Oxabicyclic alkenes have been the focus of many synthetic studies as they are versatile compounds which act as synthetic intermediates to produce a variety of useful heterocyclic, carbocyclic and acyclic products. The nucleophilic ring opening reaction of oxabenzonorbornadiene was studied. Methanol was the primary nucleophile used throughout the investigation, however various other alcohol nucleophiles were also tested for their efficacy. The effects of substitution were explored, providing ring opened products in yields of up to 81%. The [2+2] cyclodimerization reaction of oxanorbornadienes was also examined providing the first examples of dimers of this kind. The scope was expanded to include other 2,3-diester oxanorbornadienes as well as various C1 substitutions. Changing the ester moiety did not affect the reaction, however the addition of a C1 alkyl substituent did result in lower yields. Moderate yields of up to 66% were obtained. Additionally, a new ruthenium complex was discovered in the process.

Thesis (Ph.D.)--Ohio University, March, 2008. / Abstract only has been uploaded to OhioLINK. Includes bibliographical references (leaves 115-125)

Thesis (Ph.D)--Chemistry and Biochemistry, Georgia Institute of Technology, 2010. / Committee Chair: Weck, Marcus; Committee Member: Breedveld, Victor; Committee Member: Fahrni, Christoph; Committee Member: Kelly, Wendy; Committee Member: Lyon, L. Andrew. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Polysaccharides, one of three types of natural polymer, are used by living organisms for energy storage, structural support, and other vital applications. In particular, acidic polysaccharides such as alginic acid and hyaluronan play important roles in lubrication and water storage. Isolation of polysaccharides is complicated by the difficulty of purification and lack of batch-to-batch consistency. Polysaccharide synthesis has also proved challenging due to their stereochemical complexity and high density of functional groups with similar reactivity. One solution is the synthesis of mimics that possess many of the properties of natural polysaccharides, including a rigid pyranose or furanose backbone and numerous hydroxyl or carboxylic acid groups. Synthesized polysaccharide mimics include polymers with ether linkages not seen in nature, non-ether linked sugar monomers, and polymers created from non-carbohydrate sources. These mimics have been used in various applications, including biolubrication, membrane synthesis, and DNA delivery. As a first approach to a polysaccharide mimic, a polymer with a rigid cyclic backbone and several pendant water-soluble functional groups was sought. High molecular weight ester-functionalized norbornene polymers were synthesized by ring-opening metathesis polymerization of 5-norbornene-2-ethyl ester. The resulting polymers were saponified and hydroxylated along the polymer backbone without a reduction in chain length. The chemical, thermal, and mechanical properties of the various polymers were measured, indicating high thermal stability and strong solid-like character. Even in their saponified and hydroxylated form, the polymers possessed very limited water solubility. Poly-amido-saccharides, a new type of carbohydrate polymer mimetic, were synthesized by the controlled anionic ring opening polymerization of a beta-lactam glucose monomer. The primary alcohol was oxidized to investigate the effects of an ionizable carboxylic acid group, such as those found in natural polysaccharides containing glucuronic acid. Circular dichroism revealed an ordered helical secondary structure in solution that was lost following ring opening. The oxidized poly-amido-saccharides were shown to stabilize lysozyme towards freezing and dehydration stresses better than currently used methods. Glycopolymers containing the poly-amido-saccharides on a poly(acrylamide) backbone were also synthesized and characterized as a model for more complex systems.

The current airspace configuration is highly structured, fixed and is less responsive to changes causing the overall system to lack the flexibility, adaptability, and responsibility needed to handle the increasing air traffic demands in the near future. The work presented in this thesis aims at improving the flexibility and adaptability of today's airspace management in Europe in a pretactical context. We focus on the development of a method to support a process of automatic generation of a sequence of sector configurations composed of predefined sectors. Airspace configurations should be dynamically adjusted to provide maximum efficiency and flexibility in response to demand fluctuations. We dynamically build configurations by combining existing elementary sectors. In this step, any sector combination which forms controllable airspace blocks is eligible and may be used during the day of operation. In this work, we developed efficient methods to solve DAC problem. We formulated and study the sectorization problem from an algorithmic point of view. We proposed methods based on a mathematical modeling and heuristic optimization techniques. We also introduced here an approach to evaluate the workload inside sectors.

