956 resultados para metal-organic framework (MOF)


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Consumer awareness, pesticide and fertilizer contaminations and environmental concerns have resulted in significant demand for organically grown farm produce. Consumption of berries has become popular among health-conscious consumers due to the high levels of valuable antioxidants, such as anthocyanins and other phenolic compounds. The present study evaluated the influence that organic farming (OF) and integrated pest management (IPM) practise exert on the total phenolic content in 22 strawberry samples from four varieties. Postharvest performance of OF and IPM strawberries grown in the same area in the centre of Portugal and harvested at the same maturity stage were compared. Chemical profiles (phenolic compounds) were determined with the aid of HPLC-DAD/MS. Total phenolic content was higher for OF strawberry extracts. This study showed that the main differences in bioactive phytochemicals between organically and IPM grown strawberries concerned their anthocyanin levels. Organically grown strawberries were significantly higher in antioxidant activity than were the IPM strawberries, as measured by DPPH and FRAP assays.

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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.

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Metals are ubiquitous in the environment and accumulate in aquatic organisms and are known for their ability to enhance the production of reactive oxygen species (ROS). In aquatic species, oxidative stress mechanisms have been studied by measuring antioxidant enzyme activities and oxidative damages in tissues. The aim of this study was to apply and validate a set of oxidative stress biomarkers and correlate responses with metal contents in tissues of common octopus (Octopus vulgaris). Antioxidant enzyme activity (catalase — CAT, superoxide dismutase — SOD and glutathione S-transferases — GST), oxidative damages (lipid peroxidation — LPO and protein carbonyl content — PCO) andmetal content (Cu, Zn, Pb, Cd and As) in the digestive gland and armof octopus, collected in the NWPortuguese coast in different periods, were assessed after capture and after 14 days in captivity. CAT and SOD activitieswere highly responsive to fluctuations inmetal concentrations and able to reduce oxidative damage, LPO and PCO in the digestive gland. CAT activity was also positively correlated with SOD and GST activities, which emphasizes that the three enzymes respond in a coordinated way to metal induced oxidative stress. Our results validate the use of oxidative stress biomarkers to assess metal pollution effects in this ecological and commercial relevant species.Moreover, octopus seems to have the ability to control oxidative damage by triggering an antioxidant enzyme coordinated response in the digestive gland.

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Pesticides are among the most widely used chemicals in the world. Because of the widespread use of agricultural chemicals in food production, people are exposed to low levels of pesticide residues through their diets. Scientists do not yet have a total understanding of the health effects of these pesticide residues. This work aims to determine differences in terms of pesticide residue content in Portuguese strawberries grown using different agriculture practices. The Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method was conducted and shown to have good performance for multiclass pesticides extraction in strawberries. The screening of 25 pesticides residue was performed by gas chromatography–tandem mass spectrometry. In quantitative validation, acceptable performances were achieved with recoveries of 70–120 and <12 % residual standard deviation for 25 pesticides. Good linearity was obtained for all the target compounds, with highly satisfactory repeatability. The limits of detection were in the range of 0.1–28 μg/kg. The method was applied to analyze strawberry samples from organic and integrated pest management (IPM) practices harvested in 2009–2010. The results showed the presence of fludioxonil, bifenthrin, mepanipyrim, tolylfluanid, cyprodinil, tetraconazole, and malathion when using IPM below the maximum residue levels.

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The main objective of this study was to characterize the organic matter present in raw water and along the treatment process, as well as its seasonal variation. A natural organic matter fractionation approach has been applied to Lever water treatment plant located in Douro River, in Oporto (Portugal). The process used was based on the sorption of dissolved organic matter in different types of ion exchange resins, DAX-8, DAX-4 and IRA-958, allowing its separation into four fractions: very hydrophobic acids (VHA), slightly hydrophobic acids (SHA), charged hydrophilic (CHA) and hydrophilic neutral (NEU). The dissolved organic carbon (DOC) determination was used to quantify dissolved organic matter. Samples were collected monthly, during approximately one year, from raw water captured at the surface and under the bed of the river, and after each step of the treatment: pre-filtration in sand/anthracite filters, ozonation, coagulation/flocculation, counter current dissolved air flotation and filtration (CoCoDAFF) and chlorination. The NEU fraction showed a seasonal variation, with maximum values in autumn for the sampling points corresponding to raw water captured at the surface and under the bed of the river. It was usually the predominating fraction and did not show a significant decrease throughout the treatment. Nevertheless their low concentration, the same occurred for the CHA and VHA fractions. There was an overall decrease in the SHA fraction throughout the water treatment (especially after CoCoDAFF and ozonation) as well as in the DOC. The TSUVA254 values obtained for raw water generally varied between 2.0 and 4.0 L mgC-1 m-1 and between 0.75 and 1.78 L mgC-1 m-1 for treated water. It was observed a decrease of TSUVA values along the treatment, especially after ozonation. These results may contribute to a further optimization in the process of treating water for human consumption.

