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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
61

Efeito de metabólitos produzidos por actinobactérias sobre a digestibilidade in vitro e fermentação ruminal / Effect of metabolites produced by actinobacteria on in vitro digestibility and ruminal fermentation

Bruna Gomes Alves 30 March 2016 (has links)
Actinobactérias são microrganismos capazes de produzir compostos bioativos presentes em extratos brutos com ação antibiótica e ionófora. A hipótese deste estudo foi de que extratos brutos de actinobactérias apresentem eficácia similar à monensina sódica para modulação da fermentação ruminal; no aumento da digestibilidade da matéria seca e matéria orgânica, aumento da concentração de propionato e redução da produção de gases totais, da desaminação protéica e de metano. Portanto, o objetivo foi avaliar in vitro dois extratos brutos (AMC e Caat) sobre a fermentação ruminal (produção total de gases, de ácidos graxos de cadeia curta (AGCC) e de metano (CH4); digestibilidade in vitro da matéria seca (DIVMS), da matéria orgânica (DIVMO) e produção de nitrogênio amoniacal (N-NH3). O estudo foi dividido em duas fases; a primeira objetivou estabelecer a curva dose-resposta dos extratos e a segunda para avaliação com controle positivo de monensina sódica. Para ambas fases, foram utilizadas como doadoras de líquido ruminal (inóculo) três vacas da raça Holandesa em lactação, portadoras de fístula ruminal. As dietas fornecidas foram à base de silagem de milho, farelo de soja, ureia, milho moído e suplemento mineral, com relação volumoso:concentrado de 60:40. Amostras de fluido ruminal foram coletadas por meio de bomba de vácuo, armazenadas em garrafas e caixas térmicas e transportadas ao laboratório para incubação em frascos de vidro. Para a primeira fase, foram avaliadas 4 doses (0,3; 0,6; 0,9 e 1,20 mg) de 2 extratos (AMC e Caat) em ensaio in vitro de 72 horas, no qual foram mensuradas a produção de gás durante a incubação e, ao final, as concentrações de AGCC, DIVMS e DIVMO foram determinadas. Na segunda fase, o ensaio foi de 24 horas, e ao final foram feitas análises para CH4 e N-NH3, além de AGCC, DIVMS, DIVMO e produção de gás. O delineamento experimental adotado foi o inteiramente casualizado (DIC) para ambas as fases. Na primeira fase, a inclusão do Caat diminuiu linearmente a DIVMO após 72 hs e reduziu as concentrações de ácido isovalérico, butírico, da relação acetato:propionato e da produção de gás acumulado por 24, 48 e 72 h. Na segunda fase, a inclusão dos extratos causaram diminuição da produção de gás acumulada em 24 horas, sendo menor no tratamento monensina e no Caat. Houve efeito de inclusão do Caat e da monensina sobre a concentração de AGCC, aumentando a concentração de propionato e diminuindo a concentração de butirato, acetato e a relação acetato:propionato. A concentração de N-NH3 foi menor mediante inclusão do extrato Caat e da monensina enquanto que a concentração de CH4 foi maior para a inclusão dos extratos quando comparados com a inclusão de monensina, entretanto não foram maiores do que o