<p>Medium-sized cyclic ethers are challenging synthetic targets due to enthalpic and entropic barriers. Methods for the stereoselective synthesis of &#945;,&#945;&#900;-disubstituted medium-sized cyclic ethers began to appear with the discovery of naturally-occurring, ladder-shaped polycyclic ethers, such as brevetoxin B, and monocyclic ethers, such as (+)-laurencin. Despite the progress made in this field, limitations remain including competing formation of smaller ring sizes and scarcity of catalytic methods. Our aim has been to develop stereoselective syntheses for 7- and 8-membered cyclic ethers which have potential for application in natural product synthesis. The C-O bond disconnection was selected for the methods described within because cyclization and stereoinduction could be achieved simultaneously. In the case of 7-membered cyclic ethers, an organocatalytic oxa-conjugate addition reaction promoted by the gem-disubstituent (Thorpe&#8722;Ingold) effect has been developed to stereoselectively provide &#945;,&#945;&#8242;-trans-oxepanes. A gold(I)-catalyzed alkoxylation reaction has also allowed access to &#945;,&#945;&#8242;-cis-oxocenes. This method has been probed for feasibility in the stereoselective synthesis of (+)-intricenyne, an 8-membered cyclic ether belonging to the C15 nonterpenoid acetogenin natural product class. These methods have the potential to become general and efficient routes to highly functionalized oxepanes and oxocenes.</p> / Dissertation

A novel cryptand was synthesized which contained a 3,5-disubstituted-4- oxahexacyclo[5.4.1.02,6.03,10.05,9.08,11] dodecane "cage" moiety. In alkali metal picrate extraction experiments the cryptand exhibited high avidity towards Rb+ and Cs+, when compared with the corresponding model compound. A computational study of a series of cage-functionalized cryptands and their alkali metal-complexes was performed. The X-ray crystal structure of a K+-complexed bis-cage-annulated 20-crown-6 was obtained. The associated picrate anion was found to be intimately involved in stabilization of the host-guest complex. The interaction energy between the host-guest complex and picrate anion has been calculated, and the energy thereby obtained has been corrected for basis set superposition error.

Symmetrical cage-annulated podands were synthesized via highly efficient synthetic strategies. Mechanisms to account for the key reaction steps in the syntheses are proposed; the proposed mechanisms receive support from the intermediates that have been isolated and characterized. An unusual complexation-promoted elimination reaction was studied, and a mechanism is proposed to account for the course of this reaction. This unusual elimination may generalized to other rigid systems and thus may extend our understanding of the role played by the host molecules in "cation-capture, anion-activation" via complexation with guest molecules. Thus, host-guest interaction serves not only to activate the anion but also may activate the leaving groups that participate in the complexation. Complexation-promoted elimination provides a convenient method to desymmetrize the cage while avoiding protection/deprotection steps. In addition, it offers a convenient method to prepare a chiral cage spacer by introducing 10 chiral centers into the host system in a single synthetic step. Cage-annulated monocyclic hosts that contain a cage-butylenoxy spacer were synthesized. Comparison of their metal ion complexation behavior as revealed by the results of electrospray ionization mass spectrometry (ESI-MS), alkali metal picrate extraction, and pseudohydroxide extraction with those displayed by the corresponding hosts that contain cage-ethylenoxy or cage-propylenoxy spacers reveals the effect of the length of the cage spacer upon the host-guest behavior. A series of cage-annulated cryptands, cavitands and the corresponding non-cage-annulated model compounds have been synthesized. These host molecules display unusual behavior when examined by using ESI-MS techniques, i.e., they bind selectively to smaller alkali metal ions (i.e., Li+ and Na+), a result that deviates significantly from expectations based solely upon consideration of the size-fit principle. It seems likely that this behavior results from the effect of the host topology on host-guest behavior. A series of non-cage-annulated cryptands also have been synthesized. These compounds can serve as starting materials for cavitand construction.

