Cette thèse soutient que les politiques de migrations temporaires entravent la mobilité de l'individu, à partir du cas des migrants indiens dans la région du golfe persique. La pratique et le droit international définissent la mobilité comme le droit à la « liberté de mouvement » sans dispositions supplémentaires pour faciliter le choix de s’établir, permettant aux Etats de pratiquer ces politiques de convenance. Ce travail interdisciplinaire qui privilégie l’angle sociologique interroge les implications politiques et le droit international. Il montre que le non-respect prolongé des droits des migrants, surtout par les pays d’accueil, produit des conditions et des résultats restrictifs pour tous les acteurs- des indicateurs montrent l’exclusion systématique du migrant dans la société d’accueil. Cinq chapitres présentent empiriquement le « migrant » dans le golfe qui expérimente la vulnérabilité à différentes échelles : entrepreneurs, marchands-patriarches, travailleurs en col blanc, travailleurs en col bleu, et les femmes migrantes. La politique de migration temporaire des six Etats du Conseil de coopération du Golfe (GCC)- Arabie Saoudite, Oman, Émirats Arabes Unis, Qatar, Bahreïn et Koweït- constitue un exemple heuristique. Sans être un cas unique, il montre une exclusion plus sévère en raison de la nature conservatrice de ces monarchies et de la place de l’Islam comme religion d’Etat. Les politiques de migrations circulaires sont populaires aujourd’hui et les Etats en profitent à leur convenance en privilégiant la flexibilité et la non-intégration pour éviter les responsabilités vis-à-vis des migrants. Le migrant temporaire est donc, le travailleur précaire dans le marché mondial du travail. Le statut d’incertitude structurelle est aussi un des principaux éléments qui séparent « l’Indien du golfe » du reste des Indiens non-résidents (NRI). / The thesis highlights the evidence in the Arab-Gulf region with the Indian migrants to argue that the temporary migration policies hinder the individual’s mobility. International practice and law articulate mobility narrowly as merely the right to “freedom of movement” without also provision to facilitate the choice to settle, which allows states to perpetuate such expedient policies. The work is an inter-disciplinary approach, with mainly a sociological lens and interrogates the implications for policy and international law. It shows that mainly the receiving states’ prolonged non-respect of the migrant’s rights using the “temporary” frame produces limiting conditions and outcomes for all the actors- selected indicators show the systematic exclusion of the migrant in the host society. Five chapters empirically present the “guest worker” in the Gulf who experiences vulnerability at different levels: entrepreneur, trader-patriarch, white-collar worker, blue-collar worker and female migrant. The guest-worker policy practice of the six oil-rich Gulf Cooperation Council (GCC) countries- Saudi Arabia, Oman, the UAE, Qatar, Bahrain and Kuwait- is a heuristic example. The GCC region is not a unique case although it might show more severe exclusion, due to the conservative regimes as monarchies and following Islam as the state-religion. Circular migration policies are popular today and states manifest expediency by privileging flexibility and non-integration to evade responsibility for the migrant. The guest-worker is hence, the precarious worker in the global labour market. The structural uncertainty is a factor that mainly also separates the “Gulf-Indian” from the larger non-resident Indian (NRI) population elsewhere.

Doctor of Philosophy / Department of Chemistry / Mark D. Hollingsworth / The ferroelastic urea inclusion compound (UIC) of 2,10-undecanedione/urea exhibits a striking pseudoelastic memory effect. Although pseudoelasticity is possible for UICs containing only 2,10-undecanedione, introduction of a structurally similar guest impurity (2-undecanone) gives rise to rubber-like behavior, a form of pseudoelasticity. This phenomenon depends on both the crystal strain and the concentration of monoketone: above 13-14% 2-undecanone, pseudoelastic behavior is observed reliably, even at strains as high as 2.4%. The dramatic change in ferroelastic behavior over a small range of impurity content indicates that this is a critical threshold phenomenon. Because the impurity concentration has such a dramatic effect on domain switching, it was important to determine the sector-dependent patterns of incorporation of this relaxive impurity. Preliminary HPLC analyses of guest populations suggest that preferential incorporation of monoketone guests occurs between nonequivalent growth sectors, and that these patterns can be rationalized using a symmetry specific growth model. Birefringence mapping and HPLC studies of optically anomalous UICs containing mixtures of 2,9-decanedione and 2-decanone (which possess trigonal metric symmetry) suggest analogous patterns in guest incorporation and/or ordering that can also be rationalized. Although crystals of 2,9-decanedione/urea exhibit no ferroelastic strain at ambient temperature, they exhibit a proper ferroelastic phase transition near -170[degrees]C. It is proposed that differential perfection of domains gives rise to pseudoelasticity in UICs, and that relaxive impurities play an important role in the energetics of this process. Because ultrafast video studies of domain reversion kinetics demonstrate no clear correlation of observed rates with impurity content, it is proposed that the relaxive impurities facilitate spontaneous domain reversion by annealing stressed defect sites that would otherwise lead to irreversible or plastic domain switching. Following earlier work using synchrotron white beam X-ray topography, the driving force for domain reversion is thought to involve the presence of nanoscopic twins whose strain is epitaxially mismatched with neighboring daughter domains. The behavior of these nanoscopic twins was monitored with in-situ X-ray diffraction studies of stressed crystals, and this has led to a more thorough understanding of the role of these nanoscopic twins in the ferroelastic domain switching and rubber-like behavior in this class of materials.