controle. A inclusão do extrato Caat foi capaz de modificar a fermentação in vitro de forma semelhante à monensina sódica, mas não alterou a digestibilidade da fibra. Por outro lado, o AMC não alterou a fermentação ruminal, seja na digestibilidade da fibra, na produção de gases totais, metano, nitrogênio amoniacal e AGCC / Actinobacteria are microorganisms that can produce bioactive compounds present in crude extracts with antibiotic and ionophore activity. Our hypothesis was that actinobacteria crude extracts showed similar efficacy to monensin on ruminal fermentation; increasing the digestibility of dry matter and organic matter, increasing propionate concentration and reducing the total gas production, protein deamination and methane. Therefore, the objective was to evaluate two crude extracts (AMC and Caat) on in vitro ruminal fermentation (total gas, short chain fatty acids (SCFA) and methane (CH4) production; in vitro digestibility of dry matter (IVDDM), of organic matter (IVOMD) and ammonia nitrogen production (NH3-N). The study was divided into two phases: the first aimed to establish the dose-response curve of the extracts and the second aimed to evaluate a positive monensin control. For both, it was used three lactating Holstein cows with ruminal fistula as rumen fluid donors (inoculum). The diets were based on corn silage, soybean meal, urea, ground corn and mineral supplement under forage:concentrate ratio of 60:40. Ruminal fluid samples were collected by a vacuum pump, stored in bottles and coolers and transported to the laboratory for incubation in glass bottles. For the first phase, they were evaluated 4 doses (0.3; 0.6; 0.9 and 1.20 mg) of 2 extracts (AMC and Caat) on a 72 hours in vitro assay, which were measured gas production during incubation and in the end, SCFA, IVDMD and IVOMD concentrations were determined. In the second phase, it was a 24 hours assay, and include final analyzes for CH4 and NH3-N, plus SCFA, IVDMD, IVOMD and gas production. The experimental design was completely randomized (DIC) for both phases. In the first phase, the Caat inclusion linearly decreased IVOMD after 72 hours and reduced isovaleric acid and butyric acid concentration and acetate:propionate ratio and cumulative gas production by 24, 48 and 72 h. In the second stage, the inclusion of the extracts caused a reduction of the cumulative gas production in 24 hours, being lower in monensin and Caat treatments. There was an effect of Caat and monensin inclusion on SCFA concentration, increasing the propionate concentration and reducing the butyrate and acetate concentration and the acetate: propionate ratio. The NH3-N concentration was lower by Caat inclusion and monensin while the CH4 concentration was higher for the extracts inclusion as compared with monensin, however were not bigger than control. The Caat inclusion was able to modify the in vitro fermentation similarly to monensin, but did not affect the fiber digestibility. Moreover, AMC did not affect the rumen fermentation, either in fiber digestibility, total gas, methane, ammonia nitrogen and SCFA production
62

