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This thesis describes a study of the aggregational behaviour of egg yolk lecithin (EYL), a natural lecithin, and bile salt mixtures especially with respect to an increase of the ionic strength of the solvent. Mixtures of two amphiphiles with very different spontaneous curvature as EYL lecithin and bile salt form mixed micelles and vesicles in aqueous solution. Their properties have been well-studied under physiological conditions, i.e. 150 mM electrolyte concentration and pH 7- 8, while other conditions are still hardly explored. Upon increasing ionic strength the formed structures and the transitional pathways (micelles, coexistence of micelles and vesicles, and vesicles) change the generated structures completely from those observed under physiological conditions. We quantitatively determined these structures formed in a broad range of electrolyte concentrations with various scattering techniques, x-ray, light and neutron scattering and calorimetry. With calorimetry, phase diagrams in the EYL and bile salt concentration phase plane were determined at various ionic strength ranging from physiological salt concentration to up to 1000 mM. Additionally a new electrochemical approach using functionalised electrodes, i.e. sensitive and selective to bile salt, and thus to control the bile salt concentration in solution (concentrations below the critical micellar concentration (cmc)) was attempted, since bile salt removal or injection drives the micelle-to-vesicle or the vesicle-to-micelle transition, respectively, of the mixed aggregational system of EYL/bile salt. Although this control was not achieved within the framework of this thesis, promising results show directions for future experiments.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / As emissÃes de gases poluentes devido à queima de combustÃveis fÃsseis sÃo as principais fontes emissoras de gases, tais como o CO2, que causam o efeito estufa. Neste Ãmbito, a remoÃÃo de CO2 por adsorÃÃo tem sido estudada como uma alternativa para atenuar os efeitos ao ambiente. Este estudo apresenta o projeto, montagem e validaÃÃo experimental de um sistema microcalorimÃtrico de adsorÃÃo para mediÃÃes simultÃneas de isotermas e calores de adsorÃÃo aplicados à caracterizaÃÃo de materiais adsorventes. A metodologia experimental dividiu-se em trÃs etapas: calibraÃÃo elÃtrica do microcalorÃmetro, montagem do sistema volumÃtrico de adsorÃÃo e mediÃÃes simultÃneas de equilÃbrio e curvas calorimÃtricas de adsorÃÃo de CO2 em adsorventes. O microcalorÃmetro foi calibrado eletricamente pelos mÃtodos do input elÃtrico e estado estacionÃrio. Contudo, somente o valor de constante de calibraÃÃo, K, obtido pelo input elÃtrico foi considerado nos cÃlculos de calores diferenciais de adsorÃÃo, uma vez que à mais representativo da resposta calorimÃtrica à adsorÃÃo de gases. O sistema volumÃtrico foi construÃdo em aÃo inoxidÃvel e, entÃo, calibrado para obter com precisÃo o nÃmero de moles adsorvidos em cada estÃgio de equilÃbrio. Finalmente, foram obtidas isotermas e calores diferenciais de adsorÃÃo de CO2 em adsorventes. As amostras foram previamente caracterizadas em relaÃÃo as suas propriedades texturais. O carbono ativado exibiu alta Ãrea superficial BET e alto volume microporos, que à caracterÃstico desta classe de materiais. O processo de funcionalizaÃÃo do zeÃlito 13X reduziu o valor de superfÃcie especÃfica em aproximadamente 16%, devido à obstruÃÃo parcial dos poros pela soluÃÃo de amina. Nos ensaios microcalorimÃtricos de adsorÃÃo, as curvas calorimÃtricas de CO2 a 273K para o zeÃlito 13X concordaram bem com os dados disponÃveis na literatura validando, pois, o sistema microcalorimÃtrico. A reprodutibilidade do sistema foi verificada atravÃs de experimentos de adsorÃÃo de CO2 a 273 K em carbono ativado. Para o zeÃlito 13X funcionalizado, a curva calorimÃtrica diferencial revelou que o processo de fisissorÃÃo à acompanhado pelo fenÃmeno de adsorÃÃo quÃmica devido à presenÃa da amina na superfÃcie do sÃlido. / Emissions of pollutant gases from the burning of fossil fuels are the main sources of gases such as CO2, which cause the greenhouse effect. In this context, the CO2 removal by adsorption has been studied as an alternative to reduce the effects to the environment. This study presents the design, assembly and experimental validation of a microcalorimetric adsorption system for simultaneous measurements of isotherms and heats of adsorption applied to the characterization of the adsorbent material. The experimental methodology was divided into three steps: the electric calibration of the microcalorimeter, the