Student Number : 9506932W - MSc research report - School of Mechanical Engineering - Faculty of Engineering and the Built Environment / In this research project, the performance and emissions of a conventional compression ignition engine fuelled on ethanol as main fuel and dimethyl ether as ignition promoter were investigated. Tests were first conducted on diesel fuel, then on ethanol fuel with dimethyl ether and compared. All tests for both fuelling techniques were conducted at the same engine speed and injector pressure. However, engine settings with specific reference to injection timing and injector pressure were optimised to suit diesel fuel, and were left unaltered when the engine was fuelled on ethanol and dimethyl ether. The injector nozzle configuration used for diesel fuel was a standard three-hole type nozzle, whereas for ethanol fuel with dimethyl ether a standard three-hole nozzle as well as a four-hole type nozzle was used. Also investigated was the effect a catalytic converter would have on exhaust emissions, from both fuelling techniques. The performance results of ethanol/dimethyl ether fuel compared favourably to that of diesel fuel. The brake power attained for both fuelling techniques was approximately the same, however the only penalty incurred to this desired result was the simultaneous increase in the brake specific fuel consumption of ethanol/dimethyl ether fuel. The fuel conversion efficiency of ethanol/dimethyl ether fuel was also found to be lower than that of diesel fuel, this largely attributed to the difference in energy release patterns between the two fuels. The emissions results obtained showed that ethanol/dimethyl ether fuel burns cleaner, mainly due to its chemical structure containing oxygen molecules. The NOx, THC, CO and CO2 emissions, produced before the catalytic converter, of ethanol/dimethyl ether fuel were lower than those of diesel fuel. The catalytic converter further produced lower emissions, with the four-hole type nozzle producing the most desired results. In terms of catalytic converter efficiency, THC and CO emissions were more readily removed compared to NOx. In addition, virtually no smoke emissions were detected for ethanol/dimethyl ether fuel combustion.

Student Number : 9707408V - MSc(Eng) research report - School of Mechanical, Industrial and Aeronautical Engineering - Faculty of Engineering and the Built Environment / This research is an investigation into the performance and combustion characteristics of a two-cylinder, four-stroke compression ignition engine fuelled on diesel and then on dimethyl ether (DME). Baseline tests were performed using diesel. The tests were then repeated for dimethyl ether fuelling. All DME tests were performed at an injection opening pressure of 210 bar, as recommended for diesel fuelling. The tests were all carried out at constant torque with incremental increases in speed and an improved method of measuring the DME flow rate was devised. It was found that the engine’s performance characteristics were very similar, regardless of whether the engine was fuelled on diesel or DME. Brake power, indicated power and cylinder pressure, during the highest loading condition of 55 Nm, were virtually identical for diesel and DME fuelling, with the most significant finding being that the engine was more efficient when fuelled on DME than when fuelled with diesel. Another interesting finding was that the energy release of diesel decreases with increasing load, whilst the energy release of DME increases with increasing load. At the highest loading condition of 55 Nm, the energy release of DME was approximately 210 joules higher than that of diesel. This investigation concluded that DME may definitely be a suitable substitute fuel for diesel.

Esta pesquisa teve como objetivo avaliar as diferenças nos padrões de desenvolvimento ponderal, composição de carcaça e qualidade de carne entre linhagens e touros representativos da raça Nelore, com aplicação de tecnologias modernas para coleta de dados e estimação de parâmetros genéticos e fenotípicos das características em estudo. Foram utilizados dados de desenvolvimento ponderal, características de carcaça e qualidade de carne de machos da raça Nelore, terminados a pasto e confinamento e pertencentes a programas de avaliação genética. Desses animais, foram coletadas informações individuais de características de carcaça avaliadas por ultrassonografia e medidas corporais para estimação do frame de cada animal. Ao abate, foram avaliadas características de carcaça e carne, diretamente na carcaça e também através de imagens digitais do músculo Longissimus para determinação de atributos relacionados à qualidade, como maciez, perdas por cozimento, gordura intramuscular e pH. Avaliações por infravermelho com comprimentos de onda na faixa do visível próximo (VIS-NIRS) foram tomadas para associação com valores de pH, força de cisalhamento e lipídios no músculo Longissimus. Foram estimados parâmetros genéticos para todas as características avaliadas neste trabalho. As características de ganho ponderal, frame, medidas de ultrassonografia e qualidade de carne foram utilizadas para comparação entre genearcas e novos genearcas da raça Nelore. Estas informações em conjunto com a validação ferramentas auxiliares para coleta de fenótipos poderão ajudar na condução de programas de melhoramento genético de características de desempenho e qualidade de nos rebanhos dessa raça, bem como a obtenção de importantes informações sobre a variabilidade e valor genético de genearcas e touros representativos da raça Nelore. / The objective of this study was to evaluate the differences of growth, carcass composition and beef quality traits among lineages and representative Nellore sires, using new technologies to collect data and estimate genetic and phenotypic parameters. Data on growth, carcass and meat quality traits of Nellore bulls, raised in pastures and included in genetic evaluation programs were analyzed. Individual information on live ultrasound carcass measurements and frame were, also, collected. After slaughter, carcass, beef quality traits and video image analysis (VIA) of muscle Longissimus were obtained for estimation of beef quality attributes like tenderness, cooking losses, intramuscular fat and pH. Evaluations with Near Infrared Spectroscopy (VIS-NIRS) were made to quantify tenderness and lipid in Longissimus muscle. Genetic parameters were estimated for all traits analyzed in this study. Traits like performance, frame, ultrasound carcass evaluation and meat quality were used to compare lineages and representative Nellore sires. This research provide precious information to development of auxiliary tools for genetic improvement of growth, carcass and meat quality traits in Nellore herds, and provide important information about variability and genetic value of founders and representative sires of this breed.