Into the Cosmos : A Translation Study of Astronomical Proportions Focusing on Terminology, Additions and Omissions

Danheden, Robert January 2008 (has links)
The intention of this essay is to illustrate and describe various means to overcome some of the difficulties that any translator dealing with technical translations at some point or another would come upon – presented in a qualitative analysis. The text under analysis is a chapter called Into the Cosmos and is part of the book Planet Quest – The Epic Discovery of Alien Solar Systems by the American astronomer Ken Croswell. The analysis specifically focuses on terminology and two aspects that usually are part of the cultural adaptation of a text; namely additions and omissions. However, in this essay they help adapting the text towards a new target audience not so much because of culture, but rather because of my decision to fully disconnect the text from the context in which it previously functioned. And because of this, the target text was in the end given more of an educational character compared to the source text.
63

RETRAÇÃO TOTAL E PENETRAÇÃO DE CLORETOS EM CONCRETOS COMPOSTOS COM CINZA DE LODO DE ETA E OUTRAS ADIÇÕES MINERAIS / TOTAL SHRINKAGE AND CHLORIDE PENETRATION IN CONCRETE WITH WATER TREATMENT PLANT SLUDGE ASH AND OTHER MINERAL ADDITIONS

Antolini, Mariah Ben 16 December 2015 (has links)
The use of mineral additions and substitutions in concrete production is highly beneficial to society. When used as substitutes for cement, they provide an alternative destination to polluting waste while contributing to reducing the power consumption and air pollution associated with cement production. This study investigated the influence of different concentrations of additions and curing periods of concrete mixes with water treatment plant sludge ash (CLETA), rice husk ash (CCA) and blast furnace slag (EAF) on total shrinkage and chloride penetration in concrete prepared with high early strength Portland cement. Ten mixes with water/binder ratios of 0.35, 0.50 and 0.65, with wet cure periods of 3 and 7 days were tested. CLETA substitutions for Portland cement ranged from 0% to 30%. Three-component mixes with 20% CLETA and 5% EAF, 20% CLETA and 10% EAF and a four-component mix with 15% CLETA, 5% EAF and 5% CCA were also tested. Shrinkage was measured using a length comparator at 0, 7, 14, 21, 28, 35, 56, 91, 182 and 365 days after removing the sample from the controlled humidity chamber. After 91 days of drying, samples were tested for chloride penetration to check chloride penetration depths in shrinking test samples. Results indicate that even though shrinkage values at 3 days are slightly higher, no significant variation was found for different curing periods. The lowest shrinkage value was found in the reference sample for all tested periods and in the two curing periods. Next, in an increasing shrinkage values, came the following samples: 5%CLETA (5 L), 10% CLETA (10 L), 15% CLETA (15 L), which displayed, for most mixes, a similar behavior to that of 10% CLETA (10 L), followed by mixes 20% CLETA (20 L), 25 %CLETA (20 L) and 30% CLETA (30 L). Chloride penetration resistance increased when the curing time was increased from 3 to 7 days. Three- and four-component mixes showed improved performance when compared to binary samples with CLETA and Portland cement. / O uso de adições minerais e de substituições destas no processo de produção do concreto traz grande benefício à sociedade, por dar um destino a resíduos poluentes e, principalmente, por reduzir o consumo de energia e a poluição do ar gerados pela produção do cimento, ao substituir grande parte desse produto na indústria da construção civil. Neste estudo, investigou-se a influência do teor e do período de cura na utilização de misturas contendo diferentes teores de cinza de lodo de ETA (CLETA), cinza de casca de arroz (CCA) e escória de alto forno (EAF), frente à retração total e à penetração de cloretos de concretos com cimento Portland de alta resistência inicial. Para isso, foram testadas dez misturas aglomerantes, nas relações água/aglomerante 0,35, 0,50 e 0,65, com períodos de cura úmida de 3 e 7 dias. As substituições do cimento Portland por CLETA variaram de 0% a 30%, havendo ainda misturas ternárias, 20% CLETA e 5% EAF, 20% CLETA e 10% EAF, e quaternária, 15% CLETA, 5% EAF e 5% CCA. As leituras de retração foram realizadas com o uso do comparador de expansibilidade nas idades de ensaio, 0, 7, 14, 21, 28, 35, 56, 91, 182 e 365 dias após a retirada da câmara úmida. Após o período de 91 dias de secagem, foi realizado o ensaio de penetração de cloretos por imersão, a fim de analisar a profundidade de penetração de cloretos em corpos de prova em estado de retração. Dos resultados obtidos, constatou-se que, de maneira geral, embora tenham sido observados valores de retração pouco maiores para a cura de 3 dias, não foi constatada variação pronunciada entre os prazos de cura. De todas as misturas investigadas, a que apresentou menor valor de retração foi a de referência, em todas as idades de ensaio e nos dois períodos de cura. Seguido desta, em ordem crescente de retração, vem 5%CLETA (5 L), 10% CLETA (10 L), 15% CLETA (15 L), que tiveram na maioria das misturas um comportamento similar ao de 10% CLETA (10 L), seguido das misturas 20% CLETA (20 L), 25 %CLETA (20 L) e 30% CLETA (30 L). No que diz respeito à penetração de íons cloreto, houve um aumento na resistência quando o tempo de cura passou de 3 para 7 dias. Constatou-se que as misturas ternárias e quaternárias apresentam melhores desempenhos quando comparadas às misturas binárias, compostas por CLETA e cimento Portland.
64

Contribution à l'étude du comportement mécanique, du retrait et des propriétés de transport des bétons autoplaçants avec additions minérales, approche numérique et expérimentale / Contribution to the suty og mechanical, shrinkage and transport properties of SCCs with mineral admixtures experimental and numerical approach

