Comunidades de prática online: contributos para a prática letiva: um estudo de caso no âmbito da educação em ciência envolvendo professores e investigadores

As comunidades de prática (CoP), bem como a investigação-ação, têm vindo a ser apontadas na literatura como formas de promover o desenvolvimento profissional de professores, potenciando a melhoria das suas práticas letivas. Contudo, as evidências empíricas relativas às práticas letivas desenvolvidas por professores no âmbito dessas configurações sociais são escassas. Neste estudo procura-se contribuir para colmatar essa lacuna ao analisar uma CoP online, que envolveu professores de ciências e investigadores em Educação em Ciência (EC) e se constituiu no âmbito do projeto “Investigação e práticas lectivas em Educação em Ciência: Dinâmicas de interacção” (IPEC), com enfoques distintos, a que se alude abaixo. A investigação realizada envolveu uma metodologia de natureza predominantemente qualitativa, descritiva, exploratória e do tipo estudo de caso único, sendo o caso as práticas letivas desenvolvidas pelos membros da CoP referida e as dinâmicas de interação entre os mesmos. Como técnicas de recolha de dados, recorreu-se principalmente à observação mediada pela plataforma online de apoio ao desenvolvimento do projeto (dados estatísticos e as mensagens registadas automaticamente) e recolha de documentos. Quanto às técnicas de análise de dados, optou-se principalmente pela análise de conteúdo e análise documental interna, tendo-se triangulado dados de diferentes fontes. Com base no Interconnected Model of Teacher Professional Growth, que Clarke e Hollingsworth propuseram em 2002, e em instrumentos de análise resultantes da revisão de literatura, adaptados aos enfoques definidos, a análise da CoP selecionada incidiu sobre: a) os domínios externo e das práticas de desenvolvimento curricular (DC), ou seja, as suas dinâmicas de interação durante dois anos letivos; b) o domínio das consequências nas práticas letivas, no que concerne às estratégias de ensino de ciências desenvolvidas; c) a evidências do seu carater inovador; e d) aos princípios de DC operacionalizados através do módulo curricular desenhado, implementado, avaliado e disseminado pelos membros da CoP. Os resultados indicam que a) a participação dos membros variou ao longo do período de interação e que a sua dinâmica se enquadra numa adaptação das fases de desenvolvimento de CoP proposta por Wenger e colegas em 2002, com dois ciclos de investigação-ação; b) a CoP desenvolveu estratégias de ensino diversificadas, pouco exploradas por professores e coerentes com diversas recomendações da literatura, de forma consistente; c) as práticas letivas são inovadoras, do tipo challenging, tendo incluído o envolvimento de professores que lecionavam nas escolas dos professores membros da CoP; e d) a CoP operacionalizou vários princípios de DC recomendados na literatura, nomeadamente a flexibilidade e diferenciação. Os resultados empíricos permitiram ainda validar as dimensões do modelo de Clarke e Hollingsworth, assim como adaptar à especificidade do caso analisado.Pelo acima referido, embora reconhecendo as limitações do estudo, nomeadamente relativas às opções metodológicas efetuadas, foi possível inferir que o trabalho realizado no seio desta CoP online de professores e investigadores contribuiu para a inovação e melhoria de práticas letivas de EC. Do estudo resultam ainda instrumentos de análise que se consideram relevantes, dado poderem vir a ser usados em investigações futuras, assim como poderem vir a orientar professores de ciências que desejem alinhar as suas práticas de ensino com recomendações da investigação em EC. Por fim, são apresentadas recomendações relativamente ao envolvimento de professores e investigadores em CoP online, no âmbito da EC, assim como relativamente a possibilidades ao nível de investigações futuras, nomeadamente a validação dos instrumentos e das recomendações apresentadas em contextos mais abrangentes e transversais.

