Calmodulin (CaM) is a ubiquitous calcium-binding protein responsible for the binding and activation of a vast number of enzymes and signaling pathways. It contains two lobes that bind two calcium ions each, separated by a flexible central linker. This structural flexibility allows CaM to bind and regulate a large number of diverse protein targets within the cell in response to Ca2+ gradients. Voltage gated calcium channels (CaVs), as main sources of extracellular Ca2+, are crucial for a number of physiological processes, from muscle contraction to neurotransmission and endocrine function. These large transmembrane proteins open in response to membrane depolarization and allow gated entry of Ca2+ ions into the cytoplasm. Their regulation is currently the subject of intense investigation due to its pharmacological and scientific importance. CaM has been previously shown to pre-associate and act as a potent inhibitor of one class of high-voltage activated (HVA) channels called L-type channels via its interaction with their C-terminal cytoplasmic region. This interaction is primarily mediated by a conserved CaM-binding motif called the ‘IQ’ motif (for conserved isoleucine and glutamine residues), although the exact molecular details of its involvement in inactivation are currently unclear. Elucidation of these details was the primary objective of this dissertation. Recently, a novel sequence motif within this channel called ‘NSCaTE’ (N-terminal spatial calcium transforming element) has been described as an important contributor to calcium-dependent inactivation (CDI) of L-type channels. It was presumed to be unique to vertebrates, but we also show its conservation in a distantly related L-type channel homolog of Lymnaea stagnalis (pond snail). The interaction of CaM with a number of peptides representing the different regulatory motifs (IQ and NSCaTE) for both mammalian and snail isoforms was characterized in an attempt to better understand their role in CDI. Biophysical work with peptides as well as electrophysiology recordings with an N-terminal truncation mutant of Lymnaea CaV1 homolog were performed to expand our understanding of how the interplay between these channel elements might occur. In brief, the most striking feature of the interaction concerns the strong evidence for a CaM-mediated bridge between the N- and C-terminal elements of L-type channels. Further investigation of the CaM interaction with both IQ and NSCaTE peptides using Ca2+-deficient CaM mutants reveals a preference of both peptides for the Ca2+-C-lobe of CaM, and a much higher affinity of CaM for the IQ peptide, suggesting that the N-lobe of CaM is the main interaction responsible for the physiological effects of NSCaTE. These results are consistent with our electrophysiology findings that reveal a distinct buffer-sensitive CDI in wild type LCaV1 that can be abolished by the N-terminal truncation spanning the NSCaTE region. In addition to L-type channels, CaM has also been shown to have an indirect role in the regulation of low-voltage activated (LVA) or T-type channels (CaV3.x), via their phosphorylation by CaM-dependent protein kinase II (CaMKII). Using a primary sequence scanning algorithm, a CaM-binding site was predicted in a cytoplasmic region of these channels that was also previously shown to be important in channel gating. Biophysical experiments with synthetic peptides spanning this gating brake region from the three human and the single Lymnaea isoform strongly suggest that there is a novel, bona fide CaM interaction in this channel region, and also hint that this interaction may be a Ca2+-dependent switch of some sort. The results confirm a possible new role for CaM in the direct regulation of these channels, although the exact mechanism remains to be elucidated.

The aim of this study was to investigate the molecular interactions of the anti-cancer drug Doxorubicin (DOX) with poly(methacrylic acid) grafted starch nanoparticles (PMAA-g-St). In order to fully understand the DOX/PMAA-g-St system, we conducted in-depth studies on DOX dimer dissociation and DOX/PMAA-g-St binding interactions using various techniques such as isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and fluorescence and absorption spectroscopy. Based on our experimental results, we developed a quantitative thermodynamic model with relevant parameters such as dissociation constant, Kd, as well as enthalpy of binding, ΔH, in order to explain DOX/PMAA-g-St interactions. In addition, we also studied the effect of environmental factors such as pH and NaCl on DOX self-association and DOX/PMAA-g-St complex formation. In conclusion, the combination of results obtained from various techniques as well as the multispecies equilibrium model, enables us to interpret quantitatively the data of drug loading onto and release from polymeric nanoparticles.

