Les α-hélices sont des éléments clés de la reconnaissance biomoléculaire, comme en témoigne le fait qu'une quantité significative de complexes protéine-protéine, dans la banque de données protéiques (PDB), présentent des interfaces inter-hélices. Cependant, de courtes hélices peptidiques isolées dans le but de bloquer ces interactions ne sont généralement que faiblement présentes en milieu aqueux et sont sensibles à la dégradation protéolytique, limitant ainsi leur potentiel thérapeutique. Diverses approches chimiques ont été proposées pour augmenter la propension au repliement en hélice des α-peptides. Une stratégie consiste à pré-organiser les premières liaisons amides à l'aide d'une « capping box » ou d'un substitut de liaison hydrogène. Récemment, nous nous sommes intéressés à la possibilité d'interfacer des peptides-α et des foldamères afin d’élaborer des « foldamères à blocs » générant ainsi un nouveau type d’architecture mime de l'hélice-α. Dans notre laboratoire, nous avons développé des foldamers à base d’urées qui s’organisent pour former des structures hélicoïdales. Les similitudes du sens d’enroulement, du pas et de la polarité entre l’hélice-α peptidique et l’hélice-2.5 d'oligourée suggéraient qu'il serait possible de combiner ces deux squelettes. Au cours de cette thèse, nous avons montré que les chimères : oligourée/α-peptide, forment des structures hélicoïdales bien définies dans les solvants organiques polaires avec la propagation d'un réseau de liaisons hydrogène intramoléculaires continu couvrant la totalité de la séquence. Ces études ont suggéré que le squelette de l'oligourée qui possède une forte propension à adopter une structuration en hélice pourrait conduire au développement d’un « cap » permettant la pré-organisation des quatre premiers NHs ainsi que des quatre derniers groupements carbonyles d’une hélice-α peptidique. Nous avons donc étudié l'influence de courts fragments oligourées sur la stabilisation de séquences peptidiques modèles solubles dans l'eau en hélices-α, conduisant au développement de la « foldamer capping box ». Grâce à cette nouvelle stratégie de stabilisation des hélices peptidiques, nous avons pu concevoir des inhibiteurs de l’interaction protéine/protéine p53/MDM2. / Α-Helices are key elements of biomolecular recognition, as reflected by the fact that a large fraction of the protein-protein complexes in the Protein Data Bank (PDB) feature helical interfaces. However, short isolated peptide helices are generally only weakly populated in aqueous environment and are sensitive to proteolytic degradation, thus limiting their therapeutic potential. Various chemical approaches have been proposed to increase the helix folding propensity of α-peptides. One strategy is to pre-organize the first amide bonds through the use of a "capping box" or a hydrogen bond surrogate. Recently we became interested by the possibility to interface peptide and foldamer helical backbones in order to develop “block co-foldamers“, to generate new generations of α-helix mimics. In our laboratory, we have developed oligourea foldamers which are organized to form helical structures. The similarities in helix screw sense, pitch, and polarity between the peptide α-helix and the oligourea 2.5-helix suggested that it would be feasible to combine these two backbones. In this thesis, we have shown that the resulting oligourea/α-peptide chimeras form well-defined helical structures in polar organic solvents with the propagation of a continuous intramolecular hydrogen bonding network spanning the entire sequence. These studies provided a rationale for the use of the oligourea backbone which is strongly biased towards helix formation could lead to the development of pre-organized caps for the initial four amide NHs and the final four carbonyl groups of a peptide α-helix. We have therefore studied the influence of short oligourea fragments on the stabilization of model water-soluble peptide sequences in α-helices, leading to the development of the foldamer capping box. This strategy awas pplied for the first time to the design of potent inhibitors of protein/protein interactions (e.g. p53/MDM2).

