Orientador: Ciro Antonio Rosolem / Banca: Maria Helena Moraes / Banca: Juliano Carlos Calonego / Banca: Sandro Roberto Brancalião / Banca: Sônia Carmela Falcci Dechen / Resumo: O manejo inadequado do solo ocasiona a formação de camadas compactadas que prejudicam o desenvolvimento radicular das plantas, diminuindo a disponibilidade de água e nutrientes, enquanto que o acúmulo de carbono pode melhorar a qualidade do solo. Em sistemas com semeadura direta (SSD), com a menor mobilização do solo, pode-se usar, em rotação, plantas com sistema radicular vigoroso, capaz de crescer em condições adversas. Este trabalho teve como objetivo avaliar a ação de espécies de cobertura, gramíneas e uma leguminosa, em rotação com a cultura da soja, nos atributos físicos de um Latossolo, no acúmulo de carbono, nas diferentes frações da matéria orgânica e na produção da soja, em semeadura direta, ao longo de três anos. O experimento foi conduzido em um Latossolo Vermelho distroférrico de textura argilosa, na Fazenda Experimental Lageado, Unesp/Botucatu, nos anos agrícolas de 2006/2007, 2007/2008 e 2008/2009. No outonoinverno foram estabelecidas parcelas com braquiária (Brachiaria ruziziensis), sorgo granífero (Sorghum bicolor) e sorgo consorciado com braquiária. Na primavera, foram cultivados, em subparcelas, milheto (Pennisetum glaucum), cober crop [Sorghum bicolor (L.) Moench x Sorghum sudanense Piper Stapf], crotalária (Crotalaria juncea) ou pousio. A soja foi cultivada como safra de verão. Em março do primeiro ano foram retiradas amostras para caracterização da área experimental. Após o manejo das espécies cultivadas na primavera, no primeiro e terceiro ano, foram retiradas amostras indeformadas nas camadas de 0-5; 7,5-12,5; 15-20; 27,5-32,5 e 47,5-52,5 cm para determinação da densidade do solo, porosidade e curva de retenção de água no solo. Nas mesmas épocas, a estabilidade de agregados foi avaliada em amostras coletadas nas camadas de 0-5 e 5-10 cm. No terceiro ano do experimento, o intervalo hídrico ótimo (IHO) foi determinado... (resumo completo, clicar acesso eletrônico abaixo) / Abstract: Compacted layers resulting from inappropriate soil management may impair root growth, thus decreasing water and nutrient acquisition by crops. Conversely, soil quality is improved with soil carbon accumulation. In areas under no-till, crop rotation with plants with vigorous root systems may alleviate soil compaction, as well as increase soil carbon. In this experiment the effects of cover crops on soil physical properties, carbon accumulation, organic matter quality and soybean production under no-till in a compacted soil were studied for three years. The experiment was conducted on a clayey Rhodic Ferralsol, Lageado Experimental Farm, Unesp/Botucatu, in 2006/2007, 2007/2008 and 2008/2009. Congo grass (Brachiaria ruziziensis), grain sorghum (Sorghum bicolor) and a mix of both were cropped during fall-winter. Then, in the spring, pear millet (Pennisetum glaucum), cober crop [Sorghum bicolor (L.) Moench x Sorghum sudanense Piper Stapf] and indian hemp (Crotalaria juncea) were cropped and a treatment under fallow was set on sub-plots. Soybean was cropped as a summer crop. In March of the first year, samples were taken for characterization of the area. Right after spring crops were chemically desiccated in 2006 and 2008, undisturbed soil samples were taken from the layers 0-5; 7.5-12.5; 15-20; 27.5-32.5 and 47.5-52.5 cm to determine bulk density, porosity and water retention curve. At the same time, samples taken from the depths 0-5 and 5-10 cm were used to determine aggregate stability. In the third year, least limiting water range (LLWR) was evaluated in the 7.5-12.5 and 27.5-32.5 cm soil layers. Organic matter characterization was done in the third year, in the depths of 0-5 and 5-10 cm. Roots of spring crops were sampled in the layers 0-5; 5-10; 10-20; 20-40 and 40- 60 cm, one day before chemical desiccation in all growing seasons. Soybean roots were sampled in the same depths at R2 each... (Complete abstract click electronic access below) / Doutor