The persistence and propagation of bacterial antibiotic resistance presents significant challenges to the treatment of drug resistant bacteria with current antimicrobial chemotherapies, while a dearth in replacements for these drugs persists. The thiopeptide family of antibiotics may represent a potential source for new drugs and thiostrepton, the prototypical member of this antibiotic class, is the primary subject under study in this thesis. Using a facile semi-synthetic approach novel, regioselectively-modified thiostrepton derivatives with improved aqueous solubility were prepared. In vivo assessments found these derivatives to retain significant antibacterial ability which was determined by cell free assays to be due to the inhibition of protein synthesis. Moreover, structure-function studies for these derivatives highlighted structural elements of the thiostrepton molecule that are important for antibacterial activity. Organisms that produce thiostrepton become insensitive to the antibiotic by producing a resistance enzyme that transfers a methyl group from the co-factor S-adenosyl-L-methionine (AdoMet) to an adenosine residue at the thiostrepton binding site on 23S rRNA, thus preventing binding of the antibiotic. Extensive site-directed mutagenesis was performed on this enzyme to generate point mutations at key active site residues. Ensuing biochemical assays and co-factor binding studies on these variants identified amino acid residues in the active site that are essential to the formation of the AdoMet binding pocket and provided direct evidence for the involvement of an active site arginine in the catalytic mechanism of the enzyme. Certain bacteria that produce neither thiostrepton nor the resistance methyltransferase express the thiostrepton binding proteins TIP-AL and TIP-AS, that irreversibly bind to the antibiotic, thereby conferring resistance by sequestration. Here, it was found that the point mutation of the previously identified reactive amino acid in TIP-AS did not affect covalent binding to the antibiotic, which was immediately suggestive of a specific, high affinity non-covalent interaction. This was confirmed in binding studies using chemically synthesized thiostrepton derivatives. These studies further revealed structural features from thiostrepton important in this non-covalent interaction. Together, these results indicate that thiostrepton binding by TIP-AS begins with a specific non-covalent interaction, which is necessary to properly orient the thiostrepton molecule for covalent binding to the protein. Finally, the synthesis of a novel AdoMet analogue is reported. The methyl group of AdoMet was successfully replaced with a trifluoromethyl ketone moiety, however, the hydrated form (germinal diol) of this compound was found to predominate in solution. Nevertheless, the transfer of this trifluoroketone/ trifluoropropane diol group was demonstrated with the thiopurine methyltransferase.

The interaction between two 6 kDa proteins has been investigated. The studied complex of micromolar affinity (Kd) consists of the Z domain derived from staphylococcal protein A and the related protein ZSPA-1, belonging to a group of binding proteins denoted affibody molecules generated via combinatorial engineering of the Z domain. Affibody-target protein complexes are good model systems for structural and thermodynamic studies of protein-protein interactions. With the Z:ZSPA-1 pair as a starting point, we determined the solution structure of the complex and carried out a preliminary characterization of ZSPA-1. We found that the complex contains a rather large (ca. 1600 Å2) interaction interface with tight steric and polar/nonpolar complementarity. The structure of ZSPA-1 in the complex is well-ordered in a conformation that is very similar to that of the Z domain. However, the conformation of the free ZSPA-1 is best characterized by comparisons with protein molten globules. It shows a reduced secondary structure content, aggregation propensity, poor thermal stability, and binds the hydrophobic dye ANS. This molten globule state of ZSPA-1 is the native state in the absence of the Z domain, and the ordered state is only adopted following a stabilization that occurs upon binding. A more extensive characterization of ZSPA-1 suggested that the average topology of the Z domain is retained in the molten globule state but that it is represented by a multitude of conformations. Furthermore, the molten globule state is only marginally stable, and a significant fraction of ZSPA-1 exists in a completely unfolded state at room temperature. A complete thermodynamic characterization of the Z:ZSPA-1 pair suggests that the stabilization of the molten globule state to an ordered three helix structure in the complex is associated with a significant conformational entropy penalty that might influence the binding affinity negatively and result in an intermediate-affinity (µM) binding protein. This can be compared to a dissociation constant of 20-70 nM for the complex Z:Fc of IgG where Z uses the same binding surface as in Z:ZSPA-1. Structure analyses of Z in the free and bound state reveal an induced fit response upon complex formation with ZSPA-1 where a conformational change of several side chains in the binding surface increases the accessible surface area with almost 400 Å2 i.e. almost half of the total interaction surface in the complex. Two cysteine residues were introduced at specific positions in ZSPA-1 for