Escrever para aprender: estratégias, textos e práticas

Partindo da importância de que se reveste a escrita para construção e explicitação do conhecimento, e da necessidade de os professores fazerem uma mediação da aprendizagem desta vertente da escrita, procurámos analisar e perceber de que modo as práticas de escrita que os professores implementam influenciam a qualidade dos textos que os alunos produzem. No sentido de dar resposta à questão enunciada, definimos um objetivo geral: avaliar se um dispositivo didático, o MDG, construído com base no conhecimento das propriedades dos géneros e dos textos, implementado de forma explícita e intencional pelos professores, pode refletir-se, e a que níveis, na qualidade dos textos que os alunos produzem. O estudo foi realizado no contexto de um programa de formação que envolveu 14 professores dos três ciclos do ensino básico, para o qual definimos três fases distintas: (i) caracterização das práticas de escrita dos professores dos três ciclos do ensino básico antes da planificação do MDG; ii) caracterização das práticas de escrita dos alunos de uma turma do 4.º ano de escolaridade antes da implementação do MDG, e (iii) avaliação das práticas de escrita dos alunos depois de implementado o MDG pelos professores. Os dados foram recolhidos através da análise qualitativa e quantitativa das planificações dos professores e dos textos dos alunos. Os resultados evidenciam que nas fases prévias à implementação do MDG há a ausência de critérios específicos de avaliação dos textos e a utilização de instruções de escrita demasiado vagas, pouco orientadoras da produção do texto do género por parte dos alunos. Por sua vez, estes revelaram dificuldades quer na seleção de informação, ao nível da escolha dos conteúdos pertinentes, quer na produção do género pedido, já que o texto final configura uma colagem de partes de textos lidos, sem qualquer configuração adaptada ao género. Já na fase 3, e depois de planificado e implementado o MDG, os alunos demonstraram um melhor desempenho na seleção de informação e na escrita do texto. No entanto, foi também possível identificar alguns aspetos em que não apresentaram mudança ou que essa mudança não foi significativa.

Identificação de utilizadores seniores em televisão interativa (iTV) : uma matriz de decisão tecnológica

Desde que surgiu há mais de 50 anos, a televisão sofreu muitas transformações, tanto ao nível tecnológico (por exemplo com a passagem da emissão a preto/branco para cor, o som analógico para digital, a difusão digital) como a nível da sua influência nas sociedades. Entre outros fatores de ordem tecnológica, a consolidação da Internet com o seu elevado nível de personalização, da experiência de utilização, e a sua enorme quantidade de conteúdos disponíveis, catapultou a televisão no sentido de esta se tornar mais interativa. Assim, o telespectador passou a poder usufruir de uma experiência televisiva que pode, por um lado, ser mais participativa, sendo-lhe possível, por exemplo, alvitrar sobre a qualidade de um programa enquanto assiste à sua exibição, e, por outro, ser mais personalizada, possibilitando-lhe, por exemplo, receber conteúdos automaticamente adequados ao seu perfil e contexto. No entanto, esta experiência mais participativa e personalizável carece de uma identificação, idealmente automática e não intrusiva, de quem pode beneficiar da mesma – o telespectador. Contudo, e apesar de significativos avanços na área da televisão interativa, tanto ao nível da infraestrutura de suporte como ao nível dos serviços disponibilizados, a identificação dos utilizadores é, ainda, uma área de estudo com muitos aspetos por compreender. Os seniores, em particular, são grandes consumidores de televisão e representam uma fatia muito considerável das pessoas que podem beneficiar das potencialidades disponibilizadas pela interatividade presente em muitos serviços atuais. Um número crescente destes serviços são desenhados com o objetivo de promoverem um envelhecimento ativo e um concreto apoio à vida, pelo que os seniores podem beneficiar, em vários aspetos do seu quotidiano, se os utilizarem. Nesta faixa etária, a identificação de utilizadores tem, como elemento potenciador da experiência de utilização, um papel especialmente importante ao nível de um aproveitamento personalizado e dirigido destes serviços. No entanto, atendendo às diferentes combinações de características físicas, sensoriais, cognitivas e, mesmo, de literacia digital que tipificam os seniores, perspetivou-se existir uma dependência do perfil do utilizador na seleção do método de identificação mais adequado, os quais podem ser baseados, por exemplo, num leitor de impressões digitais, instalado no telecomando; na leitura de uma wearable tag ou de um cartão RFiD; no reconhecimento da face e, eventualmente, na voz do utilizador. Assim, a inerente investigação desenrolou-se em várias fases, no sentido de permitir alicerçar a construção de uma matriz de decisão tecnológica que, em função do perfil de utilizador, selecione o sistema de identificação mais adequado. O procedimento metodológico inerente à construção desta matriz de decisão, passou por um longo processo envolvendo utilizadores reais, que se iniciou com a realização de entrevistas exploratórias com o objetivo de permitir conhecer melhor os seniores e a forma como estes encaram a tecnologia e, mais concretamente, a televisão interativa. Foi depois implementado um protótipo de alta-fidelidade, completamente funcional, para a realização de testes com o objetivo de perceber qual a preferência relativamente a um subconjunto de tecnologias de identificação. Estes testes, uma vez que não permitiram testar todas as tecnologias em estudo, revelaram-se inconclusivos, porém permitiram reforçar a necessidade de identificar e caracterizar os referidos aspetos do perfil do utilizador que podem interferir na sua preferência relativamente ao sistema de identificação. As características identificadas constituíram-se como os parâmetros de entrada da matriz, sendo que para preencher as respetivas células realizaramse testes de aceitação, com um conjunto de seniores, tendo por base um protótipo, wizard of oz, especificamente implementado para permitir experienciar todas as tecnologias em estudo. Estes testes foram precedidos pela avaliação das capacidades funcionais dos participantes, nos diversos parâmetros definidos. Este texto relata, assim, todo o processo de investigação que foi conduzido, terminando com uma descrição de exemplos de utilização da matriz de decisão implementada e com a identificação de potenciais caminhos de desenvolvimento deste trabalho.

