IPSS: novas tarefas, mais poderes?

Dissertação de mestrado em Direito Administrativo

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Brazil's global aspirations and their implications for the relationship with Argentina in the framework of MERCOSUR

Dissertação de mestrado em Relações Internacionais

An innovative framework for probabilistic-based structural assessment with an application to existing reinforced concrete structures

A novel framework for probabilistic-based structural assessment of existing structures, which combines model identification and reliability assessment procedures, considering in an objective way different sources of uncertainty, is presented in this paper. A short description of structural assessment applications, provided in literature, is initially given. Then, the developed model identification procedure, supported in a robust optimization algorithm, is presented. Special attention is given to both experimental and numerical errors, to be considered in this algorithm convergence criterion. An updated numerical model is obtained from this process. The reliability assessment procedure, which considers a probabilistic model for the structure in analysis, is then introduced, incorporating the results of the model identification procedure. The developed model is then updated, as new data is acquired, through a Bayesian inference algorithm, explicitly addressing statistical uncertainty. Finally, the developed framework is validated with a set of reinforced concrete beams, which were loaded up to failure in laboratory.

Politically driven cycles in fiscal policy: in depth analysis of the functional components of government expenditures

NIPE - WP 02/2016

Caso de demonstração de uma framework para automatização do teste de APIs de aplicações SaaS

Dissertação de mestrado integrado em Engenharia e Gestão de Sistemas de Informação

Fluorescence-based approaches towards the assessment of structural and functional alterations in lysosomes and vacuoles induced by lactoferrin and acetic acid

Dissertação de mestrado em Biofísica e Bionanossistemas

Unnatural amino acids as functional building blocks for fluorophore-labelled peptides

Comunicação oral convidada - IL4

Thin films composed of Ag nanoclusters dispersed in TiO2: Influence of composition and thermal annealing on the microstructure and physical responses

Noble metal powders containing gold and silver have been used for many centuries, providing different colours in the windows of the medieval cathedrals and in ancient Roman glasses. Nowadays, the interest in nanocomposite materials containing noble nanoparticles embedded in dielectric matrices is related with their potential use for a wide range of advanced technological applications. They have been proposed for environmental and biological sensing, tailoring colour of functional coatings, or for surface enhanced Raman spectroscopy. Most of these applications rely on the so-called localised surface plasmon resonance absorption, which is governed by the type of the noble metal nanoparticles, their distribution, size and shape and as well as of the dielectric characteristics of the host matrix. The aim of this work is to study the influence of the composition and thermal annealing on the morphological and structural changes of thin films composed of Ag metal clusters embedded in a dielectric TiO2 matrix. Since changes in size, shape and distribution of the clusters are fundamental parameters for tailoring the properties of plasmonic materials, a set of films with different Ag concentrations was prepared. The optical properties and the thermal behaviour of the films were correlated with the structural and morphological changes promoted by annealing. The films were deposited by DC magnetron sputtering and in order to promote the clustering of the Ag nanoparticles the as-deposited samples were subjected to an in-air annealing protocol. It was demonstrated that the clustering of metallic Ag affects the optical response spectrum and the thermal behaviour of the films.

Light responsive multilayer surfaces with controlled spatial extinction capability

Multilayer systems obtained using the Layer-by-Layer (LbL) technology have been proposed for a variety of biomedical applications in tissue engineering and regenerative medicine. LbL assembly is a simple and highly versatile method to modify surfaces and fabricate robust and highly-ordered nanostructured coatings over almost any type of substrates and with a wide range of substances. The incorporation of polyoxometalate (POM) inorganic salts as constituents of the layers presents a possibility of promoting light-stimuli responses in LbL substrates. We propose the design of a biocompatible photo-responsive multilayer system based on a Preyssler-type POM ([NaP5W30O110]14â ) and a natural origin polymer, chitosan, using the LbL methodology. The photo-reduction properties of the POM allow the spatially controlled disruption of the assembled layers due to the weakening of the electrostatic interactions between the layers. This system has found applicability in detaching devices, such as the cell sheet technology, which may solve the drawbacks actually found in other cell treatment proposals.

Optimal behavior of responsive residential demand considering hybrid phase change materials

Due to communication and technology developments, residential consumers are enabled to participate in Demand Response Programs (DRPs), control their consumption and decrease their cost by using Household Energy Management (HEM) systems. On the other hand, capability of energy storage systems to improve the energy efficiency causes that employing Phase Change Materials (PCM) as thermal storage systems to be widely addressed in the building applications. In this paper, an operational model of HEM system considering the incorporation of more than one type of PCM in plastering mortars (hybrid PCM) is proposed not only to minimize the customerâ s cost in different DRPs but also to guaranty the habitantsâ  satisfaction. Moreover, the proposed model ensures the technical and economic limits of batteries and electrical appliances. Different case studies indicate that implementation of hybrid PCM in the buildings can meaningfully affect the operational pattern of HEM systems in different DRPs. The results reveal that the customerâ s electricity cost can be reduced up to 48% by utilizing the proposed model.

