genetic algorithm to control the joint positions. Simulations for manipulators with three or four rotational joints, considering the optimization of two objectives in a workspace without and with obstacles are developed. The results reveal that it is possible to choose several solutions from the Pareto optimal front according to the importance of each individual objective.

Memória de longo prazo nos retornos acionistas dos índices de referência da euronext, implicações para a hipótese de mercados eficientes e contributo fractal para aperfeiçoamento do capital asset pricing model

Não existe uma definição única de processo de memória de longo prazo. Esse processo é geralmente definido como uma série que possui um correlograma decaindo lentamente ou um espectro infinito de frequência zero. Também se refere que uma série com tal propriedade é caracterizada pela dependência a longo prazo e por não periódicos ciclos longos, ou que essa característica descreve a estrutura de correlação de uma série de longos desfasamentos ou que é convencionalmente expressa em termos do declínio da lei-potência da função auto-covariância. O interesse crescente da investigação internacional no aprofundamento do tema é justificado pela procura de um melhor entendimento da natureza dinâmica das séries temporais dos preços dos ativos financeiros. Em primeiro lugar, a falta de consistência entre os resultados reclama novos estudos e a utilização de várias metodologias complementares. Em segundo lugar, a confirmação de processos de memória longa tem implicações relevantes ao nível da (1) modelação teórica e econométrica (i.e., dos modelos martingale de preços e das regras técnicas de negociação), (2) dos testes estatísticos aos modelos de equilíbrio e avaliação, (3) das decisões ótimas de consumo / poupança e de portefólio e (4) da medição de eficiência e racionalidade. Em terceiro lugar, ainda permanecem questões científicas empíricas sobre a identificação do modelo geral teórico de mercado mais adequado para modelar a difusão das séries. Em quarto lugar, aos reguladores e gestores de risco importa saber se existem mercados persistentes e, por isso, ineficientes, que, portanto, possam produzir retornos anormais. O objetivo do trabalho de investigação da dissertação é duplo. Por um lado, pretende proporcionar conhecimento adicional para o debate da memória de longo prazo, debruçando-se sobre o comportamento das séries diárias de retornos dos principais índices acionistas da EURONEXT. Por outro lado, pretende contribuir para o aperfeiçoamento do capital asset pricing model CAPM, considerando uma medida de risco alternativa capaz de ultrapassar os constrangimentos da hipótese de mercado eficiente EMH na presença de séries financeiras com processos sem incrementos independentes e identicamente distribuídos (i.i.d.). O estudo empírico indica a possibilidade de utilização alternativa das obrigações do tesouro (OT’s) com maturidade de longo prazo no cálculo dos retornos do mercado, dado que o seu comportamento nos mercados de dívida soberana reflete a confiança dos investidores nas condições financeiras dos Estados e mede a forma como avaliam as respetiva economias com base no desempenho da generalidade dos seus ativos. Embora o modelo de difusão de preços definido pelo movimento Browniano geométrico gBm alegue proporcionar um bom ajustamento das séries temporais financeiras, os seus pressupostos de normalidade, estacionariedade e independência das inovações residuais são adulterados pelos dados empíricos analisados. Por isso, na procura de evidências sobre a propriedade de memória longa nos mercados recorre-se à rescaled-range analysis R/S e à detrended fluctuation analysis DFA, sob abordagem do movimento Browniano fracionário fBm, para estimar o expoente Hurst H em relação às séries de dados completas e para calcular o expoente Hurst “local” H t em janelas móveis. Complementarmente, são realizados testes estatísticos de hipóteses através do rescaled-range tests R/S , do modified rescaled-range test M - R/S e do fractional differencing test GPH. Em termos de uma conclusão única a partir de todos os métodos sobre a natureza da dependência para o mercado acionista em geral, os resultados empíricos são inconclusivos. Isso quer dizer que o grau de memória de longo prazo e, assim, qualquer classificação, depende de cada mercado particular. No entanto, os resultados gerais maioritariamente positivos suportam a presença de memória longa, sob a forma de persistência, nos retornos acionistas da Bélgica, Holanda e Portugal. Isto sugere que estes mercados estão mais sujeitos a maior previsibilidade (“efeito José”), mas também a tendências que podem ser inesperadamente interrompidas por descontinuidades (“efeito Noé”), e, por isso, tendem a ser mais arriscados para negociar. Apesar da evidência de dinâmica fractal ter suporte estatístico fraco, em sintonia com a maior parte dos estudos internacionais, refuta a hipótese de passeio aleatório com incrementos i.i.d., que é a base da EMH na sua forma fraca. Atendendo a isso, propõem-se contributos para aperfeiçoamento do CAPM, através da proposta de uma nova fractal capital market line FCML e de uma nova fractal security market line FSML. A nova proposta sugere que o elemento de risco (para o mercado e para um ativo) seja dado pelo expoente H de Hurst para desfasamentos de longo prazo dos retornos acionistas. O expoente H mede o grau de memória de longo prazo nos índices acionistas, quer quando as séries de retornos seguem um processo i.i.d. não correlacionado, descrito pelo gBm(em que H = 0,5 , confirmando- se a EMH e adequando-se o CAPM), quer quando seguem um processo com dependência estatística, descrito pelo fBm(em que H é diferente de 0,5, rejeitando-se a EMH e desadequando-se o CAPM). A vantagem da FCML e da FSML é que a medida de memória de longo prazo, definida por H, é a referência adequada para traduzir o risco em modelos que possam ser aplicados a séries de dados que sigam processos i.i.d. e processos com dependência não linear. Então, estas formulações contemplam a EMH como um caso particular possível.

Estudo da compactabilidade em laboratório de misturas betuminosas com resíduos plásticos

Dissertação para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Vias de Comunicação e Transportes

Single-objective spreading algorithm

This paper addresses the problem of finding several different solutions with the same optimum performance in single objective real-world engineering problems. In this paper a parallel robot design is proposed. Thereby, this paper presents a genetic algorithm to optimize uni-objective problems with an infinite number of optimal solutions. The algorithm uses the maximin concept and ε-dominance to promote diversity over the admissible space. The performance of the proposed algorithm is analyzed with three well-known test functions and a function obtained from practical real-world engineering optimization problems. A spreading analysis is performed showing that the solutions drawn by the algorithm are well dispersed.

On the use of particle swarm optimization to maximize bending stiffness of functionally graded structures

Functionally graded materials are a type of composite materials which are tailored to provide continuously varying properties, according to specific constituent's mixing distributions. These materials are known to provide superior thermal and mechanical performances when compared to the traditional laminated composites, because of this continuous properties variation characteristic, which enables among other advantages, smoother stresses distribution profiles. Therefore the growing trend on the use of these materials brings together the interest and the need for getting optimum configurations concerning to each specific application. In this work it is studied the use of particle swarm optimization technique for the maximization of a functionally graded sandwich beam bending stiffness. For this purpose, a set of case studies is analyzed, in order to enable to understand in a detailed way, how the different optimization parameters tuning can influence the whole process. It is also considered a re-initialization strategy, which is not a common approach in particle swarm optimization as far as it was possible to conclude from the published research works. As it will be shown, this strategy can provide good results and also present some advantages in some conditions. This work was developed and programmed on symbolic computation platform Maple 14. (C) 2013 Elsevier B.V. All rights reserved.