Participação ativa no desenvolvimento de comunidades online

Esta tese tem como objetivos identificar e caraterizar os modos de Comunicação Mediada por Computador (CMC) utilizados nas Comunidades Online (CO), relevantes para a prática de criação visual, contextualizando-os na produção de Type Design (TD). E concetualizar um modelo de CO de prática, desenvolvida segundo uma metodologia participativa, avaliando as estratégias de dinamização e viabilização no contexto nacional. Atualmente, com a disseminação das tecnologias de informação e comunicação a prática de TD, uma atividade isolada e individual, está sujeita a um paradigma de mudança—tornar-se uma atividade de partilha cada vez maior. A investigação dividiu-se em três fases. Na primeira fase procura perceber os modos relevantes de CMC para a prática de TD. Para isso, observa-se as motivações e comportamentos dos utilizadores nestas plataformas, apoiado pela recolha de dados sobre o uso destas plataformas no contexto académico. Juntamente com o desenvolvimento e avaliação de uma experiência preliminar numa plataforma online existente. Na segunda fase, apresenta-se o modelo concetual de uma CO para a produção de TD apoiado na identificação e caraterização das Virtual Community of Practice de TD existentes. E o respetivo desenvolvimento e implementação de um protótipo funcional. Na terceira fase o protótipo foi avaliado recorrendo à participação dos utilizadores—uma amostra de Type Designers profissionais portugueses—no desenvolvimento das estratégias comunitárias segundo uma abordagem participativa de Community-Centered Development. A utilização de um Focus Group de dimensões reduzidas, e as limitações temporais da investigação prática não permitem generalizar os resultados encontrados. No entanto, os resultados revelam que quanto mais específica for a atividade da prática partilhada na CO, mais especializados e restritos devem ser os modos de CMC implementados para a comunicação e interação dos membros online. A integração dos modos de CMC sobre a comunicação assíncrona através de artefactos visuais tem um potencial de comunicação mais eficaz e satisfatório para estes utilizadores. E as barreiras à participação, apesar de poderem ser minimizadas através da inovação nos modos implementados, são um desafio de sociabilização que devem ser geridos, equilibrando a comunicação explícita, os usos, perceções e expectativas dos diferentes papéis dos membros da comunidade.

