A microalga Spirulina platensis, que possui alto de teor de proteínas, vem sendo cultivada fotoautotroficamente para a produção de biomassa microbiana. Embora as fontes convencionais de nitrogênio utilizadas para a produção de Spirulina sejam os nitratos, há a possibilidade do emprego de fontes alternativas, como a uréia, utilizando o processo descontínuo alimentado, com diminuição do custo de produção. No entanto, o uso exclusivo de uréia, em função de sua hidrólise no meio de cultivo e conseqüente perda de amônia, pode levar as células a crescerem por determinados períodos sob carência da fonte de nitrogênio, uma vez que esta fonte não pode ser adicionada em grandes quantidades devido à toxicidade da amônia proveniente de sua hidrólise. Este trabalho teve como objetivo verificar se a adição de nitrato de potássio em cultivos realizados com uréia podem levar a processos com maior produtividade e/ou aumento na quantidade de biomassa produzida. Foram verificadas várias proporções entre as concentrações iniciais de nitrato de potássio e uréia, utilizando planejamento experimental e a metodologia de superfície de resposta. As variáveis dependentes foram concentração celular máxima (Xm), produtividade em células (Px) e fator de conversão de nitrogênio em células (YX/N), bem como, os teores de clorofila, proteínas e lipídios na biomassa obtida. Os resultados obtidos permitiram concluir que a associação de nitrato de potássio e uréia aumentaram a concentração celular máxima. A condição ótima obtida pela análise de regressão multivariável para Xm foi 17,3 mM de KNO3 e 8,90 mM de uréia, nessas condições foram obtidos 6077 ±199 mg/L. / The cyanobacterium Spirulina platensis, that have high protein content, has been cultivated photoautrophically for microbial biomass production. However nitrates are the conventional nitrogen sources for Spirulina, there is the possibility of use alternative source, as urea by fed batch process, decreasing the costs of production. So, the exclusive use of urea, due to urea hydrolysis in culture medium and consequently loss of ammonia, can cause the cell to growing for specific moments without nitrogen source, because urea can not be added in huge quantity due to the ammonia toxicity provide by its hydrolysis. This work have as objectives verify if the potassium nitrate addition in the culture carried out with urea can lead a process with more productivity and/or increase in the biomass quantity. It was verified many proportion between initial concentration of potassium nitrate and urea, using experimental planning and surface response methodology. The dependent variables were maximum cell concentration (Xm), cell productivity (Px) and nitrogen-cell conversion factor (YX/N), as well as biomass contents of chlorophyll, protein and lipids. The results allowed us concluded that the association of KNO3 and urea was good and improved the maximum cell concentration. The optimal condition otained by statistic analysis for Xm was 17,3 mM of KNO3 and 8,90 mM of urea. In this condition the maximum cell concentration was 6077 ±199 mg L-1.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-12T13:51:57Z No. of bitstreams: 1 2016 - Rodrigo Luiz Neves Barros.pdf: 1569971 bytes, checksum: bebc280a379491b5d376031d5427175e (MD5) / Made available in DSpace on 2017-05-12T13:51:57Z (GMT). No. of bitstreams: 1 2016 - Rodrigo Luiz Neves Barros.pdf: 1569971 bytes, checksum: bebc280a379491b5d376031d5427175e (MD5) Previous issue date: 2016-10-11 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The average productivity of common bean (Phaseolus vulgaris L.) in Brazil is one of the lowest in the world. Alternatives that can increase yield in a sustainable manner should be preconized, such as reducing the use of nitrogen fertilizers through the adoption of biological nitrogen fixation. Therefore, the objective of this study was to evaluate the influence of rhizobia inoculation and sowing nitrogen fertilization on growth and common bean yield (Phaseolus vulgaris L.). Four experiments were conducted in the field, at the Experimental Station of the Department of Crop Science at the Federal Rural University of Rio de Janeiro, Serop?dica, Brazil. So that each experiment was repeated twice in the same growing season. The experiments were conducted in the dry season and rainy the years 2013 and 2014, In a soil classified as Kanhapudalf. For both experiments, we used the common bean cultivar Carioca, indeterminate growth and high yield potential. In the first year of cultivation in the dry season and rainy the experiments were composed of three treatments: only fertilized with 20 kg N ha-1 at sowing and with 40 kg N ha-1 at 25 DAE (A); only inoculated with Rhizobium at sowing and fertilized with 40 kg N ha-1 at 25 DAE (I+N); and inoculated and fertilized with 20 kg N ha-1 at sowing and with 40 kg N ha-1 at 25 DAE (IA); and an additional treatment only inoculated with Rhizobium with no N fertilization at any phase (I-N), only evaluated in the second