No sul do Brasil a aveia branca é considerada um cereal de múltiplos propósitos. Como cobertura proporciona melhorias nas condições físico-químicas do solo. Na alimentação animal evidencia grande qualidade nutricional tanto no pastejo direto ou processado na forma de feno e silagem. No consumo humano vem recebendo grandes destaques por representar propriedades que qualificam o grão da aveia como alimento funcional. No entanto, para que a produção de biomassa da planta e dos grãos seja maximizada a adubação nitrogenada é fundamental, visto que, é o nutriente mais solicitado pela aveia. Portanto, um fator decisivo na qualidade e produtividade da cultura. Neste contexto, a dose ajustada de N a ser disponibilizada deve ser investigada buscando minimizar os excessos que comprometem a qualidade ambiental e oneram o produtor, e o que representaria um déficit que compromete a máxima expressão de biomassa e grãos. O objetivo deste trabalho é apresentar modelos que permitam elucidar a dinâmica de expressão nos caracteres de produção da aveia branca pelo aproveitamento de N-fertilizante e residual nos sistemas de cultivo e que evidencie alta e reduzida relação C/N como cobertura residual. Assim, buscar nesta espécie um ajuste mais aprimorado de interação com o nitrogênio buscando maximizar a produção e acúmulo de matéria seca total ao longo do desenvolvimento da planta associada a estímulos agrometeorológicos para inferências às condições regionais do noroeste do estado do Rio Grande do Sul. O experimento foi conduzido em condições de campo no Instituto Regional de Desenvolvimento Rural/IRDeR, localizado em Augusto Pestana, RS, pertencente ao Departamento de Estudos Agrários da UNIJUÍ. Os experimentos foram conduzidos em duas safras agrícolas em delineamento experimental de blocos casualizados com quatro repetições de arranjo fatorial 4 X 2 no sistema soja/aveia e milho/aveia. Neste sentido, as fontes de variação e seus respectivos níveis estão assim representadas: Doses de nitrogênio: 0, 30, 60 e 120 kg ha-1 e Cultivares de Aveia: Barbarasul e Brisasul avaliadas nos anos de 2011 e 2012. As equações lineares mostraram que a maior tendência de crescimento frente a taxa diária de produção de biomassa dia-1 nas doses de N-fertilizante pelas cultivares de aveia nem sempre estão diretamente ligadas a maior produtividade de grãos. Portanto, a análise da taxa de biomassa na análise do aproveitamento do nitrogênio deve ser acompanhada dos valores médios de rendimento de grãos. Além disto, observa-se que a cultivar Brisasul se mostra como de maior eficiência fisiológica no aproveitamento do N para a produção de grãos independente do sistema e anos de cultivo. Para a interpretação da dinâmica do nitrogênio nos componentes fisiológicos da aveia, verificou-se que as equações lineares são as que melhor descrevem o rendimento biológico e de palha, mostrando acréscimos nas variáveis estudadas quando a dose disponibilizada variando de 0 até 120 Kg de nitrogênio por hectare. Por outro lado, as equações quadráticas se mostraram ajustadas em explicar o rendimento de grãos e o índice de colheita nos distintos anos de cultivo. No sistema soja/aveia como o milho/aveia as modificações ocorridas nos caracteres da inflorescência da aveia pelo incremento das doses de adubação nitrogenada qualificam a massa de panícula e de grãos da panícula como as de maior sensibilidade em promover alterações. Inclusive, a correlação e trilha no ambiente com baixa relação C/N mostraram eficiência da massa de grãos em trazer maiores efeitos diretos positivos no rendimento de grãos, assim como, no índice de colheita, com elevados efeitos diretos sobre o RG e indiretos via massa de grãos da panícula. Os modelos de regressão linear múltipla qualificam a estimativa da produção de grãos, principalmente, quando incluído no modelo a dose do N-fertilizante e ao menos uma ou mais varáveis da panícula. Portanto, em condição com baixa relação C/N o índice de colheita da panícula se mostra eficiente para inclusão no modelo múltiplo, e em doses de N mais elevadas, sugere também a inclusão do NGP. Contudo, em ambiente de alta relação C/N, indica-se o índice de colheita da panícula independente das doses empregadas. Contudo, num modelo geral, o N e o sistema de cultivo são variáveis significativas para uso pela regressão múltipla. Os coeficientes de desenvolvimento do trigo que foram validados e que empregam a temperatura e o fotoperíodo para simulação se mostraram indicados para uso em aveia nestas condições de cultivo. Portanto, o modelo WE-Streck empregado para simular o desenvolvimento de trigo se mostrou adequado quando empregado para aveia. / 164 f.

