18 resultados para Crack-bridging
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Proceedings of the First International Conference on Coastal Conservation and Management in the Atlantic and Mediterranean, p. 193-200
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Dissertação apresentada para obtenção do Grau de Doutor em Ciências do Ambiente, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia
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Based on the report for the “Project III” unit of the PhD programme on Technology Assessment under the supervision of Prof. António B. Moniz. This report was discussed also at the 2nd Winter School on Technology Assessment held at Universidade Nova de Lisboa, Caparica Campus, Portugal on December 2011.
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Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the í2Ssulfide, í3Ssulfide, and Sthiolate ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe3+ and Fe2.5+ components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm-1 vs -360 cm-1, respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter ì2/k-, leads to an S ) 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe3+ center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.
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Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica
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Dissertation presented to obtain the PhD degree in Biochemistry
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Dissertation presented to obtain the Ph.D degree in Biology
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J. Am. Chem. Soc., 2003, 125 (51), pp 15708–15709 DOI: 10.1021/ja038344n
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RESUMO:As terapias biológicas revolucionaram o tratamento das doenças autoimunes nos últimos anos. Tipicamente têm como alvos mediadores importantes no mecanismo das doenças. Os antagonistas do fator de necrose tumoral-α (TNF-α) são um grupo de agentes biológicos muito prescrito, pois estão indicados no tratamento de doenças imuno-mediadas comuns, tais como artrite reumatoide, artrite idiopática juvenil, artrite psoriática, espondilite anquilosante, doença de Crohn e colite ulcerosa. Com o uso frequente de inibidores do TNF-α, tem-se tornado evidente que estes agentes têm um potencial imunogénico importante, que pode comprometer o prognóstico a longo prazo dos doentes cronicamente tratados. A produção de anticorpos anti-fármaco parece causar falência terapêutica secundária em muitos doentes. Um dos efeitos dos anticorpos anti-fármaco é o aumento da eliminação do fármaco. A eliminação do fármaco, por sua vez, varia entre indivíduos, refletindo diferentes perfis farmacocinéticos. A determinação dos níveis séricos mínimos do agente anti-TNF-α é assim muito informativa e pode auxiliar nas decisões terapêuticas. Contudo, os testes imunológicos para determinar as concentrações séricas do fármaco não estão facilmente disponíveis na prática clínica. De forma a investigar uma nova técnica potencialmente fidedigna e prática para a deteção e quantificação dos agentes biológicos anti-TNF-α, foi testada a técnica por HTRF (homogeneous time-resolved fluorescence resonance energy transfer) para a determinação de concentrações séricas de infliximab. Apesar de apresentar algumas limitações relacionadas com as condições de leitura da fluorescência, esta técnica provou obter resultados próximos das concentrações obtidas por ELISA (enzyme-linked immunosorbent assay) bridging. Adicionalmente, tem a vantagem de ser de execução muito mais fácil e rápida. Deste modo, a técnica por HTRF poderá ser otimizada e tornar-se uma valiosa ferramenta laboratorial para orientar as decisões terapêuticas em doentes autoimunes com falência da terapêutica anti-TNF-α.--------- ABSTRACT: Biologic therapies revolutionized the treatment of autoimmune diseases in the last years. Typically, they target important disease mediators. Tumor necrosis factor-alpha (TNF-α) antagonists constitute a very prescribed group of biologic agents as they are indicated for the treatment of common immune-mediated diseases, such as rheumatoid arthritis, juvenile idiopathic arthritis, psoriatic arthritis, ankylosing spondylitis, Crohn’s disease and ulcerative colitis. With the increasing use of TNF-α inhibitors it has been noticed that they have an important immunogenic potential that can compromise long-term outcomes in chronically treated patients. The production of anti-drug antibodies seems to cause secondary therapeutic failure in many patients. One of the effects of anti-drug antibodies is the enhancement of drug clearance. Drug clearance, in turn, varies among individuals, reflecting different pharmacokinetic profiles. Determination of serum anti-TNF-α drug trough levels is though very informative and could support treatment decisions. However, immunologic assays to determine drug serum concentrations are not readily available in clinical practice. In order to investigate a potentially reliable and practical new technique for detection and quantification of anti-TNF-α biologic agents, homogeneous time-resolved fluorescence resonance energy transfer (HTRF) technique was tested for determination of serum infliximab concentrations. Although presenting some limitations related with fluorescence reading conditions, this technique proved to give results close to the concentrations obtained by the widely used bridging enzyme-linked immunosorbent assay (ELISA). In addition, it has the advantage of being much easier and faster to perform. Thus, HTRF technique can be optimized and become a valuable laboratorial tool to guide treatment decisions in autoimmune patients with anti-TNF-α therapy failure.
