Orientador: Paulo Ademar Martins Leal / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agricola / Made available in DSpace on 2018-08-13T05:28:28Z (GMT). No. of bitstreams: 1 FernandesJunior_Flavio_D.pdf: 3079256 bytes, checksum: 23f61982e909bfb76e73e363ed5e4a5c (MD5) Previous issue date: 2009 / Resumo: Elevar a oferta de radiação fotossinteticamente ativa (RFA), ao longo de sacolas de cultivo de morangueiro dispostas verticalmente, foi o objetivo desse trabalho. Duas estratégias foram adotadas, o aumento do espaçamento entre as colunas e o uso de superfícies refletoras dispostas no chão das estufas sob as sacolas de cultivo. Os espaçamentos adotados foram o convencional de 1,20m entre as linhas de sacolas, 1,50m e 1,80m. As superfícies refletoras adotadas foram branca, metalizada e o próprio solo do ambiente protegido como testemunha. As superfícies refletoras foram confeccionadas por filmes plásticos que recobriram leiras de terra de 1,10m de base e 0,25m de altura no centro e sobre essas leiras foram dispostas as colunas de cultivo. A cultivar utilizada foi a Oso Grande. Os resultados dessas estratégias foram mensurados através da medida da radiação fotossinteticamente ativa (RFA) e da radiação global direta e refletida incidentes em três alturas das colunas de cultivo, sendo: A altura 3(ápice) a 2,00m, como ponto de referência e máxima RFA direta, altura 2(meio) a 1,00m e altura 1(base) a 0,35m (entre a planta mais baixa e a imediatamente superior). A produção das plantas, as características químicas dos frutos (sólidos solúveis em oBrix, acidez total titulável e pH), o acúmulo de açúcares nas folhas e os pigmentos fotossintetizantes presentes nas folhas foram as variáveis biológicas avaliadas. A RFA refletida na superfície metalizada foi superior a da superfície branca que foi superior a do solo em todas as alturas de referência. O tratamento metalizado na base teve maior RFA refletida que no meio que foi melhor que o ápice em todos os espaçamentos dentro da superfície metalizada. A soma de RFA refletida e direta foi maior no tratamento metalizado seguido do branco e do solo sem cobertura. A produção e os sólidos solúveis (oBrix) dos frutos foi superior no tratamento metalizado quando comparado ao branco que por sua vez superou o solo sem cobertura. / Abstract: The objective of this research was to increase the offer of Photosyntetically Active Radiation(PAR) trough vertical bags for strawberry production. To aim this objective two strategies were adopted the increase of distance among columns of the vertical bags and the use of reflective surfaces over the floor of the greenhouses under the bags. The distances used were 1.20m, 1.50m, and 1.80m among the bags lines. The reflective surfaces have the following colors: white, silver, and soil. These surfaces were made of plastic films, which recover the base with 1.10m of length and 0.25m of height at the center, and over them were installed the columns. The results of these strategies were measured trough Photosyntetically Active Radiation, and Direct Global radiation and reflective incident radiation at three heights of the columns. Height-3 (A3) at 2.0m top of the column, as reference point and highest direct PAR; A2 at 1.0m in the middle point of the column, and A1 at 0.35m point of lowest high of the plants. The productivity, chemical characteristics of the fruits (soluble solids content-oBrix), total titratable acidity, and pH), leaf sugar accumulation, and the photosynthesis' pigments of the leaves were the biological variables evaluated. The reflected PAR at metalized surface was superior of the white surface, and this one was superior of soil surface in all reference heights. The metalized A1 treatment had more reflected PAR than A2 treatment, which was better than A3 treatment in all distances under the metalized surface. The sum of reflected PAR and direct radiation was bigger at metalized treatment, followed by the white one, and for last the soil treatment. The productivity and soluble solids (oBrix) of the fruits were superior for the metalized treatment as compared to the white surface treatment, which was superior of the soil treatment. / Doutorado / Construções Rurais e Ambiencia / Doutor em Engenharia Agrícola

A preparação do EM Pd foi escolhida pelo fato de já terem sido estudados em nossos laboratórios os EM Ni e EM Pt. Estes três eletrodos modificados (EMs) foram utilizados nas hidrogenações eletrocatalíticas (HEC) de substratos orgânicos para comparação de suas reatividades. A preparação deste novo eletrodo modificado revestido pelo filme misto poli-[éter alílico do p-(2-etilamônio) benzeno] e co-monômero éter fenil e alílico no suporte de bastão de grafite contendo partículas de Pd foi iniciada com a síntese do éter alílico do p-(2-etilamônio) benzeno a partir da acetamida do p-(2-etilamônio). A utilização do co-monômero éter fenil e alílico na estrutura do filme polimérico se fez na tentativa de espaçar a malha polimérica para conseguir melhorar os resultados das HEC de substratos orgânicos, pois estes teriam maior facilidade de permear (difundir) pela malha e também proporcionar um aumento na quantidade de partículas de paládio incorporadas ao filme. Depois da preparação, utilização e comparação dos EMs Ni, Pd e Pt foram desenvolvidos novos EMs mistos visando aumentar a eficiência nas