Nanostructured catalysts for the development of the hydrogen economy

La catalyse joue un rôle essentiel dans de nombreuses applications industrielles telles que les industries pétrochimique et biochimique, ainsi que dans la production de polymères et pour la protection de l’environnement. La conception et la fabrication de catalyseurs efficaces et rentables est une étape importante pour résoudre un certain nombre de problèmes des nouvelles technologies de conversion chimique et de stockage de l’énergie. L’objectif de cette thèse est le développement de voies de synthèse efficaces et simples pour fabriquer des catalyseurs performants à base de métaux non nobles et d’examiner les aspects fondamentaux concernant la relation entre structure/composition et performance catalytique, notamment dans des processus liés à la production et au stockage de l’hydrogène. Dans un premier temps, une série d’oxydes métalliques mixtes (Cu/CeO2, CuFe/CeO2, CuCo/CeO2, CuFe2O4, NiFe2O4) nanostructurés et poreux ont été synthétisés grâce à une méthode améliorée de nanocasting. Les matériaux Cu/CeO2 obtenus, dont la composition et la structure poreuse peuvent être contrôlées, ont ensuite été testés pour l’oxydation préférentielle du CO dans un flux d’hydrogène dans le but d’obtenir un combustible hydrogène de haute pureté. Les catalyseurs synthétisés présentent une activité et une sélectivité élevées lors de l’oxydation sélective du CO en CO2. Concernant la question du stockage d’hydrogène, une voie de synthèse a été trouvée pour le composét mixte CuO-NiO, démontrant une excellente performance catalytique comparable aux catalyseurs à base de métaux nobles pour la production d’hydrogène à partir de l’ammoniaborane (aussi appelé borazane). L’activité catalytique du catalyseur étudié dans cette réaction est fortement influencée par la nature des précurseurs métalliques, la composition et la température de traitement thermique utilisées pour la préparation du catalyseur. Enfin, des catalyseurs de Cu-Ni supportés sur silice colloïdale ou sur des particules de carbone, ayant une composition et une taille variable, ont été synthétisés par un simple procédé d’imprégnation. Les catalyseurs supportés sur carbone sont stables et très actifs à la fois dans l’hydrolyse du borazane et la décomposition de l’hydrazine aqueuse pour la production d’hydrogène. Il a été démontré qu’un catalyseur optimal peut être obtenu par le contrôle de l’effet bi-métallique, l’interaction métal-support, et la taille des particules de métal.

Directive Cadre sur l’Eau : les pressions anthropiques et leur impact sur les indicateurs de l’état écologique des masses d’eau littorales de la façade Manche-Atlantique. Synthèse bibliographique

Within the European water framework directive (WFD), the status assessment of littoral waters is based both on the chemical quality and on the ecological quality of each water body. Quality elements enabling to assess the ecological status of a water body are, among other things, biological quality elements (phytoplankton, macroalgae, angiosperms, benthic invertebrates, fish), for each of which the member states have developed quantitative indicators. This document is one of the deliverables of a multi-annual study intended to characterize the sensitivity of these biological indicators towards the various anthropogenic pressures exerted on the French Atlantic and Channel coast: ultimately, the goal is to establish a quantitative and predictive relationship, statistically robust, between the WFD indicators used along the French channel and Atlantic coastline, and various anthropogenic pressures acting on these coasts. The aim of the WFD is indeed to restore or maintain a good chemical and biological quality of coastal waters, and thus to limit the impact of human activities potentially responsible for the degradation of ecosystems. This understanding of the linkages and interactions existing between anthropogenic pressures and ecological status of water bodies is therefore essential to identify priorities for action (challenges, substances ...), prioritize actions to implement within restoration programs (technical, fiscal, financial), but also to be able to communicate constructively and persuasively in talks between managers and the various stakeholders of coastal regions. Using the DPSIR methodology, this literature analysis has permitted to identify, for each WFD biological quality element (except fish), which pressures (or pressure types) are potentially relevant in the light of their impact on the indicators of the ecological status of water bodies. Some metrics and indicators of anthropogenic pressures used in the literature to characterize the sensitivity of the biological quality elements, within quantitative approaches, were also identified. It is also clear from this review that the biological quality elements can be particularly sensitive to intrinsic environmental conditions, and therefore to certain changes related to natural phenomena occurring at large scales (e.g. climate change, paroxysmal climate episode...). Therefore, when one is interested in the sensitivity of biological indicators to different anthropogenic pressures, two factors can complicate the analysis and are likely to weaken the resulting statistical relationships: on the one hand, the variability of biological responses depending on the natural context and, on the other hand, interactions (so called synergistic effects) between different types of anthropogenic pressures and the alterations they can generate.