Les dispersions colloïdales ont beaucoup d’applications technologiques importantes. A cause du mouvement brownien, les particules ont des collisions fréquentes entre elles. Les forces d’attraction de van der Waals,dérivant de potentiels à longue portés, conduisent à l’agrégation et à la précipitation des particules. Plusieurs méthodes ont été proposées pour diminuer ou contrebalancer l’effet d’attraction de van der Waals et augmenter la stabilité colloïdale. Par exemple, le choix du solvant possédant l’indice de réfraction le plus proche possible de celui des particules peut diminuer les forces de van der Waals. D'autres facteurs influencent la stabilité comme les interactions électrostatiques et les interactions spécifiques liées aux chaînes de polymères. Dans le cas des polymères, les chaînes peuvent être greffées à la surface des particules ou être dissoutes dans le solvant (chaînes libres). Dans ce travail de thèse, nous avons étudié l’effet de la stabilisation par déplétion dans le cas des chaînes de polymères libres (FPI, "free polymer induced interaction"). Des modèles théoriques précédents portent un caractère trop simplifié et utilisent des approximations sans vérification. De plus, l’influence des paramètres de la solution, c’est-à-dire, de la structure de polymères et de son interaction avec la surface de particule, n’a pas été étudiée.Les chaînes polymères libres ont été modélisées comme des marches aléatoires dans un champ moléculaire auto-cohérent qui satisfait à l'équation intégro-différentielle de diffusion. Pour le domaine moléculaire, nous avons utilisé un potentiel chimique qui, pour la solution de polymère semi-dilué, peut être représenté comme une expansion du viriel où nous n’avons pris en considération que les deuxième et troisième coefficients du viriel de la solution de polymère. En variant des paramètres tels que la rigidité du polymère, la longueur du polymère, la concentration en polymère et le régime du solvant (comme le solvant thêta), que ce soit pour une surface colloïdale purement répulsive, pour une surface adsorbée ou pour la surface d'une couche de polymère greffé, nous avons été en mesure d'améliorer la barrière répulsive due aux polymères libres entre les particules et donc nous avons trouvé des conditions de la stabilisation cinétique du système. / Stable colloidal dispersions with evenly distributed particles are important for many technological applications. Due to Brownian motion colloidal particles have constant collisions with each other which often lead to their aggregation driven by the long range van der Waals attraction. As a result the colloidal systems often tend to precipitate. A number of methods have been devised to minimize the effect of long-range van der Waals attraction between colloidal particles or to override the influence of the attraction in order to provide the colloidal stability.In the PhD thesis we investigated the colloidal stabilization in solutions of free polymers which is commonly referred to as depletion stabilization. Previous theoretical studies of free-polymer induced (FPI) stabilization were based on oversimplified models involving uncontrolled approximations. Even the most basic features of the depletion stabilization phenomenon were unknown. It was unclear how the PI repulsion depends on the solution parameters, polymer structure and monomer/surface interactions.The free polymer chains were modeled as random walks in a self-consistent molecular field that satisfied to diffusion-like integro-differential equation. As the molecular field we used the chemical potential that for semi-dilute polymer solution can be represented as a virial expansion where we took into account only second and third virial coefficients of the polymer solution. Varying the parameters like polymer stiffness, polymer length, polymer concentration and solvent regime (like theta solvent) whether it is for purely repulsive colloidal surface, adsorbed surface or surface with grafted polymer layer we were able to enhance the repulsive barrier due to the free polymers between the particles and therefore found conditions for kinetic stabilization of the system.

The thesis is looking into an assessment of a postural stabilization in a group of preschool children using an unused test in children testing "Kneeling with Support on Palms", which was used by its creators Voráčková and Šafářová in a group of adult sportsmen, and for comparison is used Matthias test, which is usually used in children testing. The thesis is focused on optimal body positions in the ontogenetic progress in the preschool age, the right body postural, dangers of origin of pathologies in postural stabilization, pathologies in body postural and the usually used diagnostic in the assessment of body postural. Results are showing a possibility of the using the test "Kneeling with Support on Palms" in preschool groups and at the same time showing chosen pathologies in the body postural of three and six years old children. The success in the thesis is a fact, that correlation with Matthias test shows for validity of the test "Kneeling with Support on Palms" and it brings information, that the test "Kneeling with Support on Palms" can be used in preschool age groups after confirmation of its reliability and objectivity. Key words: postural stabilization, body positions, preschool children, deflection in body postural