HEC dos substratos orgânicos. O EM misto Ni/Ni já havia sido preparado e estudado nas HEC mostrando uma eficiência moderada. Preparou-se então os EMs mistos Ni/Pd e Ni/Pt para compará-los com o EM Ni/Ni e com os EMs Ni, Pd e Pt para verificar se ocorreria um aumento na eficiência nas HEC. A preparação destes EMs mistos foi feita utilizando a técnica de electroless. A eficiência dos EMs foi verificada através da GH a partir de uma solução de ácido sulfúrico, do volume de hidrogênio gerado, medidas de potencial de circuito aberto e de reação de HEC de substratos orgânicos. A caracterização dos EMs foi feita pelo cálculo da massa de partículas incorporadas e análise de raios X e MEV-EDX. Os substratos orgânicos estudados nas HEC foram: benzaldeído, n-valeraldeído, isoforona, 2-cicloexen-1-ona, cicloexanona, acetofenona, benzofenona, eugenol, isoeugenol, fenilacetileno, 3-butin-1-ol, benzonitrila, fenilacetonitrila, malononitrila e valeronitrila. Comparando-se os EMs Ni, Pt, Pd, Ni/Ni, Ni/Pd e Ni/Pt, o que levou aos melhores rendimentos nas HEC foi o EM misto Ni/Pd. A HEC da acetofenona e benzofenona levou a resultados inéditos na literatura com a hidrogenação dos anéis aromáticos. / The modified electrode (ME) Pd was chosen because ME Ni and ME Pt had already been studied in our laboratory. These three different MEs were used in the electrocatalytic hydrogenation (ECH) of organic substrates so that their reactivity could be compared. The preparation of the new modified electrode ME Pd by using the mixed film poly-[ether allyl p-(2-ammoniumethyl) benzene] and the co-monomer allyl phenyl ether in carbon stick containing Pd particles. The preparation was initiated by synthesizing the allyl p-(2-ammoniumethyl) benzene ether through reaction with the acetamyde of the p-(2-ammoniumethyl) group. The co-monomer allyl phenyl ether in a polymeric film was used in an attempt to obtain more space between the polymeric film and to achieve better results in the ECH of organic substrates, since they could be introduced through the polymer and increase the quantity of Pd particles of incorporated in to the film. After the preparation of the MEs Ni, Pd and Pt and after they had been used and compared, new mixed MEs were developed in order to study their efficiency in the ECH of organic substrates. Mixed ME Ni/Ni had already been prepared and studied in our laboratory and it was shown to be moderately efficient for ECH. Mixed ME Ni/Pd and Ni/Pt were prepared so that they could be compared with mixed ME Ni/Ni, ME Ni, ME Pd and ME Pt. The preparation of these mixed MEs was carried out by electroless deposition. The efficiency of these MEs was verified by hydrogen generation from a mineral acid solution, hydrogen generation volume, potential of the open circuit and ECH of organic substrates. The characterization of the MEs was done by calculating the mass of incorporated particles and by SEM-EDX analyses. The organic substrates used for in ECH were benzaldehyde, n-valeraldehyde, isophorone, 2-cyclohexen-1-one, cyclohexanone, acetophenone, benzophenone, eugenol, isoeugenol, phenylacetylene, 3-butin-1-ol, benzonitrile, phenylacetonitrile, malononitrile and valeronitrile. A comparison of these MEs shows that the mixed ME Ni/Pd are the most efficient for ECH for all studied substrates. Acetophenone and benzophenone gave fully hydrogenated products; a fact that has not yet been published in the literature.

Climatério é a fase da vida da mulher em que ocorrem alterações hormonais que culminam em alterações metabólicas peculiares desse período, como por exemplo, diminuição do gasto energético e ganho ponderal. Com isso, os objetivos do presente trabalho foram mensurar o gasto energético e calcular a oxidação de carboidratos e lipídios, nos momentos basal e após uma sobrecarga lipídica, de mulheres pós-menopausadas com excesso de peso, estratificadas de acordo com o nível do estradiol plasmático (E2), bem como analisar peptídeos reguladores da fome e da saciedade nos mesmos momentos. Os grupos de mulheres foram: grupo 1- E2 39 pg/mL, 2- 40 E2 59 pg/mL, e 3- E2 60 pg/mL. As voluntárias receberam uma única refeição de 1100 kcal e 72% de lipídios, a qual caracterizou a sobrecarga lipídica. O gasto energético foi medido por calorimetria indireta por um período de cinco horas, sendo que as mensurações foram realizadas nos momentos 30, 60, 90, 150, 210 e 270 minutos. Os peptídeos reguladores da fome e da saciedade foram analisados no momento basal, após 30 e 270 minutos da sobrecarga lipídica. Os grupos foram comparados pelo teste não paramétrico Kruskal-Wallis, e para a comparação entre os momentos no mesmo grupo, foi utilizado o modelo de regressão linear com efeitos mistos, considerando p<0,05(*). Quarenta e quatro mulheres pós-menopausadas foram estudadas, com idade de 55±5 anos (média±desvio padrão), índice de massa corporal de 31±4 kg/m² e tempo de pós-menopausa de 8±7 anos. De uma forma geral, o gasto energético de repouso foi de 1337±194* kcal/dia, aumentando para 1476±295* kcal/dia nos primeiros 30´ pós-prandiais, e para 1513±318* kcal/dia ao final. Entre os grupos, não houve diferença estatística significativa. Em relação à oxidação de carboidratos, o valor basal foi de 151±95 mg/min, diminuindo para 146±95 mg/min nos primeiros 30´, e para 122±44 mg/min ao final (valores convertidos para mg/min