Les nanoparticules métalliques (MNPs) appliquées en catalyse représentent un domaine attractif en raison de leurs propriétés physiques et chimiques intéressantes. D'autre part, l'ajout d'un autre métal au métal hôte (ici nanoparticules bimétalliques, BMNPs) peut modifier les propriétés électroniques (transfert de charge, hybridation d'orbitales, etc.) et/ou géométriques (alliage, coeurcoquille, hétérodimères, etc.), ce qui peut conduire à améliorer le comportement catalytique, voire envisager une nouvelle réactivité. Le glycérol, quant à lui, possède une structure supramoléculaire complexe qui favorise l'immobilisation des MNPs, et évite leur agglomération, et donc facilite le recyclage de la phase catalytique. Des nanoparticules de Cu(0) (CuNPs) immobilisées dans du glycérol ont été synthétisées en présence de poly(vinylpyrrolidone) (PVP) comme stabilisant sous pression d'hydrogène. Les CuNPs dispersées dans le glycérol se sont avérées être un catalyseur robuste pour diverses réactions : formation de liaison C-N, synthèse d'amines propargyliques di- (via couplage croisé déshydrogénant), tri- (via un couplage aldéhyde-amine-alcyne A3) et tétra-substituées (via un couplage cétone-amine-alcyne KA2) ainsi que pour la synthèse d'hétérocycles: indolizines, benzofuranes et quinolines, par des procédés tandem de cycloisomérisation-couplage A3 en utilisant des benzaldéhydes ortho-fonctionnalisés. La phase catalytique de glycérol peut être recyclée plus de cinq fois (formation de liaisons C-N et pour le couplage A3), sans détecter de traces significatives de cuivre dans les produits organiques extraits. Des nanoparticules bimétalliques de palladium-cuivre (PdCuNPs) immobilisées dans le glycérol ont été synthétisées par des méthodes de co-réduction. Selon les différents rapports métalliques, les PdCuNPs peuvent être considérées comme des petits coeurs de Pd enrobés par du Cu (Pd/Cu = 1/1), des alliages aléatoires (Pd/Cu = 1/2) ou un mélange de nanoparticules monométalliques (Pd/Cu = 2/1). Par une voie de synthèse séquentielle, nous obtenons un mélange de nanoparticules monométalliques. La structure des PdCuNPs a également été confirmée par la réactivité observée pour l'hydrogénation des alcynes, montrant Pd1Cu1 et Pd1Cu2 comme structures bimétalliques. Ainsi, ces catalyseurs ont permis d'ajuster la sélectivité des alcènes. En outre, l'influence de Pd incorporé dans le Cu a également été étudiée dans la cycloaddition d'un azidure avec un alcyne (CuAAC). Plus intéressant, des nanoparticules bimétalliques Pd1Cu1 dans le glycérol, agissant comme système catalytique multitâche, ont été utilisées pour les réactions "onepot", notamment la réaction CuAAC et les réactions de couplage croisé C-C (Sonogashira, Suzuki- Miyaura et Heck) (catalysées au Pd). Grâce à des cinétiques différentes entre les réactions CuAAC et couplages C-C, ces procédés tandem ont permis d'obtenir les produits en rendements élevés. De plus, l'hydroaminométhylation d'oléfines catalysée par des complexes de Rh pour synthétiser les amines peut se dérouler dans le glycérol et a montré de meilleures réactivités que dans les solvants organiques. Ces résultats positifs permettent de concevoir un nouveau système biphasique dans le but de recycler la phase catalytique. / Metal nanoparticles (MNPs) applied in catalysis represent an attractive field due to their interesting physical and chemical properties. Besides, the addition of another metal to the host metal in the same entity (bimetallic nanoparticles, BMNPs) can trigger changes in electronic properties (charge transfer, orbital hybridization, etc.) and/or geometric features (alloy, core-shell, heterodimers, etc.), inducing modifications in their catalytic behavior, in terms of activity, selectivity, robustness, or even leading to new reactivity. Concerning the solvent, glycerol, showing a complex supramolecular structure, favors the dispersion of metal nanoparticles, avoiding their agglomeration and then facilitating the recycling of catalytic phase. Small and spherical zero-valent copper nanoparticles (CuNPs) immobilized in glycerol were synthesized using poly(vinylpyrrolidone) (PVP) as stabilizer under hydrogen pressure. CuNPs dispersed in glycerol proved to be a robust and versatile catalyst for a diversity of C-N bond formation reactions, synthesis of di- (via cross-dehydrogenative coupling), tri- (via aldehydeamine- alkyne A3 coupling) and tetra-substituted propargylic amines (via ketone-amine-alkyne KA2 coupling) as well as different types of heterocycles, in particular indolizines, benzofurans and quinolines, by tandem A3-cycloisomerization processes using ortho-functionalized benzaldehydes as substrates. Interestingly, the catalytic glycerol phase