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PURPOSE: Screening programs to detect visual abnormalities in children vary among countries. The aim of this study is to describe experts' perception of best practice guidelines and competency framework for visual screening in children. METHODS: A qualitative focus group technique was applied during the Portuguese national orthoptic congress to obtain the perception of an expert panel of 5 orthoptists and 2 ophthalmologists with experience in visual screening for children (mean age 53.43 years, SD ± 9.40). The panel received in advance a script with the description of three tuning competencies dimensions (instrumental, systemic, and interpersonal) for visual screening. The session was recorded in video and audio. Qualitative data were analyzed using a categorical technique. RESULTS: According to experts' views, six tests (35.29%) have to be included in a visual screening: distance visual acuity test, cover test, bi-prism or 4/6(Δ) prism, fusion, ocular movements, and refraction. Screening should be performed according to the child age before and after 3 years of age (17.65%). The expert panel highlighted the influence of the professional experience in the application of a screening protocol (23.53%). They also showed concern about the false negatives control (23.53%). Instrumental competencies were the most cited (54.09%), followed by interpersonal (29.51%) and systemic (16.4%). CONCLUSIONS: Orthoptists should have professional experience before starting to apply a screening protocol. False negative results are a concern that has to be more thoroughly investigated. The proposed framework focuses on core competencies highlighted by the expert panel. Competencies programs could be important do develop better screening programs.

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PURPOSE: Fatty liver disease (FLD) is an increasing prevalent disease that can be reversed if detected early. Ultrasound is the safest and ubiquitous method for identifying FLD. Since expert sonographers are required to accurately interpret the liver ultrasound images, lack of the same will result in interobserver variability. For more objective interpretation, high accuracy, and quick second opinions, computer aided diagnostic (CAD) techniques may be exploited. The purpose of this work is to develop one such CAD technique for accurate classification of normal livers and abnormal livers affected by FLD. METHODS: In this paper, the authors present a CAD technique (called Symtosis) that uses a novel combination of significant features based on the texture, wavelet transform, and higher order spectra of the liver ultrasound images in various supervised learning-based classifiers in order to determine parameters that classify normal and FLD-affected abnormal livers. RESULTS: On evaluating the proposed technique on a database of 58 abnormal and 42 normal liver ultrasound images, the authors were able to achieve a high classification accuracy of 93.3% using the decision tree classifier. CONCLUSIONS: This high accuracy added to the completely automated classification procedure makes the authors' proposed technique highly suitable for clinical deployment and usage.

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Agricultural workers especially poultry farmers are at increased risk of occupational respiratory diseases. Epidemiological studies showed increased prevalence of respiratory symptoms and adverse changes in pulmonary function parameters in poultry workers. In poultry production volatile organic compounds (VOCs) presence can be due to some compounds produced by molds that are volatile and are released directly into the air. These are known as microbial volatile organic compounds (MVOCs). Because these compounds often have strong and/or unpleasant odors, they can be the source of odors associated with molds. MVOC's are products of the microorganisms primary and secondary metabolism and are composed of low molecular weight alcohols, aldehydes, amines, ketones, terpenes, aromatic and chlorinated hydrocarbons, and sulfur-based compounds, all of which are variations of carbon-based molecules.

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Dissertação de Mestrado em Ambiente, Saúde e Segurança.

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Some previous studies have suggested that some of the volatile organic compounds (VOCs) found in composting plants may have a toxic effect that can influence, besides surroundings populations, workers from the composting plants. Impact of waste management to the environment and workers is already recognised as an environment and occupational health concerns. Several studies regarding the VOCs and bioaerosols emissions from composting have been conducted all over Europe and also in Asia. However, in Portugal the studies developed are scarce and normally VOCs are not studied and recognized as a risk factor present in this occupational setting. Consudering this, a study was developed in a Portuguese composting plant aiming to clarify if there was VOCs presence in the workplaces.