Directive Cadre sur l’Eau : les pressions anthropiques et leur impact sur les indicateurs de l’état écologique des masses d’eau littorales de la façade Manche-Atlantique - Développement d’une base de données quantitatives sur les pressions anthropiques littorales

Within the European water framework directive (WFD), the status assessment of littoral waters is based both on the chemical quality and on the ecological quality of each water body. Quality elements enabling to assess the ecological status of a water body are, among other things, biological quality elements (phytoplankton, macroalgae, angiosperms, benthic invertebrates, fish), for each of which member states have developed quantitative indicators. This document compiles three deliverables of a multi-annual study intended to characterize the sensitivity of these biological indicators regarding the various anthropogenic pressures exerted on the French Atlantic and Channel coast: ultimately, the goal is to establish a quantitative and predictive relationship, statistically robust, between the WFD indicators used along the French channel and Atlantic coastline, and various anthropogenic pressures acting on these coasts. These three deliverables are the following : - The reports of various interviews performed with French national referents for the biological quality elements used within the littoral part of the WFD in Channel and Atlantic (phytoplankton, subtidal and intertidal macroalgae, opportunistic blooming macroalgae, angiosperms and benthic invertebrates). These interviews aimed to specify, for each metric constitutive of the BQE indicator (if multi-metric), the "relevant" pressures, as well as the trend of this impact, - Sheets describing the "pressure" and "environment" data available, in order to characterize spatially and quantitatively these "relevant" anthropogenic pressures acting on French Channel and Atlantic coast, - A progress report dealing with the development of a database tool, for archiving quantitative data characterizing "relevant" littoral anthropogenic pressures.

Estrutura de organizações sociais: adaptação aos projetos sociais ou às pressões institucionais?

This is a study concerning in the structure of non governmental organizations, based on the institutional theory. It aims to understand the relation among structure, social projects and environmental influences, analyzing if there is coherence with project social or expresses adaptation to the institutional pressures of the environment. It introduces as theoretical support for the themes, studies about institutional theory and social structure. The research is descriptive and exploratory; it also applies to a study of case, based on the technical procedures. From the research universe, that was compound by non governmental organizations from Natal, RN, Brasil, it was chosen the Casa Renascer, a non governmental organization that works with the combat to the violence and sexual exploration of children and teenagers. The data collection process employed includes documental research, observations and semi structured research devices, guided by the organizational process proposed by Serva (1996) and by the institutional theory. The collected data were qualitatively treated. The analysis was divided into three parts, following the research matters. The social project characterization demonstrated that the organization went by three main phases. The first one, characterized by focus in women and girls education and health; the second shows the emphasis on girls in social risk situation, with preventive approach; and the last one, characterized by victims assistance of violence and sexual exploration. From the analysis using the institutional theory mechanisms, the results showed that exists coherence between structure and environmental influences, but a weak coherence between structure and social projects. It indicates as main determinant of the structure, an aspect forgotten by the institutional theory, the power. It was observed the presence from normative, coercive and mimetic mechanisms, highlighting normative influences

Anticancer drug discovery using artificial intelligence: an application in pharmacological activity prediction