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Dissertação para obtenção do Grau de Mestre em Engenharia Electrotécnica e de Computadores
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ABSTRACT - Background: Integration of health care services is emerging as a central challenge of health care delivery, particularly for patients with elderly and complex chronic conditions. In 2003, the World Health Organization (WHO) already began to identify it as one of the key pathways to improve primary care. In 2005, the European Commission declared integrated care as vital for the sustainability of social protection systems in Europe. Nowadays, it is recognized as a core component of health and social care reforms across European countries. Implementing integrated care requires coordination between settings, organizations, providers and professionals. In order to address the challenge of integration in such complex scenario, an effective workforce is required capable of working across interdependent settings. The World Health Report 2006 noted that governments should prepare their workforce and explore what tasks the different levels of health workers are trained to do and are capable of performing (skills mix). Comparatively to other European countries, Portugal is at an early stage in what integrated care is concerned facing a growing elderly population and the subsequent increase in the pressure on institutions and professionals to provide social and medical care in the most cost-effective way. In 2006 the Portuguese government created the Portuguese Network for Integrated Care Development (PNICD) to solve the existing long-term gap in social support and healthcare. On what concerns health workforce, the Portuguese government already recognized the importance of redefine careers keeping professional motivation and satisfaction. Aim of the study: This study aims to contribute new evidence to the debate surrounding integrated care and skills mix policies in Europe. It also seeks to provide the first evidence that incorporates both the current dynamics of implementing integrated care in Portugal and the developments of international literature. The first ambition of our study is to contribute to the growing interest in integrated care and to the ongoing research in this area by identifying its different approaches and retrieve a number of experiences in some European countries. Our second goal of this research is to produce an update on the knowledge developed on skills mix to the international healthcare management community and to policy makers involved in reforming healthcare systems and organizations. To better inform Portuguese health policies makers in a third stage we explore the current dynamics of implementing integrated care in Portugal and contextualize them with the developments reported in the international literature. Methodology: This is essentially an exploratory and descriptive study using qualitative methodology. In order to identify integrated care approaches in Europe, a systematic literature review was undertaken which resulted in a paper published in the Journal of Management and Marketing in Health care titled: Approaches to developing integrated care in Europe: a systematic literature review. This article was recommended and included into a list of references identified by The King's Fund Library. A second systematic literature review was undertaken which resulted in a paper published in the International Journal of Healthcare Management titled: Skills mix in healthcare: An international update for the management debate. Semi-structured interviews were performed on experts representing the regional coordination teams of the Portuguese Network for Integrated Care Development. In a last stage a questionnaire survey was developed based on the findings of both systematic literature reviews and semi-structured interviews. Conclusions: Even though integrated care is a worldwide trend in health care reforms, there is no unique definition. Definitions can be grouped according to their sectorial focus: community-based care, combined health and social care, combined acute and primary care, the integration of providers, and in a more comprehensive approach the whole health system. Indeed, models that seek to apply the principles of integrated care have a similar background and are continually evolving and depend on the different initiatives taken at national level. . Despite the fact that we cannot argue that there is one single set typology of models for integrated care, it is possible to identify and categorize some of the basic approaches that have been taken in attempts to implement integrated care according to: changes in organizational structure, workforce reconfiguring, and changes in the financing system. The systematic literature review on skills mix showed that despite the widely acknowledged interest on skills mix initiatives there is a lack of evidence on skills mix implications, constraints, outcomes, and quality impact that would allow policy makers to take sustained and evidence-based decisions. Within the Portuguese health system, the integrated care approach is rather organizational and financial, whereas little attention is given to workforce integration. On what concerns workforce planning Portugal it is still in the stage of analyzing the acceptability of health workforce skills mix. In line with the international approaches, integration of health and social services and bridging primary and acute care are the main goals of the national government strategy. The findings from our interviews clarify perceptions which show no discrepancy with the related literature but are rather scarce comparing to international experience. Informants hold a realistic but narrow view of integrated care related issues. They seem to be limited to the regional context, requiring a more comprehensive perspective. The questionnaire developed in this thesis is an instrument which, when applied, will allow policy makers to understand the basic set of concepts and managerial motivations behind national and regional integrated care programs. The instrument developed can foster evidence on the three essential components of integrated care policies: organizational, financial, and human resources development, and can give additional input on the context in which integrated care is being developed, the type of providers and organizations involved, barriers and constraints, and the workforce skills mix planning related strategies. The thesis was successful in recognizing differences between countries and interventions and the instrument developed will allow a better comprehension of the international options available and how to address the vital components of integrated care programs.