could be recycled more than five times in C-N bond formation and A3 coupling reactions, preserving their reactivity, without detecting a significant copper content in the extracted organic products. Bimetallic palladium-copper nanoparticles (PdCuNPs) dispersed in glycerol were prepared by co-reduction methodology. Depending on the different metal ratios used, Pd nanoparticles coated by Cu (Pd/Cu = 1/1), random alloy (Pd/Cu = 1/2) or mainly mixture of monometallic nanoparticles (Pd/Cu = 2/1) were obtained. By a sequential way of synthesis, a mixture of monometallic nanoparticles was mainly observed. In terms of reactivity, the effect of one metal to other one, on catalytic activity and selectivity was evaluated. The structure of the different PdCuNPs was also confirmed by the observed reactivity in the selective formation of alkenes by hydrogenation of alkynes, proving that Pd1Cu1 and Pd1Cu2 correspond to bimetallic structures. Besides, the influence of Pd incorporated into Cu on azide-alkyne cycloaddition (CuAAC) was also studied. Interestingly, Pd1Cu1 in glycerol were applied in one-pot processes acting as multitask catalytic system, involving CuAAC and Pd-catalyzed C-C cross couplings (Sonogashira, Suzuki-Miyaura and Heck). Thanks to the different rates between CuAAC and C-C couplings, these tandem processes permitted to obtain the desired products in high yields. Furthermore, Rh-catalyzed hydroaminomethylation of olefins, in order to synthesize amines, could be carried out in glycerol, generally showing a better reactivity compared to common organic solvents. These preliminary encouraging results permit to plan the design of a new biphasic system, including the recycling of the catalytic phase.

Dans un contexte de limitation de l'utilisation des pesticides, une voie de recherche prometteuse porte sur le déterminisme environnemental actionnant les mécanismes de défense de la plante, entre autres, la production de métabolites secondaires. L'objectif de mon travail de thèse a été d'étudier le compromis entre croissance et défense (métabolisme primaire vs. secondaire) dans les tissus de la plante saine ou attaquée par différents bioagresseurs, sous différentes conditions de disponibilité en ressources. Pour cela, nous avons mesuré différents paramètres de croissance, les ratios C/N des tissus, les concentrations en principaux métabolites primaires (glucides simples, amidon) et en composés de défense (acide chlorogénique, rutine, kaempferol-rutinoside et tomatine) dans différents organes de tomate en culture hydroponique en serre ou phytotron. Nous avons observé que les variations des ratios C/N total et de ressources sont positivement corrélées à celles de nombreux composés de défense quelle que soit leur composition en N et C. De plus, nous avons montré qu'en présence d'un bioagresseur, les concentrations des composés primaires et secondaires ne suivent pas la même évolution selon leur nature. La synthèse de caffeoyl putrescine est fortement induite lors de l'attaque par P. syringae alors que la concentration en acide chlorogénique est diminuée. L'inoculation de P. syringae réduit les concentrations en glucose et fructose alors que P. corrugata stimule leur synthèse. Enfin, nous avons observé qu'une faible disponibilité en azote altère le développement de P. syringae, P. corrugata et Tuta absoluta mais favorise le développement de Botrytis cinerea. Nos résultats ont montré que le ratio C/N est un indicateur fiable du compromis croissance/défense dans le cas d'une plante saine. Dans le cas d'une plante attaquée, la répartition des ressources entre les différents métabolites varie en fonction du bioagresseur. Et chaque bioagresseur réagit de façon différente aux variations de disponibilité en azote de la plante. La maîtrise des conditions de culture apparaît comme un levier agronomique pertinent pour raisonner la lutte contre les bioagresseurs même s'il est difficile d'appliquer des règles générales sur l'interaction plante/environnement/bioagresseurs / Nowadays, limiting the use of pesticides is mandatory. A promising way for research deals with the environmental determinism of plant defence mechanisms, among others, production of secondary metabolites. The aim of my PhD work was to study the trade-off between growth and defence (primary vs. secondary metabolism) in healthy plant tissues or attacked by different pests, under different conditions of resources availabilities. We measured different growth parameters, C:N ratios of tissue, concentrations of main primary metabolites (simple carbohydrates, starch) and defence metabolites (chlorogenic acid, rutin, kaempferol-rutinoside and tomatine) on healthy or attacked tomato plant grown in hydroponic culture