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No description available.

<p> This thesis describes the development of the Wittig olefination reaction of stabilized, semistabilized allylic trialkylphosphorus ylides with various aldehydes to afford E olefins mainly (E>89%). Since the steric demand of trialkylphosphorus ylides was decreased, aldehydes achieved high E selectivity. On the other hand, predominant or exclusive formation of Z olefms was achieved by using allylic triphenylphosphorus ylides and aromatic aldehydes like benzylaldehyde, while the combination of allylic triphenylphosphorus ylides and such sterically hindered aldehydes as cyclohexanecarboxaldehyde led to E olefm formation upon ylide formation with LiHMDS. In the case of olefination reactions of aldehydes with dimethyl thiazole ylide, it was shown that among the aromatic aldehydes only 4-nitrobenzaldehyde reacted with this ylide and provided a pure E olefin product (41% yield). Dimethylmalonyltributylphosphorane (DMTP) reacted with aromatic aldehydes in toluene at 125 °C to give the corresponding alkenes. 4-Nitrobenzaldehyde· gave the alkene in a much higher yield (81%), followed by 4-chlorobenzaldehyde (31%). With benzaldehyde, the corresponding olefin was isolated in only 14% yield under these conditions. Clearly, this highly stabilized ylide only enters into reaction with electron deficient aldehydes. A possible approach to Z-a, P-unsaturated aldehydes was investigated through the olefination of an acetal-ylide followed by hydrolysis. However, E acetal olefins were in fact isolated from this 2'-(1,3-dioxolanyl)-triethylphosphorus ylide with aromatic aldehydes in good yields (62%-76%). This result is still mechanistically interesting in view of the chemoselective formation of such an ylide in the presence ofthree ethyl substituents on phosphorus. </p> <p> Class of flavonoids: Sakuranetin, Naringenin and (28)-7-methoxy-6hydroxyflavanone, have been isolated from the diseased bark of Prunus sp. The structures were elucidated based on the spectroscopic data. Locations of 4-keto, 5-0H and 7-methoxy were deduced from COSY and HMBC spectra. Such compounds are of interest for their potential antibiotic activity against vancomycin-resistant strains of microbes. </p> / Thesis / Master of Science (MSc)

This study focused on the kinetic data measurements, such as diffusion coefficient D and exchange current density i_0 of the electrochemical reactions of corrosion products (Fe, Cr and Ni ions) and corrosive species (OH-), and corrosion studies of structural materials (SS 316H and Alloy 617), including static corrosion and galvanic corrosion, in molten MgCl2-NaCl-KCl and/or NaF-KF-UF4-UF3 salts in a temperature range of 600 to 800C. The study applied the semi-differential (SD) analysis method and innovative fitting method for the kinetic property data measurements in the multicomponent system of NaF-KF-UF4-UF3 salts. In molten MgCl2-NaCl-KCl salts, the measured D_(OH^- ) has the largest value followed by D_(〖Cr〗^(2+) ), D_(〖Fe〗^(2+) ), D_(〖Cr〗^(3+) ) and D_(〖Ni〗^(2+) ) at the studied temperatures, and none of the diffusion coefficients depends on the ion concentration in the studied concentration range and all of them followed the Arrhenius law. At the same temperature, the measured D_(Fe^(2+) ) and D_(〖Cr〗^(2+) ) values in molten NaF-KF-UF4-UF3 salts were slightly smaller than those obtained in molten MgCl2-NaCl-KCl salts. The non-linear curve fitting technique was applied to determine the exchange current density i_0, charge transfer coefficient α, limiting current density i_L and standard rate constant k^0 values. i_0 and k^0 followed the Arrhenius law. The obtained fundamental data can be applied to corrosion models which make the corrosion rate prediction possible in a static system from the experimental kinetic data. Corrosion studies of SS 316H and Alloy 617 in thermal purified molten NaF-KF-UF4-UF3 salts were performed for 120 hours. Based on the post-test analysis, the major metal species corrosion products were Cr, Fe and Mn in SS 316H tests, and Cr, Co, Ni in Alloy 617 tests. The measured UF4/UF3 ratio increased after corrosion tests because some of the U3+ was oxidized to U4+ by corrosive impurities and corrosion products during tests. Cr depletion and salt penetration were observed at grain boundaries (GBs) for both SS 316H and Alloy 617. For