year of both growing seasons. The experimental design used was in randomized blocks, with four replications in both years. Each plot consisted of 6 rows of 5 m spaced 0,5 m apart. At pollination, it was evaluated the number of nodules (NN), nodules dry weight (MSN), shoot dry weight (MSPA) and root dry weight (MSR). However, was observed the highest NN and MSN in treatments without nitrogen fertilization at sowing in both years. Also, it was determinate the leaf soluble proteins content (TPSF) in four developmental stages vegetative, pollination, flowering and grain filling), with higher values for the TPSF in the treatment IA flowering stage. Moreover, for the growth analysis, three plants were collected on the second line of each side of the plot, weekly from 14 DAE until physiological maturation. At physiological maturation all the plants of the two central rows were collected from each plot to evaluate the crop yield components: number of pods per plant (NV), number of grains per pod (NGV), 100 grain matter (MS100G) and grain yield (PG). As for the production of components, there was a significant difference only for PG, with IA producing the highest PG in both years. Therefore, based on these results, it can be concluded that the inoculation with Rhizobium may replace the nitrogen fertilization (20 kg ha-1) at planting without yield loss, however, the nitrogen fertilization (20 kg ha-1) combined with inoculation with Rhizobium at sowing partly inhibit the root nodulation of the common bean plants and increased its total dry weight and grain yield, in both season. However, more studies are needed to recommend these agronomic practices / A produtividade m?dia de feij?o comum (Phaseolus vulgaris L.) no Brasil ? uma das mais baixas do mundo. Alternativas que possam aumentar a produtividade de forma sustent?vel devem ser preconizadas, tais como a redu??o do uso de fertilizantes nitrogenados pela ado??o da fixa??o biol?gica de nitrog?nio (FBN). Assim, o objetivo deste estudo foi avaliar a influ?ncia da inocula??o de riz?bios e, ou da aduba??o nitrogenada de semeadura no crescimento e produtividade do feijoeiro comum. Foram instalados quatro experimentos no campo experimental do Departamento de Fitotecnia da Universidade Federal Rural do Rio de Janeiro, Serop?dica, Brasil, de modo que cada experimento fosse repetido duas vezes na mesma ?poca de cultivo. Os experimentos foram instalados nas ?pocas da seca e das ?guas dos anos de 2013 e 2014, em um solo classificado como Argissolo Vermelho Amarelo. Para ambos os experimentos, foi utilizado o cultivar de feijoeiro comum Carioca, de crescimento indeterminado e alto potencial produtivo. No primeiro ano de cultivo das ?pocas da seca e das ?guas os experimentos foram compostos por tr?s tratamentos: apenas adubado com 20 kg N ha-1 na semeadura e 40 kg N ha-1 aos 25 dias ap?s a emerg?ncia (DAE) (A), inoculado com Rhizobium e adubado com 40 kg N ha-1 aos 25 DAE (I+N), inoculado com Rhizobium e adubado com 20 kg N ha-1 na semeadura e 40 kg N ha-1 aos 25 DAE (IA) e um tratamento adicional somente inoculado com Rhizobium sem aduba??o nitrogenada em nenhum est?dio (I-N), apenas avaliado no segundo ano de ambas as ?pocas de cultivo. O delineamento experimental utilizado foi em blocos ao acaso, com quatro repeti??es em ambos os anos. Cada parcela foi constitu?da por 6 linhas de 5 m, espa?adas de 0,5 m de dist?ncia. No est?dio de poliniza??o, avaliou-se o n?mero de n?dulos (NN), massa seca de n?dulos (MSN), massa seca de parte a?rea (MSPA) e massa seca raiz (MSR), sendo observado o maior NN e MSN nos tratamentos que n?o receberam aduba??o nitrogenada na semeadura em ambos os anos. Tamb?m foram realizadas coletas de tecido foliar para determina??o do teor de prote?nas sol?veis (TPSF) em quatro est?dios de desenvolvimento (vegetativo, poliniza??o, florescimento pleno e enchimento de gr?os), com valores mais elevados para o TPSF no tratamento IA no est?dio de florescimento. Al?m disso, para an?lise de crescimento, foram coletadas tr?s plantas por parcela, semanalmente dos 14 DAE at? a matura??o fisiol?gica. Na matura??o fisiol?gica foram coletadas todas as plantas das duas linhas centrais de cada parcela, desprezando-se o meio metro final de cada extremidade, para avaliar os componentes de produ??o: n?mero de vagens por planta (NV), n?mero de gr?os por vagem (NGV), massa seca de 100 gr?os (MS100G) e produtividade de gr?os (PG). Quanto aos componentes de produ??o, ocorreu diferen?a significativa apenas para PG, com o tratamento IA apresentando rendimentos mais elevados em ambos os anos. Portanto, segundo os resultados obtidos, a inocula??o de riz?bios pode substituir a aduba??o nitrogenada com 20 kg N ha-1 na semeadura sem perda de produtividade. Al?m disso, a inocula??o com riz?bios, acrescida da aduba??o com 20 kg N ha-1 na semeadura, inibiu parcialmente a nodula??o e propiciou acr?scimo de produtividade em ambas as ?pocas. No entanto, mais estudos s?o necess?rios para recomenda??o dessas pr?ticas agron?micas.

