We report the attempted syntheses of two photochemical dimethylsilene precursors, both of which are derived from polyphenyl silanorbornadiene skeletons. Possible synthetic schemes and our results are reported herein. Photolysis of 1,2-divinyl-1,1,2,2-tetramethyl-1,2-disilane at room temperature in a cyclohexane solution of 1,3-butadiene produces 1,1-dimethyl-2-(vinyldimethylsilylmethyl) silene which is trapped in high yields to afford the E- and Z-1,1-dimethyl-2-(vinyldimethylsilylmethyl)-3-vinyl-1-silacyclobutanes in 42 and 29% yields, respectively, along with minor amounts of 1,1-dimethyl-2-(vinyldimethylsilylmethyl)-1-silacyclohex-3-ene, 9%. Low Pressure Flow Pyrolysis at 450º C of either the E- or Z-isomer provides a relatively mild thermal source of the silene in the gas phase. Two products, 1,1,3,3-tetramethyldisilacyclohex-3-ene and 2,2,5,5-tetramethyl-2,5-disilabicyclo[2.2.1]hexane, are formed from an intramolecular rearrangement of the silene. Other reactions of the 3-vinylsilacyclobutanes include geometric isomerization, ring expansion to the silacyclohex-3-ene, and a homodienyl-1,5-hydrogen shift to 3,3,6,6-tetramethyl-3,6-disiladeca-1,4,8-triene. Synthetic schemes, successful and unsuccessful, for hydrido silene, acylpolysilene, and fluorine substituted silene precursors are discussed in the final chapter.

Synthetic seismograms are a computer-generated aid in the search for hydrocarbons. Heretofore the solution has been done by z-transforms. This thesis presents a solution based on the method of finite differences. The resulting algorithm is fast and compact. The method is applied to three variations of the problem, all three are reduced to the same approximating equation, which is shown to be optimal, in that grid refinement does not change it. Two types of algorithms are derived from the equation. The number of obvious multiplications, additions and subtractions of each is analyzed. Critical section of each requires one multiplication, two additions and two subtractions. Four sample synthetic seismograms are shown. Implementation of the new algorithm runs twice as fast as previous computer program.

Slag, by itself, shows very little hydraulic activity. However, hydration is greatly accelerated by incorporation of the slag with Portland cement. This phenomenon is due to the activating role of calcium hydroxide released from the hydration of Portland cement. This study was aimed at finding other activators that will increase hydration in both synthetic and commercial slags. The effects of chemical composition and the aggregation state of the slag on the hydration process were also investigated. For the synthetic slags, the aggregation state was altered by different quenching techniques. The chemical composition was varied by synthesizing a series of slags. The degree of hydration was studied by developing a thermogravimetric analysis technique and the glass content was determined using microscopy. Minerals were determined using powder x-ray diffraction analysis.

Microbial metabolism can be tailored to meet human specifications, but the degree to which these living systems can be repurposed is still unknown. Artificial biological control strategies are being developed with the goal of enabling the predictable implementation of novel biological functions (e.g., engineered metabolism). This dissertation project contributes genetic tools useful for modulating gene expression levels (extending promoters with UP elements) and isolating transcription and translation of engineered DNA from the endogenous cellular network (expression by orthogonal cellular machinery), which have been demonstrated in Escherichia coli for the production of lycopene, a 40-carbon tetraterpene carotenoid with antioxidant activity and a number of other desirable properties.