in greenhouse or phytotron. We observed that variations of total and resources C:N ratios were positively correlated to that of several defence compounds whatever their composition in carbon and nitrogen. Moreover, we showed that, during pests attack, concentrations of primary and secondary metabolites did not follow the same evolution, depending on their nature. Caffeoyl putrescine synthesis was strongly induced by P. syringae inoculation whereas chlorogenic acid concentration decreased. Inoculation of P. syringae induced a strong decrease of concentration of glucose and fructose whereas inoculation of P. corrugata enhanced their synthesis. We observed that a low N availability alters the development of P. syringae, P. corrugata and Tuta absoluta but promotes the development of B. cinerea. Our results showed that C:N ratio is a reliable indicator of the trade-off between growth and defence in the case of healthy plant. In attacked plant, the resources allocation between different metabolites varies with pests. And each pests reacts specifically to changes of N availability for the plant. Control of culture conditions appears to be a relevant agronomic tool to monitor the control of pests even if it is difficult to apply general rules to the interaction plant/environment/pests

The PhD work "Hydroacylation and C-N coupling Reactions. Mechanistic Studies and Application in the Nucleoside Synthesis" tackle two different objectives, a) developing new methods of synthesis of nucleosides (introduction, and chapters 1 and 2) and b) to carry out a mechanistic study of the intermolecular hydroacylation and hydroiminoacylation reaction with and cationic rhodium complexes (chapter 3). Concerning the synthesis nucleosides, in chapter 1 we have explored new methods of synthesis of 2',3'-dideoxynucleosides and isonucleosides using a palladium or copper catalyzed C-N coupling reaction, aiming to overcome the stereoselectivity problems of the glycosylation reaction. The synthesis of the iodo-vinyl derivatives required as starting materials has been tried by different procedures, all of them unsuccessful. Finally, the coupling reaction has been explored in 1-iodo-glucal derivatives. Palladium catalysts were unsuccessful in coupling with benzimidazol used as model of purinic bases. Copper catalysts provided very low conversions. However, the oxidative addition of 1-iodo-glucal to palladium was proved and it was also observed that the reaction with aniline proceeds. That, suggest that the problem is in the steps involving the benzimidazol.In chapter 2, it has been developed a new method of synthesis of carbocyclic nucleosides using and enantioselective intramolecular hydroacylation reaction as a key step. This reaction leaded to the 3-hydroxymethyl-cyclopentanones in good yields and excellent enantioselectivities. When (S,S)-Me-Duphos was used the 3S-cyclopentanone was obtained, in contrast whether the (R,R)-Me-Duphos was employed the reaction proceed giving the opposite enantiomer. In both cases. The reduction of the ketone can be carried out in a stereoselective way using a hydroxyl-assited reduction with NaBH(OAc)3. Alternatively, the diastereomeric mixture obtained by a direct reduction can be resolved by using a DKR process using a combined enzyme/Ru complex catalytic system. A Mitsunobu reaction has allowed finally to link adenine to the cyclopentane moiety. In the third chapter, the mechanism of both cationic and neutral rhodium catalyst precursors in the hydroiminoacylation of alkenes was studied. The oxidative addition step was studied using both NMR and DFT techniques. Using the neutral complex, this step is a thermodynamically favoured process, as demonstrated by the isolation of the stable complex. Furthermore, DFT calculations showed the existence of an agostic intermediate on the route to the C-H activation product. In the cationic system, the oxidative addition reaction was shown by DFT calculations to be an endothermic process, hence un-favoured. This was in agreement with the NMR experiments, in which an oxidative addition product was only detected in the presence of a chloride source. Furthermore, the transition states involved in both systems were identified using DFT calculations, which proved that the presence of chloride not only stabilize the oxidative addition product but also lower the energy barrier of the overall process.Using the neutral system, it was identified the coupling product still coordinated to rhodium, which is in an enamine tautomeric form. After removal of the coupling product the stable complex [Rh(μ-Cl)(PPh3)2]2 was formed. This species was reported as a precursor for the oxidative addition step, from which the catalytic cycle can