Made available in DSpace on 2017-07-10T17:37:05Z (GMT). No. of bitstreams: 1 Angela Lemos Prestes Marcondes.pdf: 484682 bytes, checksum: 74c71be734cb296a788fd1e8a2cf9d0d (MD5) Previous issue date: 2007-02-02 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Experiments in laboratory and house of vegetation with two ground, one of arenaceous texture (PVAd) and another argillaceous one had been developed (NVdf), beyond a study the field, having for objective to evaluate the agronomic effectiveness of the nitrogen fertilization, evaluating losses of N for volatilization of different nitrogen seasonings: urea; urea + oil; urea + inhibiting of urease; urea + sulphate of ammonium and ammonium sulphate, applied in covering and superficially, the culture of the maize. In the study in laboratory, the determination of the volatilized N was carried through hermetically closed cylindrical bottles with use of collectors in two periods of evaluations, (3 and 7 days), two ground (arenaceous and argillaceous) and five nitrogen sources. In the study in vegetation house, two ground (arenaceous and argillaceous), six periods of evaluations (1, 2, 3, 4, 7 and 8 days) and five nitrogen sources had been used. One evaluated height of plant, diameter of colm, production of dry biomass and text of total N. In the study the field, had been evaluated the following sources of N in covering: urea, urea absorbed in oil, urea with inhibitor of urease and mixtures of 100 kg of N as urea with increasing doses of ammonium sulphate (0, 10, 20, 30 and 40 kg ha-1 of N). The volatilized amount of N-NH3 was measured by means of ammonia collectors installed in the two lines central offices of each parcel in 3? and 7? day after fertilization. Total N in the fabric foliar and the grains, mass of 1000 grains and productivity was determined. In the study in laboratory and house of vegetation, the texture of the ground was verified that, as well as its CTC and amount of organic substance, had influenced the losses for volatilization of N-NH3, being bigger in the ground arenaceous (PVAd) of that in the ground argillaceous (NVdf) and with urea application in both the places, while that the imbibitions of the urea in oil did not imply in reduction of the loss of NNH3. The mixture urea (100 kg ha-1 of N) + ammonium sulphate (40 kg ha-1 of N) contributed for reduction of the losses of N-NH3, in average, of 8% in the evaluation lead in laboratory and 5% in the experiment in house of vegetation in comparison with the urea in the average of ground. The urea fertilization with inhibitor of urease presented minors losses and provided to one better exploitation of the N. In the study the field, the volatilization of ammonia occurred until 7? day after application of the treatments, being the total losses of the source urea of 13% and 4% in the urea with inhibitor of urease. The dose of ammonium sulphate in mixture with urea that implied in lesser loss of N-NH3 was of 9 kg ha-1 of N. Divide to low the rain availability, did not have significant difference of seasonings nitrogen in the maize productivity, but the urea fertilization with inhibitor of urease more provided to an increment of 377 kg in comparison the urea / Foram desenvolvidos experimentos em laboratório e em casa de vegetação com dois solos, um de textura arenosa (PVAd) e outro argiloso (NVdf), além de um estudo a campo, tendo por objetivo avaliar a eficácia agronômica da adubação nitrogenada, valiando perdas de N por volatilização de diferentes adubos nitrogenados: uréia; uréia + óleo; uréia + inibidor de urease; uréia + sulfato de amônio e sulfato de amônio, aplicados em cobertura e superficialmente, na cultura do milho. No estudo em laboratório, a determinação do N volatilizado foi realizada com o uso de frascos cilíndricos hermeticamente fechados com uso de coletores em dois períodos de avaliações, (3 e 7 dias), dois solos (arenoso e argiloso) e cinco fontes de nitrogênio. No estudo em casa de vegetação, foram utilizados dois solos (arenoso e argiloso), seis períodos de avaliações (1, 2, 3, 4, 7 e 8 dias) e cinco fontes de nitrogênio. Avaliou-se altura de planta, diâmetro do colmo, produção de biomassa seca e teor de N total. No estudo a campo, foram avaliadas as seguintes fontes de N em cobertura: uréia, uréia embebida em óleo, uréia com inibidor de urease e misturas de 100 kg de N como uréia com doses crescentes de sulfato de amônio (0, 10, 20, 30 e 40 kg ha-1 de N). A quantidade de N-NH3 volatilizada foi medida por meio de coletores de amônia instalados nas duas linhas centrais de cada parcela no 3º e 7º dia após adubação. Determinou-se N total no tecido foliar e nos grãos, massa de 1000 grãos e produtividade. No estudo em laboratório e em casa de vegetação, verificou-se que a textura do solo, bem como sua CTC e quantidade de matéria orgânica, influenciaram as perdas por volatilização de N-NH3, sendo maiores no solo arenoso (PVAd) do que no solo argiloso (NVdf) e com aplicação de uréia em ambos os locais, enquanto que a embebição da uréia em óleo não implicou em redução da perda de N-NH3. A mistura uréia (100 kg ha-1 de N) + sulfato de amônio (40 kg ha-1 de N) contribuiu para redução das perdas de N-NH3, em média, de 8% na avaliação conduzida em laboratório e em 5% no experimento em casa de vegetação em comparação com a uréia na média dos solos. A adubação de uréia com inibidor de urease apresentou menores perdas e proporcionou um melhor aproveitamento do N. No estudo a campo, a volatilização de amônia ocorreu até o 7º dia após aplicação dos tratamentos, sendo as perdas totais da fonte uréia de 13% e de 4% na uréia com inibidor de urease. A dose de sulfato de amônio em mistura com uréia que implicou em menor perda de N-NH3 foi de 9 kg ha-1 de N. Devida à baixa disponibilidade de chuva, não houve diferença significativa dos adubos nitrogenados na produtividade de milho, mas a adubação de uréia com inibidor de urease proporcionou um incremento de 377 kg a mais em comparação a uréia

