Proximity problems and point set embeddability problems are fundamental and well-studied in computational geometry and graph drawing. Examples of such problems that are of particular interest to us in this dissertation include: finding the closest pair among a set P of points, finding the k-nearest neighbors to each point p in P, answering reverse k-nearest neighbor queries, computing the Yao graph, the Semi-Yao graph and the Euclidean minimum spanning tree of P, and mapping the vertices of a planar graph to a set P of points without inducing edge crossings. In this dissertation, we consider so-called kinetic version of these problems, that is, the points are allowed to move continuously along known trajectories, which are subject to change. We design a set of data structures and a mechanism to efficiently update the data structures. These updates occur at critical, discrete times. Also, a query may arrive at any time. We want to answer queries quickly without solving problems from scratch, so we maintain solutions continuously. We present new techniques for giving kinetic solutions with better performance for some these problems, and we provide the first kinetic results for others. In particular, we provide: • A simple kinetic data structure (KDS) to maintain all the nearest neighbors and the closest pair. Our deterministic kinetic approach for maintenance of all the nearest neighbors improves the previous randomized kinetic algorithm. • An exact KDS for maintenance of the Euclidean minimum spanning tree, which improves the previous KDS. • The first KDS's for maintenance of the Yao graph and the Semi-Yao graph. • The first KDS to consider maintaining plane graphs on moving points. • The first KDS for maintenance of all the k-nearest neighbors, for any k ≥ 1. • The first KDS to answer the reverse k-nearest neighbor queries, for any k ≥ 1 in any fixed dimension, on a set of moving points. / Graduate

Microarray expression analysis was carried out to identify genes with a role in epithelial ovarian cancer (EOC). The U133A Affymetrix GeneChipRTM was used to determine the expression patterns of the 3p25.3-ptel genes represented on the microarray in 14 primary cultures of normal ovarian surface epithelial (NOSE) samples, 25 frozen malignant ovarian tumor samples and four EOC cell lines. Seven genes with differential expression patterns in the tumor samples compared to the NOSE samples were identified as candidates for further analysis, starting with ARPC4, SRGAP3 and ATP2B2. Although none of the candidates had been previously studied in ovarian cancer, several had either family or pathway members that had. Expression patterns seemed unaffected by either tumor histopathological subtype or the allelic imbalances observed with loss of heterozygosity (LOH) analysis. The absence of association with genomic context suggested that differential expression was the result of transcriptional regulation rather than direct targeting.

Sulphur is an important nutrient to plants, and reports of its deficiency have been increasing worldwide. Sulphur starvation causes losses in both yield and quality, and it reduces nitrogen use efficiency of plants. As the timing for fertilisation can be decisive for avoiding deleterious effects, improvements in the description of the sulphur balance in fields are a valuable contribution for assisting fertiliser management. Sulphate is the most important inorganic form of sulphur in soils. Being the mobile form, sulphate is readily available for plants, and also prone to be leached. Therefore the description of the movement of sulphate is the key component of the sulphur balance. Leaching of sulphate from the soil can be significantly delayed by its adsorption onto the soil particles. Soil type and pH are the main factors defining the sulphate adsorption capacity; although the presence of other ions in the soil solution can have a considerable effect. It has been reported that in some soils, typically volcanic and tropical soils with variable-charge characteristics, the co-presence of sulphate and calcium can substantially enhance their retention via ion-pair adsorption (IPA). To determine the influence of cations on the movement of sulphate, series of batch and miscible displacement experiments were conducted using two New Zealand soils, of contrasting ion adsorption capacities: the Taupo sandy and Egmont loam soils. These experiments demonstrated the occurrence of cooperative adsorption of sulphate and calcium in the Egmont soil, but not in the Taupo soil. Batch experiments were conducted to examine the IPA adsorption process in the Egmont soil in more detail. Based on the analyses of the results from these two series of experiments, plus the review of published data, three different mathematical approaches for evaluating the amount of solute adsorbed as ion-pairs are proposed. A computer program was built for solving an adsorption model using these three approaches, and was used to compare the model's predictions and the observed adsorption data. An extension of this program, coupling the adsorption model with a solute transport description, was used to simulate the movement of sulphate and calcium. Comparisons between the data from the miscible displacements and the results from this model are used to demonstrate the applicability of the proposed IPA description for modelling the transport of these ions in the soil. Finally, results from a pot trial with Egmont soil are used to examine the relevance of IPA for the movement of sulphate under non-equilibrium conditions, and with active plant growth. Although the results from this experiment regarding IPA were statistically non-significant, some insights could be obtained and are discussed. More studies involving IPA under non-equilibrium experiments are needed for a better understanding of the relevance of IPA in field conditions.

Diss. (sammanfattning) Umeå : Umeå universitet, 2010.