Alloy 617 specimens, the corroded area could be divided into two parts: the first part (near the surface) where Cr was completely depleted, and the second part (underneath the first part) where Cr was partially depleted. For SS 316H specimens, the average attack depth was larger than that of Alloy 617. Mo segregation was observed in the matrix of SS 316H specimens but was found to be enriched at GBs in the second part of Alloy 617 specimens. The corrosion study of Alloy 617 with time was also conducted for 72 hours and 32 hours, respectively. A thin layer composed of Fe, Co, Ni and Mo was found on the surface of the specimen, which was different from the previous 120-hour tests. In the salt, the concentration of Cr kept increasing with time, while for the other identified corroded elements, i.e., Fe, Co, Ni and Mo, their concentrations increased first, then decreased until becoming zero or stable. In the galvanic corrosion study of Alloy 617/graphite in molten NaF-KF-UF4-UF3 salts, the galvanic corrosion rate of Alloy 617 at 750C was about four times of that at 650C in the 2-hour tests, which indicated that temperature has a significant effect on the galvanic effect. In the 120-hour galvanic corrosion test, the galvanic corrosion rate became slightly larger with time in the studied system. Similar to the previous 120-hour Alloy 617 corrosion test, the corroded area of the post-test specimen was divided into two parts. The measured attack depth in both parts were much smaller compared with that in the 120-hour Alloy 617 test. This was because of the lower corrosive impurity concentrations in the salt used in the test. The salt in the galvanic corrosion test has been used in the previous corrosion test, during which the corrosive impurities were consumed, which made the salt less corrosive. Finally, it is necessary to point out that all the salts used in the present work were only thermally purified, which is effective in the removal of moisture but not in the removal of oxide impurities. Therefore, further studies are needed to understand the oxides' impacts on the corrosion behavior, especially on the salt penetration. / Doctor of Philosophy / Molten salt is a promising candidate that can be used as fuel and coolant in the molten salt reactors (MSRs). Besides, it can also be used as thermal energy storage, heat transfer fluid in the concentrated solar power plants, because it has high heat capacity, low vapor pressure, and high thermal conductivity. However, materials corrosion is a key concern of molten salt applications, and it is known that the corrosion by molten salts is mainly impurity driven. The impurities, such as moisture in the salts, can make the salt more oxidized, thus becoming more corrosive to corrode the structural materials. The present work focus on the kinetic property of metal specie corrosion products and non-metal impurity in the molten fluoride and chloride salts, which were directly related to the mass transfer and charge transfer process during the corrosion. Especially in the measurements of fluoride salts, innovative methods were applied which were confirmed to perform well in the multicomponent system (Fe and Cr ions coexisted). The static corrosion tests of SS 316H and Alloy 617 were conducted in molten fluoride salt at high temperatures. The main purpose was to study their corrosion behavior and understand the corrosion mechanisms. The corrosion rate of SS 316H was also estimated, which could be a crucial criterion in the material selection. In addition, the corrosion of Alloy 617 with time was also investigated. The metal specie corrosion product concentration change trends were obtained, and the corrosion behavior over the different corrosion stages was analyzed. Different corrosion phenomenon was observed in different corrosion test. Thus, they shed lights on the study of how the corrosion was developed during the corrosion process. Moreover, galvanic corrosion was another major corrosion type when two or more dissimilar materials were electrically contacted. The galvanic corrosion of Alloy 617/graphite was studied in the molten fluoride salts. The galvanic corrosion rate increased with the rise of temperature, which verified that temperature was a key factor that affected the galvanic corrosion. And the galvanic effect was also turned out to increase with time in the present study.