O trabalho teve por objetivo avaliar fatores associados à ensilagem da cana-deaçúcar, com destaque para a aplicação de aditivos químicos e microbianos sobre a dinâmica fermentativa, composição bromatológica, atividade da álcool desidrogenase e desenvolvimento e diversidade da micloflora em silagens de cana-de-açúcar. No ensaio conduzido durante 110 dias o delineamento experimental adotado foi o inteiramente ao acaso, com 4 tratamentos, 2 repetições, e seis épocas de abertura (1, 3, 7, 15, 35, 110 dias). Os tratamentos foram: uréia 1% MV e os inoculantes microbianos Lactobacillus buchneri (3,65x105 ufc/g da MV) e a combinação de bactérias Pedioccocus pentosassus e Lactobacillus buchneri (1x106 ufc/g MV). As maiores variações na composição bromatológica e perdas de MS, das silagens controle ocorreram dos 7 aos 15 dias, estabilizando após esse período. As regressões ajustadas para perdas de MS e carboidratos solúveis foram bem similares e de forma contrária ao acúmulo de FDN. As perdas por gases alcançaram valores de 28,27%, de carboidratos solúveis em apenas 2,98% e FDN em torno de 67,77% da MS. Os aumentos nos teores de etanol e perda na digestibilidade nas silagens controle se extenderam até o 35º dia, com valores máximos de etanol de 12,23%. Foi possível relacionar etanol com a digestibilidade mostrando que cada 1% de aumento nos teores de etanol, 2 unidades de digestibilidade foram perdidas. Os aditivos uréia e o aditivo Lactobacillus buchneri mais Pediococcus foram eficazes em diminuir a produção de etanol (2,75 e 1,30 vs 8,27% no tratamento controle), em diminuir perdas de MS em 47 e 60%, e de carboidratos soluveis em 22 e 56% em relação à silagem controle, respectivamente. As silagens aditivadas com uréia obtiveram maiores valores de pH e maiores valores de ácido lático em relação às silagen controle. As silagens aditivadas com L. buchneri apenas foram as de maiores produções de etanol, acima da silagem controle (11.53 vs 8.27%), além de grandes perdas de matéria seca e baixa digestibilidade pelo acúmulo de FDN, comparáveis às silagens controle. A diferença entre aditivos na composição químico-bromatológica e perdas ocorreu após 7 dias de fermentação. Os dados apresentados pelos aditivos uréia e L. buchneri mais Pediococcus foram ajustados em curvas simples, através de modelos lineares, para descrever e predizer as variações durante a ensilagem. Os tratamentos controle e a aditivação com L. buchneri apenas, pelas altas taxas fermentativas, observaram melhor ajuste dos dados em polinômios de segundo e terceiro grau. Apesar dos altos teores de ácido acético em todas as silagens, principalmente nas silagens aditivadas com a combinação de bactérias, não foram verificadas efeitos deste sobre a população de leveduras. Os teores obtidos de ácido lático e ácido propiônico e a relação entre esses ácidos e o ácido acético, durante a fermentação, conseguiu explicar parte do sucesso dos tratamentos uréia e L. buchneri mais Pediococcus na redução da atividade da enzima álcool desidrogenase e na producão de etanol. A análise de grupamentos hieráquicos mostrou que os aditivos alteraram a diversidade bacteriana durante a ensilagem. / The present trial aimed to study the ensiling associated factors of sugarcane focusing on chemical and microbial additives on fermentation, chemical composition, enzymatic activity of alcohol dehydrogenase and the microflora development and diversity in sugarcane silages. A complete randomized design was set to a 110-d trial with 4 treatments, two replications within 6 opening dates (1, 3, 7, 15, 35, 110-d). Treatments were described as follows: urea 1% (wet basis), Lactobacillus buchneri (3.65x105 cfu/g of forage), a combination of Pediococus pentosassus and Lactobacillus buchneri (1x106). Major variation observed on the chemical composition and the DM losses in sugarcane silages without additives took place from the day 7 through the day 15. Losses of DM and soluble carbohydrates showed similar trend and in opposition to the NDF increase. Gases losses averaged 28.27%, while the soluble carbohydrates and NDF contents reached respectively, 2.98% and 67.77% when fermentation was stabilized. Conversely, ethanol and the digestibility were changed across the storage period up to the day 35, with ethanol content increasing to 12.23%. 1% of ethanol increase was associated with 2 percentage units of digestibility decrease. Both urea and the combination of microorganisms were effective in decrease the ethanol content (2.75, 1.30 vs 8.27% - without additives), decrease DM losses (47 and 60%) and reduce soluble carbohydrates losses (22 and 56%) when compared to the control treatment. The urea treated silages showed higher pH and lactic acid values. The L. buchneri treatment led to higher ethanol content (11.23 vs 8.27%) compared to the control, resulting in low DM recovery rate, higher losses and decreased digestibility as well as the silages without additives. The major changes on the chemical composition were noticed after the day 7 of fermentation. For the addition of urea and the combination of microorganisms L. buchneri and Pediococcus the variation was better described by linear equations whereas quadratic and cubic effects were more suitable for fitting the data from the control and the L. buchneri added silages. Even tough all silages has shown high acetic acid contents, mainly the combination of lactic bacteria, no significant effects were observed upon the yeast counts. However, the levels of lactic acid and propionic acid and the ratio of both over the acetic acid content were related to the decrease on the activity of the alcohol dehydrogenase enzyme and, furthermore, on the ethanol content of the silages. The cluster analysis based on molecular evaluation demonstrated a change promoted over the bacterial population mediated by the additives applied during the ensiling of sugarcane.