Para uma pedagogia das literacias: das conceções e práticas docentes aos conceitos e competências discentes. Um estudo da aula de língua portuguesa no 2º ciclo do ensino básico

Tese de Doutoramento em Ciências da Educação (Especialidade em Literacias e Ensino do Português)

Layer-by-layer technique to developing functional nanolaminate films with antifungal activity

The layer-by-layer (LbL) deposition method was used to build up alternating layers (five) of different polyelectrolyte solutions (alginate, zein-carvacrol nanocapsules, chitosan and chitosan-carvacrol emulsions) on an aminolysed/charged polyethylene terephthalate (A/C PET) film. These nanolaminated films were characterised by contact angle measurements and through the determination of water vapour (WVTR) and oxygen (O2TR) transmission rates. The effect of active nanolaminated films against the Alternaria sp. and Rhizopus stolonifer was also evaluated. This procedure allowed developing optically transparent nanolaminated films with tuneable water vapour and gas properties and antifungal activity. The water and oxygen transmission rate values for the multilayer films were lower than those previously reported for the neat alginate or chitosan films. The presence of carvacrol and zein nanocapsules significantly decreased the water transmission rate (up to 40 %) of the nanolaminated films. However, the O2TR behaved differently and was only improved (up to 45 %) when carvacrol was encapsulated, i.e. nanolaminated films prepared by alternating alginate with nanocapsules of zein-carvacrol layers showed better oxygen barrier properties than those prepared as an emulsion of chitosan and carvacrol. These films containing zein-carvacrol nanocapsules also showed the highest antifungal activity (30 %), which did not significantly differ from those obtained with the highest amount of carvacrol, probably due to the controlled release of the active agent (carvacrol) from the zein-carvacrol nanocapsules. Thus, this work shows that nanolaminated films prepared with alternating layers of alginate and zein-carvacrol nanocapsules can be considered to improve the shelf-life of foodstuffs.

Abordagem histórica e institucional da mudança em contabilidade de gestão: o caso da normalização nos hospitais públicos portugueses

A teoria institucional constituiu o enquadramento no qual foi suportada a pergunta geral desta investigação: como e porquê a Normalização da Contabilidade de Gestão (NCG) nos hospitais públicos portugueses surgiu e evoluiu? O objetivo geral foi compreender de forma profunda o surgimento e a mudança nas regras de NCG dos hospitais públicos portugueses no período histórico 1954-2011. Face ao enquadramento institucional que justificou uma investigação interpretativa, foi usado como método de investigação um estudo de caso explanatório. A evidência sobre o caso da NCG nos hospitais públicos portugueses foi recolhida em documentos e através de 58 entrevistas realizadas em 47 unidades de análise (nos serviços centrais de contabilidade do Ministério da Saúde e em 46 hospitais públicos, num total de 53 existentes). Quanto aos principais resultados obtidos, no período 1954-1974, as regras criadas pelo poder político para controlo dos gastos públicos e a contabilidade orçamental de base de caixa estiveram na génese dos primeiros conceitos de Contabilidade de Gestão (CG) para os serviços públicos de saúde portugueses. A transição de um regime ditatorial para um regime democrático (25 de Abril de 1974), a criação do Plano Oficial de Contabilidade (POC/77) e a implementação de um estado social com Serviço Nacional de Saúde (SNS) criaram a conjuntura crítica necessária para o surgimento de um Plano Oficial de Contabilidade para os Serviços de Saúde (POCSS/80) que incluiu regras de CG. A primeira edição do Plano de Contabilidade Analítica dos Hospitais (PCAH), aprovada em 1996, não foi uma construção de raiz, mas antes uma adaptação para os hospitais das regras de CG incluídas no POCSS/91 que havia revisto o POCSS/80. Após o início da implementação do PCAH, em 1998, ocorreram sequências de autorreforço institucionalizadoras destas normas, no período 1998-2011, por influência de pressões isomórficas coercivas que delinearam um processo de evolução incremental cujo resultado foi uma reprodução por adaptação, num contexto de dependência de recursos. Vários agentes internos e externos pressionaram, no período 2003-2011, através de sequências reativas para a desinstitucionalização do PCAH em resposta ao persistente fenómeno de loose coupling. Mas o PCAH só foi descontinuado nos hospitais com privatização da governação e rejeição dos anteriores sistemas de informação. Ao nível da extensão da teoria, este estudo de caso adotou o institucionalismo histórico na investigação em CG, quanto se sabe pela primeira vez, que se mostra útil na interpretação dos processos e dos resultados da criação e evolução de instituições de CG num determinado contexto histórico. Na condição de dependência de recursos, as sequências de autorreforço, via isomorfismo coercivo, tendem para uma institucionalização com fenómeno de loose coupling. Como resposta a este fenómeno, ocorrem sequências reativas no sentido da desinstitucionalização. Perante as pressões (políticas, funcionais, sociais e tecnológicas) desinstitucionalizadoras, o fator governação privada acelera o processo de desinstitucionalização, enquanto o fator governação pública impede ou abranda esse processo.

Pervasive business intelligence: a marketing intelligence framework proposal

Doctoral Thesis in Information Systems and Technologies Area of Information Systems and Technology