The central Florida, North Carolina, and central Tennessee phosphorite deposits account for 90% of the marketable phosphate produced in the United States. Scanning electrons and reflected light microscopy reveals that the iron-bearing minerals associated with these sedimentary phosphorites are related to the geologic setting and degree of weathering of the deposit. Pyrite and marcasite (FeS₂) are the principal iron mineral inclusions in unweathered phosphorites of Florida, North Carolina, and Tennessee, and occur as discrete, randomly disseminated microcrysts, irregularly shaped microcryst aggregates, cubes, dendrites, framboids, or bioturbation and interstitial pore space fillings. Pyrite and marcasite also fill the void spaces in skeletal phosphorites such as nerve canals in shark teeth of Florida and North Carolina and in bryozoan zooecium of Tennessee. The oxidizing conditions accompanying weathering in the terrigenous sand and clay environments of central Florida alter these inclusions to goethite (FeOOH), which occurs as pseudomorphs after the iron sulfides. However, hematite (Fe₂O₃) optically appears to be the iron sulfide pseudomorph in the phosphorites of the weathered carbonate environments in central Tennessee. The first reported occurrences of chalcopyrite (CuFeS₂), chromite (FeCr₂O₄), and an iron-potassium-silicate sheath surrounding some iron sulfide and iron oxides as inclusions in phosphorites, supergene ferrian-millisite [Ca₃(Al,Fe³⁺)₁₂(PO4)₈(OH)₁₈ • 6H₂O)] as coatings on phosphorites in the leached zone under a central Florida gossan, and secondary ferromanganese oxide spherulites as accessory minerals in Tennessee deposits are made in this study / M.S.

No / Phosphonium tosylates have been investigated as solvents for the Diels¿Alder reactions of isoprene with methyl acrylate, but-3-en-2-one and acrylonitrile. The reactions with oxygen-containing dienophiles showed high regioselectivity. Graphic

No description available.

Objetivou-se avaliar a inclusão de fontes de gordura na forma de sais de cálcio na dieta sobre o desempenho e metabolismo de vacas em início e meio da lactação mantidas em pastagens tropicais. No Capítulo 3, foi realizada uma meta-análise para avaliar os efeitos da suplementação de gordura para vacas mantidas em pastagens sobre a produção e a composição do leite. A produção de leite aumentou com a suplementação de gordura, e a suplementação com fontes insaturadas deprimiu o teor de gordura do leite. No capítulo 4, objetivou-se comparar o uso do dióxido de titânio (TiO2) como marcador externo em substituição ao óxido crômico (Cr2O3) para estimar a excreção fecal e calcular o consumo de forragem e a digestibilidade. A excreção fecal tendeu ser maior para os valores estimados pelo Cr2O3. O Cr2O3 superestimou a excreção fecal comparado com a coleta total de fezes. O consumo de forragem e o consumo de MS total foram superestimados pelo Cr2O3, enquanto não foram observadas diferenças entre os valores observados de consumo e estimados pelo TiO2. A digestibilidade aparente da MS foi subestimada tanto pelo Cr2O3 quanto pelo TiO2. No capítulo 5 objetivou-se avaliar os efeitos da suplementação de vacas em início da lactação mantidas em pastagem tropical com diferentes fontes de gordura sobre o desempenho, composição do leite e variáveis produtivas ao longo da lactação. A suplementação de sais de cálcio de óleo de soja (SCOS) aumentou a produção de leite quando comparado com o grupo controle, porém foi inferior a produção dos animais suplementados com sais de cálcio de óleo de palma (SCOP). Apesar do aumento em produção de leite com SCOS, nesse tratamento o teor de gordura do leite reduziu significativamente quando comparado com o grupo controle e ao SCOP. Durante o período residual a produção do grupo que recebeu SCOP continuou maior e refletiu na produção ao longo de toda a lactação (7328 kg lactação-1) comparado ao SCOS (6575 kg lactação-1) e ao controle (6094 kg lactação-1). No capítulo 6, objetivou-se avaliar a suplementação de duas fontes e duas doses de sais de cálcio de ácidos graxos sobre o desempenho, composição do leite, parâmetros ruminais e metabólicos e balanço energético de vacas no meio da lactação mantidas em pastagem tropical. A produção de leite foi afetada pela adição de gordura, sendo influenciada pela fonte e pela dose de gordura. O teor de gordura do leite foi influenciado pela fonte de gordura suplementada. O pH ruminal não foi afetado pelos tratamentos experimentais. A suplementação com SCOS prejudicou a