Nik nezhad, Davood 11 December 2015 (has links)
Les bétons autoplaçants (BAP), développés depuis plusieurs années sont encore à l'heure actuelle qualifiés de « nouveaux bétons » car leur utilisation reste modeste bien qu'ils possèdent un fort potentiel de développement. Ce frein peut être expliqué par leur coût plus élevé, leur sensibilité à la ségrégation et à la fissuration due à leur fort retrait ainsi que par le manque de connaissances sur leur durabilité. Les BAP se distinguent des bétons ordinaires principalement par un dosage en éléments fins plus important. Ainsi, l'utilisation de fines additions minérales plus économiques et/ou plus écologiques dans ces bétons parait judicieuse sous certaines conditions. La présente thèse s'inscrit dans ce contexte et a pour objectifs de contribuer au développement de BAP plus écologiques et à l'étude de leur durabilité. Notre choix s'est porté sur deux ciments industriels à forte teneur en additions, le ciment CEM Ill à base de laitier de haut fourneau et le ciment CEM V à base de cendres volantes et de laitier de haut fourneau ainsi que sur deux additions minérales encore peu étudiées dans la littéraire : le métakaolin et un sédiment de dragage calciné. Différentes formulations dérivées d'une formulation de BAP de parement de référence à base de CEM 1 ont été mises au point. Les résultats des essais mécaniques et physico-chimiques menés sur les différentes formulations montrent un effet plus ou moins important des additions sur le comportement mécanique au jeune âge et un effet positif certain à plus long terme. Les résultats des mesures de retrait endogène et de dessiccation de l'état frais (plastique) à l'état durci bien hydraté montrent que certaines additions augmentent le retrait de dessiccation des BAP (laitier et sédiment calciné) alors que d'autres le réduisent considérablement (le métakaolin). L'effet indéniable des additions sur l'amélioration de certains indicateurs de durabilité (diffusion des chlorures et perméabilité au gaz) et sur l'augmentation de leur sensibilité à la carbonatation a été quantifié. L'influence assez complexe des différentes additions est étudiée à la lumière des analyses physico-chimiques et microscopique. Enfin, une modélisation mésoscopique est développée et appliquée aux BAP en vue d'une une étude paramétrique. L'effet de la forme des granulats et de leur concentration sur le comportement global en compression et traction d'éprouvette de SAP ainsi que l'effet de l'endommagement mécanique sur l'évolution de la perméabilité sont étudiés. / Self-compacting concretes (SCC), developed several years ago are still considered as “•novel concrete" as their use remains modest although they have a strong development potential. This is mainly due to their higher cos, their sensitivity to segregation and cracking due to their high shrinkage and also due to the lack of information about their durability. SCCs are distinguished from ordinary concrete mainly by their high content of paste. The use of supplementary cementitious materials (SCM), grow increasingly for economic and environmental reasons. This thesis falls within this context and aims to contribute to the development of greener SCCs and to the study of their durability.Two industrial blended cements containing high amounts of SCM, slag cement CEM Ill and CEM V cement containing slag and fly ash as well as two mineral additions still little studied in the literature: metakaolin and calcined dredged sediment are used. Various SCC mixtures derived from a reference SCC based on CEM 1 cement were developed. The results of the mechanical, physical and chemical testing on the different formulations show a greater or lesser effect of SCM on the mechanical behavior at early age and some positive effect over the long term. The results of measurements of the autogenous and drying shrinkage from fresh state (plastic) to well hydrated state show that some SCMs increase the drying shrinkage of SCCs (slag and calcined sediment) while ethers significantly reduce its amplitude (metakaolin).The undeniable effect of SCMs on improving some durability indicators (chloride diffusion and gas permeability) and on increasing the sensitivity to carbonation was quantified. The rather complex influence of the different SCMs is studied in the light of physicochemical and microscopie analyzes. Finally, mesoscopic modeling is developed and applied to SCCs for a parametric investigation. The effect of the shape of aggregates and their concentration on the overall behavior in compression and tensile SCC specimen as well as the effect of the mechanical damage on the evolution of permeability are studied.
65

