Orientador: Claudio Airoldi / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T05:32:41Z (GMT). No. of bitstreams: 1 Costa_LuelcSouzada_M.pdf: 4010865 bytes, checksum: 0e6d35c0e46af757fe71fa900c8678f8 (MD5) Previous issue date: 2012 / Resumo: A síntese de sílicas mesoporosas funcionalizadas pela a rota de co-condensação tem despertado a atenção de diversos grupos de pesquisas devido a sua praticidade. Esta síntese consiste na condensação simultânea entre as moléculas dos organossilanos e as moléculas da fonte de silício (TEOS) através do método sol-gel. Isso faz com que a incorporação de grupos orgânicos na estrutura da sílica ocorra de forma direta. No entanto, em muitos casos, os híbridos preparados dessa forma podem apresenta uma má formação estrutural devido a presença dos grupos orgânicos. Nesse trabalho foram sintetizados materiais híbridos com o agente direcionador copolímero tribloco EO20-PO70-EO20 (P123 ¿ Pluronic®). Foram escolhidos grupos organossilanos contendo em suas estruturas sítios básicos Lewis tais como grupos carbonílicos, enxofre e nitrogenados. Os espectros na região do infravermelho juntamente com a análise elementar e ressonância magnética nuclear mostraram concordância que o ancoramento dos grupos orgânicos na matriz inorgânica dos híbridos ocorreu de forma satisfatória. As isotermas de sorção e dessorção de nitrogênio mostraram que todas as isotermas são do tipo IV com histerese do tipo H1 que são característicos de matérias mesoporosos e que os poros dos materiais estão na faixa de mesoporosidade, a área superficial é dependente do tamanho da molécula utilizada na funcionalização. Foram observados os sinais da reflexão típica de materiais do grupo p6mm, denominada 2D-hexagonal, análogas ao material SBA-15. Portanto, todos os híbridos foram sintetizados de forma ordenada como proposto. Os materiais híbridos foram aplicados em sorção de íons metálicos, e na sorção de corantes. Os dados experimentais foram ajustados aos modelos de isoterma de sorção de Langmuir, Freudlich e Sips usando os métodos de regressão não linear. As sílicas apresentaram boa capacidade de sorção tanto para os metais quanto para o corante. Fato esse devido aos sítios básicos de Lewis, de nitrogênio e enxofre presentes e a possibilidade desses grupos serem protonados em solução e estes sítios interagirem com os grupos sulfonados do corante. / Abstract: The synthesis of functionalized mesoporous silicas by a co-condensation route has attracted attention of many research groups due to its practicality. The synthesis consists of the simultaneous condensation among organosilane molecules and the molecules of silicon source by sol-gel method. This makes the incorporation of organic groups in the silica structure occurs directly. However, in many cases, the hybrids may this way prepared has a structural deformation due to the presence of the organic groups. In this work were synthesized hybrid materials with directing agent triblock copolymer EO20-PO70-EO20 (P123 - Pluronic ®).Were chosen organosilanes containing groups in their structures Lewis basic sites such as carbonyl groups, nitrogen and sulfur. Infrared spectra combined with elemental analysis and nuclear magnetic resonance proved that the organic chains were satisfactorily anchored to the inorganic matrices. The nitrogen adsorption-desorption analyses generated isotherms of type IV and hysteresis H1 that are typical of mesoporous materials, where asthe pore size distribution showed that the pores of the silicas are in the mesoporous range. The BET method was applied to acquire the surface areas of the solids, which were found to be dependent on the size of the molecule used for the functionalization processes. SAXS patterns of all samples demonstrated well-resolved peaks characteristic of the typical p6mm space group, called 2D-hexagonal, similar to SBA-15.The hybrid materials were applied to the sorption of metallic ion sand dyes, showing good sorption capacities for both kinds of contaminants. The nitrogen and sulfur Lewis basic sites anchored to the silica inorganic back bone can be protonated to interact with the sulfonated groups of the dyes. The experimental data were fitted to the Langmuir, Freundlich and Sips sorption isotherms using the non-linear regression. / Mestrado / Quimica Inorganica / Mestre em Química