five mutants in order to stabilize the conformation of ZSPA-1 by disulfide bridge formation. The mutants were thermodynamically characterized and the binding affinity of one mutant showed an improvement by more than a factor of ten. The improvement of the introduced cysteine bridge correlates with an increase in binding enthalpy rather than with entropy. Further analysis of the binding entropy suggests that the conformational entropy change in fact is reduced but its favorable contribution is opposed by a less favorable desolvation enthalpy change. These studies illustrate the structural and thermodynamic complexity of protein-protein interactions, but also that this complexity can be dissected and understood. In this study, a comprehensive characterization of the ZSPA-1 affibody has gained insight into the intricate mechanisms involved in complex formation. These theories were supported by the design of a ZSPA-1 mutant with improved binding affinity. / QC 20100924

Dans ce travail, un moteur Stirling de type Gamma alimenté par énergie solaire avec une faible différence de température a été étudié numériquement et expérimentalement. Un nouveau modèle appelé Polytropic Stirling Model with Losses (PSML) a été proposé et appliqué au moteur GPU-3 Stirling. Un cryoréfrigérateur basé sur un moteur Stirling intégral de type Alpha a été étudié numériquement, après avoir mesuré ses dimensions géométriques au laboratoire. Pour le moteur Stirling de type gamma du laboratoire, le modèle ait thermodynamique à vitesse finie et le modèle isotherme a été développé, incluant les bilans de masse et d’énergie à travers les différents volumes (compression, régénération et expansion) dans le moteur. Différents types de pertes thermiques et mécaniques ont été considérés dans le modèle afin d'analyser les processus thermodynamiques et les pertes dans le moteur Stirling. En outre, des études paramétriques sur les performances du moteur Stirling alimenté à l’énergie solaire ont également été étudiées expérimentalement et numériquement. La comparaison entre les résultats expérimentaux et les résultats de simulation à différents déphasages entre le déplaceur et le piston, et à différentes course de piston montre que le modèle est convaincant dans la prédiction des performances du moteur Stirling. Basé sur la méthode thermodynamique en dimension physique finie, une méthode d’algorithme génétique multi-objectives, objectifs étant la puissance fournie, le rendement énergétique et le taux de génération d'entropie a été utilisé pour optimiser la fonction et la géométrie du moteur du type Gamma. En comparant avec la méthode d'optimisation écologique, la méthode multi-objectif permet de mieux équilibrer les trois objectifs. Le nouveau modèle (PSML) proposé pour prédire les performances du moteur de type Bêta ou Gamma du moteur Stirling, il divise l'espace de travail en 5 parties (volume de compression, refroidisseur, régénérateur, chauffage et volume d'extension). Une liaison entre volume de compression et volume d'extension a été ajoutée dans le modèle adiabatique classique du moteur Stirling. Ainsi, des processus polytropiques ont été considérés dans les volumes de compression et d'expansion du moteur Stirling. Le moteur Stirling GPU-3 a été utilisé pour valider le nouveau modèle. Il a été démontré que le nouveau modèle (PSML) prédit correctement la puissance de sortie et le rendement du moteur. Dans la dernière partie de la thèse, un Cryorefroidisseur Stirling de type Alpha, a été étudié en utilisant un modèle isotherme prenant en considération différentes pertes. Les volumes de compression et d'expansion sont considérés isothermes, et la variation de la température du régénérateur est considéré linéaire. Les bilans d'énergie et d'exergie du Cryorefroidisseur ont été réalisés, et l'effet de divers paramètres sur la performance (puissance de refroidissement et puissance mécanique consommée) est étudié. Les résultats de la simulation pour PPG-102 Stirling cryocooler ont été comparés avec deux autres résultats de simulation de la littérature et des résultats expérimentaux indiquant que ce modèle est convaincant pour prédire la performance du Cryorefroidisseur. / In this work a solar powered low temperature difference Gamma type Stirling engine has been studied experimentally and numerically using an isothermal model coupled with various losses and using an objective optimization. A new model named Polytropic Stirling Model with Losses (PSML) has been proposed which was applied to the Beta type GPU-3 Stirling engine. An Alpha type integral Stirling cryocooler has been studied numerically using an isothermal model with losses. To study a Gamma type Stirling engine of our laboratory, an isothermal model coupled with finite speed method has been developed, including mass and energy balances through different spaces of the engine. The engine is divided into 3 volumes: compression volume, regeneration volume, and expansion volume. Different kind of thermal and mechanical losses have been considered in the model, in order to analyze thermodynamic processes and losses in the Stirling Engine. In addition, parameter effects on the performance of the solar powered gamma type Stirling engine have also been studied experimentally and numerically. The comparison between the experimental results and the simulation results at different phase shift between the displacer and the piston, and at different piston stroke shows that the model is convincing to