Effect of Sc Addition on the Mechanical Properties of Mg-Sc Binary Alloys

Silva, Catherine J. 06 1900 (has links)
The addition of rare earth (RE) alloying elements is a promising method for improving the strength, ductility and overall formability of magnesium (Mg) alloys. However, the underlying mechanism for this phenomenon remains unclear. An investigation on the effect of the rare earth element, scandium (Sc), on binary Mg-Sc alloys has been pursued. Tension and compression tests were performed on a series of dilute binary Mg-Sc alloys at temperatures of 298 K, 78 K and 4.2 K. As a reference, pure Mg was also investigated for comparative purposes. Differences in tension and compression stress-strain curves highlighted distinct activated mechanisms, where slip dominated in tension and twinning governed compression. The observed increase in ductility and prolonged necking was attributed to a weaker basal texture, enhanced twinning and non-basal slip. A decreased work hardening rate suggests an improvement in dislocation recovery with Sc addition. In compression, Mg-Sc alloys followed Fleischer’s theory of solution hardening, where stress scales with concentration, c, as c^1/2; however, there was a very weak fit with both Fleischer and Labusch models under tension. The strengthening rate displayed by Mg-Sc was relatively weak compared to previously studied Mg-RE systems. However, considering the estimated misfit parameters, the size and modulus misfit was not enough to account for the strengthening rate. The results suggest that hardening of the twinning mode may influence strength. Constitutive modelling, based on a self-consistent plasticity model, was used to characterize the deformation behaviour. The simulations predicted an increased relative activity of non-basal <c+a> slip with Sc addition, supporting experimental results and proposed mechanisms in literature. The results of Mg-Sc alloys have been connected to theories that identify a decrease in stacking fault energy (SFE) as the determining factor for increased strength and ductility of Mg-RE alloys. A comparison of the SFE of previously studied REEs with Sc, demonstrated strong evidence towards the theory’s validity. Sc has been shown to only moderately reduce the SFE of Mg and hence, the present experimental results have shown a moderate increase in strength and ductility. Additional modelling and detailed dislocation analysis are suggested as future steps to further support this theory. / Thesis / Master of Applied Science (MASc)
66

Are legacy effects important for the response of phytoplankton communities to nutrient and dissolved organic matter pulses?

Ágreda López, Gabriela January 2023 (has links)
Climate change predictions include increasing precipitation and runoff events that expose phytoplankton communities to colored dissolved organic matter (cDOM) and nutrient pulses of varying intensity and frequency. The consequence of different nutrient/cDOM pulse regimes on phytoplankton communities and the role of legacy effects related to the characteristics of previous exposure regimes remain largely unresolved. To investigate this, we implemented add-on bottle experiments with water collected from a mesocosm experiment conducted in Lake Erken (Sweden) with four nutrient regime treatments with varying intensity and frequency. The nutrient additions of the mesocosm experiment lasted for three weeks and were followed by a two-week recovery period. At the end of both periods, water from three mesocosm treatments was filled into microcosms and either exposed to a second single nutrient pulse or left as control. The microcosms were incubated for 8 days in the lab and changes in phytoplankton biomass and composition were analyzed to determine the legacy effect of antecedent nutrient regimes on the community response to a second nutrient addition. The results showed that past nutrient regimes created legacy effects on the community, dampening further changes in response to a second nutrient addition. However, the effects were transient, since they were not detected in the second microcosm experiment. Further, the lack of legacy effects in the second microcosm experiment suggests that the communities from the mesocosm treatments in fact recovered from the nutrient regimes they were exposed to in the two-week period. Consequently, the results of the thesis suggest that legacy effects may be important in predicting phytoplankton community response to extreme nutrient and cDOM pulses but they might be temporary.
67