Laser assisted directional solidification of zirconia-based eutectics

Directionally solidified zirconia-based eutectic (DSE) fibres were obtained using the laser floating zone (LFZ) method. Two systems were investigated: zirconia-barium zirconate and zirconia-mullite. The purpose was to take advantage of zirconia properties, particularly as an ionic conductor and a mechanical rein-forcement phase. The influence of processing conditions in the structural and microstructural characteristics and their consequences on the electrical and mechanical behaviour were the focus of this thesis. The novel zirconia-barium zirconate eutectic materials were developed in order to combine oxygen ionic conduction through zirconia with protonic conduction from barium zirconate, promoting mixed ionic conduction behaviour. The mi-crostructure of the fibres comprises two alternated regions: bands having coarser zirconia-rich microstructure; and inter-band regions changing from a homogeneous coupled eutectic, at the lowest pulling rate, to columnar colony microstructure, for the faster grown fibres. The bands inter-distance increases with the growth rate and, at 300 mm/h, zirconia dendrites develop enclosed in a fine-interpenetrated network of 50 vol.% ZrO2-50 vol.% BaZrO3. Both phases display contiguity without interphase boundaries, according to impedance spec-troscopy data. Yttria-rich compositions were considered in order to promote the yttrium incorporation in both phases, as revealed by Raman spectroscopy and corroborated by the elemental chemical analysis in energy dispersive spectros-copy. This is a mandatory condition to attain simultaneous contribution to the mixed ionic conduction. Such results are supported by impedance spectrosco-py measurements, which clearly disclose an increase of total ionic conduction for lower temperatures in wet/reduction atmospheres (activation energies of 35 kJ/mol in N2+H2 and 48 kJ/mol in air, in the range of 320-500 ºC) compared to the dry/oxidizing conditions (attaining values close to 90 kJ/mol, above 500 ºC). At high temperatures, the proton incorporation into the barium zirconate is un-favourable, so oxygen ion conduction through zirconia prevails, in dry and oxi-dizing environments, reaching a maximum of 1.3x10-2 S/cm in dry air, at ~1000 ºC. The ionic conduction of zirconia was alternatively combined with another high temperature oxygen ion conductor, as mullite, in order to obtain a broad elec-trolytic domain. The growth rate has a huge influence in the amount of phases and microstructure of the directionally solidified zirconia-mullite fibres. Their microstructure changes from planar coupled eutectic to dendritic eutectic mor-phology, when the growth rate rises from 1 to 500 mm/h, along with an incre-ment of tetragonal zirconia content. Furthermore, high growth rates lead to the development of Al-Si-Y glassy phase, and thus less mullite amount, which is found to considerably reduce the total ionic conduction of as-grown fibres. The reduction of the glassy phase content after annealing (10h; 1400 ºC) promotes an increase of the total ionic conduction (≥0.01 S/cm at 1370 °C), raising the mullite and tetragonal zirconia contents and leading to microstructural differ-ences, namely the distribution and size of the zirconia constituent. This has important consequences in conductivity by improving the percolation pathways. A notable increase in hardness is observed from 11.3 GPa for the 10 mm/h pulled fibre to 21.2 GPa for the fibre grown at 500 mm/h. The ultra-fine eutectic morphology of the 500 mm/h fibres results in a maximum value of 534 MPa for room temperature bending strength, which decreases to about one-fourth of this value at high temperature testing (1400 ºC) due to the soft nature of the glassy-matrix.

Mercaptans extraction from jet-fuel streams using ionic liquids

Desulfurization is one of the most important processes in the refining industry. Due to a growing concern about the risks to human health and environment, associated with the emissions of sulfur compounds, legislation has become more stringent, requiring a drastic reduction in the sulfur content of fuel to levels close to zero (< 10 ppm S). However, conventional desulfurization processes are inefficient and have high operating costs. This scenario stimulates the improvement of existing processes and the development of new and more efficient technologies. Aiming at overcoming these shortcomings, this work investigates an alternative desulfurization process using ionic liquids for the removal of mercaptans from "jet fuel" streams. The screening and selection of the most suitable ionic liquid were performed based on experimental and COSMO-RS predicted liquid-liquid equilibrium data. A model feed of 1-hexanethiol and n-dodecane was selected to represent a jet-fuel stream. High selectivities were determined, as a result of the low mutual solubility between the ionic liquid and the hydrocarbon matrix, proving the potential use of the ionic liquid, which prevents the loss of fuel for the solvent. The distribution ratios of mercaptans towards the ionic liquids were not as favorable, making the traditional liquid-liquid extraction processes not suitable for the removal of aliphatic S-compounds due to the high volume of extractant required. This work explores alternative methods and proposes the use of ionic liquids in a separation process assisted by membranes. In the process proposed the ionic liquid is used as extracting solvent of the sulfur species, in a hollow fiber membrane contactor, without co-extracting the other jet-fuel compound. In a second contactor, the ionic liquid is regenerated applying a sweep gas stripping, which allows for its reuse in a closed loop between the two membrane contactors. This integrated extraction/regeneration process of desulfurization produced a jet-fuel model with sulfur content lower than 2 ppm of S, as envisaged by legislation for the use of ultra-low sulfur jet-fuel. This result confirms the high potential for development of ultra-deep desulfurization application.