Neste trabalho, com objetivo de desenvolvermos dispositivos de limitação óptica, estudamos o processo de absorção de estado excitados em um grupo de tetrapiridil porfirinas com diferentes substituintes centrais (2H+, Zn2+, Ni2+, Cu2+). Para isso utilizamos a técnica de varredura – Z com pulsos de femto e picossegundos bem como com trem de pulsos. Desta forma, determinamos a dinâmica de absorção de estados excitados, para estas moléculas, obtendo parâmetros espectroscópicos tais como tempo de cruzamento intersistema, e as seções de choque de absorção dos primeiros estados excitados singleto e tripleto. Além disso, visando aproveitar os processos ópticos acumulativos de alguns materiais não lineares, em aplicação de limitação óptica, desenvolvemos uma nova geometria óptica denominada de limitador óptico de múltiplas passagens, a qual utiliza dois espelhos esféricos confocais e um espelho plano posicionado paralelamente a linha que une os espelhos esféricos. / In this work, aiming to develop optical limiting devices, we have studied excited state absorption process in a group of tetrapyridyl porphyrins with different central substitutes (2H+, Zn2+, Ni2+, Cu2+). We have employed Z-scan technique with femto and picosecond pulses as well as with pulse trains to determine the excited state absorption dynamics and obtain some spectroscopic parameters like intersystem crossing time and triplet and singlet excited state absorption cross-sections. Moreover, we have developed a new geometry for an optical limiter, named multipass optical limiter. It is formed by two confocal spherical mirrors together with a plane mirror placed in parallel with the line joining them.

Existe-t-il un consensus scientifique sur les conditions de la durabilité ? Est-il possible de construire un indicateur unique de soutenabilité faible ? Quelles sont les composantes objectives et subjectives des indicateurs ? Peut-on envisager des indicateurs objectifs de soutenabilité ? Quelles voies de recherche sont-elles nécessaires pour développer des indicateurs de développement durable ? Telles sont les questions auxquelles cet ouvrage tente de répondre. La comparaison des courants de la soutenabilité faible et de la soutenabilité forte nous sert de fil conducteur pour évaluer la part normative et la part objective du choix des paramètres et de leur méthode d'agrégation. L'agrégation arithmétique implique des hypothèses de substituabilité entre les facteurs, ce qui relève de la soutenabilité faible. La pondération, toujours normative, peut être explicite ou se traduire par le choix d'une unité ou dimension unique. Nous redéfinissons la soutenabilité faible comme étant la réduction de la complexité à une dimension unique. Il y a dès lors autant d'indicateurs de soutenabilité faible que de choix possibles de cette dimension unique. En particulier, l'empreinte écologique par habitant relève d'une forme "écologique" de soutenabilité faible. Le prix de marché est l'unité fondamentale de mesure de sa forme "économique". Nous montrons que les acteurs ne savent pas bien identifier leur intérêt et qu'ils ne sont pas parfaitement égoïstes, ce qui introduit un biais non systématique remarquable dans toute mesure en unité monétaire. La soutenabilité forte se caractérise par la multiplicité de dimensions ou "capitaux critiques" dont le dépassement d'un seul suffit à déterminer la non soutenabilité. Les différentes formes de soutenabilités faibles peuvent représenter des capitaux critiques parmi d'autres. Nous présentons une typologie des acteurs et du partage des responsabilités, également susceptible d'introduire des grandes divergences dans les résultats publiés. Quelques études de cas illustrent ces différents éléments dans des contextes contrastés. L'empreinte écologique de consommation se limite en particulier à une responsabilisation du seul consommateur, alors que les comptes nationaux permettent d'envisager la coresponsabilité de l'ensemble des acteurs. L'indicateur de "dématérialisation de l'économie" appliqué à un village indien montre la pertinence de mesurer l'utilisation absolue de matière sans pondération monétaire. Il est par ailleurs possible de minimiser le coût de dépollution sans toucher à la limite absolue d'émissions globales de centrales thermiques. Les deux dimensions, coûts sociaux et bénéfices environnementaux, peuvent donc être traitées séparément. En conclusion, il est possible d'identifier, dans chaque calcul d'indicateur de développement durable, une composante relativement objective de soutenabilité "forte" et une composante "faible", négociable, de partage des droits et responsabilités. / We study how different world views may influence how to develop sustainable development indicators. The comparison of weak sustainability and strong sustainability serves as a guide to estimate the share of objective versus normative choice of parameters and their method of aggregation. We then present a typology of actors and shared responsibilities, which may also introduce large discrepancies in the results published. Some case studies illustrate these different elements in contrasting contexts. It appears that it is possible to identify in each calculation of sustainable development indicator, a relatively objective component of sustainability and a negotiable component of shared rights and responsibilities.

