Nous avons réalisé une réaction domino qui a conduit à une diversité moléculaire importante avec de bons rendements et une large gamme de groupes fonctionnels. De plus, un contrôle total de la stéréochimie est exercé sur les centres introduits, ce qui a permis en particulier, la synthèse stéréocontrôlée de deux centres quaternaires adjacents.<br />Une amélioration a pu être apportée afin de diminuer la toxicité de la réaction, en remplaçant la moitié du tétra-acétate de plomb par du diacétate de iodo-benzène moins toxique.<br />Cette réaction permet ainsi l'élaboration de cyclohexanes hautement fonctionnalisés comportant jusqu'à cinq centres définis.<br />La famille des iridals (comportant plus de 30 représentants) s'est alors révélée une cible de choix pour l'utilisation de notre réaction domino en synthèse totale. Les iridals sont des triterpènes qui possèdent des propriétés biologiques importantes, principalement contre le cancer (un brevet a été déposé par une équipe de Montpellier). Les iridals ont tous en commun un noyau cyclohexane comportant quatre centres asymétriques adjacents, dont deux quaternaires, ce qui en fait des cibles synthétiques intéressantes.<br />Nous avons choisi l'iridal, molécule mère de la famille, comme première cible et nous proposons une approche de sa synthèse. La construction de la chaîne homofarnésyle est particulièrement traitée.

Nous étudions certains processus de fragmentation qui sont liés à des processus de coalescence. Nous nous intéressons en premier lieu au coalescent de Bolthausen et Sznitman qui, retourné dans le temps, devient un processus de fragmentation inhomogène en temps. Nous décrivons alors sa mesure de dislocation instantanée en fonction de lois de Poisson-Dirichlet et en déduisons des asymptotiques sur la taille des blocs en temps grands et petits. Nous étudions aussi une classe de coalescents additifs après retournement de temps en tant que processus de fragmentation. Nous montrons alors que les lois de tous ces coalescents additifs sont absolument continues les unes par rapport aux autres et nous explicitons cette densité. Enfin, nous caractérisons la loi des fragmentations d'intervalle en la mettant en bijection avec les fragmentations de partitions ordonnées.

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Ces travaux de thèse nous ont permis de mettre en évidence un accès à un large nombre de composés polycycliques. Les étendues des méthodes employant des cascades réactionnelles palladocatalysées et leurs limites ont été étudiées. L'initialisation de ces cascades se fait par une cyclocarbopalladation de type de 4-exo-dig, suivie par un couplage de Sonogashira. Avec des substrats et des conditions adéquats, la cascade réactionnelle continue avec une alcynilation, une électrocyclisation à huit électrons p et une électrocyclisation à six électrons p. En un nombre limité d'étapes sont ainsi obtenus des châssis moléculaires complexes : les fenestradiènes et les cyclooctatriènes. Des dérivés portant des substituants variés dans différentes positions ont été synthétisés, notamment possédant des hétéroatomes. Leurs accès a été assuré par des synthèses linéaires ou encore par une approche plateforme. Ceci a été complété par une étude in silico en vue du potentiel thérapeutique de ces châssis moléculaires.

This creative project produced a Development Plan for the 60-year-old 200+ acre Cascades Park in Bloomington, Indiana. Combining principles of historic preservation with passive forms of unfacilitized recreation provided the framework for the final design concepts. The final product was the actual master development plan and 11 other 30" x 40" sheets that illustrated a thorough inventory and analysis of the park and its context, suitabilities of the park for specific forms of recreation, concepts, and graphic illustrations. The inventory and analysis sheets have sought to identify the unique character of the park that came about from two distinct sources: 1) The natural environment that spawned the interest for the area to become a park in 1924 and, 2) The park amenities in the forms of shelters, retaining walls, play equipment, water wells, drives, etc. that were added in the past 60 years indicating man's impact upon the area. The design concepts for the park emphasized and protected this unique character. The extent of information, both written and graphic, on the 12 sheets was intended to provide the information without needing an accompanying booklet or oral explanation from the designer. In addition to the site-specific information that was illustrated in the maps, general information was also required. To understand the social framework that was responsible for the creation of Cascades Park and other parks of the time, park planning principles of the 1920's were researched. These were then compared and applied where possible to the historic development of Cascades Park. Also, developmental criteria were established for forms of recreation that were found to be in demand in Bloomington and had the potential of being accommodated in the park with a minimal disruption of its natural beauty. / Department of Landscape Architecture

