STRUCTURE-FUNCTION ANALYSIS OF MULTI-COPPER OXIDASES

Dissertation presented to obtain the Ph.D degree in Biochemistry, Structural Biochemistry

Thermo-hydro-mechanical analysis of CO2 injection into deep aquifers

One of the biggest challenges for humanity is global warming and consequently, climate changes. Even though there has been increasing public awareness and investments from numerous countries concerning renewable energies, fossil fuels are and will continue to be in the near future, the main source of energy. Carbon capture and storage (CCS) is believed to be a serious measure to mitigate CO2 concentration. CCS briefly consists of capturing CO2 from the atmosphere or stationary emission sources and transporting and storing it via mineral carbonation, in oceans or geological media. The latter is referred to as carbon capture and geological storage (CCGS) and is considered to be the most promising of all solutions. Generally it consists of a storage (e.g. depleted oil reservoirs and deep saline aquifers) and sealing (commonly termed caprock in the oil industry) formations. The present study concerns the injection of CO2 into deep aquifers and regardless injection conditions, temperature gradients between carbon dioxide and the storage formation are likely to occur. Should the CO2 temperature be lower than the storage formation, a contractive behaviour of the reservoir and caprock is expected. The latter can result in the opening of new paths or re-opening of fractures, favouring leakage and compromising the CCGS project. During CO2 injection, coupled thermo-hydro-mechanical phenomena occur, which due to their complexity, hamper the assessment of each relative influence. For this purpose, several analyses were carried out in order to evaluate their influences but focusing on the thermal contractive behaviour. It was finally concluded that depending on mechanical and thermal properties of the pair aquifer-seal, the sealing caprock can undergo significant decreases in effective stress.

Ageing on commercial automotive catalysts, a structure reactivity study

Increasingly stringed regulations for diesel engine emissions have a significant impact on the required efficiency of DOC. Lowered DOC oxidation efficiency due to thermal aging effects influences the efficiency of the exhaust aftertreatment systems downstream of the DOC. In this work carried out in the Jean Le Rond d’Alembert Institute the effect of hydrothermal aging on the reactivity and structure of a commercial DOC was investigated. The characterization of the catalytic performance was carried out on a synthetic gas bench using carrots catalyst under conditions close to the realistic conditions i.e. using a synthetic gas mixture, representative of the exhaust gases from diesel engines. Different structural characterization techniques were performed: textural and morphological proprieties were analyzed by BET and TEM, the characterization of the presented crystallographic phases was performed by DRX and the determination of the number of reducible species was possible by TPR. TEM results shown, an increase of the metal particle size with the aging caused by the agglomeration of metal particles, revealing the presence of metal sintering. DRX results also suggest the presence of support sintering. Furthermore, DRX and BET results unexpectedly reveal that the most drastic aging conditions used actually activated the catalyst surface. As expected, the aging affected negatively the catalyst performance on the oxidation of methane and CO, however an improvement of the NO oxidation performance with the aging was observed. Nevertheless, for the aging conditions used, catalytic activity results show that the influence of aging in DOC performance was not significant, and therefore, more drastic aging conditions must be used.

UAV - based imagery processing using structure from motion and remote sensing technology

With the recent advances in technology and miniaturization of devices such as GPS or IMU, Unmanned Aerial Vehicles became a feasible platform for a Remote Sensing applications. The use of UAVs compared to the conventional aerial platforms provides a set of advantages such as higher spatial resolution of the derived products. UAV - based imagery obtained by a user grade cameras introduces a set of problems which have to be solved, e. g. rotational or angular differences or unknown or insufficiently precise IO and EO camera parameters. In this work, UAV - based imagery of RGB and CIR type was processed using two different workflows based on PhotoScan and VisualSfM software solutions resulting in the DSM and orthophoto products. Feature detection and matching parameters influence on the result quality as well as a processing time was examined and the optimal parameter setup was presented. Products of the both workflows were compared in terms of a quality and a spatial accuracy. Both workflows were compared by presenting the processing times and quality of the results. Finally, the obtained products were used in order to demonstrate vegetation classification. Contribution of the IHS transformations was examined with respect to the classification accuracy.