Multicomponent Cyclization Reactions: A General Approach To Dibenzocyclooctadiene Lignan Natural Product

Gong, Wei January 2012 (has links)
No description available.
68

[pt] AVALIAÇÃO CINÉTICA DE ADITIVOS PARA BIODIESEL / [en] KINETIC EVALUATION OF BIODIESEL ADDITIVES

FLAVIA ALICE PRACA NOGUEIRA 06 February 2024 (has links)
[pt] O biodiesel, uma opção bastante promissora ao uso do combustível fóssil, apresenta como grande desvantagem o fato de, como todo derivado de ácido graxo, sofrer oxidação rancídica, o que o transforma, ao longo do tempo, em produtos com baixa ou nenhuma capacidade de produzir energia. Para que esta reação seja retardada, diversos compostos têm sido utilizados como antioxidantes, sendo que a maioria dos comercialmente disponíveis são compostos fenólicos com maior ou menor toxidez. Com o objetivo de melhor compreender tanto as diversas opções de antioxidantes como seus efeitos no combustível final, este estudo foi desenvolvido. Foram estudadas 5 famílias de compostos com relação às suas capacidades de retardar a reação de oxidação. A família da curcumina e derivados se focou na molécula de curcumina, que apresenta boa capacidade antioxidante, mas é pouco solúvel em biodiesel, e em duas moléculas dela derivadas, com melhor capacidade de dissolução. A família dos curcuminóides halogenados teve por objetivo o estudo de um grupo de compostos que é apresentado na literatura como antioxidante para biodiesel. A família dos extratos naturais estudou dois extratos liofilizados (de beterraba e de jabuticaba), além da betanina, composto também extraído da beterraba. A família dos óleos essenciais, que já é utilizada como aditivo para biodiesel, para aumentar as propriedades anticongelantes do combustível, foi estudada de forma a se compreender o impacto do óleo essencial no tempo de indução do biodiesel final. Finalmente, foi estudada também a família dos difenóis, onde os compostos 1,2-difenol, 1,3-difenol e 1,4-difenol foram comparados tanto em análise direta de tempo de indução quanto em condições de envelhecimento. Da família das curcuminas, determinou-se que o composto octohidrocurcumina apresenta boa solubilidade, tanto em biodiesel como em diesel, e grande potencial como antioxidante a ser usado em pré-diluição com diesel ou com um antioxidante sinergético. O mesmo pode ser dito acerca do composto bromado (em posição para) da família dos curcuminóides halogenados, que apresentou resultados promissores de melhoria de ponto de indução, mesmo a baixas concentrações, com boa solubilidade. Acerca dos compostos naturais, os resultados de tempo de indução do pó liofilizado de suco de jabuticaba apresentaram um aumento de tempo de indução de 25 por cento em relação ao biodiesel puro. Estudos posteriores de extração das antiocioninas da jabuticaba com objetivo de uso como antioxidante poderão trazer resultados satisfatórios. Quanto aos óleos essenciais, o óleo de limão tahiti apresentou bom desempenho pois, além de aumentar o tempo de indução, melhorou o ponto de entupimento e a viscosidade do biodiesel, podendo agir também como antioxidante sinergético. Finalmente, entre os fenóis, o isômero difenol 1,4 apresentou melhor capacidade de aumento de tempo de indução do biodiesel, enquanto o isômero 1,2 parece estabilizar o tempo de indução ao longo do tempo. / [en] Biodiesel, a promising option for fuels, has a relevant disadvantage when compared to diesel fossil: like all fatty acid derivatives, it is susceptible to rancid oxidation. This process transforms biodiesel into products with low or no capacity for producing energy. This reaction may be delayed by several compounds which have been used as antioxidants. The majority of commercially available antioxidants are phenolic compounds, which generally presents a level of toxicity. In order to better understand different antioxidant options and their effects on the final fuel, this study was developed. A group of 5 families of compounds were studied regarding their abilities to delay the oxidation reaction. Curcumin and derivatives family focused on the curcumin molecule, which has good antioxidant capacity, but poor solubility in biodiesel, and two others molecules derived from it, with better dissolution capacity. The objective of the family of halogenated curcuminoids was to study a group of compounds that were presented in literature as antioxidant for biodiesel. The family of natural extracts studied two freeze-dried extracts (from beetroot and jabuticaba), in addition to betanin, a compound also extracted from beetroot. The family of essential oils, which is already used as an additive for biodiesel, as an antifreeze additive, was studied in order to understand the impact of these essential oils on the induction time of the final biodiesel. Finally, a diphenol family was also studied, and the compounds 1,2-diphenol, 1,3-diphenol and 1,4-diphenol were compared both in direct analysis of induction time and in aging conditions. From the study of the curcumin family, it was determined that the compound octohydrocurcumin (OHC) has good solubility, both in biodiesel and diesel, and great potential as an antioxidant to be used in pre-dilution with diesel or with a synergistic antioxidant. The same can be said about the brominated compound (in para position) from the halogenated curcuminoid family, which showed promising results in improving the induction period, even at low concentrations, with good solubility in biodiesel. Regarding the natural compounds family, induction time results from the freeze-dried jabuticaba juice powder showed an increase in induction time of 25 percent compared to pure biodiesel. Further studies on antiochionins extraction from jabuticaba aiming its use as antioxidants may bring good results. Essential oils essays demonstrated that Tahiti lemon oil, in addition to increasing induction time, improves the clogging point and viscosity of biodiesel, also acting as a synergistic antioxidant. Finally, 1,4 diphenol isomer showed a better ability to increase the induction time of biodiesel, while the 1,2 isomer seems to stabilize the induction time over time.
69