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Hoje em dia, a prevenção dos resíduos de metais é uma questão muito importante para um grande número de empresas, pois necessitam optimizar o seu sistema de tratamento de águas residuais a fim de alcançarem os limites legais dos teores em iões metálicos e poderem efectuar a descarga das águas residuais no domínio hídrico público. Devido a esta problemática foram efectuados estudos inovadores relacionados com a remoção de iões metálicos de águas residuais, verificando-se que as tecnologias de membrana oferecem uma série de vantagens para o efeito. Uma dessas tecnologias, referida como Membrana Líquida de Suporte (SLM), é baseada num mecanismo de extracção. A membrana hidrofóbica, impregnada com uma solução extractora, funciona como barreira entre a água residual e uma solução, geralmente ácida. A diferença de pH entre a água residual e a solução actua como força motriz para o transporte de iões metálicos da água residual para a referida solução. Poderá ocorrer um problema de falta de estabilidade, resultante da possível fuga da solução extractora para fora dos poros das membranas. Estudos anteriores mostraram que os ácidos alquilfosfóricos ou ácidos fosfónicos, como os reagentes D2EHPA e CYANEX e hidroxioximas como o LIX 860-I podem ser muito úteis para a extração de iões metálicos como ferro, cobre, níquel, zinco e outros. A clássica extracção líquido-líquido também tem mostrado que a mistura de diferentes extractores pode ter um efeito sinergético. No entanto, não é claro que haja um efeito óptimo da razão de extractor ou que tipo de complexo é formado durante o processo de extracção. O objectivo deste projecto é investigar este comportamento sinergético e as complexas formações por meio de um método espectrofotométrico, o “Job’s method” e “Mole-ratio method”. Estes métodos são utilizados para estimar a estequiometria dos vários complexos entre dois solutos, a partir da variação de absorvância dos complexos quando comparado com a absorvância do soluto. Com este projecto, o Job’s method e mole-ratio method serão aplicados a um sistema de três componentes, para conseguir mais informações sobre a complexação de níquel (II) e a fim de determinar a razão extractor: metal dos complexos formados durante a aplicação de mistura de extractores D2EHPA e LIX 860-I. Segundo Job’s method a elavada absorvância situa-se na região de 0,015-0,040 M de LIX 860-I e uma baixa concentração de D2EHPA. Quando as diferentes experiências são encontradas num conjunto experimental foram avaliadas de acordo com o método de trabalho, o valor máximo do gráfico foi encontrado para uma baixa fração molar do ião metálico e uma maior concentração de D2EHPA. Esta mudança foi encontrado de 0,50 até 0,30, que poderia apontar para a direção da formação de diferentes complexos. Para o Mole-Ratio method, a estequiometria dos complexos metal pode ser determinada a partir do ponto de intersecção das linhas tangente do gráfico da absorbância versus a concentração do ligante. Em todos os casos, o máximo foi obtido em torno de uma concentração total de 0,010 M. Quando D2EHPA foi aplicado sozinho, absorvâncias muito baixos foram obtidas.