Monte Carlo studies of phase transitions and adsorption : application to n-6 Lennard-Jones, C60 and zeolite systems

The solid-fluid transition properties of the n - 6 Lennard-Jones system are studied by means of extensive free energy calculations. Different values of the parameter n which regulates the steepness of the short-range repulsive interaction are investigated. Furthermore, the free energies of the n < 12 systems are calculated using the n = 12 system as a reference. The method relies on a generalization of the multiple histogram method that combines independent canonical ensemble simulations performed with different Hamiltonians and computes the free energy difference between them. The phase behavior of the fullerene C60 solid is studied by performing NPT simulations using atomistic models which treat each carbon in the molecule as a separate interaction site with additional bond charges. In particular, the transition from an orientationally frozen phase at low temperatures to one where the molecules are freely rotating at higher temperatures is studied as a function of applied pressure. The adsorption of molecular hydrogen in the zeolite NaA is investigated by means of grand-canonical Monte Carlo, in a wide range of temperatures and imposed gas pressures, and results are compared with available experimental data. A potential model is used that comprises three main interactions: van der Waals, Coulomb and induced polarization by the permanent electric field in the zeolite.

Materiais à base de óxidos com estrutura do tipo perovskite e compósitos como ânodos de PCES

This work was focused on the analysis of transport, thermomechanical and electrochemical properties of a series of perovskite-like oxide materials and composites for potential applications as anodes of intermediate-temperature solid oxide fuel cells (SOFCs) with lanthanum gallate and silicate solid electrolytes. The primary attention was centered on A(Mn,Nb)O3-δ (A = Sr, Ca) and (La,Sr)(Mn,Ti)O3-based systems, lanthanum chromite substituted with acceptor-type and variable-valence cations, and various Ni-containing cermets. Emphasis was given to phase stability of the materials, their crystal structure, microstructure of porous electrode layers and dense ceramics, electronic conductivity, Seebeck coefficient, oxygen permeability, thermal and chemical induced expansion, and anodic overpotentials of the electrodes deposited onto (La,Sr)(Ga,Mg)O3- and La10(Si,Al)6O27- based electrolyte membranes. In selected cases, roles of oxygen diffusivity, states of the transition metal cations relevant for the electronic transport, catalytically active additives and doped ceria protective interlayers introduced in the model electrochemical cells were assessed. The correlations between transport properties of the electrode materials and electrochemical behavior of porous electrodes showed that the principal factors governing anode performance include, in particular, electronic conduction of the anode compositions and cation interdiffusion between the electrodes and solid electrolytes. The latter is critically important for the silicatebased electrolyte membranes, leading to substantially worse anode properties compared to the electrochemical cells with lanthanum gallate solid electrolyte. The results made it possible to select several anode compositions exhibiting lower area-specific electrode resistivity compared to known analogues, such as (La,Sr)(Cr,Mn)O3-δ.

Materials and concepts for CO2 lean ironmaking by pyroelectrolysis

The main purpose of this PhD thesis was to provide convincing demonstration for a breakthrough concept of pyroelectrolysis at laboratory scale. One attempted to identify fundamental objections and/or the most critical constraints, to propose workable concepts for the overall process and for feasible electrodes, and to establish the main requirements on a clearer basis. The main effort was dedicated to studying suitable anode materials to be developed for large scale industrial units with molten silicate electrolyte. This concept relies on consumable anodes based on iron oxides, and a liquid Fe cathode, separated from the refractory materials by a freeze lining (solid) layer. In addition, one assessed an alternative concept of pyroelectrolysis with electron blocking membranes, and developed a prototype at small laboratory scale. The main composition of the molten electrolyte was based on a magnesium aluminosilicate composition, with minimum liquidus temperature, and with different additions of iron oxide. One studied the dynamics of devitrification of these melts, crystallization of iron oxides or other phases, and Fe2+/Fe3+ redox changes under laser zone melting, at different pulling rates. These studies were intended to provide guidelines for dissolution of raw materials (iron oxides) in the molten electrolyte, to assess compatibility with magnetite based consumable anodes, and to account for thermal gradients or insufficient thermal management in large scale cells. Several laboratory scale prototype cells were used to demonstrate the concept of pyroelectrolysis with electron blocking, and to identify the most critical issues and challenges. Operation with and without electron blocking provided useful information on transport properties of the molten electrolyte (i.e., ionic and electronic conductivities), their expected dependence on anodic and cathodic overpotentials, limitations in faradaic efficiency, and onset of side electrochemical reactions. The concept of consumable anodes was based on magnetite and derived spinel compositions, for their expected redox stability at high temperatures, even under oxidising conditions. Spinel compositions were designed for prospective gains in refractoriness and redox stability in wider ranges of conditions (T, pO2 and anodic overpotentials), without excessive penalty for electrical conductivity, thermomechanical stability or other requirements. Composition changes were also mainly based on components of the molten aluminosilicate melt, to avoid undue contamination and to minimize the dissolution rate of consumable anodes. Additional changes in composition were intended for prospective pyroelectrolysis of Fe alloys, with additions of different elements (Cr, Mn, Ni, Ti).