Lewis acids are widely used in the pharmaceutical industry, generally homogeneously, to perform reactions such as C-C or C=N bond formation and acetalisation. Typically, metal salts such as those of Ti, Fe and especially Sc are used, the last typically as the triflate. Metal organic frameworks (MOFs) containing such metals should act as heterogeneous, removable and reusable catalysts for similar reactions if they can be prepared in stable forms and with large, open pores and metal cation sites that can be rendered coordinatively unsaturated. Families of novel MOFs with different structure types and cations have therefore been prepared and their activity has been examined in carbonyl ene C-C bond forming reactions, Friedel-Crafts-Michael additions and in imine formation reactions. Their activities have been compared with those of the well-known HKUST-1(Cu), MIL-100(Fe) and MIL-101(Cr) solids examined as catalysts previously. In particular, divalent transition metal bisphosphonates and dicarboxylates with pore sizes from 10 – 20 Å and scandium carboxylates (MIL-68(Sc), MIL-88D(Sc), MIL-100(Sc), MIL-101(Sc)) have been tested. Synthetic procedures were optimised according to commercial constraints for the known MOFs STA-12(Ni) and MIL-100(Sc). While good activities are observed for Ni-based MOFs and in a number of the scandium-based solids, MIL-100(Sc) is by far the best Lewis acid catalyst for a range of reactions. In particular, MIL-100(Sc) is very active even when used without pre-dehydration, is readily recyclable with minor loss of activity and shows fully heterogeneous activity. It outperforms both MIL-100(Fe) and MIL-101(Cr), each commonly reported as versatile catalysts in the literature. Careful synthesis of bulky substrates shows that the activity is derived from reactions within the internal pore system. Furthermore, MIL-100(Sc) is able to perform tandem reactions - such as dehydration followed by carbonyl ene reaction - in which the Lewis acid sites catalyse two steps. The Lewis acidic sites of the excellent Lewis acid catalyst MIL-100(Sc) has been examined in detail by in situ IR using adsorption of CO and CD₃CN as probe molecules and compared with other MIL-100 materials. The work has been extended to the examination of MOFs containing two different metals, by substitutional approaches within the metal nodes (e.g. Sc-Al, Sc-Fe, Sc-Cr, Sc-Ni, Sc-Co within the trimeric M₃O(O₂C-)₆ nodes of MIL-100). In addition, series of Sc-Fe MIL-100 materials have been prepared that contain α-Fe₂O₃ nanoparticles in the pores of the structure. These composites show higher specific catalytic activity for Lewis acid catalysis than MIL-100(Sc), even though some scandium has been replaced with iron: the origin of this behaviour is discussed. MIL-100(Sc/Fe) has also been explored as a bifunctional catalyst in tandem Friedel-Crafts-oxidation reactions. MIL-100(Sc₆₀/Fe₄₀) was found to give exceptionally high conversions in the Friedel-Crafts-oxidation tandem reaction of 2-methyl indole and ethyl trifluoropyruvate to form a ketone, outperforming the many other materials tested and giving the best balance of the two different types of catalytic sites required to catalyse the reaction. MIL-100(Sc) has also been prepared containing 50% of mono-fluorinated trimesate ligands in the framework for the first time. This fluorinated MIL-100(Sc) has been post-synthetically modified by addition of a di-phenylphosphino group as confirmed by solid state NMR. This can act as a starting point for the future generation of MOF-supported metal phosphine catalysts.

The aim of this thesis is to research the current possibilities and limitations of automatic generation of synthetic XML documents. The first part of the work discusses the properties of the most used XML data generators and compares them to each other. The next part of the thesis proposes an algorithm for XML data generation which focuses on subset of the main XML data characteristics (number of elements, number of attributes, fan-out, mixed contents etc.). The main target of the algorithm is to generate XML documents using a set of settings which are easy to understand. The last part of the work compares the proposed solution with the existing ones. The comparison focuses on how easy it is to generate XML documents, what structures can be created and finally it compares properties of the similar XML data created using different XML data generators. Powered by TCPDF (www.tcpdf.org)

The aim of this thesis is to research the current possibilities and limitations of automatic generation of synthetic XML documents. The first part of the work discusses the properties of the most used XML data generators and compares them to each other. The next part of the thesis proposes an algorithm for XML data generation which focuses on subset of the main XML data characteristics (number of elements, number of attributes, fan-out, mixed contents etc.). The main target of the algorithm is to generate XML documents using a set of settings which are easy to understand. The last part of the work compares the proposed solution with the existing ones. The comparison focuses on how easy it is to generate XML documents, what structures can be created and finally it compares properties of the similar XML data created using different XML data generators. Powered by TCPDF (www.tcpdf.org)