para facilitar a leitura). O valor basal da oxidação lipídica foi de 37±30* mg/min, aumentando para 52±24* mg/min nos primeiros 30´ pós-prandiais, e para 63±21* mg/min ao final. Entre os grupos, não houve diferença estatística significativa quanto à oxidação de carboidratos, e quanto aos lipídios, houve diferença apenas entre os grupos 1 (maiores valores, p=0,03) e 2 ao final do experimento , e entre os grupos 1 e 3 (maiores valores, p=0,04) no momento 150´. Quanto aos peptídeos, o valor basal da leptina foi de 47±29 ng/mL, diminuindo para 44±27 ng/mL nos primeiros 30´ pós-prandiais, e para 43±26 ng/mL ao final. O valor basal da grelina foi de 753±522 pg/mL, diminuindo para 705±420 pg/mL nos primeiros 30´, e para 561±343 pg/mL ao final. O valor basal do peptídeo YY foi de 92±40* pg/mL, aumentando para 153±63* pg/mL nos primeiros 30´, e para 214±66* pg/mL ao final. Quanto à colecistocinina, o valor aos 30´ foi de 1,8±2,3 pg/mL, aumentando para 2,2±1,7 pg/mL ao final. Entre os grupos, houve diferença estatística significativa apenas da colecistocinina entre os grupos 2 e 3 (maiores valores, p=0,04) ao final. Sendo assim, houve um aumento significativo e gradual do gasto energético após a sobrecarga lipídica; predomínio da oxidação de carboidratos em relação à de lipídios, havendo uma diminuição em sua oxidação e um aumento da oxidação lipídica após a sobrecarga. Quanto aos grupos, não houve diferença estatística significativa em relação ao gasto energético, bem como à oxidação de carboidratos e lipídios na maior parte do tempo. Os peptídeos leptina e grelina diminuíram após a sobrecarga lipídica, enquanto que o peptídeo YY e a colecistocinina aumentaram, não havendo diferença estatística significativa entre os grupos na maior parte do tempo. Dessa forma, as variáveis estudadas se mostraram independentes do nível de estradiol plasmático. / Climaterium is the phase of women´s life when hormonal alterations occur and lead to peculiar metabolic responses such as a decrease in energy expenditure and weight gain. Thus, the aims of this study were to measure the energy expenditure, calculate carbohydrate and lipid oxidation, at resting and after a lipid overload, of postmenopausal women stratified according to their plasma estradiol value (E2) and evaluate hunger and satiety regulatory peptides in the same moment. Women´s groups were: group 1- E2 39 pg/mL, 2- 40 E2 59 pg/mL, and 3- E2 60 pg/mL. The volunteers received a 1100 kcal and 72% fat meal, which characterized the lipid overload. Energy expenditure was measured by indirect calorimetry for a period of five hours, and measurements were performed at 30, 60, 90, 150, 210 and 270 minutes. The hunger and satiety regulatory peptides were analyzed in the resting, 30 and 270 minutes after the lipid overload. The groups were compared using the nonparametric Kruskal-Wallis test. Linear regression model with mixed effects was used to compare the moments of the same group, considering p<0.05(*). Forty-four postmenopausal women were studied. Their age was 55±5 years (mean±standard deviation), body mass index was 31±4 kg/m² and they were in menopause for 8±7 years. In general, the resting energy expenditure was 1337±194* kcal/day, increasing to 1476±295* kcal/d in the first postprandial 30´, and to 1513±318* kcal/d in the end. There was no statistically significant difference between groups. Regarding carbohydrate oxidation, the baseline value was 151±95 mg/min, decreasing to 146±95 mg/min in the first 30´ and to 122±44 mg/min in the end (values were converted to mg/min for readability). The baseline value of lipid oxidation was 37±30* mg/min, increasing to 52±24* mg/min in the first 30´ and to 63±21* mg/min in the end. There was no statistically significant difference in carbohydrate oxidation between groups, and regarding lipids, the only statistically significant difference was between groups 1 (higher values, p=0,03) and 2 at the end of the experiment, and between groups 1 and 3 (higher values, p=0,04) at time 150´. In relation to the peptides, the baseline leptin was 47±29 ng/mL, decreasing to 44±27 ng/mL within the first postprandial 30´ and to 43±26 ng/mL in the end. Baseline ghrelin was 753±522 pg/mL, decreasing to 705±420 pg/mL in the first 30´ and to 561±343 pg/mL in the end. Baseline peptide YY was 92±40* pg/mL, increasing to 153±63* pg/mL in the first 30´ and to 214±66* pg/mL in the end. Referring to cholecystokinin, the value at 30´ was 1.8±2.3 pg/mL, increasing to 2.2±1.7 pg/mL in the end. Among groups, the only statistically significant difference was related to cholecystokinin between groups 2 and 3 (higher values, p=0,04) in the end. So, after the lipid overload, there was a gradual and significant increase on energy expenditure, predominance of carbohydrate oxidation in relation to the lipids with a decrease on its oxidation, and an increase on lipid oxidation. In regard to comparison between groups, there was no statistically significant difference in relation to energy expenditure, as well as to oxidation of carbohydrates and lipids in most of the time. The peptides leptin and ghrelin decreased after the lipid overload, while peptide YY and cholecystokinin increased, with no statistically significant difference between groups for most of the time. Thus, the variables were independent of plasma estradiol levels.

