Catalytic routes to convert saccharides to furanic aldehydes

The conversion of plant biomass-derived carbohydrates (preferably non-edible) into added-value products is envisaged to be at the core of the future biorefineries. Carbohydrates are the most abundant natural organic polymers on Earth. This work deals with the chemical valorisation of plant biomass, focusing on the acid-catalysed conversion of carbohydrates (mono and polysaccharides) to furanic aldehydes, namely 2-furaldehyde (Fur) and 5-hydroxymethyl-2-furaldehyde (Hmf), which are valuable platform chemicals that have the potential to replace a variety of oil derived chemicals and materials. The investigated reaction systems can be divided into two types depending on the solvent used to dissolve the carbohydrates in the reaction medium: water or ionic liquid-based systems. The reaction temperatures were greater than 150 ºC when the solvent was water, and lower than 150 º C in the cases of the ionic liquid-based catalytic systems. As alternatives to liquid acids (typically used in the industrial production of Fur), solid acid catalysts were investigated in these reaction systems. Aiming at the identification of (soluble and insoluble) reaction products, complementary characterisation techniques were used namely, FT-IR spectroscopy, liquid and solid state NMR spectroscopy, TGA, DSC and GC´GC-ToFMS analyses. Complex mixtures of soluble reaction products were obtained and different types of side reactions may occur. The requirements to be put on the catalysts for these reaction systems partly depend on the type of carbohydrates to be converted and the reaction conditions used. The thermal stability is important due to the fact that formation of humins and catalyst coking phenomena are characteristically inherent to these types of reactions systems leading to the need to regenerate the catalyst which can be effectively accomplished by calcination. Special attention was given to fully inorganic nanoporous solid acids, amorphous or crystalline, and consisting of nano to micro-size particles. The investigated catalysts were silicoaluminophosphates, aluminosilicates and zirconium-tungsten mixed oxides which are versatile catalysts in that their physicochemical properties can be fine-tuned to improve the catalytic performances in the conversion of different substrates (e.g. introduction of mesoporosity and modification of the acid properties). The catalytic systems consisting of aluminosilicates as solid acids and water as solvent seem to be more effective in converting pentoses and related polysaccharides into Fur, than hexoses and related polysaccharides into Hmf. The investigated solid acids exhibited fairly good hydrothermal stabilities. On the other hand, ionic liquid-based catalytic systems can allow reaching simultaneously high Fur and Hmf yields, particularly when Hmf is obtained from D-fructose and related polysaccharides; however, catalyst deactivation occurs and the catalytic reactions take place in homogeneous phase. As pointed out in a review of the state of the art on this topic, the development of truly heterogeneous ionic liquid-based catalytic systems for producing Fur and Hmf in high yields remains a challenge.

Analysis of the organic matter associated to sea salt : definition of potential molecular markers based on the volatile composition and presence of glycosidic derivatives and polysaccharides