Perception and software architecture for mobile robotics

When developing software for autonomous mobile robots, one has to inevitably tackle some kind of perception. Moreover, when dealing with agents that possess some level of reasoning for executing their actions, there is the need to model the environment and the robot internal state in a way that it represents the scenario in which the robot operates. Inserted in the ATRI group, part of the IEETA research unit at Aveiro University, this work uses two of the projects of the group as test bed, particularly in the scenario of robotic soccer with real robots. With the main objective of developing algorithms for sensor and information fusion that could be used e ectively on these teams, several state of the art approaches were studied, implemented and adapted to each of the robot types. Within the MSL RoboCup team CAMBADA, the main focus was the perception of ball and obstacles, with the creation of models capable of providing extended information so that the reasoning of the robot can be ever more e ective. To achieve it, several methodologies were analyzed, implemented, compared and improved. Concerning the ball, an analysis of ltering methodologies for stabilization of its position and estimation of its velocity was performed. Also, with the goal keeper in mind, work has been done to provide it with information of aerial balls. As for obstacles, a new de nition of the way they are perceived by the vision and the type of information provided was created, as well as a methodology for identifying which of the obstacles are team mates. Also, a tracking algorithm was developed, which ultimately assigned each of the obstacles a unique identi er. Associated with the improvement of the obstacles perception, a new algorithm of estimating reactive obstacle avoidance was created. In the context of the SPL RoboCup team Portuguese Team, besides the inevitable adaptation of many of the algorithms already developed for sensor and information fusion and considering that it was recently created, the objective was to create a sustainable software architecture that could be the base for future modular development. The software architecture created is based on a series of di erent processes and the means of communication among them. All processes were created or adapted for the new architecture and a base set of roles and behaviors was de ned during this work to achieve a base functional framework. In terms of perception, the main focus was to de ne a projection model and camera pose extraction that could provide information in metric coordinates. The second main objective was to adapt the CAMBADA localization algorithm to work on the NAO robots, considering all the limitations it presents when comparing to the MSL team, especially in terms of computational resources. A set of support tools were developed or improved in order to support the test and development in both teams. In general, the work developed during this thesis improved the performance of the teams during play and also the e ectiveness of the developers team when in development and test phases.

Sustainable viticulture in Bairrada appellation: vineyard and harvest year effects on grapes oenological potential