O alquilbenzeno linear sulfonado (LAS), principal componente na formulação de detergentes e outros agentes de limpeza, é despejado constantemente em corpos de água em função da precariedade dos sistemas de tratamento de origem doméstica em países em desenvolvimento, como o Brasil. A principal motivação do presente estudo foi verificar a remoção do sabão em pó com o emprego de diferentes co-substratos em reator anaeróbio de leito fluidificado (RALF). O RALF foi preenchido com areia como material suporte e operado com tempo de detenção hidráulica (TDH) de 15 horas durante 247 dias. Substrato sintético simulando esgoto sanitário foi utilizado, cuja composição incluía solução de sais, bicarbonato de sódio, sabão em pó comercial, extrato de levedura e co-substratos como sacarose e/ou etanol. A operação do reator foi dividida em cinco fases: (1) imobilização da biomassa em circuito fechado; (2) etapa I com sacarose e etanol (50/50%), sem adição de sabão em pó e circuito aberto; (3) etapa II com sacarose e etanol (50/50%) e 6,8 ± 2,1 mg/L de LAS em circuito aberto; (4) etapa III com sacarose e etanol (50/50%) e 14,3 ± 1,5 mg/L de LAS em circuito aberto; (5) etapa IV com apenas sacarose como co-substrato e 16,4 ± 2,5 mg/L de LAS em circuito aberto. Para todas as etapas, obteve-se remoção média de DQO superior a 78 ± 8,4%, para 590,2 ± 76,2 mg/L afluente. Houve aumento de eficiência de remoção com acréscimo de sabão em pó em torno de 12% entre a etapa I e as demais etapas; estas juntas apresentaram média de 597,7 ± 83,1 mg/L de DQO afluente. A remoção média de LAS foi de 37,7 ± 13,7% para 12,4 ± 8,4 mg/L afluente. Por meio da análise estatística não foi possível determinar o nível de importância dos co-substratos na remoção de DQO e LAS. Verificou-se remoção de 39,4% de LAS, sendo 30,6% referente à degradação biológica e 8,8% à adsorção. Populações microbianas diferentes foram observadas nas diferentes etapas por meio de análise de DGGE. Microrganismos pertencentes aos filos Proteobacteria (72%), Acidobacteria (3%), Synergistetes (3%), Bacteroidetes (6,3%) e Firmicutes (6,3%) foram identificados no biofilme do material suporte da última etapa. A maioria das seqüências foi relacionada à família Rhodocyclaceae cujos membros são capazes de degradar compostos aromáticos. / Linear alkylbenzene sulphonate (LAS), main component in detergent formulation and others clean products, is constantly released in aquatic environment in face of precarious domestic wastewater treatment facilities presents in developing countries like Brazil. The main reason of this study was to verify the powder soap removal through the use of different co-substrates in anaerobic fluidized bed biological reactor (AFBBR). The AFBBR was filled with sand as support material and operated with 15 hours of hydraulic time retention (HTR) over 247 days. It was utilized synthetic sewage which composition included salt solution, sodium bicarbonate, commercial powder soap, yeast extract and co-substrate as sucrose and/or ethanol. The operation of reactor was divided in following steps: (1) biomass immobilization phase in close circuit; (2) stage I with sucrose and ethanol (50/50%) without powder soap addition in open circuit; (3) stage II with sucrose and ethanol (50/50%) and 6,8 ± 2,1 mg/L of LAS in open circuit; (4) stage III with sucrose and ethanol (50/50%) and 14,3 ± 1,5 mg/L of LAS in open circuit; and (5) stage IV with only sucrose as co-substrate and 16,4 ± 2,5 mg/L of LAS in open circuit. For all stages, it was obtained up 78 ± 8,4% average COD removal with 590,2 ± 76,2 mg/L influent. There was a increase of COD removal around 12% with powder soap addition among stage I and following stages, these last ones, together, had 597,7 ± 83,1 mg/L of average COD influent. The LAS removal was 37,7 ± 13,7% with 12,4 ± 8,4 mg/L of LAS influent. Using statistic analysis, it is not possible to define the level of co-substrates importance in COD and LAS removal. Through mass balance, it was verified 39,4% of LAS removal, with 30,6% from biological degradation and 8,8% from adsorption. Diverse microbial populations were observed from different stages by DGGE analysis. It was identified microorganisms relating to Proteobacteria (72%), Acidobacteria (3%), Synergistetes (3%), Bacteroidetes (6,3%) and Firmicutes (6,3%) phila in biomass support material from last stage. Most of sequences were closed to Rhodocyclaceae family which members are capable to degrade aromatic compounds.

Orientadores: Christoph Friedrich Deneke, Eduardo Granado Monteiro da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-25T16:50:29Z (GMT). No. of bitstreams: 1 MercesSilva_Leandrodas_M.pdf: 8926273 bytes, checksum: 010f49f410852b0ba0278adfc3e091fa (MD5) Previous issue date: 2014 / Resumo: Nanomembranas livres são definidas como filmes ultrafinos constituídos por metais, óxidos ou semicondutores, com espessuras nanométricas e vastas áreas superficiais. São obtidas em geral por um processo de subcorrosão seletiva de uma camada de sacrifício, cujo papel é liberá-las gradualmente, permitindo que o relaxamento da energia elástica nelas armazenada aconteça de maneira controlada, garantindo a integridade final das estruturas. Neste trabalho, nanomembranas livres de Si suportadas por um substrato de SOI foram utilizadas como substratos complacentes para o crescimento de ilhas de InAs em uma câmara de MBE. Além disso, nanomembranas metálicas tensionadas (Ag/Ti/Cr/Ag) foram utilizadas na obtenção de microtubos metálicos enrolados. Análises detalhadas da morfologia das amostras, das estruturas das ilhas e dos microtubos, do strain em ambos os sistemas e de suas possíveis aplicações foram realizadas. A microscopia eletrônica de varredura mostrou que as estruturas permaneceram íntegras após as deformações. A microscopia de força atômica revelou uma baixa densidade de ilhas no topo das nanomembranas de Si. Ademais, possibilitou o aperfeiçoamento de parâmetros superficiais das nanomembranas metálicas e o enrolamento de microtubos com diâmetros pré definidos, garantindo convergência com o modelo analítico. Técnicas de difração de raios X e modelagem por elementos finitos foram utilizadas para elucidar os estados de strain observados em ambas as estruturas. As simulações das curvaturas do substrato complacente de Si e do microtubo metálico sugeriram, respectivamente, um gradiente de strain