Orientador: Evandro Vagner Tambarussi / Resumo: Eucalyptus pellita F. Muell é uma das espécies de importante interesse nos programas de melhoramento visando agregar alelos complementares, por meio da hibridação com espécies amplamente cultivadas, como o E. grandis e E. urophylla. Para isto, torna-se necessário o conhecimento da variabilidade genética e identificar possíveis grupos heteróticos de modo a orientar os programas de hibridação com o E. pellita. Neste sentido, a presente pesquisa objetivou estimar a variabilidade e a distância genética existente em procedências e progênies de E. pellita, por meio de caracteres quantitativos, a fim de subsidiar possíveis estratégias a serem executadas em um programa de melhoramento da espécie. Foi avaliado um teste de procedências e progênies, com 118 progênies pertencentes a sete procedências, além de um clone comercial como controle. O experimento foi delineado em blocos casualizados com cinco repetições, em parcelas lineares com nove plantas. Foram mensurados os caracteres quantitativos diâmetro a altura do peito (DAP), altura, volume individual e sobrevivência (%) aos sete anos de idade. Os dados foram submetidos a análise REML/BLUP, obtendo-se estimativas das componentes de variância, parâmetros genéticos e valores genéticos preditos (BLUP). Foi estimada a distância genética das procedências e progênies a partir da distância generalizada de Mahalanobis (D²), e posterior formação de grupos heteróticos pelo método de agrupamento de Tocher e método da ligação média (UPGMA). Além... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Eucalyptus pellita F. Muell is an important species used in breeding programs to add complementary alleles through hybridization with widely cultivated species, such as Eucalyptus grandis and Eucalyptus urophylla. To guide hybridization programs with E. pellita, information about the genetic variability and the identification of possible heterotic groups of the species is necessary. As such, the present study aimed to estimate the variability and genetic distance among E. pellita provenances and progenies using quantitative traits. The goal was to inform possible strategies to be implemented in a species improvement program. A provenance and progeny test with 118 progenies belonging to seven E. pellita provenances was analyzed, with a commercial clone used as the control. The experiment was designed in randomized blocks with five replications in linear plots, and nine plants per plot. The following quantitative traits were measured at seven years of age: diameter at breast height (DBH), height, individual volume, and survival (%). The data were submitted to REML/BLUP analysis to obtain estimates of the variance components, genetic parameters, and predicted genetic values (BLUP). The genetic distance of the provenances and progenies was estimated from the generalized Mahalanobis distance (D²). The formation of heterotic groups was subsequently identified using Tocher’s clustering method and the unweighted pair group method with arithmetic mean (UPGMA). In addition, principal c... (Complete abstract click electronic access below) / Mestre

La tubuline est une protéine essentielle de la cellule. En polymérisant sous forme de microtubules, elle crée notamment le fuseau mitotique le long duquel migrent les chromosomes pendant la mitose. Les médicaments qui inhibent la polymérisation et/ou la dépolymérisation de la tubuline sont des composés majeurs de la thérapie anticancéreuse. Les vinca-alcaloïdes en sont des représentants importants. Ils induisent la mort des cellules par apoptose, en inhibant la dynamique des microtubules. D’autres molécules d’origine naturelle, comme la phomopsine A, se fixent sur la tubuline à proximité ou dans le même site de fixation que celui des vinca-alcaloïdes. C’est la raison pour laquelle nous avons envisagé d’élaborer des composés antimitotiques hybrides entre la vinblastine et la phomopsine A. Dans ce contexte, deux séries de composés ont été conçues. La première série d’hybrides correspondant à des dérivés de l’anhydrovinblastine fonctionnalisés en position 7’. Cependant, aucune des trois stratégies étudiées n’a permis d’accéder à ces composés. La deuxième série d’hybrides, dérivés de la 7’-homo-anhydrovinblastine a pu être synthétisée grâce à une réaction originale d’insertion d’acétylènes activés au niveau du pont gramine de la vinorelbine, suivie d’une réduction avec un contrôle totale de la régio- et stéréoselectivité. Dans un premier temps, les réactions d’insertion et de réduction ont été mise au point. Ensuite, deux familles d’hybrides portant la chaîne latérale de l’octahydrophomopsine en position 8’ ou 7’ ont été synthétisés. La plupart des composés ainsi obtenus possédent une excellente activité sur la tubuline et sont très cytotoxique. / Tubulin plays a key role in many cellular functions, like cell division. Microtubules, resulting from its polymerisation, form the mitotic spindle along which chromosomes migrate during mitosis. Tubulin-binding molecules are one of the most important classes of anti-cancer agents with major drugs already on the market and many promising compounds in clinical trials. Vinca-alkaloids are one of these antimitotic drugs inhibiting microtubules dynamics. It was shown that the vinca binding site partially overlaps with that of others natural products, like phomopsin A. In order to explore the vinca domain and to elaborate new acute derivatives, we have elaborated antimitotic vinblastine-phomopsin hybrids. We were interested in the synthesis of two series of hybrids. The first, corresponding to 7’-anhydrovinblastine derivatives could not be obtained. None of the three studied strategies lead to desired compounds. The second series of hybrids, corresponding to functionnalized 7’-homo-anhydrovinblastine derivatives, could be synthetised by an original and regioselective insertion reaction, followed by a stereoselective reduction. Firstly, the isertion reaction was studied using different activated acetylenes. Then, two different families of hybrids were obtained, thanks to the selective insertion of the octahydrophomopsin lateral chain in position 8’ or 7’. Almost all the compounds were highly active on tubulin and very cytotoxic.

