O presente estudo teve por objetivo estudar as adaptações hemodinâmicas, autonômicas e morfofuncionais cardíacas em ratos hipertensos (SHR) submetidos à estimulação colinérgica crônica, com 2 dosagens diferentes (5 e 15 mg), e associar ao treinamento físico aeróbio, utilizando diferentes enfoques: 1. Avaliação do balanço autonômico tônico da frequência cardíaca (FC) por meio do bloqueio farmacológico com atropina e propranolol; 2. Estudo do balanço autonômico fásico (variabilidade) da FC (intervalo de pulso) e pressão arterial por meio da análise espectral; 3. Análise da sensibilidade barorreflexa por meio da administração de múltiplas e aleatórias doses de fenilefrina e nitroprussiato de sódio; 4. Avaliação ecocardiográfica bidimensional. Para tanto foram utilizados 54 ratos, divididos 2 grandes grupos: treinados (n=27) e sedentários (n=27). Os animais que treinaram, deram inicio ao experimento na 18ª semana de vida, na qual tinha duração de 10 semanas; logo em seguida, os ratos eram colocados em tratamento com brometo de piridostigmina por mais 2 semanas, na 30ª semana, os ratos eram submetidos a cirurgia de canulação, para posterior análise da pressão arterial, da FC, da variabilidade da frequência cardíaca (VFC) e da variabilidade da pressão arterial (VPAS). Antecedente a cirurgia, os ratos eram levados para o exame de ecocardiografia bidimensional para análise da morfofuncionalidade cardíaca. Foram consideradas estatisticamente significantes as diferenças em que p for menor que 5%. Os resultados mostraram uma diminuição dos valores de PAS, PAD e PAM, além de diminuir a FC basal e a FC intrínseca nos ratos tratados com 5 e 15 mg de brometo, tanto sedentários quanto tratados. Também houve um aumento de LF (ms2) e uma diminuição de HF (ms2), mostrando melhora na condição autonômica cardíaca. Os principais achados na morfofuncionalidade sugerem um aumento da FE, VE, DC, IC e VDF e VSF, além de observarmos um aumento tanto da área, quanto da espessura do ventrículo esquerdo nos ratos tratados e treinados. Dessa forma, podemos concluir que o tratamento com brometo de piridostigmina foi eficaz quanto aos valores hemodinâmicos, quanto a alguns parâmetros morfofuncionais e quanto à avaliação autonômica cardíaca, sugerindo ser uma boa terapia farmacológica para o tratamento da hipertensão, entretanto, uma investigação mais aprofundada deve ser realizada para um entendimento melhor dos efeitos. Da mesma forma, que o treinamento físico aeróbio promoveu modificações benéficas aos parâmetros avaliados, potencializando a ação do tratamento com o inibidor de acetilcolinesterase. / The objective was to study the hemodynamic changes, autonomic and cardiac morphofunctional in hypertensive rats (SHR) subjected to chronic cholinergic stimulation with two different doses (5 and 15 mg), and associate with the physical training, using different approaches: 1. Assessment tonic autonomic balance, heart rate (HR) by pharmacological blockade with atropine and propranolol; 2. Study of phasic autonomic balance (variability) HR (pulse interval) and blood pressure by spectral analysis; 3. Assessment of baroreflex sensitivity by administration of multiple doses of phenylephrine and random and sodium nitroprusside; 4. Evaluation two-dimensional echocardiography. Therefore, we used 54 rats divided two groups: trained (n = 27) and sedentary (n = 27). The animals trained, gave start to experiment in the 18th week of life, which lasted for 10 weeks; soon after, the rats were placed in treatment pyridostigmine bromide for over 2 weeks, at 30 weeks, the rats were subjected to cannulation surgery for analysis of blood pressure, HR, heart rate variability (HRV) and arterial pressure variability. Antecedent surgery, the rats were brought into the test for dimensional echocardiography analysis of cardiac morfofuncionalidade. Differences were considered statistically significant when p is greater than 5%. The results showed a decrease in SAP, DBP, and MAP, and to decrease the basal HR and HR intrinsic in mice treated with 5 and 15 mg bromide, both sedentary as treated. There was also an increase in NF (MS2) and a decrease in HF (ms2), showing improvement in cardiac autonomic condition. The main findings in morfofuncionalidade suggest an increase in EF, LV, CD, CI and EDV and ESV, and observe an increase in both the area, the thickness of the left ventricle in treated and trained rats. Thus, we can conclude that treatment with pyridostigmine bromide was effective as the hemodynamic values, as some morphological and functional parameters and the cardiac autonomic assessment, suggesting that a good drug therapy for the treatment of hypertension, however, further investigation should It is performed for a better understanding of the effects. Similarly, the physical training promotes beneficial changes to the evaluated parameters, potentiating the action of treatment with acetylcholinesterase inhibitor.