The demand for protection of eyes and various types of optical sensors from laser-beam pulses has resulted in the search for optical limiting devices that have the property of being transparent at low intensity of light (normal light), but non-transparent towards high intensity (laser) light. This type of protection may be obtained by using an organic material that displays nonlinear optical (NLO) properties. Examples of NLO effects that can be used for optical limiting are reverse saturable absorption (RSA), two-photon absorption (TPA) and nonlinear refraction. The advantage of using compounds that show such NLO effects is that they can have very fast response and are self-activating, that is, there is no need for externally controlled switching to obtain optical limiting. In this work, several dialkynyl substituted thiophenes and some thiophenyl-alkynyl-platinum(II)-complexes were synthesized and tested for nonlinear absorption of light. A palladium-copper mediated coupling (Sonogashira coupling) was utilized for all reactions between terminal alkynes and aryl halides. Molecular orbital calculations were used in order to screen for suitable properties, such as the second hyperpolarizability, in compounds of interest. A quantitative structure-activity relationship (QSPR) study using a PLS approach were performed in order to identify important molecular electronic variables for optical limiting of organic compounds.

In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content. First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME. Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface. Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance. A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size. Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures. In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.

Seed heteromorphism related to chasmogamous (CH) and cleistogamous (CL) seeds can have different ecological significance in species with different functional characteristics, competitive ability and palatability. Punagrass [<i>Achnatherum brachychaetum </i> (Godr.) Barkworth], an invasive, perennial grass is common in grasslands of Argentina and it is an aggressive weed in other parts of the world. <i>Flechilla grande</i> [<i>Nassella clarazii</i> (Ball) Barkworth] is a palatable perennial grass associated with the dominant "climax" vegetation in grasslands of Argentina. Seeds of the two grasses were collected from grasslands of Argentina, and growth chamber and greenhouse experiments were conducted to determine: 1) germination, dormancy breaking, and mass of CH and CL seeds of the two species 2) effects of contrasting range condition on germination and seed mass of punagrass, 3) the relative fitness of plants from CH and CL seeds, 4) if contrasting range condition affect fitness of CH plants of punagrass, and 5) the effect of maternal nutrient environments on CH and CL seeds and on fitness in the two species. Small CH seeds of high dispersal potential were less dormant than large CL seeds of low dispersal potential in punagrass. CH and CL seeds of flechilla grande had similar mass, germination, and response to dehulling. CL seed size and CL seed production of punagrass increased with good range condition. Increasing the maternal, nutrient environment enhanced germination of CH seeds, CL seed size, growth rate, development, biomass and seed production more in punagrass than flechilla grande. Under low nutrient conditions, flechilla grande produced a few large CH seeds. CH progeny of punagrass grew fast and developed rapidly as compared to CL progeny, which in turn produced many CH seeds. CH and CL seeds of flechilla grande had similar contribution to the fitness of adult plants. In both species, the ecological significance of having seed heteromorphism is that sibling competition is probably reduced by having more diverse offspring. Heavy grazing of competitive species such as flechilla grande may favours species as punagrass with many small CH seeds, high potential for colonization as well as large CL seeds for persistence in the seed bank and seedling competition.