Stepped cascades are recognised for both aeration potential and energy dissipation, and have been employed in hydraulic structures for over 3,500 years. Yet little detailed information exists on their performance, especially pertaining to low-gradient cascades. This study presents a detailed investigation of both the macro and micro-scale flow properties on a low-gradient cascade (3.4º slope). Research is conducted on two large-size physical models: a 24m long multi-step cascade (10× 2.4m long steps), and a single-step model with identical step height and length. The large size of the model allows near full-scale data acquisition under controlled flow conditions, minimising potential scale effects. The study comprises three distinct components: 1. A global investigation of the general flow properties of nappe flow on a low-gradient, multi-step cascade. Unforeseen three-dimensional characteristics of the flow, including supercritical shockwaves and sidewall standing-waves downstream of nappe impact, are identified and examined by the study. Although comparable to similar phenomena at channel bends and expansions, these have not been previously described on stepped cascades. Energy dissipation on the cascade is investigated, and is found to be over twice that observed for a smooth chute of similar gradient. 2. A complete characterisation of the air-water structure of flow in a nappe regime. Significant outcomes of the analysis include: ⊕ Air-concentration Distribution: The air-concentration distribution at the lower nappe of the free-falling jet shows good agreement with an analytical solution of the diffusion equation. The experimental results from the study, and a reanalysis of existing data, indicate a distinct relationship between the turbulent diffusivity in the shear layer and distance from the step brink. This contradicts earlier investigations that assumed constant diffusivity. Strong aeration of the flow, with a large volume of spray, occurs downstream of the nappe impact. Depth-averaged air concentrations of 40% to 50% are observed within the spray region, decreasing towards the downstream end of the step. ⊕ Velocity Distribution: A theoretical analysis of the momentum transfer process imparts an improved understanding of the momentum transfer and velocity redistribution within the free-falling jet. An analytical solution based on twodimensional wake flow is developed, superseding existing solutions based upon a monophase free-mixing layer. ⊕ Bubble-frequency Distribution: A quasi-parabolic relationship between bubble frequency and time-average air concentration across a cross-section is observed. A theoretical explanation for the parabolic relationship is developed, and two correction factors are introduced to provide a better representation of the experimental data. ⊕ Air-bubble and Water-droplet Size Distributions: Chord-length distributions are compared with standard probability distributions, showing good agreement with standard Weibull, gamma and log-normal probability distributions within various regions of the flow on the step. A computer model is developed to model interaction between a bubbly transition from water to air and fluctuations of the free surface. 3. A parallel investigation of the oxygen aeration efficiency of a stepped cascade. Measured air-water property data is used to calculate the air-water interface area in bubbly flow, and to estimate the theoretical aeration efficiency of the stepped cascade based upon the integration of the mass transfer equation. The aeration performance of the stepped cascade model is also measured experimentally in terms of dissolved oxygen content. This analysis allows a unique, successful comparison of experimental dissolved oxygen measurements with the numerical integration of the mass transfer equation.

Ces travaux de thèse nous ont permis de mettre en évidence un accès à un large nombre de composés polycycliques. Les étendues des méthodes employant des cascades réactionnelles palladocatalysées et leurs limites ont été étudiées. L’initialisation de ces cascades se fait par une cyclocarbopalladation de type de 4-exo-dig, suivie par un couplage de Sonogashira. Avec des substrats et des conditions adéquats, la cascade réactionnelle continue avec une alcynilation, une électrocyclisation à huit électrons p et une électrocyclisation à six électrons p. En un nombre limité d’étapes sont ainsi obtenus des châssis moléculaires complexes : les fenestradiènes et les cyclooctatriènes. Des dérivés portant des substituants variés dans différentes positions ont été synthétisés, notamment possédant des hétéroatomes. Leurs accès a été assuré par des synthèses linéaires ou encore par une approche plateforme. Ceci a été complété par une étude in silico en vue du potentiel thérapeutique de ces châssis moléculaires. / This PhD thesis was focused on the study of cascade reactions and allowed the access to a large variety of polycyclic compounds. The extension of several methods employing palladocatalyzed cascade reactions and their limits have been studied. Those cascades are initiated by a 4-exo-dig cyclocarbopalladation, followed by a Sonogashira coupling. With an adequate substrate and the appropriate conditions, the cascade reaction can even be extended by an alcynilation, followed by an eight p electron electrocyclization and a six p electron electrocyclization. Complex scaffolds are thus obtained in only a few steps: fenestradienes and cyclooctatrienes. Derivatives with various substituents in different positions have been synthesized, particularly with heteroatoms. Their access has been ensured by either linear synthesis or a platform approach. This project was completed by an in silico study of the scaffolds regarding their drug-like potential.

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The area of computer vision has been making big improvements in the latest decades, equally so has the area of electronics and small computers improved. These areas together have made it more available to build small, standalone systems for object detection in live video. This project's main objective is to examine whether a small device, e.g. Raspberry Pi 3, can manage an implementation of an object detection algorithm, called Viola-Jones, to count the occupancy of sitting people in a room with a camera. This study is done by creating an application with the library OpenCV, together with the language C+ +, and then test if the application can run on the small device. Whether or not the application will detect people depends on the models used, therefore three are tested: Haar Face, Haar Upper body and Haar Upper body MCS. The library's object detection function takes some parameters that works like settings for the detection algorithm. With that, the parameters needs to be tailored for each model and use case, for an optimal performance. A function was created to find the accuracy of different parameters by brute-force. The test showed that the Haar Face model was the most accurate. All the models, with their most optimal parameters, are then speed-tested with a FPS test on the raspberry pi. The result shows whether or not the raspberry pi can manage the application with the models. All models could be run and the Haar face model was fastest. As the system uses cameras, some ethical aspects are discussed about what people might think of top-corner cameras.