Adaptação cultural e contributo para a validação da pain attitudes and believes scale for physiotherapists (PABS-PT) para a população de fisioterapeutas portugueses

RESUMO: Introdução: Vários estudos têm encontrado evidência para a relação entre as crenças e atitudes dos profissionais de saúde, a sua abordagem de tratamento, referida como orientada segundo o modelo biomédico ou modelo biopsicossocial (Bishop, 2008; Mutsaers, 2012), e os resultados obtidos. É sugerido que, no tratamento da dor lombar crónica, os profissionais que orientam o seu raciocínio e prática segundo o modelo biomédico, tendem a obter piores resultados quando comparados com os obtidos pelos profissionais que orientam o seu raciocínio e prática segundo uma abordagem biopsicossocial. Esta área de estudo tem salientado a importância de desenhar instrumentos capazes de identificar a orientação preferencial dos profissionais de saúde no tratamento da dor crónica de natureza músculo-esquelética, entre os quais se encontra a “Pain Attitudes and Beliefs Scale for Physiotherapists” (PABS-PT). Objetivo: Adaptar culturalmente a PABS-PT para a população de fisioterapeutas portugueses que intervêm em utentes com dor (lombar) crónica, e contribuir para a sua validação Metodologia: A versão original (língua inglesa) do PABS-PT foi adaptada para a língua e cultura portuguesas, através das etapas definidas nas normas orientadoras estabelecidas para este processo (Beaton et al., 2002; MAPI Institute, 2001). A avaliação das propriedades psicométricas da versão portuguesa foi realizada com recurso a uma amostra de 202 fisioterapeutas e estudantes finalistas do curso de licenciatura em Fisioterapia. Inicialmente foi realizada a análise fatorial exploratória da escala através do método das componentes principais. Posteriormente avaliou-se a consistência interna das componentes obtidas com recurso ao alpha de Cronbach (α). Para analisar a validade de constructo foram correlacionadas as componentes obtidas com a versão portuguesa da “Health Care Providers’ Pain and Impairment Relationship Scale” (HC-PAIRS), recorrendo ao cálculo do coeficiente de Spearman. Resultados: O processo de adaptação cultural não revelou dificuldades importantes sendo considerado que a versão portuguesa da PABS-PT é de fácil compreensão e preenchimento, e os seus itens adequados para avaliar as crenças e atitudes dos fisioterapeutas portugueses relativas à intervenção na dor crónica músculo-esquelética. Os resultados revelaram uma estrutura fatorial de duas componentes, identificadas com as componentes da escala original que explicam 30,96% da variância total. A consistência interna encontrada é boa, para a componente biomédica (α de Cronbach = 0,826), mas muito fraca para a componente biopsicossocial (α de Cronbach= 0,589). Relativamente à validade convergente e discriminativa, foi encontrada uma associação estatisticamente significativa e positiva, entre as componentes 1 (biomédica) da versão nportuguesa da PABS e a HC-PAIRS (Rs = 0,481, p≤ 0,005), e negativa, fraca e significativa entre a pontuação total da componente 2 (biopsicossocial) e a HC-PAIRS (Rs = -0,038, p=0,612). Conclusão: A versão portuguesa do PABS-PT é de fácil compreensão e aparenta ser um instrumento válido para a medição da orientação preferencial dos fisioterapeutas, relativamente às suas atitudes e crenças na avaliação e tratamento de utentes com dor crónica de natureza músculo-esquelética. No entanto, a componente biopsicossocial requer uma análise mais aprofundada para que possa, com rigor, ser utilizada na definição de uma orientação preferencialmente biopsicossocial.--------------ABSTRACT: Introduction: Previous studies have found a relation between the beliefs and attitudes of health professionals, their treatment approach, which can follows a biomedical or a biopsychosocial orientation (Bishop, 2008; Mutsaers, 2012), and the outcomes obtained. Therefore, is suggested that the professionals who tend to approach chronic low back pain patients according to the biomedical model have worse outcomes than professionals who use a biopsychosocial approach in there clinical reasoning. This research field has highlighted the importance of developing measures capable of identifying the preferred orientation of health professionals in the treatment of chronic pain of musculoskeletal nature, including the “Pain Attitudes and Beliefs Scale for Physiotherapists” (PABS-PT). Objective: To cross culturally adapt and validate the PABS-PT for the Portuguese population of physiotherapists. Methodology: The original version (English version) of the PABS-PT was adapted to the Portuguese language and culture, through the guidelines established for these processes (Beaton et al., 2002; MAPI Institute, 2001). The psychometric evaluation of the Portuguese version was carried out on a sample of 202 p physiotherapist and final year students of the physiotherapy course. Initially, an exploratory factorial analysis was performed through the method of the main components. Then, the internal consistence of the main components was evaluated using the Cronbach’s alpha (α). The convergent construct validity was analysed through the correlation between the obtained components of PABS-PT and the Health Care Provider’s Pain and Impairment Relationship Scale (HC-PAIRS), using the Spearmen correlation coefficient. Results: No major difficulties were found during the cultural adaptation process of PABS-PT to Portugal, which means that the Portuguese version is easy to understand and fulfill, and items are appropriated to evaluate the beliefs and attitudes of the Portuguese physiotherapists who treat chronic pain of musculoskeletal origins. The results revealed a factorial structure of two components, as the original scale, explaining 30,96% of the total variance. Internal consistence results were good, for the biomedical component (Cronbach’s α = 0,826), but very weak for the biopsychosocial componente (Cronbach’s α = 0,589). Relatively to convergent and discriminative validity, a statistically significant association was found, between the components 1 (biomedical) of the Portuguese version of PABS-PT and the HC-PAIRS (Rs= 0,481, p≤ 0,005) and negative, weak and significant between the total score of component 2 (biopsychosocial) and the HC-PAIRS (Rs = -0,038, p=0,612). Conclusion: The Portuguese Version of PABS-PT is easy to understand and seems to be a valid instrument to measure the attitudes and beliefs of physiotherapists in the management of patients with chronic low back pain. However, the biopsychosocial component requires a further deep analysis to examine a preferable biopsychosocial orientation.