predict the Stirling engine performance. Based on the Finite Physical Dimensional Thermodynamic method, a multi-objective genetic method considering output power, thermal efficiency and entropy generating rate as objective functions simultaneously, has been used to multi-objective optimize the Gamma type Stirling engine. Comparing with the ecological optimization method, the multi-objective method can better balance the three objective goals. The new model (PSML) proposed in the thesis for predicting performance of Beta or Gamma type of Stirling engine divides the working space into 5 parts (compression volume, cooler, regenerator, heater, and expansion volume). A bypass linking compression volume and expansion volume has been added in the classic adiabatic model of Stirling engine. Thus, polytropic processes have been considered in the compression and expansion volumes of the Stirling engine. The GPU-3 Stirling engine has been used to validate the new model. It was shown that the new model (PSML) predict well the output power and the thermal efficiency of the engine well. An isothermal model considering various losses was developed and presented in the last part of this thesis to study an Alpha type Stirling cryocooler, whose geometrical dimensions were measured in our laboratory. The compression and expansion volumes are supposed to be isothermal, the variation of the regenerator temperature is supposed to be linear. Energy and exergy balances of the cryocooler were developed. The effect of various parameters on the cryocooler performance (cooling power and input power) are investigated. The simulation results for PPG-102 Stirling cryocooler were compared with two other simulation results of the literature and with experimental results which indicated that this model is convincing to predict the performance of the Stirling cyocooler

Les bâtiments résidentiels et industriels munis d’un réseau de ventilation constituent des installations complexes, susceptibles d’être le siège de transferts de masse et d’énergie, selon les situations de fonctionnement. Afin d’étudier ces transferts de masse, une méthodologie permettant d’établir des expérimentations à échelle réduite pour l’étude des écoulements anisothermes a été développée. Cette méthodologie a été validée numériquement, puis appliquée à une configuration de référence, représentative du principe de fonctionnement des réseaux de ventilation qui sont rencontrés dans le domaine nucléaire. Les influences du vent et des phénomènes thermiques sur les transferts de masse au sein de cette configuration ont été étudiées dans la soufflerie climatique Jules Verne du CSTB pour différentes situations de fonctionnement du réseau de ventilation (ventilation en fonctionnement normal, arrêt de la ventilation ou régime de sauvegarde) et des scénarios de dégagement de chaleur. Ces sources thermiques peuvent être issues d’un processus industriel ou d’un incendie. Elles ont été reproduites expérimentalement par une injection d’hélium. Les effets des sources thermiques couplées ou non au vent sur les pertes ponctuelles ou totales du confinement des locaux ont été mis en évidence et analysés. La robustesse du code à zones SYLVIA, utilisé notamment pour appuyer les évaluations de sûreté des installations nucléaires, a été analysée à partir des résultats expérimentaux. La prise en compte des phénomènes physiques observés expérimentalement a été validée. Les inversions des débits de fuite causées par les phénomènes thermiques ont été reproduites avec le code SYLVIA. Une comparaison entre les calculs où la source de chaleur a été simulée avec une injection d’hélium et avec une puissance thermique a permis d’observer l’impact de l’injection de masse causé par l’hélium sur les pressions, les débits et les températures. / Residential and industrial buildings equipped with a ventilation system are complex facilities, where heat and mass transfers could occur according to the operating conditions. In order to study these mass transfers, a methodology has been developed to reduced-scale experimentations for non isothermal flows study. This methodology has been numerically validated, and then applied to a standard configuration, representing of the ventilation systems operating principle which are encounter in the nuclear field. The wind and the thermal phenomena influences on the mass transfers inside this configuration have been studied in the Jules Verne climatic wind tunnel of the CSTB for various operating ventilation system situations (normal operating ventilation system, stopping ventilation or protection rate of productivity) and scenarios of heat supply. These thermal sources can be generated by an industrial process or a fire. They have been reproduced experimentally with an helium injection. The effects of the heat sources coupled or not with wind on loss of building containment were highlighted and analyzed. The reliability of the zonal code SYLVIA, used notably to support safety assessment in nuclear buildings, has been analyzed from these experimental results. The modelling of the physical phenomena experimentally observed has been validated. The leakage flowrates reversals have been retrieved with the SYLVIA code. A comparison between the calculations where the heat source has been simulated with an helium injection and with a thermal power permitted to observe the mass injection effect has been caused by the helium on the pressures, the flowrates and the temperatures.