Sea salt is a natural product obtained from the evaporation of seawater in saltpans due to the combined effect of wind and sunlight. Nowadays, there is a growing interest for protection and re-valorisation of saltpans intrinsically associated to the quality of sea salt that can be evaluated by its physico-chemical properties. These man-made systems can be located in different geographical areas presenting different environmental surroundings. During the crystallization process, organic compounds coming from these surroundings can be incorporated into sea salt crystals, influencing their final composition. The organic matter associated to sea salt arises from three main sources: algae, surrounding bacterial community, and anthropogenic activity. Based on the hypothesis that sea salt contains associated organic compounds that can be used as markers of the product, including saltpans surrounding environment, the aim of this PhD thesis was to identify these compounds. With this purpose, this work comprised: 1) a deep characterisation of the volatile composition of sea salt by headspace solid phase microextraction combined with comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (HS-SPME/GCGC–ToFMS) methodology, in search of potential sea salt volatile markers; 2) the development of a methodology to isolate the polymeric material potentially present in sea salt, in amounts that allow its characterisation in terms of polysaccharides and protein; and 3) to explore the possible presence of triacylglycerides. The high chromatographic resolution and sensitivity of GC×GC–ToFMS enabled the separation and identification of a higher number of volatile compounds from sea salt, about three folds, compared to unidimentional chromatography (GC–qMS). The chromatographic contour plots obtained revealed the complexity of marine salt volatile composition and confirmed the relevance of GC×GC–ToFMS for this type of analysis. The structured bidimentional chromatographic profile arising from 1D volatility and 2D polarity was demonstrated, allowing more reliable identifications. Results obtained for analysis of salt from two locations in Aveiro and harvested over three years suggest the loss of volatile compounds along the time of storage of the salt. From Atlantic Ocean salts of seven different geographical origins, all produced in 2007, it was possible to identify a sub-set of ten compounds present in all salts, namely 6-methyl-5-hepten-2-one, 2,2,6-trimethylcyclohexanone, isophorone, ketoisophorone, β-ionone-5,6-epoxide, dihydroactinidiolide, 6,10,14-trimethyl-2-pentadecanone, 3-hydroxy-2,4,4-trimethylpentyl 2-methylpropanoate, 2,4,4-trimethylpentane-1,3-diyl bis(2-methylpropanoate), and 2-ethyl-1-hexanol. These ten compounds were considered potential volatile markers of sea salt. Seven of these compounds are carotenoid-derived compounds, and the other three may result from the integration of compounds from anthropogenic activity as metabolites of marine organisms. The present PhD work also allowed the isolation and characterisation, for the first time, of polymeric material from sea salt, using 16 Atlantic Ocean salts. A dialysis-based methodology was developed to isolate the polymeric material from sea salt in amounts that allowed its characterisation. The median content of polymeric material isolated from the 16 salts was 144 mg per kg of salt, e.g. 0.014% (w/w). Mid-infrared spectroscopy and thermogravimetry revealed the main occurrence of sulfated polysaccharides, as well as the presence of protein in the polymeric material from sea salt. Sea salt polysaccharides were found to be rich in uronic acid residues (21 mol%), glucose (18), galactose (16), and fucose (13). Sulfate content represented a median of 45 mol%, being the median content of sulfated polysaccharides 461 mg/g of polymeric material, which accounted for 66 mg/kg of dry salt. Glycosidic linkage composition indicates that the main sugar residues that could carry one or more sulfate groups were identified as fucose and galactose. This fact allowed to infer that the polysaccharides from sea salt arise mainly from algae, due to their abundance and composition. The amino acid profile of the polymeric material from the 16 Atlantic Ocean salts showed as main residues, as medians, alanine (25 mol%), leucine (14), and valine (14), which are hydrophobic, being the median protein content 35 mg/g, i.e. 4,9 mg per kg of dry salt. Beside the occurrence of hydrophobic volatile compounds in sea salt, hydrophobic non-volatile compounds were also detected. Triacylglycerides were obtained from sea salt by soxhlet extraction with n-hexane. Fatty acid composition revealed palmitic acid as the major residue (43 mol%), followed by stearic (13), linolenic (13), oleic (12), and linoleic (9). Sea salt triacylglycerides median content was 1.5 mg per kg of dry salt. Both protein and triacylglycerides seem to arise from macro and microalgae, phytoplankton and cyanobacteria, due to their abundance and composition. Despite the variability resulting from saltpans surrounding environment, this PhD thesis allowed the identification of a sea salt characteristic organic compounds profile based on volatile compounds, polysaccharides, protein, and triacylglycerides.

A reunião de passagem de turno e a promoção de competências no enfermeiro

Dissertação de Mestrado, Ciências da Educação, especialidade de Observação e Análise da Relação Educativa, Faculdade de Ciências Humanas e Sociais, Universidade do Algarve, 2005

Educação intercultural

Dissertação de Mestrado, Observação e Análise da Relação Educativa, Faculdade de Ciências Humanas e Sociais, Universidade do Algarve, 2007

Phytochemical studies and biological activity of carnivorous plants from the Mediterranean region

Tese de doutoramento, Ciências Biotecnológicas (Biotecnologia Vegetal), Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2010