How do current term structure model behave beyond the last liquid point?: A comparison of the DNS and Smith-Wilson methods

A Work Project, presented as part of the requirements for the Award of a Master’s Double Degree in Finance from Maastricht University and NOVA – School of Business and Economics

Social tariffs for water and waste services in mainland Portugal: An impact analysis

This paper proposes to quantify the effect of social tariffs (ST) in the Portuguese water and waste sector (WWS). It calculates the amount of subsidy implicit in ST schemes, characterising the existing tariffs in 2011 and producing a synthetic tariff scene where the regulator’s recommendation is respected. This is the first time such an exercise is undertaken and it is very relevant in a context of deep economic crisis. Results suggest that there are fewer beneficiaries than what income eligibility criteria would imply and that putting the regulator’s recommendation in practice would considerably raise subsidy amounts, potentially leading to a severe increase in non-subsidised user tariffs to allow for break-even.

Design and characterization of novel biopolymeric structure using biocompatible ionic liquids

The main objective of this thesis was the development of polymeric structures from the dissolution of FucoPol, a bacterial exopolysaccharide (EPS), in a biocompatible ionic liquid, choline acetate. The FucoPol was produced by the bacteria Enterobacter A47 using glycerol as carbon source at controlled temperature and pH (30ºC and 7, respectively). At the end of 3 days it was produced 7 g/L of FucoPol. The net yield of Fucopol in glycerol (YP/S) was 0.22 g/g and the maximum productivity 2.37 g/L.d This polymer was characterized about its composition in sugars and acyl groups (by High-Performance Liquid Chromatography - HPLC), containing fucose (35 % mol), galactose (21 % mol), glucose (29 % mol), rhamnose (3% mol) and glucuronic acid (12% mol) as well as acetate (14.28 % mol), pyruvate (2.15 % mol) and succinate (1.80 % mol). Its content of water and ash was 15% p/p and 2% p/p, respectively, and the chemical bonds (determined by Infrared Spectroscopy - FT-IR) are consistent to the literature reports. However, due to limitations in Differential Scanning Calorimetry (DSC) equipment it was not possible to determine the glass transition temperature. In turn, the ionic liquid showed the typical behavior of a Newtonian fluid, glass transition temperature (determined by DSC) -98.03ºC and density 1.1031 g/cm3. The study of chemical bonds by FT-IR showed that amount of water (8.80%) influenced the visualization of the bands predicted to in view of their chemical structure. After the dissolution of the FucoPol in the ionic liquid at different temperatures (50, 60, 80 and 100 ° C) it was promoted the removal of this by the phase inversion method using deionized water as a solvent, followed by drying in an oven at 70 ° C. The mixtures before and after the phase inversion method were characterized through the studies mentioned above. In order to explore possible application field’s biocompatibility assays and collage on balsa wood tests were performed. It was found that the process of washing with water by the phase inversion method was not totally effective in removing the biocompatible ionic liquid, since all FucoPol – IL mixtures still contained ionic liquid in their composition as can be seen by the DSC results and FT-IR. In addition, washing the mixtures with water significantly altered the composition of FucoPol. However, these mixtures, that developed a viscous behavior typical of a non-Newtonian fluid (shear-thinning), have the potential to be applied in the biomedical field as well as biological glues.