L’objectif de cette thèse est d’étudier les interactions entre polyélectrolytes (PE) de charges opposées par analyse frontale continue en électrophorèse capillaire (FACCE) et par titration calorimétrique isotherme (ITC), en fonction de la force ionique du milieu et des paramètres physico-chimiques relatifs aux deux partenaires (taux de charge chimique, masse molaire, ramification). Un copolymère statistique d’acrylamide et de 2-acrylamido-2-méthyl-propane sulfonate (PAMAMPS) de taux de charge variant entre 15% et 100% a été synthétisé et caractérisé pour cette étude. En tant que polycation modèle, la poly(L-lysine) a été retenue, sous sa forme linéaire (PLL) ou ramifiée / hyperbranchée (DGL). Des mesures par turbidimétrie ont permis d’étudier la stabilité des complexes de polyélectrolytes (PEC) en fonction de la force ionique du milieu. La détermination de la stœchiométrie des PEC par 1H-RMN a permis d’établir une règle générale pour prédire les stœchiométries de charge des PEC. Les paramètres thermodynamiques d’interactions (constantes et stœchiométries d’interaction, contribution entropique et enthalpique) ont été déterminés, par le tracé systématique des isothermes d’adsorption, en considérant le modèle d’interactions des sites indépendants de même énergie. Une dépendance linéaire entre le logarithme des constantes d’interactions et le logarithme de la force ionique a été observée. Cette dépendance en force ionique confirme le caractère entropique des interactions entre PE de charges opposées. Elle permet aussi de quantifier le nombre de contre-ions relargués lors de la formation du PEC. Cette quantité de contre-ions libérés a pu être comparée à la quantité totale de contre-ions condensés. Cette modélisation permet, en outre, de prédire les constantes d’interaction pour des taux de charge intermédiaires et à différentes forces ioniques. / The aim of this thesis is to study the interactions between oppositely charged polyelectrolytes (PE) by frontal analysis continuous capillary electrophoresis (FACCE) and isothermal titration calorimetry (ITC) as a function of the ionic strength of the medium and the physico-chemical properties related to the two partners (chemical charge density, molar mass, ramification). Statistical copolymers of acrylamide and 2-acrylamido-2-methyl-propane sulfonate (PAMAMPS) with chemical charge densities varying between 15% and 100% were synthesized and characterized for this study. Poly(L-lysine) under their linear (PLL) or ramified/hyperbranched (DGL) forms were used as model polycations. Turbidity measurements allowed the study of the stability of the polyelectrolyte complexes (PEC) as a function of the ionic strength of the medium. PEC charge stoichiometries were measured by 1H-NMR, and a general predictive rule that estimates the PEC charge stoichiometry was enounced. The thermodynamic binding parameters (binding constant, stoichiometry, enthalpic and entropic contributions) were determined, by systematically plotting the isotherms of adsorption, and using the model of independent and identical interacting sites. A linear dependence between the logarithm of the binding constants and the logarithm of the ionic strength was observed. This linear dependence confirmed the entropic character of the interactions between oppositely charged PE and allowed quantifying the number of released counter-ions that were compared to the total number of condensed counter-ions. Furthermore, this modelling allowed predicting the binding constants for intermediate chemical charge densities and at different ionic strengths.