[pt] A utilização de inclusões passivas para reforços de solos, técnica comumente conhecida como solo grampeado, vem tendo aceitação crescente junto a profissionais de engenharia civil, em especial no Rio de Janeiro. Esta técnica, porém, carece de um estudo detalhado sobre a influência dos parâmetros relevantes na deformabilidade de maciços grampeados. Os grampos são inclusões rígidas, instaladas suborizontalmente, sem tensão ou trecho livre, pois as barras de aço são introduzidas em um furo preenchido com calda de cimento. As forças axiais nos grampos são obtidas através da descompressão lateral causada pela escavação do solo. O grampeamento é feito na massa de solo à medida que escavações são executadas em etapas, obtendo se uma zona reforçada que atua como suporte da massa de solo posterior, sem reforço. A face frontal da escavação é usualmente protegida por concreto projetado, sem funções estruturais. Esta pesquisa objetiva avaliar a influência dos diversos parâmetros geotécnicos e geométricos no comportamento tensão deformação de escavações grampeadas com face vertical e superfície do terreno horizontal. A análise paramétrica foi realizada pelo FLAC (Fast Lagrangian Analysis of Continua) que é um programa computacional baseado no método das diferenças finitas. Este programa simula o comportamento bidimensional de estruturas reforçadas, constituídas de solo e ou rocha, que possam ser submetidos a escoamento plástico quando o limite de resistência é atingido. Os resultados mostram que o módulo de Young (E) e a coesão do solo (c) são de grande relevância para o projeto de estruturas grampeadas. Adicionalmente, as análises indicam que a resistência ao cisalhamento na interface solo-grampo (qs) é também um parâmetro importante, particularmente nos casos com grampos de comprimento (L) inferior a 80 por cento da profundidade de escavação (H) (L/H < 0,80). Recomenda-se que o valor de qs seja determinado diretamente a partir de ensaios de arrancamento no campo. No que se refere à inclinação dos grampos, os resultados mostram que não há diferenças significativas nos deslocamentos do maciço reforçado para lambda menor ou igual a 10 graus. Estes resultados são particularmente interessantes do ponto de vista de execução, pois inclinações da ordem de 10 graus facilitam os procedimentos de injeção no campo. Os resultados obtidos nesta pesquisa indicam o uso de comprimentos de grampos maiores que 70 por cento da altura de escavação (L/H > 0,70) na técnica do solo grampeado. / [en] The use of passive inclusion for soil reinforcements, technique usually known as soil nailing, has been gaining growing acceptance within civil engineering professionals,especially in Rio de Janeiro. However this technique lacks a more detailed study on the elevant parameters influencing the deformability of soil nailed masses. The nails are rigid inclusions, sub horizontally positioned, without tension or free space between the nail and the surrounding soil mass. The axial forces on the nails are developed due to lateral decompression caused by soil excavation. As the excavation stages proceed, the nails are successively being installed, producing a reinforced zone, which acts as a support for the soil mass. The frontal face of the excavation is usually protected by shotcrete, and has no structural functions. This research aims at evaluating the influence of the various geotechnical and geometric parameters on the stress strain behavior of nailed excavations, with vertical face and horizontal soil surface. The parametric analysis was performed using FLAC (Fast Lagrangian Analysis of Continua), which is a computer program based on the finite difference method. This program simulates bi dimensional behavior of reinforced structures of soils and or rocks,which may be submitted to plastic flow when the strength limit is reached. The results show that the Youngs modulus (E) and soil cohesion (c ) have a very significant influence on the displacement of a soil nailing structure. The analysis also indicates that the mobilized shear strength at the soil nail interface (qs) is also an important parameter, particularly for nail lengths (L) smaller than 0,80 of the excavation height (H) (L/H < 0,80). It is therefore recommended that qs be directly determined by pullout in situ tests. Regarding nail inclination the results suggests no significant influence on the reinforced soil mass displacement for alpha less or equal than 10 degrees. These results are particularly relevant for engineering practice, because a 10 degrees inclination facilitates grouting injections in the field. The results in this research indicates the use of nail lengths (L) greater than 0,70 of the excavation height (H) (L/H greater than 0,70) in soil nailing technique.

Slurry is the fluid within a drilled excavation that is introduced when an excavation is deeper than the water table or where additional stability is needed for loose sandy dry soils. Although construction practices vary greatly throughout the country and the world, slurry levels should be maintained above the existing ground water level by a suitable margin. The most widely used slurry type is mineral slurry formed by mixing dry clay powder with water; either bentonite or attapulgite powder may be used (attapulgite being used in saline water conditions). Regardless of whether the slurry material is mineral, polymer or natural, the construction practice must address the slurry properties to ensure the stability of the excavation is never compromised. Proper performance of slurries used to stabilize drilled shaft excavations is maintained by assuring the density, viscosity, pH, and sand content stay within specified limits. These limits have been set either by past experience, research findings and/or by manufacturer recommended values. However, field slurry testing is time consuming as all measurements are manually performed. With the overwhelming advances in digital down-hole devices, it is not unreasonable to assume that slurry property tests are equally applicable to this trend. This formed the basis of this project. The most commonly used test to indicate slurry viscosity is the Marsh Funnel Test which is essentially a timed flow for a fixed volume of slurry to exit a falling head funnel. Using a library of unique pressure versus flow rate responses for a wide range of slurry viscosities, an automated downhole device was designed and tested that incorporated this information to estimate viscosity in the excavation without the need to remove slurry in order to test. Direct measurement of slurry density was also incorporated into the device and the sand content was computed from density and the viscosity where the suspended solids that make up the density stems from both the slurry products and the soil cuttings.