Does ownership structure matter? Three essays in finance

Management

The Multidimensional and Centred Structure of Our Interested Perception in Hierocles

O objectivo desta dissertação é identificar a estrutura da percepção tal como ela é desenhada por Hiérocles nos <,(#= >1!(?$%&'(). Para alcançar este objectivo focar-me-ei na análise que o filósofo estóico leva a cabo em torno da percepção. O foco começa por incindir sobre a distinção entre percepção de si e percepção do exterior, com todas as suas subtilezas. Tal análise implicará então a consideração da importância da não-indiferença nessa estrutura de percepção. O objectivo é compreender como a percepção é sempre relacional e interessada. . Centrar-me-ei então na noção de !"#$%&'(), tentanto explorar a complexidade e multiplicidade do fenómeno em causa. Será também estabalecida a relação com o fragmento de Estobeu (6.671), que é, a par da obra, a fonte mais importante do pensamento de Hiérocles. Através desta relação introduzir-se-á a estrutura circular e concêntrica de uma percepção relacional e interessada. Toda esta dissertação será levada a cabo focando-se principalmente nos textos do próprio Hiérocles.

Inovcity- Structure of trials evaluation

In 2007, the UK government commissioned the Energy Demand Research Project to conduct a large scale experiment of smart metering technologies to test the impacts from many different forms of feedback to residential consumers. A full evaluation of the results was completed in 2011. In Portugal, EDP is also conducting smart meter trials in a project called InovCity in the city of Évora whose results will be evaluated during 2012. In this work, the case of Great Britain is studied as a reference on how an evaluation of trial results should be conducted. I also discuss potential limitations of the experiments, implications for national roll-out decisions, and finally draw some lessons that can be applied to the Portuguese case.

Impact of chromossomal structure on the evolution of Schizosaccharomyces pombe undergoing Mutation Accumulation

Large chromosomal rearrangements are common in natural populations and thought to be involved in speciation events. In this project, we used experimental evolution to determine how the speed of evolution and the type of accumulated mutations depend on the ancestral chromosomal structure and genotype. We utilized two Wild Type strains and a set of genetically engineered Schizosaccharomyces pombe strains, different solely in the presence of a certain type of chromosomal variant (inversions or translocations), along with respective controls. Previous research has shown that these chromosomal variants have different fitness levels in several environments, probably due to changes in the gene expression along the genome. These strains were propagated in the laboratory at very low population sizes, in which we expect natural selection to be less efficient at purging deleterious mutations. We then measured these strains’ changes in fitness throughout this accumulation of deleterious mutations, comparing the evolutionary trajectories in the different rearrangements to understand if the chromosomal structure affected the speed of evolution. We also tested these mutations for possible epistatic effects and estimated their parameters: the number of arising deleterious mutations per generation (Ud) and each one’s mean effect (sd).

Orthogonal models, structure crossing, nesting and inference

We intend to study the algebraic structure of the simple orthogonal models to use them, through binary operations as building blocks in the construction of more complex orthogonal models. We start by presenting some matrix results considering Commutative Jordan Algebras of symmetric matrices, CJAs. Next, we use these results to study the algebraic structure of orthogonal models, obtained by crossing and nesting simpler ones. Then, we study the normal models with OBS, which can also be orthogonal models. We intend to study normal models with OBS (Orthogonal Block Structure), NOBS (Normal Orthogonal Block Structure), obtaining condition for having complete and suffcient statistics, having UMVUE, is unbiased estimators with minimal covariance matrices whatever the variance components. Lastly, see ([Pereira et al. (2014)]), we study the algebraic structure of orthogonal models, mixed models whose variance covariance matrices are all positive semi definite, linear combinations of known orthogonal pairwise orthogonal projection matrices, OPOPM, and whose least square estimators, LSE, of estimable vectors are best linear unbiased estimator, BLUE, whatever the variance components, so they are uniformly BLUE, UBLUE. From the results of the algebraic structure we will get explicit expressions for the LSE of these models.

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

Garland, since 1776- a unique ownership structure

The case is based on Garland, a 240 years old Portuguese family business, now owned by the Dawson family. It focuses on a decision made 50 years ago, aligned with what had been the company’s history, about the ownership rules for family members, which influences the ownership structure of the firm. It addresses the main issues about ownership in family businesses, and tackles the problem of succession planning and fair process. It contains a teaching note to support the utilization of the case in a classroom context, with learning objectives, target audience, a teaching plan, questions and proposed answers, and theory that relates to the case. It is also complemented with an epilogue and an overview of the case.