Sparse military satellite constellations were designed using two methods: a traditional approach and a genetic algorithm. One of the traditional constellation designs was the Discoverer II space based radar. Discoverer II was an 8 plane, 24 satellite, Low Earth Orbit (LEO), Walker constellation designed to provide high-range resolution ground moving target indication (HRR-GMTI), synthetic aperture radar (SAR) imaging and high resolution digital terrain mapping. The traditional method designed 9-ball, 12-ball, 18-ball, and 24- ball Walker constellations. The genetic algorithm created constellations by deriving a phenotype from a triploid genotype encoding of orbital elements. The performance of both design methods were compared using a computer simulation. The fitness of each constellation was calculated using maximum gap time, maximum revisit time, and percent coverage. The goal was to determine if one design method would consistently outperform the other. The genetic algorithm offered a fitness improvement over traditional constellation design methods in all cases except the 24-ball constellation where it demonstrated comparable results. The genetic algorithm improvement over the traditional constellations increased as the number of satellites per constellation decreased. A derived equation related revisit time to the number of ship tracks maintained. / US Navy (USN) author.

Ces travaux s’inscrivent dans le cadre du contrat d’objectifs AQUAL dont le but est la lutte contre les pollutions diffuses en milieu rural. Ils portent sur la compréhension des mécanismes de rétention du cuivre dans les sols viticoles. Afin de s’affranchir de la complexité des sols, sept constituants ont été sélectionnés (quartz,calcite, kaolinite, matière organique, goethite, ferrihydrite et birnessite). Le comportement du cuivre a été étudié sur les constituants seuls puis dans des mélanges de complexité croissante, afin d’évaluer l’implication de chacun d’entre eux, en fonction du pH et de la concentration en cuivre. L’influence du vieillissement et de la concentration sur la répartition géochimique du cuivre a ensuite été évaluée dans des sols synthétiques et naturels contaminés. L’ensemble des résultats a été obtenu grâce à la combinaison de plusieurs techniques permettant d’obtenir des informations complémentaires aux échelles macroscopique, microscopique (STEM-EDX et μ-XRF) et moléculaire (XANES).Les résultats montrent d’une part, que les principaux constituants responsables de la rétention du cuivre sont la matière organique et les oxydes de fer et de manganèse et d’autre part, que l’existence d’interactions organo-minérales influe significativement sur la rétention du cuivre. Lacombinaison d’expériences de sorption et d’extractions séquentielles a permis de mettre en évidence que les processus de rétention du cuivre se produisant dans le sol naturel peuvent être mimés dans un sol synthétique, ce dernier pouvant ainsi être utilisé comme modèle. / This work is a part of the AQUAL research program which aims to strive against diffuse pollution in rural environment. It deals with the understanding of copper retention mechanisms in vineyard soils.To overcome the soil complexity, seven constituents were selected (quartz, calcite, kaolinite,organic matter, goethite, ferrihydrite and birnessite). The copper behavior was firstly studied on the single constituents, then on increasing complexity constituents mixtures in order to assess their implication as a function of pH and copper concentration. The influence of aging time and copper concentration was evaluated on the copper geochemical partitioning in synthetic and natural soils.Conclusion could be drawn by combination of several techniques providing complementary information at macroscopic, microscopic (STEM-EDX, μ-XRF) and molecular (XANES) scales.The results showed on the one hand, that organic matter and iron and manganese oxides are the main constituents involved in copper retention and on the other hand, that the presence of organo-mineral interactions also significantly influences the copper retention. Sorption experiments combined with sequential extractions emphasized that copper retention processes occurring in a natural soil can be mimicked in a synthetic soil which could then be used as a model.

Four new synthetic methods employing an oxidative dearomatization - rearomatization strategy are presented. In Chapter 2, a new oxidative dearomatization - radical cyclization - rearomatization approach to form fused oxygen-containing heterocycles is presented. Origins, design, reaction, and optimizations are discussed. In Chapter 3, meta-selective alkylation of catechol mono-ethers is described employing an oxidative dearomatization - radical addition - rearomatization approach using trialkylboranes as source of alkyl radicals. In Chapter 4, a metal-free method to synthesize fluorinated indoles from aniline starting materials is described. Chapter 5 lays the groundwork for para-selective functionalization of catechol mono-ethers. Chapters 6 and 7 highlight the work related to pharmaceutical drug analyses. Chapter 6 presents the FDA approved drugs organized in Disease Focused Posters. Chapter 7.1 and 7.2 present the drug analysis of Sulfur- and Fluorine-Containing Drugs, and Nitrogen-Heterocycle Containing Drugs, respectively.