Hematological cancers are a heterogeneous family of diseases that can be divided into leukemias, lymphomas, and myelomas, often called “liquid tumors”. Since they cannot be surgically removable, chemotherapy represents the mainstay of their treatment. However, it still faces several challenges like drug resistance and low response rate, and the need for new anticancer agents is compelling. The drug discovery process is long-term, costly, and prone to high failure rates. With the rapid expansion of biological and chemical "big data", some computational techniques such as machine learning tools have been increasingly employed to speed up and economize the whole process. Machine learning algorithms can create complex models with the aim to determine the biological activity of compounds against several targets, based on their chemical properties. These models are defined as multi-target Quantitative Structure-Activity Relationship (mt-QSAR) and can be used to virtually screen small and large chemical libraries for the identification of new molecules with anticancer activity. The aim of my Ph.D. project was to employ machine learning techniques to build an mt-QSAR classification model for the prediction of cytotoxic drugs simultaneously active against 43 hematological cancer cell lines. For this purpose, first, I constructed a large and diversified dataset of molecules extracted from the ChEMBL database. Then, I compared the performance of different ML classification algorithms, until Random Forest was identified as the one returning the best predictions. Finally, I used different approaches to maximize the performance of the model, which achieved an accuracy of 88% by correctly classifying 93% of inactive molecules and 72% of active molecules in a validation set. This model was further applied to the virtual screening of a small dataset of molecules tested in our laboratory, where it showed 100% accuracy in correctly classifying all molecules. This result is confirmed by our previous in vitro experiments.

Modelling the distribution of bats in relation to landscape structure in a temperate mountain environment

1. Landscape modification is often considered the principal cause of population decline in many bat species. Thus, schemes for bat conservation rely heavily on knowledge about species-landscape relationships. So far, however, few studies have quantified the possible influence of landscape structure on large-scale spatial patterns in bat communities. 2. This study presents quantitative models that use landscape structure to predict (i) spatial patterns in overall community composition and (ii) individual species' distributions through canonical correspondence analysis and generalized linear models, respectively. A geographical information system (GIS) was then used to draw up maps of (i) overall community patterns and (ii) distribution of potential species' habitats. These models relied on field data from the Swiss Jura mountains. 3. Fight descriptors of landscape structure accounted for 30% of the variation in bat community composition. For some species, more than 60% of the variance in distribution could be explained by landscape structure. Elevation, forest or woodland cover, lakes and suburbs, were the most frequent predictors. 4. This study shows that community composition in bats is related to landscape structure through species-specific relationships to resources. Due to their nocturnal activities and the difficulties of remote identification, a comprehensive bat census is rarely possible, and we suggest that predictive modelling of the type described here provides an indispensable conservation tool.

Macrophyte community structure and species occurrence in relation to environmental determinants in the ephemeral aquatic habitats of Gavdos, Greece

The aims of this study were to explore the environmental factors that determine the distribution of plant communities in temporary rock pools and provide a quantitative analysis of vegetation-environment relationships for five study sites on the island of Gavdos, southwest of Crete, Greece. Data from 99 rock pools were collected and analysed using Two-Way Indicator Species Analysis (TWINSPAN), Detrended Correspondence Analysis (DCA) and Canonical Correspondence Analysis (CCA) to identify the principal communities and environmental gradients that are linked to community distribution. A total of 46 species belonging to 21 families were recorded within the study area. The dominant families were Labiatae, Gramineae and Compositae while therophytes and chamaephytes were the most frequent life forms. The samples were classified into six community types using TWINSPAN, which were also corroborated by CCA analysis. The principal gradients for vegetation distribution, identified by CCA, were associated with water storage and water retention ability, as expressed by pool perimeter and water depth. Generalised Additive Models (GAMs) were employed to identify responses of four dominant rock pool species to water depth. The resulting species response curves showed niche differentiation in the cases of Callitriche pulchra and Tillaea vaillantii and revealed competition between Zannichellia pedunculata and Chara vulgaris. The use of classification in combination with ordination techniques resulted in a good discrimination between plant communities. Generalised Additive Models are a powerful tool in investigating species response curves to environmental gradients. The methodology adopted can be employed for improving baseline information on plant community ecology and distribution in Mediterranean ephemeral pools.