ALL–CARBON ENE–TYPE CYCLIZATIONS FROM CYCLOHEXADIENETRICARBONYLIRONDERIVATIVES

Beach, Keith B. 01 September 2016 (has links)
No description available.
70

Radical additions of hydrocarbons, ethers and acetals to alkenes via allyl transfer reaction: A new chain reaction for C-H bond functionalization

Patil, Shradha Vasant 10 May 2013 (has links)
Functionalization of hydrocarbons via a free-radical based allyl transfer reaction using various allyl bromide substrates has been previously studied. The work described in this dissertation focuses on the replacement of Br by phthalimido-N-oxyl (PINO ) which helps make this chemistry environmentally friendly. To replace Br with PINO , replacement of previously used allyl-bromide substrates with new allyl-PINO substrates were necessary. Various allyl- PINO compounds were synthesized and the use of these allyl-phthalimido-N-oxyl (allyl-PINO) compounds for the functionalization of various alkyl aromatic hydrocarbons is demonstrated. Kinetic studies were performed to observe the efficiency of the new chain reaction compared to the previously reported studies with allyl-bromides. We recently discovered that these allyl substrates are useful for the functionalization of ethers and acetals. The functionalization of various cyclic and acyclic ethers was performed using these allyl transfer reactions. This reaction was also performed in-solution, which allowed us to perform these reactions at low reagent concentrations. Kinetic chain lengths were measured for these reactions. High chain lengths were observed for all used ethers. Kinetic studies to investigate the rate of radical addition-elimination processes were performed using laser flash photolysis and competition kinetics. These experiments helped us to measure the reactivity and selectivity of PINO as a chain carrier in comparison with Br. Additionally, a new competition experiment was designed to study the relative rate constant for the &#1049109;-fragmentation process. For this experiment a novel substrate that contains two leaving groups, Br and PINO, was synthesized, and the relative rates of elimination of Br vs PINO were compared. / Ph. D.

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