Made available in DSpace on 2014-06-11T19:24:02Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-08-22Bitstream added on 2014-06-13T20:51:14Z : No. of bitstreams: 1 schiavoni_je_me_bauru.pdf: 1404536 bytes, checksum: 4a1eed19c43fae7291503dbbabcd42b6 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Esta pesquisa constitui-se uma análise da linguagem audiovisual. O objetivo é verificar como o sentido é produzido nas vinhetas de abertura de alguns telejornais (Globo, Record, Bandeirantes e SBT) e, a partir disso, evidenciar como os aspectos audiovisuais podem contribuir para reforçar a identidade dos programas em questão. Para isso, utilizamos o instrumental teórico da semiótica francesa / This research consists of one analysis of audiovisual language. The goal is to verify how the sense is produced in the opening videos of some TV news (Globo, Record, Bandeirantes and SBT) and, based on it, to make evident how the audiovisual aspects contribute to make stronger the identity of these programs. For this, we will make use of the french methods semiotics

La littérature économique s’intéresse depuis le 13ème siècle aux inégalités et au développement des échanges, mais la relation positive entre ces deux concepts n’est pas toujours vérifiée. Les résultats des travaux ne sont pas homogènes et ne permettent pas une conclusion définitive sur le sujet. Ce travail porte sur la relation entre le développement des échanges (la mondialisation) et le développement social (matérialisé par la réduction des inégalités). Nous analysons la relation qui peut s’instaurer entre l’ouverture et les évolutions économique, démographique et éducative. L’analyse des données statistiques de 125 pays présente des évolutions plus marquées pour les données économiques que pour les données démographiques ou éducatives. Les écarts qui existaient entre les pays, entre les continents ne se comblent que très lentement. Nous avons cherché à valider les corrélations entre ces trois séries. Nous constatons que les corrélations entre les indicateurs économiques, démographiques et éducatifs sont fortes lorsque l’on demeure à un niveau d’agrégation élevé mais qu’elles sont moins fortes lorsque l’on décompose les indicateurs. Le niveau de développement, le continent influent sur les corrélations. Leur stabilité n’est pas forte dans le temps. L’ouverture ne permet pas de façon certaine d’améliorer les conditions de vie des populations et de réduire les inégalités. Nous avons ensuite analysé des données statistiques chinoises afin de voir si l’évolution économique favorable de ce pays pouvait représenter un modèle pour d’autres pays en voie de développement. Nous concluons que la spécificité de la Chine ne permet pas d’en faire un modèle. / Economic survey has studied inequalities and international trade expansion since the 13 th century, but the positive correlation between these 2 concepts has not always been verified. Studies results are not homogeneous and do not make it possible to draw a final conclusion on the topic. This work deals with the correlation between international trade expansion (globalization) and social development (that is to say reduced inequalities). We analyse the possible correlation between trade opening and the evolution of economy, demography and education. The analysis of 125 countries statistical data indicates that this evolution is higher in terms of economy than in terms of demography or education. Prior gaps between countries or continents only very slowly narrow. We tried to verify the correlation between the 3 series of data. We notice that the correlations between economic, demographic and educational indicators are strong when the indicators are amalgamated but not so strong when the indicators are disaggregated. The correlations are also affected by the development level or the continent, and they are not constant in time. To conclude, trade opening cannot be said for certain to improve the populations’ living conditions and to reduce inequalities. We then analyzed Chinese statistical data in order to see whether this country’s positive economic evolution could be a model for other developing countries. We conclude that because of China’s specificity, it can’t.

This thesis examines the 2008 Beijing Olympics Opening Ceremony, which was an unprecedented effort by the Chinese Party-state to reinvent Chinese national culture for consumption at home and abroad. Director Zhang Yimou delivered a spectacular event – three-thousand chanting Confucian scholars, two-thousand Ming Dynasty sailors, a grid of giant dancing printing blocks and an endless display of fireworks presented a sensational spectacle of Chinese culture and history. How should we interpret these symbols representing a romantic Chinese past? I argue that the “ancient” history on display in the Opening Ceremony is actually a product of China’s recent past: its interactions with the West, revolution, nationalism and communism, and the turn toward capitalism and authoritarianism. This thesis pulls the Opening Ceremony back into this historical context, closely examining three of its most prominent symbols: Zheng He and his voyages to the Indian Ocean, the Four Great Inventions, and Confucius. My results show that, 1) far from being a product of China’s history alone, these symbols are a co-production of China and the West, in which both identities were mutually constituted; 2) they are created in the context of political power, and take on different meanings in response to political shifts; 3) they suggest a state desire for power and status rather than simply a revival of cultural heritage. This research will contribute to an understanding of the modern political uses of Chinese history. / Graduate

