Thesis (M.Phil.) - University of Queensland, 2003. / Includes bibliography.

Thesis (Ph.D.) - University of Queensland, 2003. / Includes bibliography.

Thesis (Ph. D.)--West Virginia University, 2005. / Title from document title page. Document formatted into pages; contains xvii, 207 p. : ill. Includes abstract. Includes bibliographical references (p. 97-101).

Presented as thesis (Ph. D.)--University of Wisconsin--Madison, 1931. / Collective title from added t.p. Reprinted from Journal of the American Chemical Society: Part 1: vol. 53 (1931), p. 1095-1097 -- Part 2: vol. 53 (1931), p. 1416-1419 -- Part 3: vol. 53 (1931), p. 1420-1424 -- Part 4: vol. 53 (1931), p. 2714-2720 -- Part 5: vol. 54 (1932), p. 1138-1145 -- Part 6: vol. 54 (1932), p. 1145-1154. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Th.--Biochim. et biol. appl.--Toulouse--I.N.P., 1983. N°: 74.

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Au cours de cette étude, une méthode inédite de fonctionnalisation chimique de la matière lignocellulosique a été développée. Des groupes acyles de taille et de fonctionnalité variées ont ainsi été greffés à l’intérieur du bois, grâce à une réaction de transestérification entre les esters d’énol et les groupes hydroxyles des polymères lignocellulosiques. Les greffages ont été confirmés grâce aux spectroscopies infrarouge et RMN du 13C en phase solide. La stabilité dimensionnelle du bois acétylé à partir de l’acétate de vinyle ainsi que sa résistance aux attaques fongiques a été également évaluée, de même que la photostabilité du bois estérifié à partir des esters de vinyle aromatiques. / Abstract

Orientador: Maria Izabel Camargo Mathias / Banca: Gislaine Cristina Roma / Banca: Gilberto Orivaldo Chierice / Banca: Roberta Cornelio Ferreira Nocelli / Banca: Gervasio Henrique Bechara / Resumo: O presente trabalho traz informações que mostram a interferência dos ésteres do ácido ricinoléico extraídos do óleo de mamona (Ricinus communis), no ciclo secretor das glândulas salivares e na vitelogênese de fêmeas do carrapato Rhipicephalus sanguineus, agindo diretamente nos processos de alimentação e de reprodução, respectivamente. Para a realização deste estudo, coelhos hospedeiros infestados com carrapatos, foram alimentados com ração comercial comum (controle-GC) e com ração enriquecida com os ésteres em diferentes concentrações (tratamento- GT). As glândulas salivares sofreram danos, e tiveram o citoplasma das células acinares alterado, trazendo prejuízos ao seu funcionamento, além desta substância ter acelerado a degeneração do órgão como um todo. Os ésteres interferiram na atividade de secreção celular alterando a composição da glicoproteína salivar, especialmente nas células glandulares dos ácinos II. O efeito dos ésteres na vitelogênese foi observado nos ovócitos dos carrapatos do grupo tratamento (GT), os quais apresentaram células germinativas com alterações citoplasmáticas, inibição do desenvolvimento dos ovócitos I e II para os estágios avançados (IV e V), além da interferência na maturação dos ovócitos V. Além disso, nas ampolas dos ovários dos indivíduos tratados, espermatozóides não foram observados no seu interior confirmando a ação dos ésteres no processo de reprodução. Ficou demonstrado também que os danos causados pelos ésteres nas células das glândulas salivares e dos ovários desses ectoparasitas, aumentaram na mesma proporção que houve aumento das concentrações do produto, provocando intensa degeneração dos órgãos / Abstract: The present study brings information which shows the interference of ricinoleic acid esters extracted from castor oil (Ricinus communis) on the secretory cycle of Rhipicephalus sanguineus female ticks' salivary glands and vitellogenesis, acting directly on the feeding and reproduction processes respectively. To perform this study, host rabbits were infested with ticks, fed with regular commercial rabbit food (control-CG) and with food enriched with ester in different concentrations (treatment- TG). The salivary glands were damaged and had the cytoplasm of acinar cells altered, impairing their functioning, and the toxic substance also accelerated the degeneration of the organ as a whole. The esters interfered in the cellular secretion activity altering the composition of salivary glycoproteins, especially in the glandular cells of acini II. The effect of the esters in the vitellogenesis was observed in the oocytes of ticks belonging to the treatment group (TG), whose germinative cells presented cytoplasmic alterations, inhibition of the development of oocytes I and II for advanced stages (IV and V) and interference in the maturation of oocytes V. In addition, spermatozoa were not observed in the interior of the ovaries ampoules, confirming the acaricidal potential of the esters. It was also demonstrated that the damages caused by esters in the salivary glands cells and ovary cells of these ectoparasites increased in the same proportion of the increase in the concentrations of the toxic product, causing intense degeneration of the organs / Mestre

