The development and optimization of a modified single-drop microextraction method for organochlorine pesticides determination by gas chromatography-tandem mass spectrometry

We have developed a new method for single-drop microextraction (SDME) for the preconcentration of organochlorine pesticides (OCP) from complex matrices. It is based on the use of a silicone ring at the tip of the syringe. A 5 μL drop of n-hexane is applied to an aqueous extract containing the OCP and found to be adequate to preconcentrate the OCPs prior to analysis by GC in combination with tandem mass spectrometry. Fourteen OCP were determined using this technique in combination with programmable temperature vaporization. It is shown to have many advantages over traditional split/splitless injection. The effects of kind of organic solvent, exposure time, agitation and organic drop volume were optimized. Relative recoveries range from 59 to 117 %, with repeatabilities of <15 % (coefficient of variation) were achieved. The limits of detection range from 0.002 to 0.150 μg kg−1. The method was applied to the preconcentration of OCPs in fresh strawberry, strawberry jam, and soil.

Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter

A QuEChERS method has been developed for the determination of 14 organochlorine pesticides in 14 soils from different Portuguese regions with wide range composition. The extracts were analysed by GC-ECD (where GC-ECD is gas chromatography-electron-capture detector) and confirmed by GC-MS/MS (where MS/MS is tandem mass spectrometry). The organic matter content is a key factor in the process efficiency. An optimization was carried out according to soils organic carbon level, divided in two groups: HS (organic carbon>2.3%) and LS (organic carbon<2.3%). Themethod was validated through linearity, recovery, precision and accuracy studies. The quantification was carried out using a matrixmatched calibration to minimize the existence of the matrix effect. Acceptable recoveries were obtained (70–120%) with a relative standard deviation of ≤16% for the three levels of contamination. The ranges of the limits of detection and of the limits of quantification in soils HS were from 3.42 to 23.77 μg kg−1 and from 11.41 to 79.23 μg kg−1, respectively. For LS soils, the limits of detection ranged from 6.11 to 14.78 μg kg−1 and the limits of quantification from 20.37 to 49.27 μg kg−1. In the 14 collected soil samples only one showed a residue of dieldrin (45.36 μg kg−1) above the limit of quantification. This methodology combines the advantages of QuEChERS, GC-ECD detection and GC-MS/MS confirmation producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Optimization and validation of organochlorine compounds in adipose tissue by SPE-gas chromatography

Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid-phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C18-E), benzenesulfonic acid modified silica cation exchanger (SA), poly (styrene-divinylbenzene (EN) and EN/RP18 SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C18-E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries>70% with standard deviations (SD)<15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′-DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd.

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.

Design and performance of a novel low-density parity-check code for distributed video coding

Low-density parity-check (LDPC) codes are nowadays one of the hottest topics in coding theory, notably due to their advantages in terms of bit error rate performance and low complexity. In order to exploit the potential of the Wyner-Ziv coding paradigm, practical distributed video coding (DVC) schemes should use powerful error correcting codes with near-capacity performance. In this paper, new ways to design LDPC codes for the DVC paradigm are proposed and studied. The new LDPC solutions rely on merging parity-check nodes, which corresponds to reduce the number of rows in the parity-check matrix. This allows to change gracefully the compression ratio of the source (DCT coefficient bitplane) according to the correlation between the original and the side information. The proposed LDPC codes reach a good performance for a wide range of source correlations and achieve a better RD performance when compared to the popular turbo codes.