start again. However in the cationic system, the system did not yield any stable rhodium species and quickly evolved towards decomposition. / Durante la última década la terapia del SIDA ha experimentado una evolución notable. El conocimiento del modo de actuación y proliferación del virus ha permitido incrementar el número de dianas biológicas para su neutralización. Así, hoy en día se conocen compuestos que inhiben la entrada del virus en la célula, la transcripción del RNA en DNA, la integración del DNA vírico en DNA celular, la producción del envolvente proteico del virus, entre otros. Todo ello, ha permitido la realización de tratamientos dirigidos a diferentes dianas, que han neutralizado la evolución del virus mejorando la calidad de vida de los pacientes.Existen numerosas metodologías diseñadas para obtener los retrovirales mencionados anteriormente, pero en la mayoría de ellas se requieren numerosos pasos de síntesis y además en muchas de ellas se obtienen mezclas de los isómeros α/β. De este modo se pretende diseñar una alternativa sintética general para la preparación de la familia de nucleósidos arriba indicadas y al mismo tiempo que sea una alternativa práctica y eficaz a los métodos descritos hasta el momento.En el capítulo uno la obtención de isonucleosidos y 2',3'-dideoxinucleosidos se abordó utilizando como etapa clave de reacción el acoplamiento C-N entre los derivados de 4-halo-2,3-dihidrofurano y 5-halo-2,3-dihidrofurano con bases púricas y pirimidínicas, la posterior hidrogenación enantioselectiva del doble enlace nos permitiría obtener los mencionados compuestos de una forma sencilla. En el estudio realizado bajas conversiones de los productos de acoplamiento cruzado fueron detectados aunque actualmente se están intentado mejorar los resultados.Referente a la obtención de carbociclonucleosidos abordada en el capítulo 2, se ha llevado cabo una nueva metodología sintética en la que se ha aplicado la reacción de hidroacilación intramolecular enantioselectiva catalizada por rodio. Así pentenales substituidos en posición cuatro han sido convertidos en las ciclopentanonas correspondientes. En función de la quiralidad de la fosfina empleada se han obtenido tanto los enantiomeros R como S con excelentes conversiones y enantioselectividades.Con el fin de incorporar la base nitrogenada en la ciclopentanona la reducción diastereoselectiva se ha llevado a cabo dos procedimientos: a) reducción racémica de la ciclopentanona y posterior resolución cinética dinámica, b) reducción diastereoselectiva utilizando como agente reductor el triacetoxiborohidruro de sodio. En ambos casos se obtuvieron diastereoselectividades excelentes pudiendo así obtener un distereoisomero u otro en función del procedimiento y el enantiomero utilizado como material de partida. La posterior reacción de Mitsunobu sobre el alcohol y la desprotección del grupo protector nos ha permitido obtener el carbociclonucleosido con buenos rendimientos y excelentes esteroselectividades.En el capitulo tres se ha realizado un estudio sobre la reacción de hidroacilación intramolecular de alquenos cataliza por rodio, donde se ha estudiado la diferencia de comportamiento de los sistemas catiónicos y neutros de rodio en la etapa de adición oxidante. Estos estudios se han realizado utilizando técnicas espectroscópicas de resonancia magnética nuclear y cálculos teóricos mediante técnicas DFT. El estudio computacional ha mostrado que en el caso de los sistemas neutros la etapa de adición oxidante es una etapa termodinámicamente favorable hecho que se gratifica con el hecho de que el producto de adición oxidante es estable y aislable. Además se ha encontrado la existencia de un intermedio agóstico en el proceso de activación del enlace C-H. Sin embargo, en los sistemas catiónicos la etapa de adición oxidante resultó ser un proceso endotérmico. Los estados de transición encontrados no solo han demostrado que la presencia de cloruro estabiliza el producto de adición oxidante sino que también disminuye la barrera energética del proceso global. La etapa de inserción del alqueno también fue estudiada para ambos sistemas utilizando estireno como sustrato. En el sistema neutro se detectó una nueva especie de rodio la cual no había sido descrita anteriormente y fue completamente caracterizada mediante RMN multinuclear.En el sistema catiónico se consiguió detectar el hidruro correspondiente al producto de adición oxidante el cual también fue completamente caracterizado por técnicas de RMN. Sin embargo, en el estudio de la inserción del alqueno no se observó la ningún producto que indicase que el mencionado proceso se llevará acabo indicado que la inserción de alqueno es además la etapa lenta del proceso.