Diss. (sammanfattning) Umeå : Umeå universitet, 2010.

Líquidos iônicos imidazólios (LIIs) associados a ânions com caráter básico foram sintetizados, caracterizados e seu comportamento estudado em solução. Inicialmente a troca isotópica H/D preferencial no grupo C2-CH3 de sais de 1-nbutil-2,3-dimetilimidazólio (BMMI) foi avaliada. Ficou evidente que o contato entre os pares de íons e a atuação do ânion como uma base neutra influenciaram fortemente a deuteração. Após a análise dos resultados de RMN, cálculos de DFT (Teoria do Funcional de Densidade) e Difração de Raios X, um complexo entre uma molécula de água e alguns LI foi sugerido, modificando fortemente a estrutura organizacional e afetando também a troca isotópica nestes sais. Através do mecanismo reacional proposto, surgiu a possibilidade de deuteração de novos substratos contendo H ácidos, usando os LIIs como catalisadores. A reação de troca isotópica em alcinos e cetonas foi estudada e bons resultados foram obtidos. O efeito da variação de cátions e ânions na atividade catalítica foi analisado, assim como a variação dos substituintes dos substratos. Além disso, um estudo cinético foi realizado através de análises de RMN de 1H e o mecanismo reacional foi proposto. Por fim, a capacidade de formação de pares iônicos em soluções aquosas de LIIs foi avaliada na captura de CO2. Ótimos resultados foram obtidos e atribuídos à ocorrência de sorção física e química devido à ativação da água pelo LII. / Imidazolium based ionic liquids (ImIL) associated with basic anions were synthesized, characterized and studied. Initially the preferred H/D isotopic exchange to C2-CH3 group of 1-nbutyl-2,3-dimethylimidazolium salts (BMMI) was studied. In this context, it became evident that the ion-pairing formation and the anion action as a neutral base strongly influence the deuteration reaction. NMR analysis, theoretical calculation (Density Functional Theory) and X-ray Diffraction have been performed and a complex between a water molecule and the IL have been suggested, strongly modifying the IL structure and characteristics. The isotope exchange reaction in alkynes and ketones was studied using imidazolium based ionic liquids as catalysts and good results obtained. The effect of cation and anion variation on the catalyst activity were analyzed, also a variation of the substrate substituent’s. Also, a kinetic study was performed by 1H NMR analyzes and the reaction mechanism were proposed. Finally, the ability to form ion pair contact of ILs in aqueous solutions was evaluated for CO2 capture. Great results were obtained and this success can be attributed to the occurrence of physical and chemical sorption due to water activation by the IL.

Le concept de “paires frustrées de Lewis” (plus communément désignés par l’acronyme anglais FLPs) a suscité un vif intérêt depuis sa formulation en 2006. Initialement décrit à partir d’une phosphine encombrée comme base de Lewis et d’un borane comme acide de Lewis pour l’activation coopérative d’hydrogène sans métal, ce concept a été ensuite très largement développé en utilisant divers éléments du groupe principal (N/B, P/Al, N/Al …). Le concept a ensuite été étendu aux métaux de transitions pour pallier cette faiblesse: sont ainsi apparues les premières paires frustrées de Lewis organométalliques (OmFLPs). Dans le but de développer de telles OmFLPs, nous nous sommes intéressés à la synthèse de complexes cationiques titanocèniques et zirconocèniques en présence d’une amine. La première partie de cette thèse présente les travaux précédemment décrits sur les ligands azotés, en vue de synthétiser des complexes du groupe 4 N-fonctionnalisés. Une description plus détaillée du concept de FLP est ensuite réalisée, et un parallèle est fait avec des concepts connexes (coopérativité métal-ligand, systèmes ambiphiles). La seconde partie de ce manuscrit développe la synthèse de nouveaux ligands (aminomethyl)cyclopentadiènylure de potassium ainsi qu’une étude de leur coordination aux métaux du groupe 4. Cette étude a permis d’accéder à toute une série de nouveaux complexes dichlorotitanocènes et zirconocènes porteurs d’une fonction amine tertiaire encombrée (diisopropylaminyl et 2,2,6,6-tétraméthylpipéridine) à proximité du centre métallique. Ces travaux ont montré que l’amine ne se coordine pas audit centre métallique. Les métallocènes ainsi formés ont ensuite été transformés en cation afin de renforcer le caractère acidité de Lewis du centre métallique. Ces espèces ont montré une réactivité inattendue donnant lieu à des réarrangements par activation CH au voisinage de l’atome d’azote. Ces réarrangements ainsi que des études mécanistiques font l’objet du troisième chapitre. La quatrième partie de ce mémoire porte sur la synthèse de complexes phosphido- et amidotitanocènes cationiques. Ces complexes montrent une très bonne activité en catalyse d’hydrogénation de petites molécules dans des conditions relativement douces, vraisemblablement pour des raisons d’effets coopératifs entre le métal et le ligand. Dans une dernière partie, la synthèse de complexes titanocéniques cationiques portant une fonction iminophosphorane est développée, suivie d’une étude de réactivité de ces complexes en tant que paires frustrées de Lewis organométalliques. / In 2006, the concept of “frustrated Lewis pairs” (called FLPs) was introduced. The main characteristic of these compounds is their ability to activate cooperatively small molecules without the use of a metal (H2, CO2, alkene alkyne…). Initially based on P/B combination, the concept has been extended to several other main group elements (N/B, P/Al, N/Al …). Recently, FLPs have been extended to the transition metal realm. These organometallic FLPs (OmFLPs) are obviously non-metal free systems but they extend significantly the scope of FLP applications. Seeking to develop such systems, a research toward new omFLP combinations (N/Ti+, N/Zr+) has been initiated in our group, based on the synthesis of N-based titanocene and zirconocene complexes. The first part of this manuscript deals with a survey of the literature of such compounds, and a more detailed presentation of FLPs and related concepts (metal-ligand cooperativity, ambiphilic ligands) are also developed. In a second chapter, the synthesis of new N-based cyclopentadienyl ligands and their coordination to group 4 metals is presented. The formation of a cationic complex is then developed in a third part on selected titanocenes. In these complexes, the amine function undergoes CH activation by the cationic metal centre, leading to unexpected rearrangements. Investigations on their plausible mechanism are also presented. In a fourth part, the synthesis of new cationic phosphido- and amidotitanocenes, discovered in the course of our study on OmFLPs, is developed. The cationic amidotitanocenes are shown to be catalytically active towards hydrogenation of small molecules. Lastly, the potential of cationic titanocenyl iminophosphoranes as OmFLPs, was developed.