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This paper studies strategies to attract students from outside Europe to European preexperience masters. We characterize the value added by such masters through interviews with key players at the universities and multinational recruiting corporations. We considered a strategy for segmenting international students in the US and extended it to the European market. We have analyzed data from international applications to Nova SBE as a proxy for applications in European institutions. Based on that analysis we conclude with recommendations to attract suitable candidates from outside Europe. In particular we also provided three different solutions to attract students from the southern hemisphere: we conclude that European institutions should (a) increase the spring semester intake, (b) provide bridging courses for some students, or (c) could place some accepted candidates in internships before starting classes.
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Emigration has been a very present word in Portugal. Due to the effects of the Economic Crisis and the Memorandum of Understanding policies, we have witnessed a significant yearly migration outflow of people searching for better conditions. This study aims to measure the factors affecting this flow as well as how much the probability of emigrating has evolved during the years bridging 2006 to 2012. I shall consider the decision of emigrating as Discrete Choice Random Utility maximization use a conditional Logit framework to model the probability choice for 31 OECD countries of destination. Moreover I will ascertain the compensating variation required such that the probability of choice in 2012 is adjusted back to 2007 values, keeping all other variables constant. I replicate this exercise using the unemployment rate instead of income. The most likely country of destination is Luxembourg throughout the years analyzed and the values obtained for the CV is of circa 1.700€ in terms of Income per capita and -11% in terms of the unemployment rate adjustment.
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Linear logic has long been heralded for its potential of providing a logical basis for concurrency. While over the years many research attempts were made in this regard, a Curry-Howard correspondence between linear logic and concurrent computation was only found recently, bridging the proof theory of linear logic and session-typed process calculus. Building upon this work, we have developed a theory of intuitionistic linear logic as a logical foundation for session-based concurrent computation, exploring several concurrency related phenomena such as value-dependent session types and polymorphic sessions within our logical framework in an arguably clean and elegant way, establishing with relative ease strong typing guarantees due to the logical basis, which ensure the fundamental properties of type preservation and global progress, entailing the absence of deadlocks in communication. We develop a general purpose concurrent programming language based on the logical interpretation, combining functional programming with a concurrent, session-based process layer through the form of a contextual monad, preserving our strong typing guarantees of type preservation and deadlock-freedom in the presence of general recursion and higher-order process communication. We introduce a notion of linear logical relations for session typed concurrent processes, developing an arguably uniform technique for reasoning about sophisticated properties of session-based concurrent computation such as termination or equivalence based on our logical approach, further supporting our goal of establishing intuitionistic linear logic as a logical foundation for sessionbased concurrency.
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Esta dissertação apresenta os resultados de um conjunto de ensaios sobre lajes fungiformes, armadas com um novo sistema de armaduras de punçoamento. Adicionalmente, também foram testadas lajes fungiformes com um novo sistema de armaduras horizontais. O sistema de armaduras de punçoamento consiste em estribos de ramos verticais produzidos a partir de malhas de varões eletrossoldados, ancorados na armadura longitudinal superior por um varão transversal eletrossoldado. As vantagens deste sistema são a simplicidade, a rapidez de instalação e o baixo custo. O sistema de armaduras horizontais é formado por um conjunto de malhas de varões eletrossoldados sobrepostas em camadas. Foram ensaiadas cinco lajes quadradas, com dimensões em planta de 1650 x 1650 mm e 150 mm de espessura. Os resultados experimentais mostraram que a capacidade resistente das lajes armadas com armaduras específicas pode aumentar até 72%, quando comparadas com lajes sem armaduras de punçoamento. Quanto à capacidade de rotação da laje, o aumento foi ainda mais significativo. A capacidade de deformação da laje com maior quantidade de armaduras de punçoamento aumentou três vezes, quando comparada com a laje de referência. No respeitante às armaduras horizontais, os resultados obtidos demonstram que este sistema pode contribuir para o aumento da capacidade resistente pós-colapso da laje. Os resultados experimentais foram comparados com as estimativas segundo algumas normas de dimensionamento atuais e a Critical Shear Crack Theory. Em lajes com grande quantidade de armaduras de punçoamento o EC2 pode sobrestimar a resistência ao punçoamento quando a rotura ocorre por esmagamento do betão junto do pilar, ou quando a rotura ocorre pelo exterior da zona com armaduras de punçoamento. Os resultados mostraram que o MC2010 subestima significativamente a resistência ao punçoamento com rotura no interior da zona com armaduras de punçoamento.