Ce travail porte sur l'étude de l'impact environnemental des esters méthyliques utilisés comme biodiesel et concerne plus particulièrement la cinétique de formation des oxydes d'azote (NOX). Les objectifs de ce travail de thèse visent (i) à étudier la cinétique d’oxydation d’un ester méthylique saturé, le Butanoate de Méthyle (MB), afin de disposer une base de données expérimentales en condition de flamme laminaire de pré-mélange, (ii) et tester des mécanismes cinétiques détaillés de l'oxydation du MB disponibles dans la littérature sur la formation du NO précoce. Pour prendre en compte la chimie de l’azote, nous avons ajouté à ces mécanismes un sous-mécanisme de formation du NO récemment validée au laboratoire PC2A. Cinq flammes CH4/MB/O2/N2 ont été stabilisées à basse pression (5,3 kPa) avec des quantités connues d'ester (0%, 20% et 50% dans le mélange combustible). Les mélanges étudiés sont caractérisés de manière à évaluer l'effet du facteur de richesse et du rapport C/O sur la formation de NO. Les profils d’espèces ont été mesurés par couplage de techniques in situ de spectroscopie laser (Fluorescence Induite par Laser, LIF) et de techniques analytiques après prélèvement des gaz (Chromatographie en Phase Gazeuse (CPG), spectroscopie Infra Rouge à Transformée de Fourrier (IRTF)). Les résultats expérimentaux montrent que la substitution du CH4 par le MB dans la flamme CH4/air diminue la fraction molaire de NO. Cette diminution est plus importante lorsque la richesse diminue par rapport à la flamme de CH4/air. Les profils expérimentaux ont été confrontés aux profils simulés issus de trois modèles cinétiques détaillés, indiquant des variations notables d’un modèle à l’autre. Il a été observé que le modèle de Dooley et al. (2008) donne des accords assez satisfaisants en comparaison avec les résultats expérimentaux. L’analyse des voies réactionnelles a permis de mettre en évidence les réactions prépondérantes de la consommation du MB et celles impliquées dans la formation du NO précoce. / This work is focused on the study of the environmental impact of methyl esters used as biodiesel and concerns more particularly the kinetic of nitrogen oxides formation in flame conditions. The aim of this PhD is (i) to study the kinetics of oxidation of a methyl ester saturated, as Methyl Butanaote (MB), in order to have an experimental database on condition of laminar premixed flame, (ii) to test detailed kinetic mechanisms of oxidation of MB available in the literature on the formation of prompt-NO. To account for the nitrogen chemistry, we added these mechanisms a sub-mechanism of NO formation recently validated in PC2A laboratory. Five flames CH4/MB/O2/N2 have been stabilized at low pressure (P = 5.3 kPa) with known amounts of ester (0%, 20% and 50% in the fuel mixture). The mixtures studied are characterized so as to evaluate the effect of the equivalence ratio and the C/O ratio on NO formation. The species profiles were measured by coupling laser spectroscopy techniques in situ (Laser Induced Fluorescence (LIF)) and analytical techniques after gas probe sampling through a quartz microprobe (Gas Chromatography (GC), Fourier Transform Infrared Spectroscopy (IRTF)). The experimental results show that the substitution of CH4 by MB in the CH4/air flame decreases the mole fraction of NO. This reduce is higher when the equivalence ratio decreases compared to the stoichiometric CH4/air flame. The experimental profiles were compared with profiles modeled from three detailed kinetic models, showing significant variations from one model to another. It was observed that the model of Dooley et al. (2008) gives quite satisfactory agreements compared with experimental results. The analysis of reaction pathways allowed to highlight the predominant reactions in consumption of MB and those involved in the formation of prompt NO.