dependente da posição lateral de cada ilha na nanomembrana e coeficientes de strain constantes nas nanomembranas de Ti e Cr. Finalmente, cálculos envolvendo elasticidade contínua sugeriram que para uma nanomembrana de Si com espessura adequada, o InAs pode transferir strain suficiente para possibilitar o crescimento epitaxial coerente. Ainda, medidas de espectroscopia Raman em moléculas auto organizadas de 1-octadecanethiol, adsorvidas em Ag e aprisionadas entre as paredes dos microtubos metálicos, sugeriram que tal sistema pode ser utilizado como um dispositivo SERS para self-assembled monolayers / Abstract: Freestanding nanomembranes (NMs) are defined as metallic, semiconductor or oxide ultrathin films with nanometer thickness and macroscopic surface areas. In general, they are obtained by a process of selective underetching of a sacrificial layer, whose role is gradually release them, allowing relaxation of their stored elastic energy in a controlled way, ensuring integrity of the final structure. In this work, freestanding edge-supported Si nanomembranes are used as compliant substrate to the InAs growth on a SOI substrate in a MBE chamber. Furthermore, strained metallic nanomembranes (Ag / Ti / Cr / Ag) are used to obtain rolled-up metallic microtubes. A detailed analysis of sample morphology, InAs island and metallic microtube structure, strain on both systems and their possible applications is carried out. Scanning electron microscopy shows the structures stay intact during and after deformation. Atomic force microscopy reveals a lower island density on the top of the freestanding membranes. Moreover, it allowed optimizing the surface parameters of the strained metallic membranes, rolling-up tubes with pre-defined diameters and ensuring convergence with the proposed analytical model. X-ray diffraction and finite element modeling is used to elucidate the observed strain states in both structures. The bending simulations of compliant Si substrate and rolled up metallic microtube suggest, respectively, a lateral strain distribution depending on the island position on the freestanding membrane and a constant strain distribution on the Ti/Cr strained NMs. Finally, continuous elasticity calculations suggest that for a Si nanomembrane with adequate thickness, the InAs can transfer enough strain to enable coherent epitaxial growth. In addition, Raman spectroscopy measurements of 1-octadecanethiol self-assembled molecules adsorbed on an Ag nanomembrane and trapped between the microtube Ag walls suggest the system could be used as a SERS sensor for self-assembled monolayers / Mestrado / Física / Mestre em Física

Made available in DSpace on 2014-08-20T14:33:11Z (GMT). No. of bitstreams: 1 Dissertacao_Rafael_Ucker_Brahm.pdf: 2089912 bytes, checksum: 8700b9d818a6d894ba0f1cd729523bd8 (MD5) Previous issue date: 2010-12-22 / The growth of the species of juçara palm Tree Euterpe edulis (Mart.) and royal palm Roystonea regia (Kunth) has no record of studies focusing on south region of Rio Grande do Sul State. It is necessary to identify a system that ensures the proper growth of plants of these species. In this context, these works provide alternatives for producing seedlings with adaptability for family farms of southern half of Rio Grande do Sul. The effect of different substrates on initial growth of the seedlings and the appropriate level of shading for their initial development were determined. The seedlings were grown on Estação Experimental Cascata, Embrapa Clima Temperado. The experiments reported in Chapters I determine the effect of different substrates. The seedlings grew from seeds originated in a family farm located in the municipalities of Tabai and Pelotas, RS. A combination of different substrates was used, represented by the treatments T1 - Plantmax®, T2 - forest soil, T3 - clayey soil, T4 - forest soil:clayey soil 1:1 (v:v), T5 - forest soil:carbonized rice husk 3:1 (v:v), T6 - forest soil:carbonized rice husk 1:1 (v:v), T7 - forest soil:rice husk in natura 1:1 (v:v), T8 - clayey soil:carbonized rice husk 3:1 (v:v), T9 - clayey soil:carbonized rice husk 1:1 (v:v), T10 - clayey soil:rice husk in natura 1:1 (v:v). The experimental design consisted of randomized blocks and the study used a (1 specie x 10 substrates) factorial scheme. Four replicates were used in each experimental design with four seedlings. The seedlings were transplanted into 2 dm³ plastic bags in greenhouse conditions, from January to September, 2009. The experiments were assessed fortnightly considering plants length, stem diameter, number of leaves, number of leaflets, leaflets length, roots length, physical properties of the substrates, macronutrients content of the substrates, and percentage of plants survival at the end of last evaluation. The experiments reported in Chapters II used plants grown from seeds of a family farm located in the municipality of Pelotas, RS. The effect of luminous intensity on palm trees growing in the field was assessed in the experiments. The palm trees were planted in different shading levels: S1 - 0%, S2 - 16%, S3 - 42% and S4 - 73%. 10 The shading was obtained with shade screen for each level of reduced incident radiant, it was placed over each plot represented by a structure of wooden beams with 2.10 m long, 0.70 m tall and 0.50 m wide. The experimental design was randomized blocks consisting of four replications. Each sampling unit was represented by three plants of each species, using 0.30 m row spacing, in the field during nine months. These experiments evaluated fortnightly plants length, stem diameter, number of leaves, number of leaflets, leaflets length, solar radiant incident on the plants, chlorophyll content of plants, roots length, soil physical properties, macronutrients content of soil, and percentage of survival at the end of last evaluation. Data were analyzed using the program statistical program WinSat. / O cultivo das espécies de palmeira-juçara Euterpe edulis (Mart.) e da palmeira-real Roystonea regia (Kunth) não possui registros de estudos focados para o Sul do Rio Grande do Sul, tornando-se necessário identificar um sistema com potencial para assegurar bom desenvolvimento das plantas destas espécies. Neste contexto, estes trabalhos forneceram alternativas de produção de mudas adaptadas à metade sul do Rio Grande do Sul, passível de utilização na agricultura