No description available.

Le développement de variétés productives et adaptées aux conditions de déficit hydrique est toujours au cœur du défi de l'amélioration variétale chez le tournesol. Pour une nouvelle orientation de la sélection, ce travail se propose d'identifier de nouvelles cibles phénotypiques au travers d'une démarche couplant le phénotypage écophysiologique, la modélisation biophysique et la génétique quantitative. Les cibles potentielles ont été identifiées sur la base de leur variabilité génotypique, leur impact sur le rendement, leur héritabilité et leur facilité de mesure. Des paramètres génotypiques du modèle SUNFLO-CLIMATOR relatifs à la phénologie, l'architecture foliaire et l'accès aux réserves hydriques du sol ont été testés. 19 lignées et 125 hybrides ont été phénotypés au champ et sous serre. La structure génétique des populations d'hybrides a permis d'évaluer l'héritabilité des paramètres génotypiques et leur mode de transmission.La date thermique de la floraison a présenté la variabilité génotypique la plus restreinte, mais l'héritabilité la plus élevée (H²=0.78). Ce trait est un bon indicateur de la précocité de la floraison mais peu pertinent pour améliorer la précocité à la maturité. La date de la maturité physiologique a présenté un déterminisme environnemental important et une amélioration de sa représentation dans le modèle est nécessaire. Les traits caractéristiques de l'architecture ont présenté la plus grande variabilité génotypique. Leur héritabilité était par contre peu élevée (0.20 ≤ H² ≤ 0.39). L'interaction des traits architecturaux était plus importante que leur contribution individuelle dans la variabilité de la productivité. Des investigations plus approfondies sur l'interaction des traits d'architecture devraient apporter plus de précision sur la stratégie d'intégration de ces caractères en sélection. L'utilisation du trait, position de la plus grande feuille, A2gen, et surface foliaire de la plus grande feuille, A3gen, en sélection sur valeur propre des lignées, peut cependant déjà permettre une amélioration de l'efficience d'interception des hybrides durant la phase reproductive et particulièrement dans des conditions de déficit hydrique en fin de cycle. Le trait Indice d'extraction de l'eau IEgen caractéristique de la capacité d'extraction de l'eau du sol, constitue le trait le plus prometteur. Il présente une héritabilité élevée (0.77 ≤ H² ≤ 0.83). La réponse du rendement à sa variabilité est linéaire, avec un gain de 0.8 à 1.5 q ha-1 pour une augmentation de 1 % de la teneur en eau minimale d'extraction de l'eau.La recherche de marqueurs moléculaires pour ces paramètres génotypiques d'intérêt peut être faite et dans le but d'une stratégie de sélection assistée par la modélisation biophysique et le marquage moléculaire. / This work was an attempt to assist sunflower breeding program by crop physiology knowledge to sustain and to improve productivity under water deficit. The approach was based on using SUNFLO-CLIMATOR, a biophysical crop modelling to identify the limiting factors to plant productivity. These factors were considered as potential new traits for breeding program. Their assessment for this objective corresponded to four criteria: genotypic variability, impact on plant productivity, heritability and simplified phenotyping method. Thus, traits related to genotypic parameters of three processes were analysed: phenology, architecture and soil water uptake. Their variability was evaluated on field and greenhouse experiments carried out with 19 inbred lines and 125 hybrids. Sensitivity analysis of plant yield, simulated with SUNFLO-CLIMATOR model, was then done to estimate the impact of the parameter variability among the studied genotypes. Quantitative genetic analyses were used to evaluate their heritability and the combining ability of the parental inbred lines.Large phenotypic variability was observed for each parameter with a significant “genotype” effect. Thermal time for flowering displayed high heritability about H² = 0.78. Thermal time to physiological maturity (M3) displayed high environmental effect on its variability. Its genotypic variability would probably need new way of modelling such as the development of a seed growth module. Architectural traits related to canopy size and shape presented also lower heritability (0.20 ≤ H² ≤ 0.39) and their impact on plant productivity depends on their interaction. However the trait position of the largest leaf A2gen and its leaf area A3gen could be yet used to screen the best inbred lines for improving radiation interception efficiency of the hybrids during the grain-filling phase.Root depth is a relevant trait for deeper soil. Its access remains difficult and time consuming. For shallower or medium depth soil, higher water extraction capacity seemed allow higher plant yield with linear relationship about 0.8 – 1.5 q ha-1 more per 1% decrease of soil water content minimal for water extraction. The index of water extraction (IEgen) displayed high value of heritability (0.77 ≤ H² ≤ 0.83). The genotypic parameters A2gen, A3gen, IEgen were confirmed with genetic resources to enhance plant productivity under water deficit. Research for their molecular marker would be a next step for this work and an issue for a new selection assisted by marker molecular and plant modelling.