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Actualmente, os sistemas embebidos estão presentes em toda a parte. Embora grande parte da população que os utiliza não tenha a noção da sua presença, na realidade, se repentinamente estes sistemas deixassem de existir, a sociedade iria sentir a sua falta. A sua utilização massiva deve-se ao facto de estarem practicamente incorporados em quase os todos dispositivos electrónicos de consumo, telecomunicações, automação industrial e automóvel. Influenciada por este crescimento, a comunidade científica foi confrontada com novos problemas distribuídos por vários domínios científicos, dos quais são destacados a gestão da qualidade de serviço e gestão de recursos - domínio encarregue de resolver problemas relacionados com a alocação óptima de recursos físicos, tais como rede, memória e CPU. Existe na literatura um vasto conjunto de modelos que propõem soluções para vários problemas apresentados no contexto destes domínios científicos. No entanto, não é possível encontrar modelos que lidem com a gestão de recursos em ambientes de execução cooperativos e abertos com restrições temporais utilizando coligações entre diferentes nós, de forma a satisfazer os requisitos não funcionais das aplicações. Devido ao facto de estes sistemas serem dinâmicos por natureza, apresentam a característica de não ser possível conhecer, a priori, a quantidade de recursos necessários que uma aplicação irá requerer do sistema no qual irá ser executada. Este conhecimento só é adquirido aquando da execução da aplicação. De modo a garantir uma gestão eficiente dos recursos disponíveis, em sistemas que apresentam um grande dinamismo na execução de tarefas com e sem restrições temporais, é necessário garantir dois aspectos fundamentais. O primeiro está relacionado com a obtenção de garantias na execução de tarefas de tempo-real. Estas devem sempre ser executadas dentro da janela temporal requirida. O segundo aspecto refere a necessidade de garantir que todos os recursos necessários à execução das tarefas são fornecidos, com o objectivo de manter os níveis de performance quer das aplicações, quer do próprio sistema. Tendo em conta os dois aspectos acima mencionados, o projecto CooperatES foi especificado com o objectivo de permitir a dispositivos com poucos recursos uma execução colectiva de serviços com os seus vizinhos, de modo a cumprir com as complexas restrições de qualidade de serviço impostas pelos utilizadores ou pelas aplicações. Decorrendo no contexto do projecto CooperatES, o trabalho resultante desta tese tem como principal objectivo avaliar a practicabilidade dos conceitos principais propostos no âmbito do projecto. O trabalho em causa implicou a escolha e análise de uma plataforma, a análise de requisitos, a implementação e avaliação de uma framework que permite a execução cooperativa de aplicações e serviços que apresentem requisitos de qualidade de serviço. Do trabalho desenvolvido resultaram as seguintes contribuições: Análise das plataformas de código aberto que possam ser utilizadas na implementação dos conceitos relacionados com o projecto CooperatES; Critérios que influenciaram a escolha da plataforma Android e um estudo focado na análise da plataforma sob uma perspectiva de sistemas de tempo-real; Experiências na implementação dos conceitos do projecto na plataforma Android; Avaliação da practicabilidade dos conceitos propostos no projecto CooperatES; Proposta de extensões que permitam incorporar características de sistemas de tempo real abertos na plataforma Android.

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Grande parte dos triples-stores são open source e desenvolvidos em Java, disponibilizando interfaces standards e privadas de acesso. A grande maioria destes sistemas não dispõe de mecanismos de controlo de acessos nativos, o que dificulta ou impossibilita a sua adopção em ambientes em que a segurança dos factos é importante (e.g. ambiente empresarial). Complementarmente observa-se que o modelo de controlo de acesso a triplos e em particular a triplos descritos por ontologias não está standardizado nem sequer estabilizado, havendo diversos modelos de descrição e algoritmos de avaliação de permissões de acesso. O trabalho desenvolvido nesta tese/dissertação propõe um modelo e interface de controlo de acesso que permite e facilite a sua adopção por diferentes triple-stores já existentes e a integração dos triples-stores com outros sistemas já existentes na organização. Complementarmente, a plataforma de controlo de acesso não impõe qualquer modelo ou algoritmo de avaliação de permissões, mas pelo contrário permite a adopção de modelos e algoritmos distintos em função das necessidades ou desejos. Finalmente demonstra-se a aplicabilidade e validade do modelo e interface propostos, através da sua implementação e adopção ao triple-store SwiftOWLIM já existente, que não dispõe de mecanismo de controlo de acessos nativo.

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Electricity markets are complex environments with very particular characteristics. A critical issue regarding these specific characteristics concerns the constant changes they are subject to. This is a result of the electricity markets’ restructuring, which was performed so that the competitiveness could be increased, but it also had exponential implications in the increase of the complexity and unpredictability in those markets scope. The constant growth in markets unpredictability resulted in an amplified need for market intervenient entities in foreseeing market behaviour. The need for understanding the market mechanisms and how the involved players’ interaction affects the outcomes of the markets, contributed to the growth of usage of simulation tools. Multi-agent based software is particularly well fitted to analyze dynamic and adaptive systems with complex interactions among its constituents, such as electricity markets. This dissertation presents ALBidS – Adaptive Learning strategic Bidding System, a multiagent system created to provide decision support to market negotiating players. This system is integrated with the MASCEM electricity market simulator, so that its advantage in supporting a market player can be tested using cases based on real markets’ data. ALBidS considers several different methodologies based on very distinct approaches, to provide alternative suggestions of which are the best actions for the supported player to perform. The approach chosen as the players’ actual action is selected by the employment of reinforcement learning algorithms, which for each different situation, simulation circumstances and context, decides which proposed action is the one with higher possibility of achieving the most success. Some of the considered approaches are supported by a mechanism that creates profiles of competitor players. These profiles are built accordingly to their observed past actions and reactions when faced with specific situations, such as success and failure. The system’s context awareness and simulation circumstances analysis, both in terms of results performance and execution time adaptation, are complementary mechanisms, which endow ALBidS with further adaptation and learning capabilities.

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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.