Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

Aplicação de algoritmos genéticos para sintonia de controladores

Mestrado em Engenharia Electrotécnica e de Computadores

Modelação de células de combustível

Neste trabalho serão apresentados e discutidos vários aspectos relacionados com células de combustível, com particular enfoque na modelação de células de combustível de membrana de permuta protónica. Este trabalho está dividido em vários capítulos. No Capítunlo 1 são apresentadas as motivações e os objectivos da tese. No Capítulo 2 serão apresentadas as células de combustível em geral, a sua origem, os diversos tipos, o que as diferencia das restantes tecnologias de geração de energia e as suas vantagens e desvantagens. No Capítulo 3 discute-se a modelação de células de combustível. Serão expostos e explicados os diferentes tipos de modelos, seguindo-se uma apresentação do modelo selecionado para estudo, com referência aos fundamentos teóricos exposição detalhada da fórmulação matemática e os parâmetros que caracterizam o modelo. É também apresentado a implementação do modelo em Matlab/Simulink. No Capítulo 4 será discutida e apresentada a abordagem utilizada para a identificação dos parâmetros do modelo da célula de combustível. Propõe-se e prova-se que uma abordagem baseada num algoritmo de optimização inteligente proporciona um método eficaz e preciso para a identificação dos parâmetros. Esta abordagem requer a existência de alguns dados experimentais que são também apresentados. O algoritmo utilizado designa-se por Optimização por Enxame de Partículas – Particle Swarm Optimization (PSO). São apresentados os seus fundamentos, características, implementação em Matlab/Simulink e a estratégia de optimização, isto é, a configuração do algoritmo, a definição da função objectivo e limites de variação dos parâmetros. São apresentados os resultados do processo de optimização, resultados adicionais de validação do modelo, uma análise de robustez do conjunto óptimo de parâmetros e uma análise de sensibilidade dos mesmos. O trabalho termina apresentando, no último capítulo, algumas conclusões, das quais se destacam: - O bom desempenho do algoritmo PSO para a identificação dos parâmetros do modelo da célula de combsutível; - Uma robustez interessante do algoritmo PSO, no sentido em que, para várias execuções do método resultam valores do parâmetros e da função objectivo com variabilidade bastante reduzidas; - Um bom modelo da célula de combustível, que quando caracterizado pelo conjunto óptimo de parâmetros, apresenta, sistematicamente, erros relativos médios inferiores a 2,5% para um conjunto alargado de condições de funcionamento.

Fuzzy Monte Carlo model for transmission power systems reliability based decision making

This thesis presents the Fuzzy Monte Carlo Model for Transmission Power Systems Reliability based studies (FMC-TRel) methodology, which is based on statistical failure and repair data of the transmission power system components and uses fuzzyprobabilistic modeling for system component outage parameters. Using statistical records allows developing the fuzzy membership functions of system component outage parameters. The proposed hybrid method of fuzzy set and Monte Carlo simulation based on the fuzzy-probabilistic models allows catching both randomness and fuzziness of component outage parameters. A network contingency analysis to identify any overloading or voltage violation in the network is performed once obtained the system states. This is followed by a remedial action algorithm, based on Optimal Power Flow, to reschedule generations and alleviate constraint violations and, at the same time, to avoid any load curtailment, if possible, or, otherwise, to minimize the total load curtailment, for the states identified by the contingency analysis. For the system states that cause load curtailment, an optimization approach is applied to reduce the probability of occurrence of these states while minimizing the costs to achieve that reduction. This methodology is of most importance for supporting the transmission system operator decision making, namely in the identification of critical components and in the planning of future investments in the transmission power system. A case study based on Reliability Test System (RTS) 1996 IEEE 24 Bus is presented to illustrate with detail the application of the proposed methodology.

A literature review on the optimization of legged robots

Over the last two decades the research and development of legged locomotion robots has grown steadily. Legged systems present major advantages when compared with ‘traditional’ vehicles, because they allow locomotion in inaccessible terrain to vehicles with wheels and tracks. However, the robustness of legged robots, and especially their energy consumption, among other aspects, still lag behind mechanisms that use wheels and tracks. Therefore, in the present state of development, there are several aspects that need to be improved and optimized. Keeping these ideas in mind, this paper presents the review of the literature of different methods adopted for the optimization of the structure and locomotion gaits of walking robots. Among the distinct possible strategies often used for these tasks are referred approaches such as the mimicking of biological animals, the use of evolutionary schemes to find the optimal parameters and structures, the adoption of sound mechanical design rules, and the optimization of power-based indexes.

Optimization of Cu(II) biosorption onto ascophyllum nodosum by factorial design methodology

A Box–Behnken factorial design coupled with surface response methodology was used to evaluate the effects of temperature, pH and initial concentration in the Cu(II) sorption process onto the marine macroalgae Ascophyllum nodosum. The effect of the operating variables on metal uptake capacitywas studied in a batch system and a mathematical model showing the influence of each variable and their interactions was obtained. Study ranges were 10–40ºC for temperature, 3.0–5.0 for pH and 50–150mgL−1 for initial Cu(II) concentration. Within these ranges, the biosorption capacity is slightly dependent on temperature but markedly increases with pH and initial concentration of Cu(II). The uptake capacities predicted by the model are in good agreement with the experimental values. Maximum biosorption capacity of Cu(II) by A. nodosum is 70mgg−1 and corresponds to the following values of those variables: temperature = 40ºC, pH= 5.0 and initial Cu(II) concentration = 150mgL−1.