familiar. Foi avaliado o efeito de diferentes substratos sobre o desenvolvimento inicial das mudas, bem como, identificou-se o nível de sombreamento adequado para o desenvolvimento inicial das mudas. Os trabalhos foram executados na Estação Experimental Cascata, Embrapa Clima Temperado. Para o Capítulo I, Estudos do efeito de diferentes substratos, utilizou-se plantas produzidas através de sementes em uma propriedade agrícola familiar localizada nos Municípios de Tabai-RS e Pelotas-RS. Foi utilizada a combinação de diferentes substratos representados pelos tratamentos: T1 - Plantmax®, T2 - solo mato, T3 - solo argiloso, T4 - solo mato:solo argiloso 1:1 (v:v), T5 - solo mato:casca de arroz carbonizada 3:1 (v:v), T6 - solo mato:casca de arroz carbonizada 1:1 (v:v), T7 - solo mato:casca de arroz in natura 1:1 (v:v), T8 - solo argiloso:casca de arroz carbonizada 3:1 (v:v), T9 - solo argiloso:casca de arroz carbonizada 1:1 (v:v), T10 - solo argiloso:casca de arroz in natura 1:1 (v:v). O delineamento experimental adotado foi de blocos ao acaso, com quatro repetições e cada unidade experimental composta por quatro plantas, sendo transplantadas para sacos plásticos de 2 dm3, em condições de casa de vegetação, no período de janeiro a setembro de 2009. Determinaremos para estes experimentos avaliar com intervalos quinzenais o comprimento das plantas; diâmetro do colo; número de folhas; número de folíolos; comprimento de folhas; comprimento das raízes; propriedades físicas dos substratos; teor de macronutrientes dos substratos; e 8 percentagem de sobrevivência das plantas ao final da ultima avaliação. Já para os experimentos Capítulo II, utilizou-se plantas produzidas através de sementes de uma propriedade familiar localizada no Município de Pelotas-RS, avaliado o efeito da intensidade luminosa sobre o desenvolvimento das palmeiras a campo, sendo estas plantadas em diferentes níveis de sombreamento: S1 - 0%, S2 - 16%, S3 - 42% e S4 - 73% de sombreamento. Estes sombreamentos foram obtidos com tela de sombrite para cada nível de redução da radiação incidente, colocada sobre cada parcela representada por uma estrutura de caibros de madeira medindo 2,10 m de comprimento, 0,70 m de altura e 0,50 m de largura. O delineamento experimental adotado foi de bloco ao acaso, compostos por quatro repetições, sendo cada unidade amostral representada por três plantas de cada espécie com espaçamento de 0,35 m entre linha, durante nove meses a campo. Determinamos para estes experimentos avaliar com intervalos quinzenais o comprimento das plantas; diâmetro do colo; número de folhas; número de folíolos; comprimento folhas; radiação solar incidente sobre as plantas; teor de clorofila das plantas; propriedades físicas do solo; teor de macronutrientes do solo; e percentagem de sobrevivência das plantas ao final da ultima avaliação. Os dados obtidos dos experimentos Capítulos I e II foram analisados através do programa estatístico WinStat.

A l'échelle nanométrique, les solides peuvent changer de forme par diffusion de surface, et présentent alors des propriétés de mouillage qui s'apparentent à celles des liquides. Dans cette thèse, nous nous sommes plus particulièrement intéressés au comportement de mouillage des nano-solides sur des substrats nanopatternés, comportant par exemple des piliers ou des tranchées. Sur ces substrats, les nanoparticules (ou ilots) solides peuvent être multi-stables : c'est-à-dire qu'ils peuvent présenter plus d'un état localement stable. Comme les liquides, les solides ont été observés par exemple dans des états dits de Wenzel (pénétrant dans la structure du substrat) ou de Cassie-Baxter (ne pénétrant pas). Grâce à une combinaison de simulations Monte Carlo Cinétiques et de modèles analytiques, nous avons étudié la stabilité de ces états et leur dynamique de transition. Plus particulièrement, avons mis en évidence le rôle de la diffusion de surface et de la nucléation bidimensionnelle sur la dynamique de transition. Nous avons aussi montré que les contraintes élastiques augmentent la stabilité des états de Cassie-Baxter, et mènent à de nouveaux états, avec des morphologies asymétriques ou partiellement empalées dans les nanostructures. Finalement, nous avons proposé de contrôler les transitions de mouillage à l'aide de l'électromigration induite par un faisceau d'électrons. Nos résultats ouvrent la voie vers une nouvelle direction pour les investigations expérimentales / At the nanometer scale, solids can change shape thanks to surface diffusion and therefore display wetting properties that can be likened to those of liquids. This doctoral thesis intends to study particularly the wetting behaviour of nano-solids located on nanopatterned substrates, containing for instance pillars or trenches. Upon these substrates, solid nanoparticles (or islands) can be multi-stable – that is to say they can display more than one locally-stable state. Just like liquids, solids have been observed for example in the context of the so-called Wenzel state (penetrating the very structure of the substrate) and Cassie-Baster state (no penetration). By combining Kinetic Monte Carlo simulations with analytical models, we conducted a study on the stability of these states along with their dynamics of transition. In particular, we highlighted the specific roles that surface diffusion and bidimensional nucleation play in regards to the dynamics of transition. We also demonstrated that elastic constraints increase the stability of Cassie-Baxter states and lead to new states, with either asymmetric morphologies or morphologies that are partially impaled into the nanostructures. Last but not least, we proposed to control wetting transitions using the electromigration brought on by an electron beam. Our results pave the way for a new direction in the field of experimental investigations