assembly of the volumetric adsorption system and the simultaneous measurements of the equilibrium and calorimetric curves of adsorption of CO2. The microcalorimeter was calibrated by the electrical input and the steady state methods. However, only the value of calibration constant, K, obtained by the electrical input was considered in the calculation of the differential heats of adsorption, because of it is more representative of the calorimetric response for the adsorption of gases. The volumetric system was constructed in stainless steel and then calibrated accurately to get the exact number of adsorbed moles at each equilibrium stage. Finally, it was obtained isotherms and differential heats of adsorption of CO2 on representative adsorbents. The samples were previously characterized for their textural properties. The activated carbon exhibited high BET surface area and micropore volume, which is characteristic of this type of material. The process of functionalization of the zeolite 13X has reduced the value of specific surface in approximately 16% due to the partial blockage of the pores by amine. In the microcalorimetric adsorption analysis, the calorimetric curves of CO2 at 273 K for the zeolite 13X agreed well with the available data in the literature, validating the microcalorimetric system. The reproducibility of the system was verified through experiments of adsorption of CO2 at 273 K on activated carbon sample. For the functionalized zeolite 13X, the differential calorimetric curve showed that the physisorption process is accompanied by the chemical adsorption phenomenon due to the presence of the amine on the surface of the solid.

Orientador: Claudio Airoldi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T06:00:07Z (GMT). No. of bitstreams: 1 Lima_IlaurodeSouza_D.pdf: 2562790 bytes, checksum: aa2ef4f0974aa06620a64c9745f925c7 (MD5) Previous issue date: 2005 / Doutorado / Quimica Inorganica / Doutor em Quimica

This diploma thesis deals with the use of thermal analysis in the study on effects of microbial inhibitors. The main aim of this work was to determine the utilization of the method, which is mainly used in different fields of science and research. Three bacterial strains: Cupriavidus necator H16, its mutant strain Cupriavidus necator PHB-4 and Halomonas halophila, were used as model microorganisms. The inhibitory effect of levulinic acid on growth and metabolic activity was monitored by microcalorimetry. It was found that bacteria were able to adapt to levulinic acid to a certain concentration - Cupriavidus necator to 5 g/l and Halomonas halophila to 2 g/l. The thermal analysis results were compared to a conventional method, which is commonly used to study the growth of microorganisms.

Les Metal-Organic Framework (MOF) sont des adsorbants très prometteurs pour la séparation des gaz. Formés de centres métalliques reliés par des ligands organiques, ces matériaux présentent une structure organisée avec des pores de taille contrôlée ainsi que des surfaces et des volumes poreux très élevées. La possibilité de faire varier à la fois le centre métallique et le ligand organique donne aux MOFs une très grande diversité qu'on ne retrouve pas chez les zéolithes et les charbons actifs.L'objectif de cette étude a été d'évaluer le potentiel des MOFs en tant qu'adsorbants pour quatre procédés de séparation de gaz. En raison du grand nombre de MOFs disponibles, il a été nécessaire d'élaborer une stratégie pour identifier les matériaux les plus prometteurs dans chaque cas. Cette méthodologie comprend quatre étapes : une étape de criblage, une étape expérimentale, une étape de calcul et une étape d'évaluation.Pour l'étape de criblage, un nouvel appareil dit « à haut débit » a été développé pour mesurer des isothermes approximatives. Ensuite, un certain nombre de matériaux ont été retenus pour faire une étude plus approfondie de leurs propriétés d'adsorption. Des isothermes très précises ont été mesurées par gravimétrie tandis que les enthalpies d'adsorption ont été obtenues par microcalorimétrie. Dans l'étape de calcul, le modèle IAST a été utilisée pour prédire les sélectivités à partir des données en gaz pur. Enfin, les adsorbants ont été classés à l'aide d'un nouveau paramètre de sélection qui regroupe la sélectivité, la capacité efficace et l'enthalpie d'adsorption, où l'importance de chacun des paramètres peut être ajustée en fonction des besoins du procédé. / Metal-Organic Frameworks (MOFs) are seen to be one of the most promising classes of adsorbents for gas separations. Consisting of metal clusters connected by organic linkers to form a fully crystalline network, these materials