Submitted by CAMILA MARIA ANDRADE DOS SANTOS null (camilaandr@gmail.com) on 2016-09-08T21:45:05Z No. of bitstreams: 1 Tese Camila Maria Andrade dos Santos.pdf: 6338259 bytes, checksum: b6c2f381dc20c8377b2481a922179786 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-09-12T21:19:54Z (GMT) No. of bitstreams: 1 santos_cma_dr_araiq.pdf: 6338259 bytes, checksum: b6c2f381dc20c8377b2481a922179786 (MD5) / Made available in DSpace on 2016-09-12T21:19:54Z (GMT). No. of bitstreams: 1 santos_cma_dr_araiq.pdf: 6338259 bytes, checksum: b6c2f381dc20c8377b2481a922179786 (MD5) Previous issue date: 2016-08-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho os efeitos da variação da concentração de Al sobre as transformações de fase e as propriedades mecânicas das ligas Cu-7%Al-10%Mn-3%Ag, Cu-10%Al-10%Mn- 3%Ag e Cu-11%Al-10%Mn-3%Ag foram estudadas utilizando-se metalografia por microscopias óptica (MO), eletrônica de varredura (MEV) e eletrônica de transmissão (MET), calorimetria exploratória diferencial (DSC), difratometria de raios X (DRX), ensaios de tensão-deformação, análise por dispersão de energias de raios X (EDXS), medidas de variação da resistividade elétrica com a temperatura e medidas de variação da microdureza com a temperatura e o tempo de envelhecimento. Os resultados obtidos para as ligas inicialmente submetidas a tratamento térmico de recozimento e inicialmente submetidas a tratamento térmico de têmpera mostraram que o aumento de 7 para 9%Al não modifica o comportamento térmico e a dureza das ligas Cu-7%Al-10%Mn-3%Ag e liga Cu-9%Al- 10%Mn-3%Ag, pois as curvas obtidas apresentaram o mesmo perfil, indicando que elas passam pelas mesmas transições. Porém, o aumento de 9 para 11%Al provoca uma mudança nas transformações pelas quais a liga passa, modificando assim o seu comportamento térmico e os valores da microdureza. Nas ligas inicialmente recozidas foi possível notar a ocorrência da decomposição espinodal em decorrência da retenção das fases 1 e 3 durante o resfriamento lento das amostras. Os resultados obtidos a partir das ligas submetidas a tratamento térmico de envelhecimento mostraram que aumento da dureza durante este processo está principalmente relacionado à precipitação bainítica. A partir das curvas de variação da microdureza com o tempo de envelhecimento foi possível obter os parâmetros cinéticos (n, k e Ea), utilizando-se as equações de Johnson-Mehl-Avrami-Kolmogorov (JMAK) e Arrhenius. Os valores de energia de ativação obtidos mostraram que o aumento na concentração de Al diminui Ea para o processo de precipitação. A diminuição destes valores deve estar associada principalmente à ocorrência da reação de precipitação de uma fase rica em Ag, que deve ocorrer com razoável intensidade na liga com 7%Al e vai diminuindo até não mais ser detectada na liga contendo 11%Al. Os resultados obtidos pelos testes de tensãodeformação indicaram que as ligas com maior teor de Al são mais frágeis. / In this work, the effects of changes in the Al concentration on the phase transformations and the mechanical properties of the Cu-7%Al-10%Mn-3% Ag, Cu-10%Al-10%Mn-3%Ag and Cu-11%Al-10%Mn-3% Ag alloys were studied using metallography by optical microscopy (OM), scanning electron microscopy (SEM) and electronic transmission mycroscopy (TEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), stress-strain tests, analysis by X-ray energy dispersing (EDXS), measurements of the variation of electrical resistivity with temperature and microhardness changes measurements with temperature and aging time. The results obtained for alloys initially annealed and initially quenched showed that the increase from 7 to 9% Al does not modify the thermal behavior and hardness of the Cu-7%Al- 10%Mn-3%Ag and Cu-9%Al-10%Mn-3%Ag alloys. However, the increase from 9 to 11%Al causes a change on the transformations of the alloys, thereby modifying their thermal behavior and values of microhardness. In the annealed alloys it was possible to notice the occurrence of the spinodal decomposition due to the retention of 1 and 3 phases during the slow cooling of the samples. The results obtained from aged alloys showed that the hardness increasing observed during this process is mainly related to bainitic precipitation. The