Les cryptophanes constituent une famille de molécules chirales qui comportent une cavité dans laquelle elles peuvent accueillir des espèces invitées de taille et de nature variables (halogénométhanes, xénon, cations). Nous nous sommes intéressés aux propriétés d’encapsulation présentées par trois espèces solubles dans l’eau : le cryptophane-A hexa-hydroxyle, le cryptophane-A penta-hydroxyle et le cryptophane-A hexa-acide carboxylique. La chiralité de ces systèmes a été utilisée pour en étudier les propriétés de complexation au moyen de techniques chiroptiques : la polarimétrie, le dichroïsme circulaire électronique (ECD) et le dichroïsme circulaire vibrationnel (VCD), cette dernière technique étant associée à des calculs de chimie théorique. Les effets de différents paramètres, tels que le pH de la solution et la nature des contre-ions, sur la complexation de molécules invitées ont été analysés. Les modifications conformationnelles induites sur les cryptophanes lors de l'encapsulation ont également été déterminées. De plus, des propriétés d'énantiodiscrimination de ces cryptophanes hydrosolubles énantiopurs vis-à-vis de petites molécules invitées chirales ont été mises en évidence. Enfin, ces cryptophanes ont montré une affinité exceptionnelle pour le cation césium Cs+ en solution aqueuse. Ces deux derniers résultats permettent d’envisager des applications intéressantes de ces systèmes en chromatographie chirale d’une part, et en chimie de l’environnement pour la détection de césium radioactif d’autre part. / Cryptophanes derivatives are a family of chiral molecules containing a cavity which enables them to encapsulate guest species with variable size and nature (halogenomethanes, xenon, cations). We have been interested in the encapsulation properties of three different water soluble cryptophanes: hexa-hydroxyl cryptophane-A, penta-hydroxyl cryptophane-A and hexa-carboxylic acid cryptophane-A. The chirality of these systems have been exploited to study their complexation properties using chiroptical techniques: polarimetry, electronic circular dichroism (ECD) and vibrational circular dichroism (VCD), the latter being associated with theoretical calculations. The effects of different parameters such as the pH of the solution and the nature of the counter-ions on the complexation of guest molecules have been analyzed. The conformational changes induced on the cryptophanes upon encapsulation have been also determined. In addition, enantiodiscrimination properties of these enantiopure water soluble cryptophanes toward small chiral guest molecules have been evidenced. Finally, these cryptophanes have shown an exceptional affinity for the cesium cation Cs+ in aqueous solution. These last two results allow to consider interesting applications of these systems in chiral chromatography and environmental chemistry, in particular for the detection of radioactive cesium, respectively.