Les travaux précédents du laboratoire Hubert Curien ont permis d’élaborer des films photosensibles Ag : TiO2 sur verre, support de marquage de motifs actualisables ou permanents. Une adaptation de ces travaux aux supports plastiques et papiers est ici proposée afin d’élargir les domaines d’application potentiels au marquage sécurité des produits par exemple. Des techniques d’élaboration de films Ag : TiO2 compatibles avec les substrats considérés ont donc été développées. Deux voies ont été envisagées. La première utilise la chimie du Sol-Gel combinée à la méthode EISA et des procédés de dépôt tel le spin-coating, le jet d’encre ou la flexographie pour former un film mésoporeux de TiO2 sur les supports. Des traitements basés sur une extraction par solvant ou un recuit infrarouge ont été imaginés afin de libérer la porosité du film sans dégradation du support. Pour réaliser les films sur papier, un sel d’argent est ajouté au Sol avant son dépôt. Dans les cas des films élaborés sur plastique, l’argent est incorporé par imprégnation du matériau dans une solution de sel d’argent. La deuxième voie d’élaboration propose de formuler une encre aqueuse jet d’encre de nanoparticules de TiO2 et d’ions argent, en adaptant la composition d’une suspension commerciale de TiO2 aux exigences du jet d’encre. Après dépôt, l’encre est séchée par recuit infrarouge. Le comportement photochromique sous expositions lumineuses UV et visible des différents films permet leur coloration et décoloration de façon réversible. Les films Sol-Gel déposés sur plastique peuvent également être support de photo-inscriptions permanentes générées par irradiation par une lumière visible d’une certaine intensité / Previous research conducted at laboratory Hubert Curien led to the development of photosensitive Ag: TiO2 films on glass as support for updatable or permanent patterns. An adaptation of this work to plastic and paper substrates is proposed here to broaden the possible application areas such as goods secure labeling, for example. Fabrication techniques of Ag: TiO2 films compatible with flexible substrates have been developed, using two different paths. The first uses the combination of Sol-Gel chemistry with the EISA method. Deposition processes such as spin coating, inkjet or flexographic printing are used to form a mesoporous film of TiO2 on substrates. Treatments based on solvent extraction or infrared annealing have been devised to release the porosity of the film without damaging the supports. Silver salt is either introduced into the titania pores by soaking the films into a silver salt solution or added to the sol before its coating. The second developed option proposes formulating an aqueous ink jet ink made of TiO2 nanoparticles and silver ions by adapting the composition of a commercial suspension of TiO2 with the requirements of the ink jet process. After printing, the ink is dried by infrared annealing. The photochromic behavior under UV and visible light exposures of fabricated films allows to get coloring and bleaching reversibly. Sol-Gel films coated on plastic can also be a support for permanent colored patterns realized by irradiation with a visible light of certain intensity

Dans cette thèse nous avons eu pour but d’étudier la réactivité des complexes à bas degré d’oxydation du fer stabilisés par des ligands phosphines vis-à-vis des substrats insaturés. Cet objectif s’inscrit dans une démarche plus large d’accès à des systèmes catalytiques au fer capables de transformer de manière sélective l’éthylène, par la réaction d’oligomérisation, vers des alpha-oléfines linéaires courtes (butène-1, héxène-1, octène-1), ce qui n’a jamais été rapporté dans la littérature. Pour se faire, le passage par le mécanisme métallacyclique de transformation de l’éthylène est la voie privilégiée. Cependant, les propriétés électroniques et géométriques de ligand requises pour suivre un tel mécanisme, et en particulier son étape clé de couplage oxydant de deux molécules d’éthylène sur le centre métallique, ne sont pas clairement identifiées. Nous rapportons ici dans un premier temps la synthèse d’une bibliothèque de complexes de fer(II) et fer(III) à base de ligands phosphines présentant des propriétés électroniques et géométriques variées. Ces nouveaux complexes sont opportunément testés en tant que catalyseurs, d’une part pour la réaction d’oligomérisation de l’éthylène; mais également en tant qu’espèces réduites in situ en association avec des diènes (isoprène, butadiène) conduisant à leur polymérisation. Afin de nous rapprocher davantage de notre objectif d’accès aux espèces à bas degré d’oxydation du fer, l’emploi d’une voie de réduction en une étape et en conditions douces est rapportée; conduisant à l’isolement et la caractérisation de neuf complexes phosphorés de fer(0) à 18 et à 16 électrons. Bien qu’a priori inactifs vis-à-vis de l’éthylène ou des oléfines plus longues, nous montrons la capacité de ces complexes à promouvoir des réactions de couplage oxydant de substrats insaturés (alcynes) le couplage catalytique de l’éthylène et du butadiène et l’activation de divers composés tels que les silanes ou les halogénures d’alkyles, posant ainsi un premier jalon vers leur optimisation et application en tant que catalyseurs d’autres réactions, et potentiellement dans l’avenir, pour la transformation de l’éthylène. / In this thesis our aim was to study the reactivity of phosphine-based low-valent iron complexes towards unsaturated substrates. This goal is part of a wider approach of access to an iron catalytic system able to transform ethylene in a selective manner, by the reaction of oligomerization, towards short linear alpha-olefins (1-butene, 1-hexene, 1-octene), which is unreported in the literature. To achieve this, going through the metallacyclic mechanism of ethylene transformation is the most likely way. However, the electronic and geometrical features of the ligand required to follow this mechanism, and in particular the key step of the oxidative coupling of two molecules of ethylene to the metal center, are ill-defined. We thus report here in a first part the synthesis of a library of P-based iron(II) and iron(III) complexes bearing varied electronic and geometrical features. These novel complexes are opportunistically screened as catalysts for ethylene oligomerization on one hand, and as in situ reduced species in association with dienes (isoprene, butadiene) leading to the polymerization of the latter substrates, on the other hand. In order to get closer to our goal of access to low-valent iron complexes, the use of a one-pot reduction methodology under mild conditions is reported, leading to the isolation and characterization of nine 18- and 16-electron iron(0) complexes. Even though they do not show reactivity towards ethylene or longer olefins, we demonstrate the ability of these complexes to promote reactions involving the oxidative coupling elementary step of unsaturated substrates (alkynes), the catalytic coupling of ethylene and butadiene and the activation of various compounds such as silanes and organic halides, representing a first milestone towards their optimization and application as catalysts for other reactions, including potentially in the near future, for ethylene transformation