isothermal ageing kinetics for this precipitation was studied considering four different ageing temperatures and the kinetic parameters n, k and Ea were obtained using the Johnson-MehlAvrami-Kolmogorov (JMAK) and the Arrhenius equations. The results showed that the increase on the Al concentration decreases the activation energy values for the precipitation process. This should be mainly associated with the occurrence of the precipitation reaction of an Ag-rich phase, that should occur with reasonable intensity in the alloy with 7%Al and decreases until it is no longer detectable in the alloy containing 11%Al. The results obtained for stress-strain testing indicated that the increase in the Al content increases the fragility of the alloys.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:25:12Z No. of bitstreams: 0 / Made available in DSpace on 2017-10-27T12:25:12Z (GMT). No. of bitstreams: 0 / Nas ultimas décadas o processo de biossorção tem alcançado grande relevância no tratamento de efluentes contendo metais potencialmente tóxicos. O uso de bactérias nesse processo tem obtido destaque, uma vez que possuem inúmeras vantagens. O presente estudo pretendeu avaliar o mecanismo envolvido no processo de biossorção dos íons Pb(II) e Hg(II) por meio das linhagens Cupriavidus metallidurans (CH34) e Cupriavidus metallidurans (CH34/pCM3). Dentre os modelos estudados a isoterma de Langmuir foi a que melhor se ajusta ao processo de adsorção, apresentando uma capacidade máxima de adsorção (qmax) de 0,98 mg.g-1 para o Hg(II) e 86,2 mg.g-1 para o Pb(II), para a linhagem selvagem. Já para a linhagem recombinante o qmax obtido foi 3,4 mg.g-1 para o mercúrio e 172,4mg g-1 para o chumbo. Baseado nos valores referentes à energia livre de Gibbs (ΔG) o processo de retenção ocorreu de forma química e espontânea. A influencia do pH foi avaliada por meio de estudo competitivo entre os íons metálicos, em níveis equimolares. O valor que melhor contemplou a adsorção para ambos os íons foi o pH 7,0, tendo o Pb(II) demonstrado maior capacidade de retenção. Em pH 2,0 houve maior retenção do Hg (II), já em pH 10,0 o Pb(II) obteve maior retenção. Indicando que o meio influencia diretamente na competição dos íons metálicos pelos sítios ativos. Constatou-se que a retenção do metal é robusta e estável ao longo de 6 meses. Os resultados indicam que a Cupriavidus metallidurans (CH34/pCM3) pode ser uma boa opção para biossorção de íons metálicos por meio de biorreator. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Submitted by Erika Demachki (erikademachki@gmail.com) on 2014-10-23T17:14:40Z No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2014-10-23T18:50:27Z (GMT) No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-10-23T18:50:27Z (GMT). No. of bitstreams: 2 Dissertação - Mário Henrique Gomes Brito - 2013.pdf: 6257761 bytes, checksum: 3ff568c727b44a8a7e645c8475216a03 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2013-04-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The overall objective of this research, which was essentially experimental, is to study the influence of the isothermal period and the maximum temperature of the thermal cure cycle steam under atmospheric pressure in the development of compressive strength of concrete blocks over time. The influences of two other types of curing are also being investigated; curing by enveloping with plastic sheet and open air curing, considered the last case scenario for reference. This study specifically aimed to further our understanding on how to; a) evaluate and quantify the importance of adopting procedures for curing the average resistance (Fbm) and characteristic (fbk) strength to compression of concrete blocks, comparing the processes of thermal curing and curing by enveloping plastic sheet to open air curing; b) evaluate statistically the aging effect of blocks over its compressive strength; c) evaluate the interaction effects of the variables "type of cure" and "age analysis" of the results of compressive strength of concrete blocks; and d) identify the main changes in the microstructure of the blocks subjected to a thermal curing process, especially observing eventual delayed ettringite formation in the internal structure