degradação da fibra, reduziu a produção de AGV\'s, reduziu a síntese microbiana e a produção de gordura do leite quando comparado com a fonte de SCOP. Portanto, as estimativas de consumo e digestibilidade foram melhores preditas com o uso do dióxido de titânio como marcador. Além disso, a suplementação com sais de cálcio de óleo de palma aumentou a produção de leite na lactação, não reduziu o consumo e nem a degradação da fibra. / The objective of this study was to evaluate inclusion of different sources of fat as calcium salts in the diet on performance and metabolism of early lactation cows grazing tropical pastures. In Chapter 3, a meta-analysis was performed to evaluate the effects of fat supplementation to grazing dairy cows on milk yield and milk composition. Milk yield increased with fat supplementation, and supplementation with unsaturated sources depressed milk fat content. In Chapter 4, the objective was to compare the use of titanium dioxide (TiO2) as an external marker to replace chromium oxide (Cr2O3) to estimate fecal excretion and calculate forage intake and digestibility. Fecal excretion tended to be greater for values estimated by Cr2O3. The Cr2O3 overestimated and TiO2 tended to overestimate fecal excretion compared to total fecal collection. Forage intake and total DM intake were overestimated by Cr2O3, while no differences were observed between the observed values of consumption and estimated by TiO2. The apparent DM digestibility was underestimated by both Cr2O3 and TiO2. In the chapter 5, it was evaluated the effects of fed different sources of fat to early lactation cows (from 15 to 105 DIM) grazing a tropical pasture on production variables throughout lactation (until 280 DIM). Calcium salts of soybean oil (CSSO) increased milk yield compared to control, but was lower than the production of animals supplemented with calcium salts of palm oil (CSPO). Despite the increase in milk yield with CSSO, this treatment decreased milk fat content and yield when compared with control and CSPO. During the residual period (from 106 to 280 DIM) the group that received CSPO had greater milk yield and reflected in the greater milk yield throughout lactation (7328 kg lactation-1) compared to CSSO (6575 kg lactation-1) and the control (6094 kg lactation-1). In chapter 6, the objective was to evaluate the supplementation with two sources (CSSO vs. CSPO) and two doses (400g vs 700g/day) of calcium salts of fatty to mid lactating dairy cows grazing a tropical pasture on performance, milk composition, ruminal and metabolic parameters and energy balance. Milk yield was increased by the addition of fat, being influenced by source and by dose. The milk fat was influenced by source of fat supplementation. The ruminal pH was not affected by experimental treatments. Supplementation with CSSO damaged the fiber degradation, reduced production of VFA \'s, reduced microbial synthesis and the production of milk fat compared with the source of CSPO. In conclusion, DM intake and digestibility were better predicted with the use of titanium dioxide as a marker. Furthermore, supplementation with calcium salts of palm oil increased milk production in lactating without decreasing DM intake and degradation of the fiber.

Objetivou-se avaliar a inclusão de fontes de gordura na forma de sais de cálcio na dieta sobre o desempenho e metabolismo de vacas em início e meio da lactação mantidas em pastagens tropicais. No Capítulo 3, foi realizada uma meta-análise para avaliar os efeitos da suplementação de gordura para vacas mantidas em pastagens sobre a produção e a composição do leite. A produção de leite aumentou com a suplementação de gordura, e a suplementação com fontes insaturadas deprimiu o teor de gordura do leite. No capítulo 4, objetivou-se comparar o uso do dióxido de titânio (TiO2) como marcador externo em substituição ao óxido crômico (Cr2O3) para estimar a excreção fecal e calcular o consumo de forragem e a digestibilidade. A excreção fecal tendeu ser maior para os valores estimados pelo Cr2O3. O Cr2O3 superestimou a excreção fecal comparado com a coleta total de fezes. O consumo de forragem e o consumo de MS total foram superestimados pelo Cr2O3, enquanto não foram observadas diferenças entre os valores observados de consumo e estimados pelo TiO2. A digestibilidade aparente da MS foi subestimada tanto pelo Cr2O3 quanto pelo TiO2. No capítulo 5 objetivou-se avaliar os efeitos da suplementação de vacas em início da lactação mantidas em pastagem tropical com diferentes fontes