Ce travail de thèse concerne le développement de nouvelles architectures hôte et invité à base de polysaccharide et leur application dans la conception de nanoparticules molles à structure hiérarchique et d’hydrogels supramoléculaires pour l’encapsulation et la libération de médicaments. Dans la première partie du manuscrit, nous décrivons une voie de synthèse de polymères hôtes et invités comprenant des chaînons espaceurs poly(éthylène glycol) hydrophile (PEG) entre le squelette de dextrane et soit le groupement b-cyclodextrine (bCD)(polymère hôte) ou le groupement adamantane (Ada) (polymère invité). La présence des bras espaceurs PEG a conduit à une amélioration substantielle de la disponibilité des groupes Ada du polymère invité par rapport à la situation avec un bras espaceur court et hydrophobe. Nous avons ensuite étudié la formation de nanoassemblages entre les différents types de polymères hôtes et invités. Une fois de plus, les espaceurs PEG ont eu un impact significatif sur la taille et la structure interne des nanoassemblages. La deuxième partie de ce travail décrit la synthèse d’une nouvelle série de dextranes greffés par des chaînons PEG et Ada, préparés par réactions de cycloaddition d'azoture-alcyne catalysées le cuivre (I) (CuAAC). Les degrés substitution (DS) en chaînons PEG greffés (5000 g/mole) sont de l’ordre de 20 mol.% tandis que les DS par les groupements Ada sont variés de 0 à 10 mol.%. L’affinité de ces polymères pour la bCD native, ainsi que leur capacité à former des couches superficielles avec des polymères de b-cyclodextrine (pbCD et pbCDN+), s'avèrent dépendre fortement du DS en groupements Ada, ce qui résulte de la coopérativité des interactions impliquées. Dans la dernière partie, nous avons décrit une stratégie de modification non covalente de microgels sensibles à la température à base de poly (N- isopropylacrylamide) (pNIPAm), pour les recouvrir d’une couronne de pbCDN+. Cette stratégie s'appuie sur l’auto-assemblage électrostatique entre pbCDN+ et les chaînes de poly(acide acrylique) chargés négativement (pAAc) et greffées à la surface des microgels. Dans le cas d’une charge globalement neutre des microgels pNIPAm/bCDN, la stabilisation colloïdale a pu être réalisée à l’aide de dextranes greffés (PEG, Ada) en utilisant une procédure d’assemblage hiérarchique. Enfin, à l'aide de dextrane modifié par des groupements Ada (DT-Ada), les microgels pNIPAm/bCDN ont pu être associés pour produire des hydrogels 3D hiérarchiques (10wt %). Leur température de transition sol-gel est décalée vers le bas pour atteindre la gamme des températures physiologiques (37-41°C) par rapport à celle observée dans un hydrogel hôte-invité uniforme bCDN/DT-Ada (51°C) / This PhD work is based on the development of new architectures of polysaccharide-based host and guest polymers and their application in the design of hierarchically structured soft nanoparticles and supramolecular hydrogels with interesting drug delivery profiles. In the first section of the manuscript we describe a synthetic pathway to host and guest polymers with hydrophilic poly(ethylene glycol) PEG spacer between the dextran backbone and either b-cyclodextrin (bCD) host or adamantane (Ada) guest grafted groups. The presence of the PEG spacer led to a substantial improvement of the availability of Ada groups of the guest polymer as compared to its counterpart, where Ada are linked to the backbone with a short hydrophobic spacer. This was followed by the study of nanoassemblies formation between the different types of host and guest polymers. Once again, PEG spacer had a significant impact on the size and internal structure of the resulting nanoassemblies. The second part of this work describes synthesis of a series of new (PEG, Ada)-grafted dextrans prepared by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The degrees of substitution (DS) by PEG grafts (5000 g/mole) are close to 20 mol% while the DS by Ada-groups are varied from 0 to 10 mol.%. The affinity of these polymers to monomeric bCD, as well as their ability to form superficial layers with b-cyclodextrin polymers (pbCD, pbCDN+), are strongly dependent on the DS by Ada, giving an indication of cooperativity effects between them. In the last part we described a strategy to a non-covalent modification of thermoresponsive poly(N-isopropylacrylamide) (pNIPAm)-based microgels with a pbCDN+ host polymer shell. It uses on electrostatic self-assembly between pbCDN+ and negatively charged poly(acrylic acid) (pAAc) chains grafted to the surface of microgels. The resulting pNIPAm/bCDN microgels with neutral overall charge could be colloidally stabilized with (PEG, Ada)-grafted dextrans via a hierarchical self-assembly procedure. Finally, using Ada-modified dextrans (DT-Ada), pNIPAm/bCDN microgels could be physically cross-linked to yield hierarchical 3D hydrogels (at 10 wt%). Their gel-sol transition temperature is shifted down to the physiological temperature range (37-41°C) as compared to uniform pbCDN/DT-Ada host-guest hydrogels (51°C