of the material. To examine the influence of maximum curing temperature, two levels were adopted; 65°C and 85°C. As for analyzing the influence of isothermal period, three levels were adopted; 3 hours, 4 hours and 5 hours. The age analysis was evaluated in five levels; 1, 3, 7, 28 and 91 days. The results showed that the worst condition for curing, or curing type, was the open air curing (curing time approximately equal to 24 hours), which led to a lower overall average result of compressive strength of concrete blocks, proving the importance of adopting procedures of curing to optimize the mechanical performance of concrete blocks. Furthermore, it was also determined that the best curing conditions were the curing with enveloping plastic sheet (curing time approximately equal to 24 hours) and the thermal curing with steam under atmospheric pressure isotherm of 65°C and isothermal period of 3 hours (curing time approximately equals 8.5 hours), which were considered statistically equal. It was also observed that there was no significant influence of the curing in maximum temperature in relation to the compressive strength of the blocks. In the other hand, the isothermal period was very significant; the best condition was 3 hours, while 4 hours and 5 hours were considered statistically equal. Regarding the delayed ettringite formation, it was only verified for thermal curing conditions of isothermal of 85°C and isothermal period of 4 hours and 5 hours. / O objetivo geral desta pesquisa, de caráter essencialmente experimental, é estudar a influência do período isotérmico e da temperatura máxima do ciclo de cura térmica a vapor sob pressão atmosférica no desenvolvimento da resistência à compressão de blocos de concreto ao longo do tempo. Paralelamente, foram investigadas ainda as influências de dois outros tipos de cura, a saber: cura por envelopamento com lona plástica e cura ao ar livre, considerada esta última a situação de referência. De modo específico, o estudo visou ainda: a) avaliar e quantificar a importância da adoção de procedimentos de cura nas resistências média (fbm) e característica (fbk) à compressão de blocos de concreto, comparando os processos de cura térmica e cura por envelopamento com lona plástica com a cura ao ar livre; b) avaliar estatisticamente o efeito da idade dos blocos sobre a sua resistência à compressão; c) avaliar a interação dos efeitos das variáveis “tipo de cura” e “idade de análise” sobre os resultados de resistência à compressão dos blocos de concreto; e d) identificar as principais transformações ocorridas na microestrutura dos blocos submetidos aos processos de cura térmica, em especial observando eventual formação de etringita tardia na estrutura interna do material. Para analisar a influência da temperatura máxima de cura, foram adotados dois níveis: 65°C e 85°C. Já para analisar a influência do período isotérmico, foram adotados três níveis: 3 horas, 4 horas e 5 horas. Por sua vez, a idade de análise foi avaliada em cinco níveis: 1, 3, 7, 28 e 91 dias. Os resultados mostraram que a pior condição de cura, ou seja, o tipo de cura que conduziu ao menor resultado médio global de resistência à compressão dos blocos de concreto, foi a cura ao ar livre (tempo de cura aproximadamente igual a 24 horas), comprovando a importância da adoção de procedimentos de cura para a otimização do desempenho mecânico dos blocos de concreto. Além disso, foi verificado ainda que as melhores condições de cura foram a cura por envelopamento com lona plástica (tempo de cura aproximadamente igual a 24 horas) e a cura térmica a vapor sob pressão atmosférica com isoterma de 65°C e período isotérmico de 3 horas (tempo de cura aproximadamente igual a 8,5 horas), os quais foram considerados, estatisticamente, iguais. Também foi verificado que não houve influência significativa da temperatura máxima de cura em relação à resistência à compressão dos blocos. Já o período isotérmico foi significativo, de modo que a melhor condição foi 3 horas, enquanto 4 horas e 5 horas foram considerados, estatisticamente, iguais. Quanto à formação de etringita tardia, esta só foi verificada para as condições de cura térmica com isoterma de 85°C e períodos isotérmicos de 4 horas e 5 horas.