have record breaking surface areas and pore volumes as well as a wide variety of pore structures and sizes. This, coupled with the possibility to use virtually any transition metal as well as functionalized linkers, gives MOFs the chemical and physical versatility often lacking in traditional adsorbents such as zeolites and activated carbons.The purpose of this study was to evaluate the potential of MOFs as adsorbents for four gas separations of interest to the petrochemical industry. Because of the diversity and number of MOFs available, a methodology was needed to help identify the most promising materials in each case. The proposed methodology comprises four stages: a screening step, an experimental step, a computational step and finally an evaluation step. For the first stage, a high-throughput setup was developed to measure rough adsorption isotherms. A number of materials were then selected for a more thorough investigation of their adsorption properties. Highly accurate isotherms were measured gravimetrically while precise adsorption enthalpies were obtained by microcalorimetry. Step three involved predicting the co-adsorption behaviour from the pure gas isotherms using the Ideal Adsorbed Solution Theory. Finally, the adsorbents were ranked based on a new selection parameter regrouping selectivity, working capacity and adsorption enthalpy where the importance of each term can be adjusted depending on the requirements of the process.

This work was dedicated to quantify and distinguish the radio- and chemitoxic effects of environmentally relevant low doses of uranium on the metabolism of microorganisms and multicellular organisms by a modern and highly sensitive microcalorimetry. In such low-dose regime, lethality is low or absent. Therefore, quantitative assays based on survival curves cannot be employed, particularly for multicellular organisms. Even in the case of microbial growth, where individual cells may be killed by particle radiation, classical toxicity assessments based on colony counting are not only extremely time-consuming but also highly error-prone. Therefore, measuring the metabolic activity of the organism under such kinds of conditions would give an extremely valuable quantitative measure of viability that is based on life cell monitoring, rather than determining lethality at higher doses and extrapolating it to the low dose regime. The basic concept is simple as it relies on the metabolic heat produced by an organism during development, growth or replication as an inevitable byproduct of all biochemical processes. A metabolic effect in this concept is defined as a change in heat production over time in the presence of a stressor, such as a heavy metal. This approach appeared to be particular versatile for the low dose regime. Thus, the thesis attempted in this case to measure the enthalpy production of a bacterial population as a whole to derive novel toxicity concepts. In the following chapters, an introduction about the properties of ionizing radiation will be briefly presented, in addition to a review about the isothermal calorimetry and its application in studying the bacterial growth. Later in chapter 2, the effect of uranium on the metabolic activity of three different bacterial strains isolated form a uranium mining waste pile together with a reference strain that is genetically related to them will be investigated. Due to the lack of published dedicated calibration techniques for the interpretation of heat production of bacterial cells under the conditions of calorimetric recordings, additional experiments, thorough investigations of the effects of experimental conditions, have been carried out in order to guide the interpretation of calorimetric results. In chapter 3, the differentiation between chemi- and radiotoxicity of uranium has been addressed by isotope exchange, which was a key effort in this thesis as it opens new experimental approaches in radioecology. In chapter 4, through investigating the role of the tripeptide glutathione (GSH) in detoxifying uranium, it will be shown to which degree the intrinsically unspecific signal provided by metabolic heat can be related to highly specific metabolic pathways of an organism, when combined with genetic engineering. The demonstration of gaining molecule-specific information by life metabolic monitoring was another experimental challenge of this thesis and provides proof of principle that can be extended to many organisms. Finally in chapter 5, an attempt has been undertaken to establish a minimal food chain, in order to study the effects of the exposure of a multicellular organism to uranium through its diet.