Resumo: Na cultura do milho (Zea mays L.), um dos mais importantes cereais cultivados e comercializados no mundo, o suprimento inadequado de nitrogênio (N) é considerado um dos principais fatores limitantes da produtividade de grãos. Também a densidade inadequada de plantas é uma das causas dos baixos rendimentos das lavouras de milho no Brasil. O trabalho teve como objetivo avaliar a influência da aplicação de doses de N e de densidades de plantas nos componentes de produção, na produtividade de grãos, no teor foliar de N e na receita líquida em cultura de milho. A área experimental foi instalada em Latossolo Vermelho-Amarelo distrófico, textura argilosa, cultivada em sistema de plantio direto, localizada no município de São Raimundo das Mangabeiras, MA. Os tratamentos foram constituídos pela combinação de cinco doses de N (0; 50; 100; 150 e 200 kg ha-1) e quatro densidades de plantas (25.000, 50.000, 75.000 e 100.000 plantas por hectare). O delineamento experimental utilizado foi o de blocos casualizados, com quatro repetições e os tratamentos segundo o arranjo em um esquema fatorial 5 x 4. As maiores produtividades de grãos de milho foram obtidas quando foram aumentadas concomitantemente as doses de nitrogênio e a densidade de plantas, atingindo a máxima produtividade técnica de grãos de milho com 120 kg ha-1 de N e densidade de 83.000 plantas por hectare. O nível crítico de N na folha do milho foi de 25 g kg-1, acima do qual ocorreu o consumo de luxo. A utilização dos insumos (dose de nitrogênio e densidade de plantas) de forma combinada e equilibrada proporcionou valor de receita líquida técnica de US$ 1.493,00 ha-1 e econômica de US$ 1.502,00 e a relação beneficio/custo técnica e econômica de 1,70 e 1,71, respectivamente / Abstract: In the corn (Zea mays L.) crop, one of the most important cultivated and marketed cereals in the world, the inadequate nitrogen (N) supply is one of the main limiting factors to the kernel productivity. In Brazil, the inadequate plant density reduces the corn cropping income. This research aimed to evaluate, in the corn crop the influence of different levels of N application and plant density upon the production components, productivity, leaf N content and the best economical return. In the experimental area, located in São Raimundo das Mangabeiras, MA, Brazil, the soil is a dystrophic loamy textured Red Yellow Latosol, cultivated under the no tillage system. The treatments were made up by the combination of five rates of N (0; 50; 100; 150, and 200 kg ha-1) and four plant densities (25,000, 50,000, 75,000, and 100,000 plants per ha). The completely randomized experimental design, with four repetitions was used, with treatments arranged in a 5 x 4 factorial. The results showed that the greatest grain yields were achieved when increasing both population density and nitrogen level. The highest kernel productivity was obtained with 120 kg ha-1 of N and 83,000 plants per ha. The leaf critical N level was 25 g kg-1, above which occurring the luxury consumption. The use of inputs (nitrogen rates and plant density) in a combined and balanced way provided a U.S. $ 1,493.00 ha-1 technical net revenues and a U.S. $ 1,502.00 economical net revenue, with a benefit/technical and a benefit/economical cost ratio of 1.70 and 1.71, respectively / Orientador: José Eduardo Corá / Coorientador: Milton José Cardoso / Banca: Luiz Evaldo de Moura Pádua / Banca: Adeodato Ari Cavalcante Salviano / Banca: José Carlos Barbosa / Banca: Edson Luiz Mendes Coutinho / Doutor

Les silicones auto-cicatrisants de façon autonome (sans stimulus externe) présentent de faibles propriétés mécaniques, limitant leur utilisation industrielle. L’objectif de cette étude était de dépasser cette limitation. Nos travaux se sont intéressés aux copolymères segmentés PDMS-urée constitués de blocs souples (SS) et rigides (HS). Tout d’abord, nous avons étudié la relation entre la structure des bis-urées et les propriétés macroscopiques. Nous avons ainsi montré que la symétrie des HS gouverne la rigidité de ces matériaux. Toutefois, la présence de HS symétriques inhibe la cicatrisation du matériau. Puis, nous avons développé un nouveau concept permettant d’accélérer leur cinétique de cicatrisation. Un stoppeur de chaine macromoléculaire a été ajouté à la formulation de ces silicones thermoplastiques, créant un défaut dans l’assemblage supramoléculaire, conduisant à des clusters organiques plus petits et plus dynamiques. Néanmoins, contrairement aux plastifiants, la chute du module de Young observée par rapport à la matrice est limitée. D’ailleurs, nous reportons la synthèse d’un copolymère PDMS-urée avec un module de traction de 1MPa dont 90% de la contrainte à rupture peut être récupérée après cicatrisation pendant 24h à 25°C. Ce concept a aussi été adapté à un thermoplastique commercial (GENIOMER80). Enfin, notre défi a été d’optimiser la balance entre rigidité et autocicatrisation. Dans ce contexte, nous avons synthétisé de nouvelles matrices plus rigides, ainsi que des additifs avec des groupements associatifs de plus grande énergie cohésive. Nous avons alors pu repousser la limite de rigidité accessible aux silicones auto-cicatrisants de façon autonome (3MPa). / Autonomous self-healable (without external stimulus) silicones exhibit too low mechanical properties restricting their use in industry. The aim of this study was to overcome this limitation. We focused our work on segmented PDMS-urea copolymers made of soft (SS) and hard segments (HS). First the investigation of the relationship between the bis-urea chemical structure and the macroscopic properties was made. Results shown that, the symmetry of HS governs materials rigidity. Moreover, with a too symmetrical HS, the material does not exhibit self-healing abilities. We have developed a new concept improving the healing efficiency of these materials. The idea was to add to the formulation of these silicone thermoplastics a macromolecular chain stopper. The new additive creates a defect in the supramolecular assembly which leads to smaller and more dynamic H-bonding clusters and hence a faster healing kinetic. Unlike plasticizers, this additive deteriorates the tensile modulus only marginally. We therefore report a stress at break recovery of 90% after 24 hours at room temperature for a PDMS-urea copolymer with a tensile modulus of 1MPa. The concept was also extented to a commercial thermoplastic (GENIOMER80). Finally, our last challenge was to manage the balance between rigidity and chains dynamics allowing self-healable materials with good mechanical properties. In this context we have synthesized new matrixes with higher HS percentage and additives with stickers with higher cohesive energy. These new syntheses have led to an improvement of the rigidity limit reachable by the autonomous self-healable silicones (3MPa).