A primeira parte desta Tese incluiu a funcionalização em solução de polietileno linear de média densidade (LMDPE) com alil glicidil éter (AGE), na presença de peróxido de benzoíla (BPO) como iniciador de reações radicalares. A caracterização foi feita por espectroscopia no infravermelho com transformada de Fourier (FTIR) e o grau de funcionalização (GF) foi estimado por meio de duas curvas de calibração. Foi observado efeito do tipo de solvente sobre o GF. A segunda parte consistiu na funcionalização superficial por radiação ultravioleta (UV). Como monômeros foram usados AGE, anidrido maléico (MAH) e anidrido tetraidroftálico (THFAH). Como iniciadores, BPO e benzofenona (BP). A caracterização das superfícies foi realizada por medidas de ângulo de contato. THFAH apresentou a melhor performance. A terceira tratou da funcionalização por processamento reativo do LMDPE com AGE, na presença de BPO. A caracterização se deu por FTIR e o GF foi estimado conforme descrito acima. A funcionalização foi confirmada (indiretamente) por calorimetria diferencial exploratória, que evidenciou a diminuição do grau de cristalinidade com a funcionalização. Não foi possível confirmar a funcionalização por meio de análise elementar, termogravimetria e difração de raios X. A fragmentação das cadeias do LMDPE funcionalizado do ensaio 13 (e 13A) foi evidenciada por decréscimo no torque e nas propriedades mecânicas. Contudo, o índice de fluidez, surpreendentemente, diminuiu. Os valores relativamente superiores de resistência à tração e módulo de Young dos compósitos e blendas obtidos com LMDPE funcionalizado, contra os obtidos com LMDPE virgem, evidenciaram a interação favorável entre os grupos epóxidos inseridos nas cadeias do LMDPE e os grupos hidroxilas presentes no polissacarídeo. O aumento da adesão entre a matriz polimérica e as fibras de celulose foi confirmado por microscopia eletrônica de varredura e, qualitativamente, por quantidades relativamente maiores de resíduos remanescentes após extração em xileno sob refluxo. / The first part of this work included the functionalization in solution of linear medium density polyethylene (LMDPE) with allyl glycidyl ether (AGE), in the presence of benzoyl peroxide (BPO) as free radical reaction initiator. The characterization was made by Fourier transform infrared spectroscopy (FTIR) and the degree of functionalization was estimated by means of two calibration curves. The type of solvent influenced the DF. The second part comprised the surface functionalization by ultraviolet (UV) radiation. AGE, maleic anhydride (MAH) and tetrahydrophthalic anhydride (THFAH) were used as monomers and BPO and benzophenone (BP) as initiators. Contact angle measurements were used to characterize the surfaces. THFAH showed the best performance. The third part dealt with the functionalization by reactive processing of LMDPE with AGE, in the presence of BPO. FTIR was used to characterize the samples and the degree of functionalization was estimated as described above. The functionalization was (indirectly) confirmed by differential scanning calorimetry. The degree of crystallinity decreased with the functionalization. The functionalization couldn?t be confirmed by elemental analysis, thermogravimetry and X-ray diffraction. The chain scissions of the chemical modified LMDPE of trial 13 (and 13A) were evidenced by reduction of torque and mechanical properties. However, the melt flow index diminished. The favorable interaction between epoxide groups inserted on LMDPE chains and hydroxyl groups present in polysaccharide caused the increase in tensile strength and Young?s modulus values for composites and blends in relation to those obtained with virgin LMDPE. The increase in adhesion between the polymeric matrix and cellulose fibers was also confirmed by scanning electron microscopy and, qualitatively, by relatively large amounts of remaining residues after extraction in refluxing xylene.