Chapter 2 of the thesis describes a highly efficient in situ method for the reduction of amides to aldehydes and aryl O-carbamates to phenols and other transformations involving hydrozirconations. The method, as a three-component-type reaction, involves in situ generation of the Schwartz reagent (Cp2Zr(H)Cl) from Cp2ZrCl2 and the reductant, LiAlH(O-t-Bu)3, and immediate reaction with a substrate. Substrates include aliphatic and aromatic tertiary amides which are reduced to aldehydes, aryl O-carbamates which are reduced to phenols, and alkynes which undergo other transformations via hydrozirconation. Compared to prior methods, this method has advantage in that reagents are inexpensive and stable, reaction times are short, and reaction temperatures are generally conveniently at room temperature. The use of the in situ method described herein instead of the requirement for the synthesis of the commercially available Schwartz reagent is estimated to provide more than 50% reduction in cost. Chapter 3 of the thesis describes the discovery and development of efficient and regioselective Ru-catalyzed amide-directed C-H, C-N, C-O activation/C-C bond forming reactions, ester-directed C-O activation/C-C bond forming reaction, and amide-directed C-O activation/hydrodemethoxylation reactions under a simple RuH2(CO)(PPh3)3/toluene catalytic system. Of these, the amide-directed C-H activation/cross coupling reaction proceeds well but uniquely on furan 3-amide substrates while the ester-directed C-O activation is effective on the 2-MeO-1-naphthoic acid methyl ester. On the other hand, the amide-directed C-N and C-O activation/coupling reactions are broadly applicable on benzamides and naphthamides. All of these achievements of directed C-H, C-N, C-O activation/coupling reactions complement and may supercede the DoM (directed ortho metalation)-cross coupling strategy, and establish the catalytic base-free DoM-cross coupling process at non-cryogenic temperature as a convenient, economical and green alternative. The new catalytic amide-directed ortho-hydrodemethoxylation reaction has potential value in links to aromatic electrophilic substitution and DoM chemistries. Furthermore, a new borylation reaction via Ru-catalyzed amide-directed C-H activation/C-B bond forming process is also reported herein. / Thesis (Ph.D, Chemistry) -- Queen's University, 2010-12-21 11:12:35.564

Over recent years microbial oil has attracted much attention due to its potential to replace traditional oil sources in the production of biofuels and nutraceuticals. Its advantages arise from its independence of the food supply chain and its ease of production compared to conventional plant oils. Also, as concerns for the environment grow, microbially-synthesized oil emerges as potential competitor for the sustainable production of biodiesel. However, the high cost of its production currently hinders its large scale application. The bottlenecks to industrial microbial oil production are the cost of substrate and cultivation. Current research is focusing on process improvements to make microbial oil more competitive and worthwhile to produce. Several types of microorganisms have been explored so far and waste substrates have been utilised as cheap feedstocks. The overall cost is affected by the fermentation stage, therefore it is imperative to design cultivations with little operating requirements and high yields. Consequently, the present thesis aims to contribute to the field by developing and investigating a simple process for oleaginous yeast cultivation, focusing mainly on enhancing the yields during the bioreactor stage. Oleaginous yeasts were screened for their ability to grow on glycerol and the most promising strain was selected for further research. Then, the necessary conditions for its growth and oil accumulation were defined. Shake-flask cultivations showed that the specific growth rate and glycerol consumption of Rh. glutinis were higher at lower glycerol concentrations (smaller or equal to40 g/L), while higher C/N elemental ratios enhanced oil content. Experimental data were used to construct an unstructured kinetic model to describe and predict the system's behaviour. The Monod-based model took into account double substrate growth dependence and substrate inhibition. Following that, bioreactor cultivations extended the range of parameters studied, to include the influence of aeration rate and oxygen supply on cellular growth and microbial oil production. Cultivations at different air flow rates were performed in a 2 L bioreactor and showed that a low aeration rate of 0.5 L/min gave the best glycerol and nitrogen uptake rates, resulting in a concentration of biomass of 5.3 g/L with oil content of 33% under simple batch operation. This was improved by 68% to 16.8 g/L (cellular biomass) with similar oil content (34%) by applying a fed-batch strategy. Finally, different glycerol feeding schemes were evaluated in terms of their effect on oil accumulation. The concept of targeting first a cell proliferation stage, limited by the availability of nitrogen, followed by a lipid accumulation stage, fuelled by glycerol was tested. Continual feeding and pulsed feedings, delivering the same total amount of nitrogen (and glycerol), resulted in similar elevated values of both cellular biomass (~25 g/L) and oil content (~40%). Addition of glycerol at higher rates but giving the same total amount of nitrogen led to a further increase in oil content to 53%, resulting in an overall oil yield of more than 16 g/L (the highest achieved throughout the project). With comparable yields to those reported in the literature but achieved with a much poorer medium, there is every reason to be optimistic that microbial oil production from glycerol could be commercially viable in the future.