The sustainable viticulture of a region passes, among other aspects, for maximizing the varieties potential minimizing subsequent interventions during winemaking, which should contribute to the production of quality wines maintaining their typicity and rationalizing costs. The detailed knowledge of each Appellation specificities, namely vineyard parcel (soil type and topographical peculiarities) and harvest climatic conditions is crucial for sustainability in this sector. Thus, in line with this current trend, the starting point for the development of this PhD thesis was to evaluate the oenological potential of different varieties cultivated throughout Bairrada Appellation (Portugal). During maturation several changes in grape varieties occur, namely berries become sweeter, less acidic, and they develop flavour, aroma and colour properties. The development of these characteristics is essential to define grapes oenological potential, i.e. to estimate the possibility of their usage to produce specific wines. A three years sampling plan was designed to evaluate the effect of harvest year and parcel characteristics on V. vinifera cv. Arinto, Bical, Sauvignon Blanc, Baga, Castelão, Touriga Nacional, and Sousão grapes composition. For each variety, 3 parcels with different characteristics were selected. Several physicochemical parameters were evaluated, during maturation: berry weight, pH, titratable acidity, sugar and phenolic contents, antiradical activity, and volatile composition (free fraction). Special attention was devoted to grapes at technologic maturity, since, besides these parameters, glycosidically-linked fraction was also considered. By using the results obtained at technologic maturity, a comprehensive approach was applied to identify the significance of harvest and parcel characteristics effects on each variety composition. Considering all the parameters under study, it may be highlighted some significant differences. According to the obtained results determined during maturation, it was possible to conclude that Arinto, Bical and Sauvignon Blanc grapes from parcels with clay-sandy and clay-calcareous soils have higher phenolic content and antiradical activity. Otherwise, Sauvignon Blanc presented similar volatile composition for grapes cultivated in the 3 parcels, while Arinto and Bical exhibited higher volatile content in grapes from claysandy and clay-calcareous soils. For Baga, Castelão and Touriga Nacional red varieties, grapes with higher phenolic content, antiradical activity, and volatile content were obtained from clayey and clay-calcareous soils. Furthermore, for Touriga Nacional, parcels altitude seems also to modulate grapes composition. Beyond parcel effect, harvest year conditions also influence grapes composition: 2011 harvest was related with lower phenolic and volatile contents, as well as lower antiradical activity.For grapes collected at technologic maturity, analysis of variance-simultaneous component analysis (ASCA) was applied combining all the parameters under study, in order to assess the influence of harvest and parcel characteristics on each variety oenological potential. The results obtained using this comprehensive approach is closely related with those observed during maturation and revealed that harvest was the main factor that influenced grapes composition (53% to 68% of the total data set variance) followed by parcel characteristics, explaining ca. 15-19% of the total data set variance. The oenological potential of each variety may be different from one parcel to another, i.e., clay-sandy and clay-calcareous related-environments seem to favour Arinto and Bical white grapes composition, but for the red varieties, grapes composition was favoured by clayey and clay-calcareous soils. Besides, also higher altitude seems to favour Touriga Nacional grapes composition. Sauvignon Blanc seems to be a variety well adapted to the different parcel characteristics. In order to go forward in the valuation of these varieties, the aroma properties of 6 monovarietal wines were studied based on an aroma network-approach, linking molecular data related to volatile composition and aroma data about the key odor active molecules. This approach allowed to identify different wine aroma properties and to infer about the consumer’s sensory perception. It was found that aroma properties differ from one wine variety to another: while Arinto and Sauvignon Blanc wine exhibited higher tree fruity, sweety and flowery aromas, related essentially with ester compounds and C13 norisoprenoids, the opposite was obtained for Bical wine, corroborating the aroma sensory perceptions of the trained panel. Sauvignon Blanc also exhibited higher toasted aromas (related with thiols, mainly with 2-methyl-3-furanthiol). Touriga Nacional red wine exhibited higher tree, tropical, and berry fruits notes (sensory described as sweet fruits), toasted and flowery aromas, while these are similar for the other red wines under study. Besides Portuguese Bairrada wines, this aroma network approach is a tool that can be used to explain the aroma properties of wines worldwide. The grape and wine data generated under the present PhD thesis, in the context of Bairrada Appellation, shows the unique character of each variety, and may be used by growers and wine producers as a support for decisionmaking based on objective criteria, increasing the sustainability in this sector. For instance, it is possible to take advantage of the natural resources and produce products with different characteristics obtained from the same variety, minimizing costs during the winemaking process.

Phase transitions and nonlinear phenomena in neuronal network models

Communication and cooperation between billions of neurons underlie the power of the brain. How do complex functions of the brain arise from its cellular constituents? How do groups of neurons self-organize into patterns of activity? These are crucial questions in neuroscience. In order to answer them, it is necessary to have solid theoretical understanding of how single neurons communicate at the microscopic level, and how cooperative activity emerges. In this thesis we aim to understand how complex collective phenomena can arise in a simple model of neuronal networks. We use a model with balanced excitation and inhibition and complex network architecture, and we develop analytical and numerical methods for describing its neuronal dynamics. We study how interaction between neurons generates various collective phenomena, such as spontaneous appearance of network oscillations and seizures, and early warnings of these transitions in neuronal networks. Within our model, we show that phase transitions separate various dynamical regimes, and we investigate the corresponding bifurcations and critical phenomena. It permits us to suggest a qualitative explanation of the Berger effect, and to investigate phenomena such as avalanches, band-pass filter, and stochastic resonance. The role of modular structure in the detection of weak signals is also discussed. Moreover, we find nonlinear excitations that can describe paroxysmal spikes observed in electroencephalograms from epileptic brains. It allows us to propose a method to predict epileptic seizures. Memory and learning are key functions of the brain. There are evidences that these processes result from dynamical changes in the structure of the brain. At the microscopic level, synaptic connections are plastic and are modified according to the dynamics of neurons. Thus, we generalize our cortical model to take into account synaptic plasticity and we show that the repertoire of dynamical regimes becomes richer. In particular, we find mixed-mode oscillations and a chaotic regime in neuronal network dynamics.