Les glutathion transférases (GSTs) constituent une famille multigénique d’enzymes présentes dans les trois domaines du vivant. Cette présence ubiquitaire souligne l’origine sans doute très ancienne de ces enzymes ainsi que des fonctions fondamentales conservées au cours de l’évolution. Ces enzymes sont impliquées notamment dans la détoxication cellulaire de molécules toxiques et dans le métabolisme secondaire. Les analyses phylogénétiques regroupent les GSTs des organismes photosynthétiques au sein de quatorze classes qui peuvent être séparées en deux grands groupes selon le résidu catalytique : les GSTs à sérine catalytique qui possèdent des activités de conjugaison du glutathion (GSH) et/ou peroxydase tandis que les GSTs à cystéine catalytique présentent des activités thioltransférase, déshydroascorbate réductase et de déglutathionylation. Les GSTs à sérine catalytique de la classe Phi (GSTF) sont présentes chez les organismes photosynthétiques et certains basidiomycètes. Chez les plantes, cette classe comprend un nombre de gènes plus important que les autres classes de GSTs. Ceux-ci sont parmi les plus régulés en réponse à divers stress et ils ont été fortement étudiés chez les plantes céréalières en raison de l’activité de détoxication des herbicides des protéines correspondantes. Pourtant, à quelques exceptions près, les rôles physiologiques des GSTFs restent inconnus et la redondance d’isoformes dans cette classe reste incomprise. Par des approches moléculaires, biochimiques et structurales, l’analyse structure-fonction des huit GSTFs de l’arbre modèle Populus trichocarpa a été réalisée au cours de cette thèse. L’analyse phylogénétique des GSTFs chez les organismes photosynthétiques a montré que cette classe est apparue au moment de l’apparition terrestre des végétaux et que différents groupes pouvaient être identifiés avec des motifs catalytiques distincts. L’analyse transcriptionnelle a montré que les gènes relatifs aux GSTFs de peuplier sont principalement exprimés dans les fleurs femelles, les pétioles et les fruits. Certains aspects du mécanisme réactionnel ont été caractérisés en déterminant notamment les paramètres cinétiques et d’interaction des huit GSTFs et de plusieurs variants mutés pour des résidus clés vis-à-vis de substrats modèles. Les structures de cinq des huit GSTFs ont été résolues et ces protéines dimériques adoptent un repliement GST canonique et des spécificités structurales au niveau du site actif ont pu être observées. De plus, au regard de la capacité des orthologues des GSTFs à lier des hormones et des flavonoïdes ainsi que de l’expression récurrente des GSTFs de peuplier dans les fruits et les fleurs femelles, deux organes riches en ces molécules, il peut être supposé qu’elles ont aussi des propriétés de type ligandine. Des résultats préliminaires ont également été obtenus pour la recherche de substrats physiologiques à partir de métabolites extraits de différents organes de peuplier. A terme, l’identification de ces substrats permettra de déterminer le mode d’action (catalytique vs ligandine) de chaque enzyme et d’identifier clairement les fonctions in planta de ces enzymes / Glutathione transferases (GSTs) belong to a multigenic family whose presence in most eukaryotes, prokaryotes and archaea reflects their widespread nature and very likely important functions. These enzymes represent a major group of enzymes involved in xenobiotic detoxification and secondary metabolism. From the most recent genomic and phylogenetic analyses, the GST family is subdivided into 14 classes that can be separated into two main groups based on the catalytic residue which is either a serine (Ser-GST) or a cysteine (Cys-GST). Ser-GSTs usually catalyze glutathione (GSH) conjugation and/or peroxide reduction. On the other hand, Cys-GSTs cannot perform GSH-conjugation reactions but instead catalyze thiol-transferase, dehydroascorbate reductase and deglutathionylation reactions. Ser-GSTs from the Phi class (GSTF) are present in photosynthetic organisms and some basidiomycetes. This class is composed of a large number of genes compared to other GST classes which are amongst the most stress-inducible. The corresponding proteins have been extensively studied in crops with regard to their detoxification activities toward herbicides. However, with a few exceptions, very little is known about their roles in planta and it is not well understood why this class has expanded. By combining molecular, cellular, biochemical and structural approaches, the eight isoforms from the model tree Populus trichocarpa have been characterized during this PhD project. Phylogenetic analysis of GSTFs in the green lineage shows that the apparition of this class is concomitant with the appearance of terrestrial plants and that different groups can be distinguished based on the active site signature. RT-PCR analysis of the eight isoforms of GSTFs showed that transcripts mostly accumulate in female flowers, petioles and fruits. Some aspects of the reaction mechanism have been characterized by determining kinetic parameters of the eight poplar GSTFs and of several mutated variants for key residues towards model substrates. The structures of five GSTFs have been solved and these dimeric proteins display a typical GST fold but specificities have been observed at the catalytic site level. Moreover, considering the demonstrated capacity of GSTF orthologs to bind hormones, anthocyanins or flavonoids, and the consistent high expression of poplar GSTFs in female flowers and fruits, two organs rich in these molecules, we speculate that they may also possess ligandin properties. Preliminary results have been obtained regarding the nature of the substrates in various poplar organs by analyzing protein thermostability in the presence of putative ligands. In order to assess whether a functional redundancy between poplar Phi GSTs exists and to identify their mode of action (catalytic vs ligandin functions), we started to isolate and identify physiological substrates