Submitted by Caroline Periotto (carol@ufscar.br) on 2016-09-26T13:02:22Z No. of bitstreams: 1 DissJCF.pdf: 2193556 bytes, checksum: 67658416b8d80c61ed4a7d39c48b586a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T20:47:49Z (GMT) No. of bitstreams: 1 DissJCF.pdf: 2193556 bytes, checksum: 67658416b8d80c61ed4a7d39c48b586a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T20:47:56Z (GMT) No. of bitstreams: 1 DissJCF.pdf: 2193556 bytes, checksum: 67658416b8d80c61ed4a7d39c48b586a (MD5) / Made available in DSpace on 2016-09-26T20:48:02Z (GMT). No. of bitstreams: 1 DissJCF.pdf: 2193556 bytes, checksum: 67658416b8d80c61ed4a7d39c48b586a (MD5) Previous issue date: 2016-03-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Several researches suggests heterotrophic metabolism in some strains of cyanobacteria, allowing its application in the development and consumption of organic molecules and nutrients in wastewater. Vinasse is the main wastewater from sugarcane processing, both in terms of composition and volume, and this presents a considerable variation in chemical composition, directly affecting their relationship carbon:nitrogen (C/N). Aphanocapsa holsatica is a unicellular cyanobacterium with proven foto-heterotrophic growth. Geitlerinema sp it is a filamentous cyanobacterium that has the ability to form aggregates, sedimenting in culture medium. In this context, the study aimed to evaluate the cultivation of cyanobacteria in sugarcane vinasse adjusted with different initial C/N ratio. The experiments were firstly set up in shake flasks for screening of the C/N ratio that allowed the largest biomass production and/or carbon and nitrogen uptakes. In the C/N ratio selected, experiments were set up in a bench bioreactor, with aeration and mixing, in addition to online monitoring of pH and gases. Results showed growth of both microorganisms to the C/N ratio range tested, with high productivities in 5 and 40 and larger carbon and nitrogen removal by Geitlerinema. In the bench bioreactor, Aphanocapsa presents low oxygen demand, carbon and nitrogen removal about 25 and 18%, respectively, and a maximum specific growth rate about five times higher (0.5 h-1) obtained in the shake flasks. For Geitlerinema sp, in C/N ratio 5 presents carbon consumer first-order kinetics, enabled high removals around 85%. Experimental data indicate the feasibility of growing in both cyanobacteria vinasse in the C N ratio range from 5 to 40, with high conversion of biomass to unicellular cyanobacterium and high carbon removal for filamentous cyanobacterium. / Diversas pesquisas indicam metabolismo heterotrófico em algumas linhagens de cianobactérias, possibilitando sua aplicação na incorporação e consumo de moléculas orgânicas e nutrientes em águas residuárias. A vinhaça constitui a principal água residuária do setor sucroenergético, tanto em termos de composição quanto de geração, sendo que esta apresenta uma considerável variação em termos de composição química, afetando diretamente a sua relação carbono:nitrogênio. Aphanocapsa holsatica é uma cianobactéria unicelular com comprovado crescimento fotoheterotrófico. Geitlerinema sp é uma cianobactéria filamentosa que apresenta a capacidade de formar agregados, sedimentando naturalmente em meios de cultivo. Neste contexto, o trabalho teve como objetivo avaliar o cultivo das cianobactérias em vinhaça de cana-de-açúcar ajustada com diferentes razões C/N iniciais. Os experimentos foram conduzidos primeiramente em sistema de frascos agitados para seleção da razão C/N que possibilitava a maior produção de biomassa e/ou consumo de carbono e nitrogênio do meio. Na razão C/N selecionada, foram conduzidos ensaios em biorreator de bancada, com ajuste de aeração e agitação, além do monitoramento em linha de pH e gases. Os resultados indicaram crescimento de ambos micro-organismos para a faixa de razão C/N testada, com elevadas produtividades na razão C/N 5 e 40 e maiores remoções de carbono e nitrogênio para Geitlerinema. O ensaio em biorreator de bancada com Aphanocapsa indicou baixa demanda de oxigênio, remoções de carbono e nitrogênio em biorreator da ordem de 25 e 18%, respectivamente, além de uma velocidade específica de crescimento máximo cerca de cinco vezes superior (0,5 h-1) ao obtido em frascos agitados. Para Geitlerinema sp. na razão C/N 5, cinética de consumo de carbono de primeira ordem possibilitou elevadas remoções em torno 85% em biorreator de bancada. Os dados experimentais indicam a viabilidade do cultivo de ambas cianobactérias em vinhaça na faixa de razão C/N de 5 a 40, com elevada conversão em biomassa para a cianobactéria unicelular e elevada remoção de carbono para a cianobactéria filamentosa.