Treatment of aqueous effluents contaminated with ionic liquids

Ionic liquids are a class of solvents that, due to their unique properties, have been proposed in the past few years as alternatives to some hazardous volatile organic compounds. They are already used by industry, where it was possible to improve different processes by the incorporation of this kind of non-volatile and often liquid solvents. However, even if ionic liquids cannot contribute to air pollution, due to their negligible vapour pressures, they can be dispersed thorough aquatic streams thus contaminating the environment. Therefore, the main goals of this work are to study the mutual solubilities between water and different ionic liquids in order to infer on their environmental impact, and to propose effective methods to remove and, whenever possible, recover ionic liquids from aqueous media. The liquid-liquid phase behaviour of different ionic liquids and water was evaluated in the temperature range between (288.15 and 318.15) K. For higher melting temperature ionic liquids a narrower temperature range was studied. The gathered data allowed a deep understanding on the structural effects of the ionic liquid, namely the cation core, isomerism, symmetry, cation alkyl chain length and the anion nature through their mutual solubilities (saturation values) with water. The experimental data were also supported by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS), and for some more specific systems, molecular dynamics simulations were also employed for a better comprehension of these systems at a molecular level. On the other hand, in order to remove and recover ionic liquids from aqueous solutions, two different methods were studied: one based on aqueous biphasic systems, that allowed an almost complete recovery of hydrophilic ionic liquids (those completely miscible with water at temperatures close to room temperature) by the addition of strong salting-out agents (Al2(SO4)3 or AlK(SO4)2); and the other based on the adsorption of several ionic liquids onto commercial activated carbon. The first approach, in addition to allowing the removal of ionic liquids from aqueous solutions, also makes possible to recover the ionic liquid and to recycle the remaining solution. In the adsorption process, only the removal of the ionic liquid from aqueous solutions was attempted. Nevertheless, a broad understanding of the structural effects of the ionic liquid on the adsorption process was attained, and a final improvement on the adsorption of hydrophilic ionic liquids by the addition of an inorganic salt (Na2SO4) was also achieved. Yet, the development of a recovery process that allows the reuse of the ionic liquid is still required for the development of sustainable processes.

Contributos da educação em Geociências para o desenvolvimento: uma abordagem ao tempo geológico

Perante os desafios do mundo contemporâneo, marcado pela complexidade, pelo ritmo acelerado de mudança e pela incerteza, o desenvolvimento dos alunos como cidadãos cientificamente cultos é um fator crítico. Neste contexto, a educação em Geociências, em geral, e a compreensão do tempo geológico, em particular, podem contribuir para um aprofundamento da cultura científica e da responsabilidade do cidadão promotor do desenvolvimento sustentável, numa matriz Ciência/Tecnologia/Sociedade. Assim, com este estudo, pretende-se alcançar duas grandes finalidades: a) contribuir para o desenvolvimento de um quadro teórico e concetual, no âmbito da educação em geral e das Geociências em particular, visando o desenvolvimento dos alunos como cidadãos cientificamente cultos numa lógica de sustentabilidade; b) conceber, implementar e avaliar estratégias, fundamentadas no corpus de referência, no âmbito da Geologia no ensino secundário. Corresponde a uma investigação-ação desenvolvida pelo professor de Biologia e Geologia com alunos do 11.º ano e organizada em três fases: i) desenvolvimento de um quadro teórico de referência e concetual; ii) conceção, desenvolvimento e avaliação de uma intervenção didática iii) elaboração de uma proposta metodológica fundamentada para o aprofundamento de uma cultura científica que promova o desenvolvimento da sustentabilidade na Terra a partir do ensino do tempo geológico. Os resultados do estudo apontam para a importância de trabalhar de modo articulado os conceitos de tempo geológico e de desenvolvimento sustentável na formação de cidadãos cientificamente cultos, capazes de dar resposta às questões complexas da sociedade atual. Por outro lado, a análise da intervenção didática confirma a importância das atividades exteriores à sala de aula e do trabalho prático para o desenvolvimento da cidadania, em alunos do ensino secundário, e como facilitadoras da compreensão de conceitos complexos como o de tempo geológico.