Orientador: Daniel Barrera-Arellano / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-07-28T11:40:51Z (GMT). No. of bitstreams: 1 Facioli_NaraLucia_D.pdf: 42352647 bytes, checksum: e79cb63c13578f796f470a9771b0cd78 (MD5) Previous issue date: 2001 / Resumo: A esterificação (produção de ésteres metílicos e etílicos) da matéria saponificável do destilado de desodorização do óleo de soja (DDOS) é uma etapa importante para utilização deste resíduo, como matéria-prima, na produção de extratos ou concentrados de tocoferóis (Vit. E) e esteróis. Nesta pesquisa, foram otimizados três processos de esterificação da matéria saponificável do DDOS: 1- esterificação enzimática, utilizando álcool etílico comercial (96%) e Lipozyme'M(uma lipase imobilizada sn-1,3-específica do Mucor miehe/) como catalisador; 2- esterificação química ácida direta, usando álcool etílico anidro e ácido sulfúrico concentrado como catalisador e 3- saponificação/acidulaçãolesterificação com NaOH, H2SO4e álcool etílico. Para otimizar as condições de processo e se obterem as melhores taxas de conversão dos ácidos graxos (AG) em ésteres etílicos, preservando os tocoferóis, foi empregada a Metodologia de Superfície de Resposta, obtida através de um planejamento fatorial de 28 ordem. As condições ótimas de reação encontradas para a esterificação enzimática dos ácidos graxos livres (AGL) do DDOS foram: temperatura de 44 a 56°C; enzima de 12,6 a 17,4% e etanollAGL de 1,5 a 2,5:1, com taxas de conversão acima de 90%. As condições ótimas para a esterificação ácida direta dos AGL do DDOS foram: etanollAGL de 6,5 a 11,2:1, concentração de H2SO4de 0,9 a 1,5% e tempo de reação de 1,3 a 2,6 horas, com taxas de conversão acima de 94%. E para a esterificação dos ácidos graxos totais (AGT) do DDOS, as melhores condições de reação foram: a) saponificação: elação molar NaOH/AGT = 1,5:1, temperatura de 80°C e tempo de reação de 40 minutos; b) a acidulação da mistura foi realizada usando H2S04 com excesso molar de 50% sobre o total de sabões formados e c) as condições ótimas para a esterificação dos AGT foram as mesmas obtidas para a esterificação ácida direta, mas utilizando a variável, relação molar etanollAGT, obtendo-se taxas de conversão acima de 98%. Todas as variáveis estudadas têm efeito significativo sobre a taxa de conversão dos AG (p < 0,05). Os resultados mostraram excelente ajuste entre os modelos matemáticos e os resultados experimentais, nas diferentes condições estudadas, tornando estes modelos preditivos e estatisticamente significativos (p < 0,05). O processo 3 foi considerado o melhor, para esterificação do DDOS. Não foram observadas perdas significativas de tocoferóis durante os processos. / Abstract: The esterification of the soybean oil deodorizer distillate (SODD) saponifiable material is a very important step for the utilization of this residue from the refining oil industry, used as a raw material in tocopherol (Vit. E)and sterol extracts or concentrated production. In this research work, three esterification processes of the SODD unsaponifiable matter were optimized: 1- enzymatic esterification, using commercial ethyl alcohol (96%) and LipozymelM(an immobilized lipase sn-1,3 from Mucor miehel) as the catalyst; 2- direct acid esterification, using anhydrous ethyl alcohol and concentrated sulfuric acid as the catalyst and 3- saponification/acidulation/esterification with NaOH, H2SO4and ethyl alcohol. In order to determine the optima processes conditions to get the higher conversion rates of fatty acid (FA) to ethylic esters, preserving the tocopherols, the response surface methodology (RSM) in a 2nd order factorial planning was utilized to analyze the results. The optima reaction conditions achieved for the enzymatic esterification of SODD free fatty acid (FFA) were: temperature from 44 to 56°C; enzyme concentration from 12.6 to 17.4% and ethanol:FFA molar ratio from 1.5 to 2.5:1, with conversion rates up to 90%. The optima conditions for the direct acid esterification of SODD FFA were: ethanol:FFA from 6.4 to 11.2:1, H2SO4concentration from 0.9 to 1.5% and reaction time from 1.3 to 2.6 h, with conversion rates up to 94%. And for the esterification of total fatty acid (TFA) in SODD the best reaction conditions were: a) saponification: molar ratio NaOHITFA = 1.5/1, temperature of 80°C and reaction time of 40 minutes; b) the acidulation was done using 50% of molar excess H2SO4based on total soaps formed and c) the optima conditions for the esterification of TFA formed were the same for the direct acid esterification, but using the variable, molar relation ethanollTFA, with conversion rates up .to 98%. Ali variables studied had significant effect on the FA conversion (p<0.05). Results showed a good adjustment between mathematical models and experimental results obtained from the different conditions studied, making these models predictive and statistically significant (p<0.05). Process 3 was selected as the best to esterify SODD. No significant tocopherollosses were observed during these processes. / Doutorado / Doutor em Tecnologia de Alimentos