Quantitative characterization of physico-chemical properties of the active layers of reverse osmosis and nanofiltration membranes, and their relation to membrane performance

The main objectives of this dissertation were: (i) to develop experimental and analytical procedures to quantify different physico-chemical properties of the ultra-thin (~ 100 nm) active layers of reverse osmosis (RO) and nanofiltration (NF) membranes and their interactions with contaminants; (ii) to use such procedures to evaluate the similarities and differences between the active layers of different RO/NF membranes; and (iii) to relate characterization results to membrane performance. Such objectives were motivated by the current limited understanding of the physico-chemical properties of active layers as a result of traditional characterization techniques having limitations associated with the nanometer-scale spatial resolution required to study these ultra-thin films. Functional groups were chosen as the main active layer property of interest. Specific accomplishments of this study include the development of procedures to quantify in active layers as a function of pH: (1) the concentration of both negatively and positively ionized functional groups; (2) the stoichiometry of association between ions (i.e., barium) and ionized functional groups (i.e., carboxylate and sulfonate); and (3) the steric effects experienced by ions (i.e., barium). Conceptual and mathematical models were developed to describe experimental results. The depth heterogeneity of the active layer physico-chemical properties and interactions with contaminants studied in this dissertation was also characterized. Additionally, measured concentrations of ionized functional groups in the polyamide active layers of several commercial RO/NF membranes were used as input in a simplified RO/NF transport model to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) at different pH values based on rejection results at one pH condition. The good agreement between predicted and experimental results showed that the characterization procedures developed in this study serve as useful tools in the advancement of the understanding of the properties and structure of the active layers of RO/NF membranes, and the mechanisms of contaminant transport through them.

Carbon structure and porosity of carbonaceous adsorbents in relation to their adsorption properties

A number of carbonaceous adsorbents were prepared by carbonisation at 600 degrees C following acidic oxidation under various conditions. Effects of the chemical nature of the precursor, such as the ratio of aromatic to aliphatic carbons and oxygen content, on the chemical and structural characteristics of the resultant chars were investigated using C-13 NMR and Raman spectroscopy, respectively. The C-13 NMR spectral parameters of the coal samples show that as the severity of oxidation conditions increased, the ratio of aromatic to aliphatic carbons increased. Furthermore, it was also found that the amount of disorganised carbon affects both the pore structure and the adsorption properties of carbonaceous adsorbents. It is demonstrated that higher amount of the disorganised carbon indicates smaller micropore size. (C) 1999 Elsevier Science Ltd. All rights reserved.

On the relation between ownership structure and capital structure

The agency relationship between managers and shareholders has the potential to influence decision-making in the firm which in turn potentially impacts on firm characteristics such as value and leverage. Prior evidence has demonstrated an association between ownership structure and firm value. This paper extends the literature by examining a further link between ownership structure and capital structure. Using an agency framework, it is argued that the distribution of equity ownership among corporate managers and external blockholders may have a significant relation with leverage. The empirical results provide support for a positive relation between external blockholders and leverage, and non-linear relation between the level of managerial share ownership and leverage. The results also suggest that the relation between external block ownership and leverage varies across the level of managerial share ownership. These results are consistent with active monitoring by blockholders, and the effects of convergence-of-interests and management entrenchment.

Abundance of two Dendrocincla woodcreepers (aves: Dendrocolaptidae) in relation to forest structure in Central Amazonia

Few studies have been conducted to verify how the structure of the forest affects the occurence and abundance of neotropical birds. Our research was undertaken between January 2002 and July 2004 at the Reserva Ducke, near Manaus (02º55',03º01'S; 59º53',59º59'W) in central Amazonia, to verify how the forest structure affects the occurrence and abundance of two bird species: the Plain-brown Woodcreeper Dendrocincla fuliginosa and the White-chinned Woodcreeper Dendrocincla merula. Bird species occurrence was recorded using lines of 20 mist-nets (one sample unit), along 51 1-km transects distributed along 9 pararel 8 km trails covering an area of 6400 ha. Along these transects, we placed 50 x 50m plots where we recorded forest structure components (tree abundance, canopy openness, leaf litter, standing dead trees, logs, proximity to streams, and altitude). We then related these variables to bird occurence and abundance using multiple logistic and multiple linear regression models, respectively. We found that D. fuliginosa frequently used plateau areas; being more abundant in areas with more trees. On the other hand, D. merula occurred more frequently and was more abundant in areas with low tree abundance. Our results suggest that although both species overlap in the reserve (both were recorded in at least 68% of the sampled sites), they differ in the way they use the forest microhabitats. Therefore, local variation in the forest structure may contribute to the coexistence of congeneric species and may help to maintain local alpha diversity.