Le traitement définitoire des noms de plantes herbacées dans le Petit Robert

La présente étude, de type métalexicographique, s'insère dans une perspective de recherche visant à dresser le bilan de la pratique lexicographique réservée aux noms d'espèces naturelles dans les dictionnaires usuels du français. Elle porte sur le traitement définitoire de tous les noms de plantes herbacées répertoriés dans le Petit Robert (édition électronique 1996). Son objectif principal est de décrire très précisément la pratique définitoire en cause. Nous commençons par passer rapidement en revue les différents procédés définitoires illustrés par notre corpus, avant de procéder à l'analyse détaillée du procédé le plus exploité, celui de la définition par inclusion. Notre méthode d'analyse est basée sur la segmentation et l'examen comparatif des différentes composantes sémantiques et formelles présentes dans les définitions par inclusion de notre corpus. Elle permet non seulement de mieux connaître la pratique du Petit Robert , mais aussi d'en extraire un certain savoir-faire. Nous étudions quatre grandes catégories d'éléments descriptifs bien représentées dans notre corpus: les éléments de classification, les éléments de localisation, les éléments de valorisation ainsi que les éléments de morphologie en lien avec ces derniers. Nous donnons, de la métalangue utilisée et des principaux modèles de description exploités, un portrait relativement précis qui pourra alimenter la réflexion des lexicographes et autres linguistes qui s'intéressent à la description des noms d'espèces naturelles en général et des noms de plantes en particulier.

La Bibliothèque du Code civil : un ouvrage au confluent de la tradition et de la modernité

La Bibliothèque du Code civil de Charles-Chamilly de Lorimier et Charles-Albert Vilbon, parue au cours de la seconde moitié du XIXe siècle, demeure un des ouvrages de référence marquants de la production juridique québécoise. Les artisans de cet ouvrage présentent le droit civil comme un héritage du passé. L’oeuvre, par sa valorisation des anciens auteurs, propose une lecture du Code civil qui s’inscrit dans la tradition. En même temps, elle se révèle un outil adapté à la transformation que connaît alors la pratique du droit. La Bibliothèque constitue un témoin éloquent de l’évolution de la culture juridique québécoise.

Antioxidant and phenolic compounds in sweet potato peels and leaves: food applications and health benefits

Tese de doutoramento, Ciências Biotecnológicas (Biotecnologia Alimentar), Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014

Bacterial peroxide forming enzymes

Dissertação de mestrado, Engenharia Biológica, Faculdade de Ciências e Tecnologia, Universidade do Algarve; Instituto de Tecnologia Química e Biológica António Xavier, Universidade Nova de Lisboa, 2015

Formação de técnicos de ação educativa

Trabalho de projeto de mestrado, Ciências da Educação (Formação de Adultos), Universidade de Lisboa, Instituto de Educação, 2013

Contribuição para o estudo dos subprodutos de uma ETAR: gradados e areias

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil, na Área de Especialização de Hidráulica

Plano de negócios para a inovação, fabrico e comercialização de biscoitos portugueses, envolvendo a componente empresarial e social do empreendedorismo

O empreendedorismo tem-se assumido cada vez mais como uma área impulsionadora do desenvolvimento económico dos vários países. O empreendedor tem-se mostrado como um indivíduo capaz de forçar este desenvolvimento através da implementação das suas ideias e projetos criativos e/ou através da sustentabilidade em áreas menos desenvolvidas. De notar que o empreendedorismo atua nas mais diversas áreas, desde a tecnologia, passando pelo turismo, agricultura, atividades industriais ou até mesmo ao nível da responsabilidade e atuação social. Não é portanto, um veículo de desenvolvimento de países ricos ou pobres, desenvolvidos ou em vias de desenvolvimento, é sim, um meio de alcançar mais e melhores resultados, funcionando como força motriz igualmente importante, em grandes metrópoles ou em meios locais rurais. Para que os projetos de empreendedorismo avancem (ou não), é essencial saber reter do plano de negócio a sua real utilidade. Esta ferramenta ao serviço do empreendedor visa ajudar na tomada de decisão, tornando todos os elementos direta ou indiretamente ligados ao projeto, efetivamente visíveis, para que seja viável analisar o seu impacto. Deste modo, pretende-se com esta dissertação dar resposta a questões relacionadas com a viabilidade económico-financeira do projeto em estudo, procurando impulsionar a economia local e nacional através da recuperação e valorização de biscoitos nacionais. É também intuito incluir a perspetiva da Responsabilidade Social neste projeto, para que haja um real intercâmbio de saberes com a comunidade.