Clinical management of esophageal adenocarcinoma (EAC) relies on radiation therapy, yet radioresistance is a pervasive challenge in this disease. The mechanisms of EAC radioresistance remain largely unknown due to a paucity of validated preclinical models. The present studies report on the development of seven primary xenograft models established from patient tumours. These models are used to interrogate the range of radiosensitivities and mechanisms of radioresistance in EAC tumours. We found that radiation enriches the tumour-initiating cell population in two xenograft lines tested. Furthermore, three tested xenograft lines respond to irradiation by upregulating Hedgehog transcripts, a pathway involved in stem cell maintenance and proliferation. Upregulation occurs in autocrine and paracrine patterns simultaneously, suggesting that Hedgehog signalling may have a complex role in the radioresponse of EAC tumours. These findings suggest that inhibiting stem cell pathways in combination with radiotherapy may have an important role in the clinical management of EAC.

In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content. First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME. Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface. Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance. A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size. Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures. In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.

Seed heteromorphism related to chasmogamous (CH) and cleistogamous (CL) seeds can have different ecological significance in species with different functional characteristics, competitive ability and palatability. Punagrass [<i>Achnatherum brachychaetum </i> (Godr.) Barkworth], an invasive, perennial grass is common in grasslands of Argentina and it is an aggressive weed in other parts of the world. <i>Flechilla grande</i> [<i>Nassella clarazii</i> (Ball) Barkworth] is a palatable perennial grass associated with the dominant "climax" vegetation in grasslands of Argentina. Seeds of the two grasses were collected from grasslands of Argentina, and growth chamber and greenhouse experiments were conducted to determine: 1) germination, dormancy breaking, and mass of CH and CL seeds of the two species 2) effects of contrasting range condition on germination and seed mass of punagrass, 3) the relative fitness of plants from CH and CL seeds, 4) if contrasting range condition affect fitness of CH plants of punagrass, and 5) the effect of maternal nutrient environments on CH and CL seeds and on fitness in the two species. Small CH seeds of high dispersal potential were less dormant than large CL seeds of low dispersal potential in punagrass. CH and CL seeds of flechilla grande had similar mass, germination, and response to dehulling. CL seed size and CL seed production of punagrass increased with good range condition. Increasing the maternal, nutrient environment enhanced germination of CH seeds, CL seed size, growth rate, development, biomass and seed production more in punagrass than flechilla grande. Under low nutrient conditions, flechilla grande produced a few large CH seeds. CH progeny of punagrass grew fast and developed rapidly as compared to CL progeny, which in turn produced many CH seeds. CH and CL seeds of flechilla grande had similar contribution to the fitness of adult plants. In both species, the ecological significance of having seed heteromorphism is that sibling competition is probably reduced by having more diverse offspring. Heavy grazing of competitive species such as flechilla grande may favours species as punagrass with many small CH seeds, high potential for colonization as well as large CL seeds for persistence in the seed bank and seedling competition.

For the aim of production of poly(ethylene terephthalate), PET based flame retardant composites / boron based flame retardant additives, 3.5 mole hydrated zinc borate and boron phosphate were synthesized. Zinc borate was synthesized with the reaction of boric acid and zinc oxide in both laboratory and pilot scale reactors. Effects of reaction parameters on kinetics of reaction and final product particle size were evaluated. Boron phosphate was synthesized via dry, wet and microwave methods. In addition to the synthesized flame retardant additives, several non-halogenated flame retardant additives, which were commercially available, were also used. Composites were prepared using twin screw extruder and molded by injection molding, followed by characterization in terms of flame retardancy behavior, mechanical and thermal properties, and morphologies. Based on the results of first stage experiments, aiming to determine effective additives, different amounts and combinations of triphenyl phosphate, triphenyl phosphine oxide, zinc borate and microwave produced boron phosphate were chosen and used in PET matrix. Flame retardancy of the composites were determined by conducting horizontal burning rate and limiting oxygen index (LOI) tests. Smoke emissions during fire were also measured. According to the LOI test results, LOI of neat PET was determined as 21%, and with the addition of 5% boron phosphate and 5% triphenyl phosphate together, LOI was increased up to 36%. The smoke density analysis results implied that, boron phosphate was a successful smoke suppressant for PET matrix. In addition to flammability properties, tensile and impact properties of the composites were also improved with flame retardant additives and expecially with the addition of triphenyl phosphate.