Doctor of Philosophy / Department of Civil Engineering / Alok Bhandari / Human activities generate large amounts of chlorinated phenolic chemicals that are often introduced into the soil environment during pesticide and insecticide application, industrial releases, and accidental spills. For example, 2,4-dichlorophenol (DCP), a derivative of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) can been found in soil within 24 hours of 2,4- D application. Horseradish peroxidase (HRP)-mediated polymerization has been proposed as an approach to remediate soils and groundwater contaminated by phenolic pollutants. Treatment with HRP results in the transformation of phenols into polyphenolic oligomers that sorb strongly or precipitate on soils surfaces. Although HRP-mediated chlorophenol stabilization has been studied extensively in surface soils, very limited scientific data is available that supports the application of this technology in subsurface materials. Hence, the focus of this study was to evaluate sorption and binding of DCP and products of HRP-mediated polymerization of DCP to model geosorbents representing subsurface geomaterials. These sorbents included two humin-mineral geomaterials and one mineral geosorbent derived from surface soils. Soil-water phase distribution of total solute in the HRP-amended systems was observed to reach equilibrium within 7 days in woodland humin-mineral soil (WHM), and within 1 day in agricultural humin-mineral (AHM) and model mineral geomaterials. For all the geomaterials used, water extraction data indicated the development of contact time-dependent resistance to extraction/dissolution of soil-associated DCP and DPP. Solute associated with WHM geomaterial was higher at the end of the study than that associated with AHM. Contact time increased DCP stabilization at all initial aqueous DCP concentrations studied. Results of this study suggest that DCP stabilization in organic geosorbents results from a combination of sorption and cross-coupling of DCP and precipitation of DPP; in inorganic soils, precipitation of DPP macromolecules is the dominant process. HRP-mediated stabilization of DCP in soils was effective and independent of the solution ionic concentration. The amount of DCP stabilized in the mineral soil was comparable to that stabilized in humin-mineral geomaterials. The research reported in this dissertation demosntrates the potential of HRP enzyme to stabilize DCP in subsurface geomaterials under variable contaminant and salt concentrations, thereby restricting its transport in the environment.

This Master´s Thesis is focused on two areas of human resource management which are motivation and stabilization of employees and the link between them. The aim of my Master´s Thesis is to analyze the structure and quality of management of employee motivation and stabilization in a particular company through my own questionnaire survey and internal company data collection. The questionnaire survey is mainly focused on identifying motivation profiles of the company's employees and factors that have a positive impact on their job satisfaction. Thanks to analysis, the relevant conclusions and suggestions are made to strengthen or stabilize the company's strengths and reduce their weaknesses in area of motivation and stabilization management. The outputs of my Master´s Thesis can be used by the company management in order to improve the quality of human resources management and stabilize company's employees.