In this thesis, density functional theory is employed in the study of two kinds of systems that can be considered to be biomimetic in their own ways. First, three binuclear metal complexes, synthesized by the group of Prof. Ebbe Nordlander, have been investigated. The complexes are designed to resemble the active sites of phosphatase enzymes and have been examined in complexes where either two Zn(II) ions or one Fe(III) and one Mn(II) ion are bound. These dinuclear compounds were studied as catalysts for the hydrolysis of bis(2,4-dinitrophenyl) phosphate and the transesterification of 2-hydroxypropyl p-nitrophenyl phosphate, which are model systems for the same reactions occurring in DNA or RNA. It was found that the two reactions take place in similar ways: a hydroxide ion that is terminally bound to one of the metal centers acts either as a nucleophile in the hydrolysis reaction or as a base in the transesterification. The leaving groups depart in an effectively concerted manner, and the formed catalyst-product complexes are predicted to be the resting states of the catalytic cycles. The rate-determining free energy barriers are identified from the catalyst-product complex in one catalytic cycle to the transition state of nucleophilic attack in the next. Another type of biomimetic modeling is made with an aim of imitating the conceptual features of selective binding of guests and screening them from solute-solvent interactions. Such features are found in so-called nanocontainers, and this thesis is concerned with studies of two capsules synthesized by the group of Prof. Julius Rebek, Jr. First, the cycloaddition of phenyl acetylene and phenyl azide has experimentally been observed to be accelerated in the presence of a capsule. Computational studies were herein performed on this system, and a previously unrecognized structure of the capsule is discovered. Two main factors are then identified as sources of the rate acceleration compared to the uncatalyzed reaction, namely the reduction of the entropic component and the selective destabilization of the reactant supercomplex over the transition state. In the second capsule study, the alkane binding trends of a water-soluble cavitand was studied. It is found that implicit solvation models fail severely in reproducing the experimental equilibrium observed between binding of n-decane by the cavitand monomer and encapsulation in the capsule dimer. A mixed explicit/implicit solvation protocol is developed to better quantify the effect of hydrating the cavitand, and a simple correction to the hydration free energy of a single water molecule is proposed to remedy this. The resulting scheme is used to predict new hydration free energies of the cavitand complexes, resulting in significant improvement vis-à-vis experiments. The computational results presented in this thesis show the usefulness of the quantum chemical calculations to develop understanding of experimental trends observed for substrate binding and catalysis. In particular, the methodology is shown to be versatile enough such that experimental observations can be reproduced for such diverse systems as studied herein. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.</p>

Aim of this thesis is to create analyze business plan of guest house named Třináctka, which will be built in southern Moravia with support of EU funds. The thesis is divided into 2 parts, theoretical and applicative. There is described meaning of business plan and EU structural funds in the first, theoretical part. There is also defined structure of business plan and all items of this plan are described. Specialized literature and author´s knowledge gained during studies at University of Economics in Prague were used as a source of this theoretical part. Applicative part consist of business plan and process how to get subsidy from EU structural fund and how this subsidy will influence comprehensive impact on the guesthouse Třináctka. At the end of the thesis there is a conclusion about potential success of the project with regards the business plan in applicative part.

The diploma thesis deals with the solution of the end house building. The guesthouse is designed with a restaurant with a café and a kitchen on the ground floor. On the upper floors there are guest rooms, including a barrier-free room, a two-room apartment for families with children, a meeting room for corporate meetings and terraces for a more comfortable stay in the guesthouse. The building is a three-storey and a partial basement. Roofing will be done with a sloping roof on one side with a hump and on the other with a shield. The building has an atypical floor plan that copies the shape of a building plot. The project is processed using AutoCad Architecture.

The diploma thesis deals with a proposal to improve the marketing mix of the pension with restaurant Koliba pod skalami. The thesis consists of three parts, theoretical part, analytical part and the proposal. The introductory, theoretical part deals with the definitions of basic concepts associated with marketing, marketing mix and forms the theoretical framework of the work. The analytical part of the work deals with the characteristics of the company, a description of the current situation, analysis of the external and internal environment, marketing mix and the results of a questionnaire survey. Based on the results of the analytical part, the proposal part of the thesis contains suggestions for improving the marketing mix.

This thesis describes the preparation of a project documentation for construction of a mountain guest house. The building is situated in the outskirts of the village Řeka on sloping land. It is a four-storey building with a basement and three floors. Peripheral bearing structures in the basement and first floor are in indirect contact with the soil and are lined with shuttering and a monolithic concrete. Perimeter and interior bearing walls are lined with ceramic blocks. The ceiling structure consists of a pramic - concrete panels. Stairways and elevator shafts are reinforced with a concrete . The building is covered with a gable roof, which is divided in the centre by an aisle roof. The part of the loft is used as an attic.

Master´s thesis contain project documents of design building. It deals with new build guest house. It is situated in the town Brno - Bohunice. The building has got three floors, it hasn´t got basement and it has got flat roof.