Les LIMKs sont deux protéines kinases responsables de la régulation de la dynamique du cytosquelette d’actine et des microtubules. Leur dérégulation peut jouer un rôle prépondérant dans l’apparition de certaines maladies telles que la neurofibromatose de type 1, le cancer ou la sclérose latérale amyotrophique.Au cours de ce projet collaboratif, nous avons cherché à concevoir des inhibiteurs à la fois puissants et sélectifs des LIMKs en nous inspirant du composé le plus performant de l’époque développé par Lexicon Pharmaceuticals.Nous avons, dans un premier temps, travaillé sur la base hétérocyclique en remplaçant la pyrrolo[2,3-d]pyrimidine par différentes pyridopyrimidines et une triazolopyridopyrimidine. Cette dernière modification a ouvert la voie à un sujet de méthodologie autour du réarrangement de Dimroth. Nous avons ensuite modifié le cycle central pipérazine par une 3,6-dihydropyridine ou une pipéridine différemment substituée et avons fait varier la substitution au niveau de l’arylurée. Enfin, nous sommes revenus apporter quelques modifications structurales à la pyrrolo[2,3-d]pyrimidine de départ.Finalement, nous avons créé, à l’aide de méthodologies de synthèse efficaces, un large panel de composés originaux qui ont été testés in vitro et in cellulo sur nos cibles.Au travers de ce projet de chimie médicinale, nous avons pu approfondir les relations structure-activité afin de concevoir des inhibiteurs des LIMKs très prometteurs. / LIMKs are two protein kinases involved in regulating cytoskeleton and microtubule actin dynamics. Their deregulation can play a major role in the onset of several diseases such as neurofibromatosis type 1, cancer or amyotrophic lateral sclerosis.During this collaborative project, we have sought to design both potent and selective LIMKs inhibitors based on one of the most efficient compounds of the day developed by Lexicon Pharmaceuticals.We first worked on the heterocyclic base by replacing the pyrrolo[2,3-d]pyrimidine by different pyridopyrimidines and a triazolopyridopyrimidine. This last modification lead to a directed synthetic methodology study around the Dimroth rearrangement. We then modified the piperazine central ring with a differently substituted 3,6-dihydropyridine or piperidine and varied the substitution at the arylurea. Lastly, we made some further structural changes to the starting pyrrolo[2,3-d]pyrimidine.In conclusion, we have created, using effective synthetic methodology, a wide range of original compounds that have been tested in vitro and in cellulo on our targets.Through this medicinal chemistry project, we now have a better understanding of the structure-activity relationships needed in order to design very promising LIMK inhibitors.

To date, there has been little research into the role of microbial community structure in the functioning of the soil ecosystem and on the links between microbial biomass size, microbial activity and key soil processes that drive nutrient availability. The maintenance of structural and functional diversity of the soil microbial community is essential to ensure the sustainability of agricultural production systems. Soils of the same type with similar fertility that had been under long-term organic and conventional crop management in Canterbury, New Zealand, were selected to investigate relationships between microbial community composition, function and potential environmental impacts. The effects of different fertilisation strategies on soil biology and nitrogen (N) dynamics were investigated under field (farm site comparison), semi-controlled (lysimeter study) and controlled (incubation experiments) conditions by determining soil microbial biomass carbon (C) and N, enzyme activities (dehydrogenase, arginine deaminase, fluorescein diacetate hydrolysis), microbial community structure (denaturing gradient gel electrophoresis following PCR amplification of 16S and 18S rDNA fragments using selected primer sets) and N dynamics (mineralisation and leaching). The farm site comparison revealed distinct differences between the soils in microbial community structure, microbial biomass C (conventional > organic) and arginine deaminase activity (organic > conventional). In the lysimeter study, the soils were subjected to the same crop rotation (barley (Hordeum vulgare L.), maize (Zea mays L.), rape (Brassica napus L. ssp. oleifera (Moench)) plus a lupin green manure (Lupinus angustifolius L.) and two fertiliser regimes (following common organic and conventional practice). Soil biological properties, microbial community structure and mineral N leaching losses were determined over 2½ years. Differences in mineral leaching losses were not significant between treatments (total organic management: 24.2 kg N per ha; conventional management: 28.6 kg N per ha). Crop rotation and plant type had a larger influence on the microbial biomass, activity and community structure than fertilisation. Initial differences between soils decreased over time for most biological soil properties, while they persisted for the enzyme activities (e.g. dehydrogenase activity: 4.0 and 2.9 µg per g and h for organic and conventional management history, respectively). A lack of consistent positive links between enzyme activities and microbial biomass size indicated that similarly sized and structured microbial communities can express varying rates of activity. In two successive incubation experiments, the soils were amended with different rates of a lupin green manure (4 or 8t dry matter per ha), and different forms of N at 100 kg per ha (urea and lupin) and incubated for 3 months. Samples were taken periodically, and in addition to soil biological properties and community structure, gross N mineralisation was determined. The form of N had a strong effect on microbial soil properties. Organic amendment resulted in a 2 to 5-fold increase in microbial biomass and enzyme activities, while microbial community structure was influenced by the addition or lack of C or N substrate. Correlation analyses suggested treatment-related differences in nutrient availability, microbial structural diversity (species richness or evenness) and physiological properties of the microbial community. The findings of this thesis showed that using green manures and crop rotations improved soil biology in both production systems, that no relationships existed between microbial structure, enzyme activities and N mineralisation, and that enzyme activities and microbial community structure are more closely associated with inherent soil and environmental factors, which makes them less useful as early indicators of changes in soil quality.