京都大学 / 0048 / 新制・課程博士 / 博士(生命科学) / 甲第22021号 / 生博第418号 / 新制||生||55(附属図書館) / 京都大学大学院生命科学研究科統合生命科学専攻 / (主査)教授 福澤 秀哉, 教授 河内 孝之, 教授 荒木 崇 / 学位規則第4条第1項該当 / Doctor of Philosophy in Life Sciences / Kyoto University / DFAM

<p> The nitrogen and hydrogen-deuterium isotope effects have been measured for the base-promoted elimination reactions of cis-and trans-2-phenylcyclopentyltrimethylammonium ions and cis-and trans-2-phenylcyclohexyltrimethylammonium ions. The observations have been interpr eted as indicative of a concerted E2 mechanism for both trans and cis elimination processes. In the cis eliminations, however, proton transfer to base is far advanced at the transition state resulting in a much higher degree of carbanionic character ass ociated with the transition state than for the trans eliminations. </p> <p> The kinetic isotope effect results for these cyclic systems establish that the two bond-rupture processes complement each other; the greater the extent of proton transfer to base at the transition state, the smaller is the extent of C-N bond weakening. These observations are interpreted in terms of the coupling of the motion which extends the lengths of the H-C and C-N bonds at the transition state and the approach to coplanarity of the bonds involved in the elimination process. </p> / Thesis / Doctor of Philosophy (PhD)

Se investigó la estructura y la dinámica de las raíces finas a lo largo de un gradiente altitudinal en un bosque montano de lluvioso en el sur de Ecuador. Se estudió la biomasa y la necromasa de las raíces finas, la distribución espacial, la morfología de las raíces vivas y muertas asi como su distribución temporal en tres localidades ubicadas a 1890 m, 2380 m y 3060 m sobre el nivel del mar.Se pudo comprobar un incremento de la masa de las raíces finas en la capa orgánica y en el suelo mineral (0-20 cm) con el aumento de altitud. La misma tendencia se observó en la biomasa de las raíces finas y en la necromasa, que aumentaron de 393 a 978 g m-2 y de 640 a 2398 g m-2, respectivamente. El contenido de agua en el suelo se matuvó entre 20 y 30 Vol. %. La relación de bio- y necromasa varió bastante. La fluctuación temporal de las raíces finas no mostró ninguna concordancia con las temporadas climáticas. La producción de las raíces finas aumentó con la altitud de 676 a 2193 g m-2, así como también la producción de necromasa de raíces finas que aumentó de 523 a 2085 g m-2. El tiempo de vida de las raíces finas se estimó entre 0.75 y 0.44 años aproximadamente, al mismo tiempo la masa de las raíces finas era renovada. Experimentos sobre la descomposición biológica con bolsas de hojarasca (litter bags) monstraron que la tasa de descomposición disminuye con el aumento de altitud. La superficie específica de las raíces (SRA) también diminuyó con el aumento de altitud asi como la superficie específica de las ojas (SLA). El índice areal des las raíces (RAI) aumentó por causa del aumento de la biomasa de las raíces finas. La producción de hojarasca disminuyó con el aumento de altitud, mientras que simultaneamente crecía la masa de las raíces finas y disminuía la altura de los árboles.Se pudo comprobar estadísticamente una relación entre la masa de las raíces finas y la producción de hojarasca con la altitud sobre el nivel del mar. La superficie específica de las raíces (SRA), la producción de las raíces finas y su mortalidad monstraron también una dependencia con la altitud, la temperatura del aire, el contenido de nitrógeno, los parámetros morfológicos (SLA, SRA), la altura media del tronco y el diámetro medio del tronco (medido a un 1.3 m). Se encontró una correlación negativa entre la precipitación y la tasa de retorno y la expectativa de vida de las raíces finas.