This thesis describes a computational investigation of the mutagenicity of 5-bromouracil (BrU). In Chapter 1, three models of spontaneous and BrU-induced base mispairing (rare tautomer, wobble pair, and ion) are reviewed. Chapter 2 presents the computational techniques used: electronic structure methods (Hartree–Fock-based and density functional theory) and molecular dynamics. Chapter 3 presents optimisations of the keto and enol tautomers of BrU and uracil (U) in water clusters. The enol tautomer of BrU is found to be more stable than that of U. Chapter 4 is a molecular dynamics study of the keto-enol tautomerism of BrU and U in a periodic water box. The pKₐ of BrU at N3 is found to be lower than that of U. Chapter 5 is a study of stacked base dimers containing BrU, U, or thymine (T) stacking with natural bases. Some structures were taken from the Protein Data Bank, while others were generated using an in-house methodology. BrU is found to stack more strongly than T in vacuo, but solvation and thermal effects nullify this difference. Chapter 6 discusses the significance of the results in Chapters 3–5 in terms of BrU-induced mutagenesis. Appendices A and B–D provide supplementary material to Chapters 2 and 5, respectively. Appendix E is an investigation of the “base flipping” pathway of 2-aminopurine (2AP). Both 2AP/N and A/N dinucleosides (N = thymine or guanine) are found to adopt a wide range of energy-minimum conformations – not only stacked and “flipped”, but also intermediate – and the stacked are not the most favourable by free energy. Appendix F is a list of publications and papers in preparation. One publication concerns BrU stacking. The other is a conformational study of the dipeptide tyrosine-glycine: the theoretical results are shown to be consistent with experiment (R2PI spectra) if thermal effects are taken into account.

This master thesis work concerns monitoring implementing methods on cutting operations for high cost part in the aeronautics and space fields. The final goal is to set tools to support industrial implementing but even more sustain acknowledgments and methods beyond the mission. This mission covers both a technical and a project management issue with related human factors. In this report, the following axis will be developed: • Monitoring on cutting operations stat of the Art. • The developed simulation function to secure monitoring. • Technical modifications at Numerical Command (NC) programming level and Programmable Logic Controller (PLC) level to obtain a simplified use of monitoring and reach the targeted production functioning. • The obtained results and expectations.

The following MA thesis is concerned with the interaction among students of Czech as a foreign language in classes of low proficiency and working in pairs. It mainly concentrates on the process of overcoming obstacles that arise during communication. The objective of the thesis is to examine the students' choice of communication strategies and describe the process of negotiation of meaning. In order to achieve that, an analysis of transcribed recordings of interactions during a language lesson was made. During the lesson students had to complete two two-way tasks, which should offer as many opportunities to negotiate meaning as possible. Keywords: Czech as a foreign language, interaction, negotiation of meaning, communication strategies, pair work