This thesis describes a series of four experiments designed to evaluate the role of the supply of protein in livestock grazing high quality pasture during mating and during pregnancy. The first two studies investigated the effects of high crude protein content of spring or autumn re-growth pasture on the reproductive performance of dairy cows and of ewes at mating. The last two studies investigated how the dietary supply of protein, body condition and their interactions contribute to the breakdown of immunity during the peri-parturient period in ewes and investigated underlying endocrine mechanisms. In the first study (Chapter 3) cows were blood sampled via the tail vein during the breeding period in spring. Plasma was then analysed for urea concentration. Cows with high plasma urea (HPU) or low plasma urea (LPU) were defined as those with plasma urea concentrations of ≥ or < 44.9 mg/dl respectively. Lactating cows (n = 200) were also categorized into high milk producers (HMP) or low milk producers (LPM) relative to an average daily yield of 26.6 l/d. Pasture clipping showed an average pasture CP (crude protein) content of 223 g/kg DM. Concentrations of plasma urea ranged from 26.6 to 64.4 mg/dl. No correlation was observed between plasma urea concentration and either reproductive indicators or milk parameters. Mean blood urea concentration of HPU cows was 50.8 compared to 38.5 mg/dl in LPU cows. There was a trend for more animals (P = 0.09) in the HPU group than in the LPU group not to return to oestrus. Cumulative pregnancy rate in HPU and LPU was similar except at week 6 after the start of mating when more (P < 0.01) HPU than LPU cows were pregnant. Calving to conception interval, calving interval and interval between conception and first service were similar (P > 0.05) between HPU and LPU cows. Gestation length, calving rate, milk yield and milk components were also similar (P > 0.05) between LPU and HPU cows. There was no difference (P > 0.05) in plasma urea concentrations between HMP and LMP milk producers. However, calving to conception interval, interval between calving and first service and calving interval were longer (P < 0.001), submission rate higher (P < 0.001) and NRR (Non-return rate) higher (P < 0.05) in LMP than HMP. The number of services, the interval between first and second service, gestation length and CR (calving rate) were similar (P > 0.05) between HMP and LMP cows. HMP had lower (P < 0.001) milk protein and fat concentrations than LMP cows. This information indicates that, despite the fact that plasma urea was consistently higher than levels in the literature which have been associated with reduced fertility in dairy cows; no impairment of reproductive performance was observed. In the second experiment (Chapter 4) mature and dry Coopworth ewes were blocked by weight, body condition and previous prolificacy (high, HP vs low twinning frequency, LP) into two groups and thereafter randomly allocated to diet which were designed to provided either 1) high protein (163 g/kg DM, ryegrass/red clover pasture, HPP) or low protein (119 g/kg DM, hay and barley grain, HB) supply at joining. These were designed to provide high and low plasma urea concentration. Over a period of 17 days, ewes recorded as mated were examined by laparoscopy, at which time there was no difference in blood urea concentration (58.6 vs 56.1 mg/dl) between HPP and HB groups. Fifty days after the start of joining the number of foetuses present was counted using ultrasonography. As a consequence of lack of difference in the plasma urea concentration, irrespective of treatment group, individual animals were categorized into high (HU) and low plasma urea (LU) status based on whether plasma urea concentration was higher or lower than the sample mean of 51.5 mg urea/dl. Lambs which weighed greater than the mean plus one standard deviation for their litter size were classified as oversize. Ovulation rate and conception rate were similar (P > 0.05) between HPP and BH and between HU and LU ewes. Ewes with previous high reproductive performance (HP) as would be expected had higher ovulation rate (P < 0.001) and conception rate (P < 0.01) than LP ewes. Embryo losses was not (P = 0.06) different between HB and HPP ewes. Urea category (HU vs LU) did not (P > 0.05) influence embryo mortality. Foetal loss, neonatal loss, total reproductive loss and mean lamb birth weight was were not affected by diet, nor urea category (P > 0.05). Single ovulations had tended (P = 0.08) to contribute to higher embryo loss compared to multiple ovulations, and, single foetuses suffered higher (P<0.001) losses compared to multiples. While the study did not achieve large differences in plasma urea concentrations between diets, the levels of plasma urea operating were high yet reproductive wastage rates were similar to those recorded in the literature. Together with similar apparent lack of effect on a high plasma urea environment, the data suggest either that previous findings from controlled studies have a more complex aetiology or that pastoral animals can adapt to high tissue ammonia/urea status. The third trial (Chapter 5) was designed to provide information on the supply of amino acids to the abomasum from protein supplementation which have previously been found to overcome dietary scarcity associated with limitation of peri-parturient increase in FEC. Twin-suckling ewes were fitted with rumen and abomasal cannulae and grazed a ryegrass/clover sward (C) or the same sward but with a 500 g/h/d protein supplement (S). The trial was designed as a cross-over with two 14 day adaptation periods followed by two five-day digesta-sampling periods. All ewes were treated with anthelmintic 14 days after lambing. Weekly analysis of blood glucose was carried on whole blood and analysis of amino acids in plasma. The flows of amino acids (AA) and dry matter (DM) at the abomasum were measured during both sampling periods using intra-ruminally infused markers. Live weight and faecal egg count (FEC) were recorded weekly. Diurnal variation in AA flow at the abomasum peaked between 12:00 and 15:00 h and was greatest in S ewes. Flows of AA, including DAPA, were increased by supplementation by 16%, while sulphur amino acids (SAA) were the most enhanced (by 21%) and flows of leucine, lysine, glutamine and aspartate were increased by about 20%. There were significant time effects in rumen and abomasal pH (P < 0.01; in both cases in both periods) reflecting increase in pH after 09.00 h. During Period II, rumen pH in digesta of C ewes was significantly higher (P < 0.001) than that of S ewes (6.7 ± 0.05 vs 6.4 ± 0.05 for C and S ewes, respectively). Plasma AA concentrations (P < 0.01) were lower in S ewes 21 days after parturition, but similar (P > 0.05) to those of C ewes at other times. Forty-three days after lambing (after cross over), the order was reversed as plasma methionine and cysteine concentrations of C ewes became low (P < 0.05). These changes in plasma AA were accompanied by changes in body condition score between day 23 and 70 post-partum whereby C ewes lost more body condition than S ewes. There was evidence