Contributo para a construção de um code set da classificação internacional de funcionalidade, incapacidade e saúde, para terapeutas ocupacionais, em unidades de cuidados continuados integrados

A CIF é uma ferramenta universal desenvolvida pela OMS que permite a classificação de funcionalidade e incapacidade, através de uma visualização global do que condiciona o desempenho do indivíduo na concretização de atividades e na participação em ocupações. A ideologia da CIF e os seus componentes interrelacionam-se com a essência da TO, indo ao encontro dos modelos da profissão. As UCCI constituem uma atualidade em Portugal e o terapeuta ocupacional é um dos profissionais obrigatórios na equipa multidisciplinar destas unidades. Atendendo à relevância internacional da CIF, à sua ligação com a TO e à necessidade de tornar a CIF operacional na prática clínica diária dado que é uma ferramenta complexa e extensa, é objetivo deste estudo contribuir para a construção de um code set da CIF para terapeutas ocupacionais que exercem funções em UCCI, especificamente em UC, UMDR e ULDM. Para a concretização desta investigação, utilizou-se a técnica de Delphi, que envolveu duas rondas. Na primeira ronda foi possível contar com a participação de 37 terapeutas ocupacionais experientes na área, uma vez que exercem funções em UCCI, e na segunda ronda contou-se com a participação de 20 elementos. Obtiveram consenso na última ronda de Delphi um total de 96 categorias, constituindo esta listagem uma proposta de code set para UCCI. No que se refere às tipologias de unidades, 69 categorias obtiveram consenso em UC, 91 em UMDR e 41 em ULDM. Concluiu-se que a criação de code sets poderá constituir uma mais-valia em contexto de equipa multidisciplinar das UCCI, sendo uma forma de tornar a CIF operacional na prática clínica diária.

Logistic optimization in tourism networks

55th European Regional Science Association Congress, Lisbon, Portugal (25-28 August 2015).

Planeamento do consumo de energia eléctrica

O objectivo deste trabalho é optimizar o planeamento de produção tendo como meta a redução do custo total da energia eléctrica consumida. Este trabalho está dividido em 3 etapas distintas: na 1ª etapa foi feito um levantamento do problema, das restrições do mesmo e da escolha do modelo para a sua resolução. Na etapa seguinte, fez-se a escolha da ferramenta a usar, que foi o Xpress, e fez-se a implementação do problema nessa mesma ferramenta. E por fim, na 3ª etapa, foi feita a validação do modelo e análise das soluções obtidas com comparações com que o era feito antes. Recorrendo a programação inteira foi desenvolvido um modelo de optimização para atingir o objectivo em causa e consequentemente foi escrito o código que reflectisse o modelo matemático. Todos os passos necessários à sua implementação foram concluídos e validados com comparação com o que antes se fazia, notando-se assim melhorias ao nível de eficiência energética na ordem dos 8%, mas também uma melhoria no aproveitamento de recursos humanos e tempo que eram despendidos para desenvolver planos de produção de forma manual. Essa melhoria temporal que se compreende entre quatro a seis horas semanais pode ser aplicada noutras actividades da empresa com maior valor acrescentado.

Code offloading on real-time multimedia systems: a framework for handling code mobility and code offloading in a QoS aware environment

Actualmente, os smartphones e outros dispositivos móveis têm vindo a ser dotados com cada vez maior poder computacional, sendo capazes de executar um vasto conjunto de aplicações desde simples programas de para tirar notas até sofisticados programas de navegação. Porém, mesmo com a evolução do seu hardware, os actuais dispositivos móveis ainda não possuem as mesmas capacidades que os computadores de mesa ou portáteis. Uma possível solução para este problema é distribuir a aplicação, executando partes dela no dispositivo local e o resto em outros dispositivos ligados à rede. Adicionalmente, alguns tipos de aplicações como aplicações multimédia, jogos electrónicos ou aplicações de ambiente imersivos possuem requisitos em termos de Qualidade de Serviço, particularmente de tempo real. Ao longo desta tese é proposto um sistema de execução de código remota para sistemas distribuídos com restrições de tempo-real. A arquitectura proposta adapta-se a sistemas que necessitem de executar periodicamente e em paralelo mesmo conjunto de funções com garantias de tempo real, mesmo desconhecendo os tempos de execução das referidas funções. A plataforma proposta foi desenvolvida para sistemas móveis capazes de executar o Sistema Operativo Android.

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.

Sensing Cloud Optimization applied to a non-convex constrained economical dispatch

Conferência: 39th Annual Conference of the IEEE Industrial-Electronics-Society (IECON) - NOV 10-14, 2013

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.