Internet au service du patrimoine. Cartographie dynamique de l'inventaire des géotopes d'importance nationale

L'inventaire des géotopes d'importance nationale, aujourd'hui proche de son état final, est le fruit d'un long travail de sélection, de documentation ainsi que de définition et de numérisation des périmètres des sites initié dans les années 1990 par le groupe de travail pour la protection des géotopes en Suisse (Strasser et al. 1995, Berger et al. 2008). Il représente un outil au service de la diffusion et à la promotion du géopatrimoine suisse, auprès de la population en général et des professionnels des géosciences en particulier, dans un but de valorisation patrimoniale et de protection et par une sensibilisation à la valeur particulière et à la vulnérabilité des géotopes.¦C'est dans cet objectif qu'a été développée une interface cartographique rendant accessible sur Internet le contenu de cet inventaire. L'outil de web mapping utilisé - GoogleMaps API - permet en effet d'enrichir une interface de navigation intuitive de diverses fonctions additionnelles offertes par la cartographie sur internet (Kraak 2004, Plewe 2007). La carte n'est donc pas seulement une représentation de la réalité permettant la localisation de différents objets, mais également un outil de recherche thématique et spatiale ainsi qu'un index reliant chaque objet cartographié à diverses informations.¦Porte d'accès aux données des site à une échelle individuelle ou globale, mais aussi outil d'exploration, cette interface propose plusieurs niveaux d'utilisation, correspondant aux diverses interactions possibles avec ces données : naviguer et découvrir les sites, réaliser des sélections multiples, comparer les géotopes à d'autres données, comme l'inventaire fédéral des paysages. L'utilisateur peut ainsi produire à chaque fois la carte qui répond à ses besoins et à ses questions. En donnant à tous accès au contexte et aux particularités de chaque site par delà la globalité abstraite de l'inventaire, cette application se veut avant tout un outil au service de la médiation du géopatrimoine.

Latent Variable Models for Stochastic Discount Factors.

Latent variable models in finance originate both from asset pricing theory and time series analysis. These two strands of literature appeal to two different concepts of latent structures, which are both useful to reduce the dimension of a statistical model specified for a multivariate time series of asset prices. In the CAPM or APT beta pricing models, the dimension reduction is cross-sectional in nature, while in time-series state-space models, dimension is reduced longitudinally by assuming conditional independence between consecutive returns, given a small number of state variables. In this paper, we use the concept of Stochastic Discount Factor (SDF) or pricing kernel as a unifying principle to integrate these two concepts of latent variables. Beta pricing relations amount to characterize the factors as a basis of a vectorial space for the SDF. The coefficients of the SDF with respect to the factors are specified as deterministic functions of some state variables which summarize their dynamics. In beta pricing models, it is often said that only the factorial risk is compensated since the remaining idiosyncratic risk is diversifiable. Implicitly, this argument can be interpreted as a conditional cross-sectional factor structure, that is, a conditional independence between contemporaneous returns of a large number of assets, given a small number of factors, like in standard Factor Analysis. We provide this unifying analysis in the context of conditional equilibrium beta pricing as well as asset pricing with stochastic volatility, stochastic interest rates and other state variables. We address the general issue of econometric specifications of dynamic asset pricing models, which cover the modern literature on conditionally heteroskedastic factor models as well as equilibrium-based asset pricing models with an intertemporal specification of preferences and market fundamentals. We interpret various instantaneous causality relationships between state variables and market fundamentals as leverage effects and discuss their central role relative to the validity of standard CAPM-like stock pricing and preference-free option pricing.

Tests of Conditional Asset Pricing Models in the Brazilian Stock Market

In this paper, we test a version of the conditional CAPM with respect to a local market portfolio, proxied by the Brazilian stock index during the 1976-1992 period. We also test a conditional APT model by using the difference between the 30-day rate (Cdb) and the overnight rate as a second factor in addition to the market portfolio in order to capture the large inflation risk present during this period. The conditional CAPM and APT models are estimated by the Generalized Method of Moments (GMM) and tested on a set of size portfolios created from a total of 25 securities exchanged on the Brazilian markets. The inclusion of this second factor proves to be crucial for the appropriate pricing of the portfolios.