for a lower FEC in S ewes, being 46 vs. 670 epg, respectively for S and C groups (P = 0.08) 21 days after anthelmintic treatment. There were higher (P < 0.05) blood glucose levels in C compared to S ewes at day +35 relative to lambing which was reversed and significantly higher (P < 0.01) for S ewes by day +56 from lambing (after treatments were reversed). There was no significant effect of treatment on live weight and lamb performance. There are limited data in amino acid supply on lactating ewes on pasture and the present study contributes additional information on the supply of amino acids at the abomasum. The prediction that flow rates that sulphur amino acids may have been enhanced to the greatest degree could be significant since sulphur amino acids are needed for the synthesis of glutathione for immune response. It can be calculated that supplementation to supply the quantities of S-amino acid at pasture would be needed, since it would not be possible for sheep to increase pasture intake to achieve similar S-amino acid flow. Increase in bypass amino acids in S ewes at certain times in the day probably suggests influence by protein supplementation at certain times of the grazing cycle. Reduced plasma free amino acids at day +21 relative to lambing, may indicate sparing of body protein breakdown by protein supplementation. However, the difference in blood glucose on day 35 and day 56 may indicate re-adjustment of hormonal settings, responsible for nutrient partitioning. The last study (Chapter 6) used ewes during the peri-parturient period on pasture. Eighty pregnant ewes were allocated into four groups balanced for anticipated number of lambs. Group 1 had a high body condition score (BCS) of 4.0 which was maintained throughout pregnancy by pasture allowance (HM; n = 20). Group 2 (n= 40) had medium body condition (BCS 3.0) and were split into two subgroups; one was offered pasture to allow gain of condition (MH; n = 20) and the second allowed to lose condition by offering a low grazing allowance (ML; n = 20). Group 3 were thin ewes (BCS 2.4) and pasture allowance was designed to maintain this condition (LM; n = 20). These feeding regimes were maintained for 3 weeks from week -8 of pregnancy. During week -5 to -4 all ewes were acclimatized to a protein supplement (60 g/d). A glucose tolerance test (GTT) was conducted during week -4 after which half of the ewes in each group were offered a protein supplement at the rate of 500 g/d, creating –S and –NS groups. During wk -2, a second GTT was carried out. Animals were treated with an anthelmintic 3 wks before lambing, and were then challenged with a dose of 10 000 Teladorsagia circumcincta larvae on weeks -2 and -1 relative to lambing. Weekly recording of FEC, live weight and body condition was carried out. Lambs were weighed within 24 h of birth and again at 44 and 65 d of age. Computed tomography body scanning was carried out on ewes at weeks -8, -3 and +8 relative to lambing. There were no differences (P > 0.05) in lamb performance due to body condition or protein supplementation. FEC of all groups was low (≈ 9 peg) and there was no (P > 0.05) significant difference between ewes of different body condition or due to effects of protein supplementation. Ewes bearing/bearing multiple lambs had the highest FEC at day -32 and +12 relative to lambing, which was significant (P < 0.05) on the latter date. There were no significant effects of supplementation on parasite status. There were differences in basal plasma glucose concentration between groups (P < 0.001), being highest in HM/S and least in ML/NS ewes and was generally higher (P <0.001) during GTT 2 than GTT 1. Ewes carrying a single foetus had higher (P <0.001) basal glucose than those carrying multiple lambs (2.2 vs. 1.7 mmol/L, respectively). Other plasma glucose response indexes were similar (P <0.05) between groups. There were differences in insulin responsiveness between groups (P < 0.001), being highest in MH/S and least in ML/S ewes. Insulin responsiveness tended (P = 0.06) to be lower during GTT 1 than GTT 2, but was higher (P < 0.01) in ewes carrying singles than multiples. There was tendency for higher though non-significant, basal insulin concentrations in HM ewes. Insulin trends over time after glucose infusion suggest greater insulin response at GTT 1. Basal insulin was not correlated with CT muscle weight. Despite differences in body muscle mass at the start of the trial and differences induced by nutrition during late pregnancy, positive gains in muscle mass occurred during early pregnancy and muscle mass was similar in all groups by day 56 of lactation. Animals with greatest fat content at parturition (HM) mobilised the greatest amount and those with least fat (LM) deposited fat during lactation. Further experimentation may consider the use of the hyperinsulinemic-euglycemic clamp approach to more precisely estimate whether hormonal re-setting through insulin resistance may be involved in relaxation of immunity during the peri-parturient period.

<p>Transition metals have played an important role in synthetic organic chemistry for more than a century, and offer catalytic transformations that would have been impossible with classical chemistry. One of the most useful and versatile of the transition metals is palladium, which over the years has catalyzed many important carbon-carbon forming reactions. Popular cross-coupling reactions such as the Suzuki, Stille and the Heck reaction are all catalyzed by palladium, or more correctly, by palladium in its ground state, Pd(0). </p><p>Recently, interest in palladium(II)-catalyzed transformations has started to grow, partly due to the development of the vinylic substitution reaction, commonly called the oxidative Heck reaction, presented in this thesis. This Pd(II)-catalyzed, ligand-modulated reaction occurs under air at room temperature, and for the first time a general protocol employing a wide range of olefins and arylboronic acids was obtained. Ligand screening showed that the bidentate nitrogen ligand, 2,9-dimethyl-1,10-phenanthroline (dmphen), was the most suitable ligand. Dmphen is believed to facilitate regeneration of active Pd(II), increase catalytic stability and improve the regioselectivity in the reaction. A mechanistic investigation was conducted using electrospray ionization mass spectrometry (ESI-MS), making it possible to observe cationic intermediates in a productive oxidative Heck arylation. The results obtained are in agreement with the previously proposed catalytic cycle.</p><p>The emerging discipline of high-speed synthesis is making contributions to society’s growing demand for new chemical entities. This inspired the development of two ultrafast, microwave-accelerated carbonylation reactions with dicobalt octacarbonyl acting both as an in situ carbon monoxide supplier and reaction mediator. A wide range of symmetrical benzophenones was produced in only 6 to 10 s, using aryl iodides as the substrate. The second carbonylation reaction provided symmetrical and unsymmetrical ureas in process times ranging from 10 s to 40 minutes using primary and secondary amines.</p>