This Thesis describes the synthesis and characterisation of new Group 2, Group 3 and lanthanide amide, alkyl, halide, borohydride and alkoxide complexes, and their uses as catalysts for the living ROP and immortal ring-opening polymerisation (iROP) of rac-, L, D- and meso-lactide. <strong>Chapter One</strong> introduces cyclic esters and possible mechanistic pathways leading to polyesters by ROP. Living and immortal ROP, including their kinetic characteristics are discussed. An overview of ROP from an industrial perspective and a literature review are also given. <strong>Chapter Two</strong> describes the synthesis and characterisation of a new series of magnesium and zinc amide, alkyl, halide, borohydride and alkoxide complexes supported by a carbazole-bis(dimethyloxazoline) ligand. Their activities towards the ROP of rac-, L- and meso-lactide are presented. Detailed mechanistic studies using spectroscopic techniques are discussed and a new mechanism is proposed. <strong>Chapter Three</strong> describes the synthesis and characterisation of a new series of calcium, strontium, yttrium, lanthanum and samarium amide, alkyl, halide, borohydride and alkoxide complexes supported by a carbazole-bis(dimethyloxazoline) ligand. Their activities towards the ROP of rac-, L- and meso-lactide are presented. Detailed mechanistic studies using spectroscopic techniques are discussed. <strong>Chapter Four</strong> describes the synthesis and characterisation of a new series of magnesium, calcium, strontium, yttrium, lanthanum and samarium amide, halide and borohydride complexes supported by a chiral carbazole-bis(isopropyloxazoline) ligand. Their activities towards the ROP of rac-, L-, D- and meso-lactide are presented. <strong>Chapter Five</strong> contains experimental details and characterising data for the new complexes reported in this Thesis. <strong>CD Appendix</strong> contains .CIF files for all the new crystallographically-characterised complexes.

Dicyclopentadiene (DCPD), a tricyclic olefin, is available from the C5 fraction of petroleum feedstocks. Owing to its high reactivity (due to the presence of a strained alkene), low cost, and lack of other commercial uses, DCPD has been extensively pursued as a monomer for use in ring-opening metathesis polymerization processes. The olefin metathesis reaction, for which Yves Chauvin, Robert H. Grubbs, and Richard R. Schrock received the 2005 Nobel prize, is among the most attractive approaches to polymerize olefins, allowing production of high-molecular weight polymers including linear macromolecules, block copolymers, and crosslinked materials. Polydicyclopentadiene (PDCPD), which can be produced using a variety of early- and late-transition metal catalysts, is a thermoset polymer with a highly crosslinked structure. PDCPD has excellent impact strength, high storage modulus, good chemical resistance, wide service temperature range, and low density. As a result, it has found broad commercial utility in industrial manufacturing. Additionally, the reaction injecting molding (RIM) process used for DCPD polymerization makes it possible to precisely control the shape and dimensions of PDCPD products. Owing to its lack of chemical functionality, however, polydicyclopentadiene has many limitations. Previously, our research group developed a modified dicyclopentadiene monomer by adding an electron withdrawing group – a methyl ester functional group – on the pendent cyclopentene ring of the monomer. Polymerization of this functionalized monomer led to a novel thermoset material – methyl ester functionalized polydicyclopentadiene (fPDCPD) – that exhibits tunable surface hydrophobicity. In experiments described in this dissertation, my collaborators and I confirmed the thermal crosslinking mechanism of fPDCPD using a combination of solution-state and solid-state NMR, FTIR, and Raman spectroscopy. We also explored the surface chemistry of our novel material, by harnessing the embedded functional group in order to exert finer control over hydrophobicity, and to control interactions with biological organisms through the conjugation of biologically relevant functional groups. To further extend the utility of our functionalized dicyclopentadiene monomer, we synthesized a series of statistical polymers: fPDCPD-stat-PDCPD. Once again, we used a wide range of characterization methods, and showed that we can both tune the surface hydrophobicity of the copolymers and manipulate the mechanical properties by adjusting the molar fractions of functionalized and non-functionalized monomers. Chemical structures of these copolymers were interrogated by NMR, FTIR, and Raman spectroscopy. Frontal ring-opening metathesis polymerization was applied in an effort to study the kinetics of (co)polymerization. Finally, to lay the groundwork for future fPDCPD manufacturing, we successfully optimized the production of fDCPD monomers to half-kilo scale and fPDCPD polymers at 20-gram scale, while developing a reaction-injection molding process that permitted the production of dimensionally controlled fPDCPD objects. This in turn allowed us to conduct a rigorous assessment of the mechanical properties of our fDCPD through dynamic mechanical analysis (DMA), which established for the first time that our functionalized material has a comparable storage modulus to that of the parent (unmodified) PDCPD. The development of fPDCPD is approaching a new stage where it is ready to be commercialized and mass produced. We hope that our novel fPDCPD material will soon play a crucial role in replacing traditional metallic components in vehicle design and engineering material manufacturing. / Graduate / 2021-12-14