Orientador: José de Alencar Simoni / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-18T09:26:47Z (GMT). No. of bitstreams: 1 Bertelli_AmandaCarolinaCovizzi_M.pdf: 2819233 bytes, checksum: 46d59767321577cc8d69294f0d62bb43 (MD5) Previous issue date: 2011 / Resumo: Este estudo investiga a influência de práticas agrícolas na atividade microbiana de solos, utilizando-se a calorimetria. Foram estudados solos sobre três diferentes condições de manejo. Os solos foram retirados da região de Pirassununga, Estado de São Paulo e são de condições: solo de mata natural, cultivado com citros e cultivado com cana-de-açúcar. As coordenadas: mata natural (21°56'33,54"S; 47°19'51,85"O), citros (21°56'25,14"S; 47°19'53,31"O) e cana-de-açúcar (21°56'35,25"S; 47°;9'54,64"O). O estudo calorimétrico corresponde ao registro da energia dissipada em função do tempo, utilizando-se glicose como substrato. As amostras de foram também caracterizadas por diversas análises químicas (teor de carbono, pH e acidez total), e biológica (contagem de microorganismos), além das técnicas térmicas como TGA e DSC. Os resultados de calorimetria evidenciam diferenças entre os diferentes manejos em relação a parâmetros como: eficiência de assimilação da matéria orgânica (hH), constante de crescimento microbiano (k), e a quantidade biomassa viva formada (DX). O valor de "peak time" obedeceu a ordem citros<cana-de-açúcar<mata natural, tanto aos 3, 8 meses ou 1 ano de coleta. Após a adição de fenol esses valores se tornaram mais próximos um dos outros e após a adição do 4-clorofenol esses valores se tornaram bem mais elevados, mas a ordem permaneceu inalterada. Os três tipos de solo apresentaram microorganismos capazes de metabolizar o fenol. Após a adição de fenol, houve um aumento da quantidade de energia desprendida para os três solos, quando se comparam os metabolismos de glicose. Consequentemente, houve uma diminuição da biomassa acumulada hH %, e um aumento da emissão de CO2. Após a adição de 4-clorofenol foi observado efeito térmico com a adição da glicose apenas para o solo de citros e mata natural e também foi observado um aumento da energia liberada em comparação à situação sem adição prévia de 4-clorofenol / Abstract: This study investigates the influence of agricultural practices on soil microbial activity, using calorimetry. Soils were studied under three different management conditions. The soils were obtained from the region of Pirassununga, State of São Paulo and the conditions are: soil of natural forests, cultivated with citrus and cultivated with sugarcane. The coordinates were: natural forest (21 ° 56'33,54 "S; 47 ° 19'51,85" O), citrus ((21 ° 56'25, 14 "S; 47 ° 19'53, 31" O) and sugarcane (21 ° 56'35, 25 "S; 47 ° 19'54, 64" O). The calorimetry study corresponds to the record of the dissipated energy versus time, using glucose as substrate. The samples were also characterized by various chemical analyses (carbon content, pH and total acidity) and biological (microbial count), and thermal techniques such as TGA and DSC. The calorimetric results revealed differences between the different management systems in relation to parameters such as efficiency of assimilation of organic matter (hH), microbial growth constant (k), living biomass formed and the amount (DX). The value of peak time obeyed the order citrus<sugarcane<natural forest, both at 3, 8 months and 1 year of collection. After the addition of phenol these values become closer to each other and after the addition of 4-chlorophenol these values became much higher, but the order remained unchanged. The three types of soil microorganisms were able to metabolize phenol. After the addition of phenol, there was an increased amount of energy given off by the three soils, when comparing the metabolism of glucose. Consequently, there was a decrease of the biomass, hH% and an increase in CO2 emissions. After addition of 4-chlorophenol a thermal effect waas observed with the addition of glucose only for the citrus and forest soils together an increasing of the energy given off when compared to the situation where the 4-chlorophenol waas not previously added / Mestrado / Físico-Química / Mestre em Química