de gordura sobre o desempenho, composição do leite e variáveis produtivas ao longo da lactação. A suplementação de sais de cálcio de óleo de soja (SCOS) aumentou a produção de leite quando comparado com o grupo controle, porém foi inferior a produção dos animais suplementados com sais de cálcio de óleo de palma (SCOP). Apesar do aumento em produção de leite com SCOS, nesse tratamento o teor de gordura do leite reduziu significativamente quando comparado com o grupo controle e ao SCOP. Durante o período residual a produção do grupo que recebeu SCOP continuou maior e refletiu na produção ao longo de toda a lactação (7328 kg lactação-1) comparado ao SCOS (6575 kg lactação-1) e ao controle (6094 kg lactação-1). No capítulo 6, objetivou-se avaliar a suplementação de duas fontes e duas doses de sais de cálcio de ácidos graxos sobre o desempenho, composição do leite, parâmetros ruminais e metabólicos e balanço energético de vacas no meio da lactação mantidas em pastagem tropical. A produção de leite foi afetada pela adição de gordura, sendo influenciada pela fonte e pela dose de gordura. O teor de gordura do leite foi influenciado pela fonte de gordura suplementada. O pH ruminal não foi afetado pelos tratamentos experimentais. A suplementação com SCOS prejudicou a degradação da fibra, reduziu a produção de AGV\'s, reduziu a síntese microbiana e a produção de gordura do leite quando comparado com a fonte de SCOP. Portanto, as estimativas de consumo e digestibilidade foram melhores preditas com o uso do dióxido de titânio como marcador. Além disso, a suplementação com sais de cálcio de óleo de palma aumentou a produção de leite na lactação, não reduziu o consumo e nem a degradação da fibra. / The objective of this study was to evaluate inclusion of different sources of fat as calcium salts in the diet on performance and metabolism of early lactation cows grazing tropical pastures. In Chapter 3, a meta-analysis was performed to evaluate the effects of fat supplementation to grazing dairy cows on milk yield and milk composition. Milk yield increased with fat supplementation, and supplementation with unsaturated sources depressed milk fat content. In Chapter 4, the objective was to compare the use of titanium dioxide (TiO2) as an external marker to replace chromium oxide (Cr2O3) to estimate fecal excretion and calculate forage intake and digestibility. Fecal excretion tended to be greater for values estimated by Cr2O3. The Cr2O3 overestimated and TiO2 tended to overestimate fecal excretion compared to total fecal collection. Forage intake and total DM intake were overestimated by Cr2O3, while no differences were observed between the observed values of consumption and estimated by TiO2. The apparent DM digestibility was underestimated by both Cr2O3 and TiO2. In the chapter 5, it was evaluated the effects of fed different sources of fat to early lactation cows (from 15 to 105 DIM) grazing a tropical pasture on production variables throughout lactation (until 280 DIM). Calcium salts of soybean oil (CSSO) increased milk yield compared to control, but was lower than the production of animals supplemented with calcium salts of palm oil (CSPO). Despite the increase in milk yield with CSSO, this treatment decreased milk fat content and yield when compared with control and CSPO. During the residual period (from 106 to 280 DIM) the group that received CSPO had greater milk yield and reflected in the greater milk yield throughout lactation (7328 kg lactation-1) compared to CSSO (6575 kg lactation-1) and the control (6094 kg lactation-1). In chapter 6, the objective was to evaluate the supplementation with two sources (CSSO vs. CSPO) and two doses (400g vs 700g/day) of calcium salts of fatty to mid lactating dairy cows grazing a tropical pasture on performance, milk composition, ruminal and metabolic parameters and energy balance. Milk yield was increased by the addition of fat, being influenced by source and by dose. The milk fat was influenced by source of fat supplementation. The ruminal pH was not affected by experimental treatments. Supplementation with CSSO damaged the fiber degradation, reduced production of VFA \'s, reduced microbial synthesis and the production of milk fat compared with the source of CSPO. In conclusion, DM intake and digestibility were better predicted with the use of titanium dioxide as a marker. Furthermore, supplementation with calcium salts of palm oil increased milk production in lactating without decreasing DM intake and degradation of the fiber.