Na montagem de um farol automobilístico são utilizados diversos materiais, tais como insertos metálicos nas fixações, vidros nas lâmpadas, materiais poliméricos nas lentes, carcaças, molduras, vedações e refletores, além de vernizes, tintas, película de metal para reflexão do feixe luminoso. Há cerca de quatro décadas foi iniciada a confecção dos refletores utilizando o BMC (bulk moulding compound), sigla em inglês para composto para moldagem em forma de massa, que é um compósito polimérico termofixo. Este material apresenta inúmeras vantagens sobre o metal, tal como forma e geometria que podem se integrar facilmente ao desenho do carro, elevada produtividade, baixo custo e da elevada resistência térmica. Contudo, apresentam o inconveniente de não poderem ser reciclados. Uma opção ao BMC tem sido o PEI [poli (éter imida)], que é um material polimérico termoplástico de alto desempenho que apresenta propriedades atrativas para essa utilização. Oferece também elevada produtividade, porém com um custo elevado se comparado ao BMC. Tem a vantagem de pode ser reciclado. De modo a analisar o potencial dos dois materiais e extrair deles suas vantagens competitivas, bem como determinar suas possíveis limitações, o presente trabalho apresenta os resultados de caracterização mecânica, análise térmica, ensaios de impacto, ensaios de temperatura de deflexão térmica (HDT) e reaproveitamento de resíduos de BMC, incorporando-o ao PVC [poli (cloreto de vinila)], resultando uma nova blenda polimérica. O estudo conclui que ambos os materiais podem ser utilizados para fabricação de refletores automobilísticos. No entanto, o preço do PEI é maior que o do BMC, o que desestimula sua utilização em produtos de alta escala de produção, como, por exemplo, o produto do presente trabalho. O BMC por sua vez não pode ser reciclado, exigindo um custo adicional para seu reaproveitamento de maneira a evitar seu descarte em aterro sanitário. / For assembly of an automobile headlight a lot of materials are used such as metallic inserts anchors, glass in the lamps, lens of polymeric materials, bezels, frames, fences and reflectors as well as paints, metallic sheet for reflection of the luminous beam. About four decades ago begun the manufacturing of BMC reflectors, which is a thermoset composite material. This material presents countless advantages on the metal, such as shape and geometry that can easily integrate the designing of cars, high productivity, low cost and high heat resistance. However, they have the disadvantage of not being able to be recycled. An option to the BMC has been the PEI [poly (ether imide)], which is a high performance polymeric thermoplastic material which brings attractive properties for the production of reflectors. It also offers high productivity, however with a high cost compared to BMC. It also has the advantage of being recycled. In order to analyze the potential of both materials and extract their competitive advantages, as well as determine their possible limitations, this study presents the results of mechanical characterization, thermal analysis, impact tests, tests on heat deflection temperature (HDT) and the reuse of BMC waste, incorporating it to PVC [poly (vinyl chloride)], resulting in a new polymeric blend. The study concludes that both materials can be used for manufacturing automobile reflectors. However, the price of PEI is higher than the one of BMC, which discourages their use in high-scale production products, as the one of this work. The BMC for your time can not be recycled, demanding an extra cost for their reuse, avoiding its disposal in landfill.

No description available.

Diminuer les émissions de CO2, principal gaz à effet de serre, constitue un des enjeux majeurs de notre ère actuelle. De nombreuses mesures existent déjà mais sont encore insuffisantes. C’est dans ce cadre que le projet ANR DIGAS a vu le jour. Durant ces travaux, des matériaux catalytiques composés de CuO/ZnO/ZrO2 ont été développés par coprécipitation classique et ont été testés sous une pression de 50 bar pour la synthèse de méthanol à partir de l’hydrogénation de CO2. Ces catalyseurs ont ensuite été optimisés à l’aide d’un système développé au laboratoire : la synthèse microfluidique en continu. Elle a permis de rendre les catalyseurs plus homogènes et ainsi plus efficaces. Le catalyseur le plus performant a, par la suite, été couplé à un catalyseur acide, une zéolithe ZSM5, pour permettre la synthèse directe de diméthyléther (DME) à partir de l’hydrogénation de CO2. Dans le cas de la synthèse de méthanol ainsi que pour la synthèse de DME, les catalyseurs développés sont compétitifs et plus performants que les catalyseurs actuellement sur le marché. / Reducing CO2 emissions, the main greenhouse gas, is one of the major challenges of our current era. Many measures already exist but are still insufficient. It is in this context that the ANR project called DIGAS was funded. During this work, catalytic materials composed of CuO/ZnO/ZrO2 were developed by classical coprecipitation and tested under a pressure of 50 bar for the methanol synthesis from CO2 hydrogenation. Then, these catalysts were optimized using a system developed in the laboratory: microfluidic continuous synthesis. It has made the catalysts more homogeneous and thus more efficient. The most efficient catalyst was subsequently coupled to a ZSM5 zeolite to allow direct dimethyl ether (DME) synthesis from the CO2 hydrogenation. In the case of methanol as well as for DME synthesis, the developed catalysts are competitive and more efficient than the catalysts currently on the market.