Ce travail de thèse a porté sur l’étude des méthodes de traitement des sédiments de dragage en vue de leur remédiation et leur valorisation : la méthode électrocinétique et la méthode solidification/stabilisation. Deux dispositifs expérimentaux (à deux échelles différentes) ont été développés et une série d’essais électrocinétiques ont été effectués sous différentes conditions (valeurs du potentiel électrique, système ouvert/fermé, solutions d’électrolyte : EDTA, EDDS, NTA et Acide citrique). Chaque chélatant fournit une efficacité d’extraction sur un métal donné. Les résultats obtenus montrent que le contrôle de pH à la cathode par l’acide citrique et l’ajout d’un tensio-actif (Tween 20) peuvent augmenter l’effet de remédiation des métaux. Par ailleurs, lorsque le système est fermé, l’efficacité d’électroremédiation est plus élevée. Les abattements obtenus pour les métaux dans la matrice des sédiments sous des conditions optimales peuvent atteindre 60 %. Pour ce qui est de la solidification/stabilisation, plusieurs formulations (de chaux, de ciment et de fumée de silice) associées au sédiment ont été testées dans le but de reconstituer un matériau résistant et durable dans l’objectif de son utilisation dans les remblais routiers. Les éprouvettes de sédiment traitées ont été soumises à des conditions sévères de température et d’humidité. Des essais de lixiviation ont été effectués sur le matériau obtenu afin de déterminer la capacité des formulations à stabiliser les éléments polluants contenus dans le sédiment. Les résultats obtenus avec 12 différentes formulations ont montré que la résistance requise est obtenue avec des proportions raisonnables d’ajouts, tandis que l’exigence de durabilité nécessite une plus grande proportion de chaux. / This thesis research is devoted to investigate the treatment methods of dredged sediments in order their restoration and valorisation: electroremediation and solidification/stabilization. Two experimental set-up (at two different scales) have been designed and a series of tests were performed under different conditions (electric potential values, opened/closed system, electrolyte solutions: EDTA, EDDS, NTA and Citric Acid). Each chelating agent provides an extraction efficiency for a given metal. The obtained results show that the pH control at the cathode by citric acid and its combinations with a surfactant (Tween 20) can increase the metal removal effect. Moreover, under closed system condition, metal removal efficiency became stronger. The obtained metal removals values within the matrix of sediment under optimal conditions can reach 60%. As regard to the solidification/stabilization, serval formulations (of lime, cement and silica fume) associated to the sediment were tested in order to create a resistant and sustainable material forwarding to be used as a road embankments. The specimens of treated sediment were submitted to severe conditions of temperature and wettability. Leaching tests were carried out on the obtained material in order to assess a capability of used formulations to stabilize pollutant elements contained in the sediment. The obtained results from 12 different formulations showed that the required resistance is obtained with the reasonable proportions of binders, while the sustainability requirement need higher lime content in the formulation.

Most soils in the Eastern Cape Province, South Africa are shallow and are low in organic matter. Therefore these soils are structurally fragile and highly susceptible to inherent degradative processes like hardsetting. The objective of this study was to determine the effect of cattle manure, scalping and soil wetness on aggregate stability, penetration resistance and early maize growth in hardsetting soils. Glasshouse and field studies were conducted to determine the effect of cattle manure on aggregate stability and penetration resistance of freshly exposed topsoils by scalping at 0, 10 and 20 cm depths. In the glasshouse cattle manure was applied at 0 and 20 Mg/ha and matric suction was kept at ~ 30 and ~ 400 kPa; contrasting high and low soil wetness. Three soils were put in pots and arranged in a randomized complete block 3 2 2 factorial design. The field study was done at the University of Fort Hare research farm and the treatments were arranged in a split-plot complete randomized design with three replications. Scalping treatment was the main plot whilst the quantity of the cattle manure applied was the sub plot. Cattle manure increased mean weight diameter (MWD) by between 48% and 71% under glasshouse and between 18% and 33% under field conditions, depending on the soil wetting rate. Cattle manure reduced MWD when the soil under field condition was subjected to mechanical shaking. Soil penetration resistance decreased linearly, with increasing soil wetness but it rapidly increased with increase in matric suction up to ~200 kPa and thereafter the rate of increase reduced. In the glasshouse, all treatments had no significant effects on shoot dry weight but low matric suction increased root dry weight by 133%. Interaction of cattle manure and low matric suction reduced shoot length by 6%, shoot fresh weight by 25%, root surface area by 36%, root length by 5% and root fresh weight by 29% compared to the control. In contrast, application of cattle manure and high matric suction increased shoot length by 37%, shoot fresh weight by 136%, root surface area by 159%, root length by 94% and root fresh weight by 119%. In the field, cattle manure application increased root length density and shoot dry matter by 26% and 30% respectively. Cattle manure improved the stability of aggregates of the hardsetting soil under rapid or slow water intake conditions experienced during rainfall or irrigation. However, under field conditions cattle manure acted as a deflocculant and decreased the stability of aggregates when mechanical stress was applied. The effectiveness of cattle manure in improving maize growth in hardsetting soils was determined by matric suction.

My theses scope is description of the Spanish relationship to European Union from the first integration tendencies after the WW II till the preferential agreement ratification in 1970. I will try to analyze part of the Spanish economic history within the context of west-European integration. This period precedes the political transformation of autocratic Spain to modern democracy. These democratic cabinets were able to aspire seriosusly to fully-fledged European Union membership. In my opinion it is not possible to view political transformation as a start-up for democratically elected governments to setup new relationships with EU but it is necessary to understand it as an important condition which is part of a long-term process of Spanish convergence to west-European integration. In my theses I primarily concentrate on the economic development but I mean that it is important to mention the political situation as well.