Multi-criteria design optimization study of solvent extraction in mixer–settler units

Solvent extraction is considered as a multi-criteria optimization problem, since several chemical species with similar extraction kinetic properties are frequently present in the aqueous phase and the selective extraction is not practicable. This optimization, applied to mixer–settler units, considers the best parameters and operating conditions, as well as the best structure or process flow-sheet. Global process optimization is performed for a specific flow-sheet and a comparison of Pareto curves for different flow-sheets is made. The positive weight sum approach linked to the sequential quadratic programming method is used to obtain the Pareto set. In all investigated structures, recovery increases with hold-up, residence time and agitation speed, while the purity has an opposite behaviour. For the same treatment capacity, counter-current arrangements are shown to promote recovery without significant impairment in purity. Recycling the aqueous phase is shown to be irrelevant, but organic recycling with as many stages as economically feasible clearly improves the design criteria and reduces the most efficient organic flow-rate.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Optimization of a microplate-based assay to assess esterase activity in the alga Pseudokirchneriella subcapitata

The present work describes the optimization of a short-term assay, based on the inhibition of the esterase activity of the alga Pseudokirchneriella subcapitata, in a microplate format. The optimization of the staining procedure showed that the incubation of the algal cells with 20 μmolL−1 fluorescein diacetate (FDA) for 40 min allowed discrimination between metabolic active and inactive cells. The shortterm assay was tested using Cu as toxicant. For this purpose, algal cells, in the exponential or stationary phase of growth, were exposed to the heavy metal in growing conditions. After 3 or 6 h, cells were subsequently stained with FDA, using the optimized procedure. For Cu, the 3- and 6-h EC50 values, based on the inhibition of the esterase activity of algal cells in the exponential phase of growth, were 209 and 130 μg L−1, respectively. P. subcapitata cells, in the stationary phase of growth, displayed higher effective concentration values than those observed in the exponential phase. The 3- and 6-h EC50 values for Cu, for cells in the stationary phase, were 443 and 268 μgL−1, respectively. This short-term microplate assay showed to be a rapid endpoint for testing toxicity using the alga P. subcapitata. The small volume required, the simplicity of the assay (no washing steps), and the automatic reading of the fluorescence make the assay particularly well suited for the evaluation of the toxicity of a high number of environmental samples.

Demand response management in power systems using a particle swarm optimization approach

Competitive electricity markets have arisen as a result of power-sector restructuration and power-system deregulation. The players participating in competitive electricity markets must define strategies and make decisions using all the available information and business opportunities.

Nonmonotone hybrid tabu search for inequalities and equalities: an experimental study

The main goal of this paper is to analyze the behavior of nonmono- tone hybrid tabu search approaches when solving systems of nonlinear inequalities and equalities through the global optimization of an appro- priate merit function. The algorithm combines global and local searches and uses a nonmonotone reduction of the merit function to choose the local search. Relaxing the condition aims to call the local search more often and reduces the overall computational e ort. Two variants of a perturbed pattern search method are implemented as local search. An experimental study involving a variety of problems available in the lit- erature is presented.

Convex optimization framework for intermediate deadline assignment in soft and hard real-time distributed systems

It is generally challenging to determine end-to-end delays of applications for maximizing the aggregate system utility subject to timing constraints. Many practical approaches suggest the use of intermediate deadline of tasks in order to control and upper-bound their end-to-end delays. This paper proposes a unified framework for different time-sensitive, global optimization problems, and solves them in a distributed manner using Lagrangian duality. The framework uses global viewpoints to assign intermediate deadlines, taking resource contention among tasks into consideration. For soft real-time tasks, the proposed framework effectively addresses the deadline assignment problem while maximizing the aggregate quality of service. For hard real-time tasks, we show that existing heuristic solutions to the deadline assignment problem can be incorporated into the proposed framework, enriching their mathematical interpretation.

A preliminary idea for an 8-competitive, log2 DMAX + log2 log2 1/U asymptotic-space, interface generation algorithm for two-level hierarchical scheduling of constrained-deadline sporadic tasks on a uniprocessor

Consider a single processor and a software system. The software system comprises components and interfaces where each component has an associated interface and each component comprises a set of constrained-deadline sporadic tasks. A scheduling algorithm (called global scheduler) determines at each instant which component is active. The active component uses another scheduling algorithm (called local scheduler) to determine which task is selected for execution on the processor. The interface of a component makes certain information about a component visible to other components; the interfaces of all components are used for schedulability analysis. We address the problem of generating an interface for a component based on the tasks inside the component. We desire to (i) incur only a small loss in schedulability analysis due to the interface and (ii) ensure that the amount of space (counted in bits) of the interface is small; this is because such an interface hides as much details of the component as possible. We present an algorithm for generating such an interface.

A fuzzified systematic adjustment of the robotic Darwinian PSO

The Darwinian Particle Swarm Optimization (DPSO) is an evolutionary algorithm that extends the Particle Swarm Optimization using natural selection to enhance the ability to escape from sub-optimal solutions. An extension of the DPSO to multi-robot applications has been recently proposed and denoted as Robotic Darwinian PSO (RDPSO), benefiting from the dynamical partitioning of the whole population of robots, hence decreasing the amount of required information exchange among robots. This paper further extends the previously proposed algorithm adapting the behavior of robots based on a set of context-based evaluation metrics. Those metrics are then used as inputs of a fuzzy system so as to systematically adjust the RDPSO parameters (i.e., outputs of the fuzzy system), thus improving its convergence rate, susceptibility to obstacles and communication constraints. The adapted RDPSO is evaluated in groups of physical robots, being further explored using larger populations of simulated mobile robots within a larger scenario.

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.