Environmental awareness, production costs and operating expenses have provided a large incentive for the investigation of novel and more efficient fluid power technologies for decades. In the earth-moving sector, hydraulic hybrids have emerged as a highly efficient and affordable choice for the next generation hydraulic systems. Displacementcontrolled (DC) actuation has demonstrated that, when coupled with hydraulic hybrids, the engine power can be downsized by up to 50% leading to substantial savings. This concept has been realized by the authors‘ group on an excavator prototype where a secondary-controlled hydraulic hybrid drive was implemented on the swing. Actuatorlevel controls have been formulated by the authors‘ group but the challenge remains to effectively manage the system on the supervisory-level. In this paper, a power management controller is proposed to minimize fuel consumption while taking into account performance. The algorithm, a feedforward and cost-function combination considers operator commands, the DC actuators‘ power consumption and the power available from the engine and hydraulic hybrid as metrics. The developed strategy brings the technology closer to the predicted savings while achieving superior operability.

Preliminary unpublished work at the Salt Lake City Laboratory of the Division of Sugar Plant Investigations, Bureau of Plant Industry, United States Department of Agriculture, indicates that beets showing the Y color factor (9) were larger than sugar-beet types recessive for this color factor (y y). It was suggested to the writer that an investigation be made to determine whether or not yield and sugar content were correlated with color factors in beets. Linkages between the R and Y color factors have been reported by Keller (9), and the results indicate a close linkage betwen color factorsR and Y, with about 7.5 percent recombinations. Abegg (1) has found linkage between the R color factor and the factor B for annual habit with a crossover percentage of about 15.5 percent. Unpublished data from the Division of Sugar Plant Investigations indicate several additional color factors in the R Y B linkage group. Yield and sugar analysis, as related to presence and absence of the R factor, have been studied by Nuckols (10). Nuckols' studies were made from a commercial variety and plants recessive for the red color (genotype r r) were separated from plants with red hypocotyls (genotypes R r and R R) at thinning time. He reports no significant difference between the 2 color classes in yield or sugar content. Since these data were taken from a commercial variety of beets by thinning to color classes, no critical information was secured regarding possible genetic linkages; but satisfactory data were secured showing 1 color to be as good as the other as far as production of sugar is concerned. In the present study hybrids were made between a sugar beet and a mangel wurzel. The sugar beet was a high sugar type of genetic constitution R r y y for color. The mangel wurzel was a high yield and low sugar type and of genetic constitution r r Y Y for color. A large F2 population resulting from hybrids between the sugar beet and the mangel made possible a critical study of the association of the R and Y color factors with yield and sugar analysis.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20402号 / 工博第4339号 / 新制||工||1672(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 中條 善樹, 教授 澤本 光男, 教授 古賀 毅 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

With gas prices on the rise, the demand for high-mileage and low pollution vehicles has taken on an unprecedented role in our society. The production and implementation of electric and hybrid-electric vehicles has recently been a large focus of all major automobile manufacturers. Although these new vehicles have begun to solve much of the expensive fuel consumption and air pollution problems that our economy faces, the initial cost of these vehicles has proven to still be too expensive to capture a significant portion of the market. The further advancement of this technology must not only continue to focus on better fuel efficient and decreased pollution producing vehicles, but also decrease the cost of these vehicles to make them more available and enticing to the general public. Results from this research include one potential solution to reduce the cost of electric and hybrid-electric vehicles. Previous research performed in this area has led to the investigation and bench-top testing of a special type of mechanical system known as a Planetary Differential (PD). An exploration of the functionality of this system has shown that the PD can simplify expensive and complex electronic control systems for electric and hybrid-electric vehicles, thus reducing the cost to the consumer. In this study, fundamental speed, torque and power relationships for the PD were developed and tested under various loading conditions. Advantages and disadvantages of the PD, as compared to other similar mechanical systems, are identified and outlined. Recommendations for future work and implementation of the PD in electric and/or hybrid-electric vehicles are presented herein.