Lipossomos de cloreto de dioctadecildimetilamonio (DODAC) com 0,51µ de diâmetro externo médio e transição de fase ocorrendo em uma faixa estreita de temperaturas (0,5-1,0°C) foram obtidos por vaporização de clorofórmio e comparados com vesículas sonicadas de DODAC (cerca de 250 Å de diâmetro externo). Sacarose foi impermeante através de lipossomos grandes de DODAC ou de vesículas sonicadas de DODAC podendo ser utilizada para determinações de volume interno em ambas as preparações. Volume interno aparente para lipossomos grandes de DODAC foi 9,7 ± 1,3 1/mol e para vesículas sonicadas de DODAC, 0,33 ± 0,20 1/mol (adsorção de sacarose à bicamada de, respectivamente, 0,64 ± 0,30 e 0,20 ± 0,08 1/mol). Lipossomos grandes de DODAC comportaram-se como osmômetros em relação à sacarose e ao KCl (0-50mM KCl). Já as vesículas sonicadas de DODAC foram osmoticamente não-responsivas em relação à sacarose, floculando em presença de KCl. Essa não-responsividade osmótica foi interpretada como decorrente da presença única e exclusiva de água de hidrataçao no compartimento aquoso interno das vesículas sonicadas. Outras propriedades de lipossomos grandes de DODAC foram análogas às apresentadas por lipossomos de fosfolípides. Permeabilidades relativas (KCl como referência incorporado ao compartimento aquoso interno) do NaCl, HCl e sacarose foram similares às descritas para lipossomos de fosfatidilcolina; NaCl e sacarose sendo tão impermeantes quanto o KCl e HCl, sendo ligeiramente mais permeante que o KCl. Nas vizinhanças da temperatura de transição de fase, ocorreu um acentuado aumento da velocidade inicial de encolhimento e a extensão total de encolhimento chegou a um mínimo. A comparaçao de algumas propriedades físicas e funcionais de vesículas sonicadas e de lipossomos grandes de DODAC permitiu concluir que lipossomos grandes de DODAC constituem um modelo mais adequado para estudos de transporte. Adicionalmente, o método de vaporização de clorofórmio foi testado para o dihexadecilfosfato de Na+ (DCP) sendo obtidas dispersões homogêneas desse anfifílico capazes de incorporar um volume de 13 ± 4 1/mol e de responderem como osmômetros a gradientes osmóticos de sacarose, um soluto que praticamente nao é adsorvido à bicamada de DCP e que resultou impermeante através da mesma. / Dioctadecyldimethylammonium chloride (DODAC) liposomes with 0.51µ mean external diameter and sharp phase transitions were obtained by chloroform vaporization and compared with (small) sonicated DODAC vesicles. Sucrose was impermeant through large DODAC liposomes and sonicated vesicles and was used for internal volume determinations. The apparent internal volumes for large DODAC liposomes and sonicated DODAC vesicles were, respectively, 9.7 ± 1.3 and 0.33 ± 0.20 1/mol. (External sucrose adsorption were, respectively, 0.64 ± 0.30 and 0.20 ± 0.08 l/mol). Ideal osmometer behaviour towards KCl over the 0-50mM concentrations range and towards sucrose were observed only for large DODAC liposomes. Sonicated DODAC vesicles were osmotically non responsive towards sucrose and floculate with KCl. Other properties of large DODAC liposomes closely resembled those of phospholipid liposomes. At temperatures near the phase transition temperature, a steep increase in the initial shrinkage rate and a minimum for the total extent of shrinkage occured. Relative permeabilities (KCl as reference entrapped inside) to NaCl, HCl and sucrose were similar to those of phosphatidyl choline liposomes. NaCl and sucrose were as impermeant as KCl, and HCl slighthly more permeant than KCl. Large DODAC liposomes are proposed as an adequate synthetic membrane model, in contrast to sonicated DODAC vesicles. In addition, the chlroform vaporization method was tested for sodium dihexadecylphosphate (DCP). Large DCP liposomes were demonstrated to be impermeant towards sucrose entrapping 13 ± 4 l/mol and behaving as an osmometer towards this solute.

Neste trabalho é apresentado o estudo de alguns dos principais parâmetros envolvidos na fabricação de filmes finos de brometo de tálio (TlBr) por meio da técnica de spray pyrolysis. Investigamos a possibilidade desta técnica vir a se tornar um método alternativo para fabricação de filmes finos de TlBr com qualidade adequada para a confecção de dispositivos detectores de radiação de altas energias, como raios-X e raios-γ. O tempo de fabricação e a qualidade dos filmes eram limitados pelo problema da formação de gotas d’água na parte superior da câmara de deposição, o que resultava na incidência destas gotas sobre os filmes, posteriormente. O problema foi resolvido por meio de um sistema de aquecimento extrínseco ao equipamento. A investigação dos parâmetros citados se deu pela variação dos fluxos de nitrogênio e da solução de TlBr, pelas variações da posição dos substratos no porta substrato, da temperatura e do grau de saturação das soluções. As propriedades cristalinas e estruturais dos filmes foram verificadas pela técnica de difração de raios-X e por microscopia eletrônica de varredura, respectivamente. Os resultados mostram que o pico de intensidade dos planos cristalinos preferenciais dos filmes tendem a se tornar mais intensos para soluções saturadas, fabricados com baixo fluxo de nitrogênio e a temperaturas próximas de 100oC. No entanto, dependendo da posição dos filmes sobre o porta-substrato, a intensidade dos picos, assim como a rugosidade superficial, variam significativamente. Com efeito, conseguimos estender o processo de deposição para qualquer tempo desejado, o que implica, a princípio, em filmes mais espessos e de melhor qualidade. / This work presents the results about the investigation of the importance of some of the main parameters related to the fabrication of thin films of thallium bromide (TlBr) using the spray pyrolysis technique. We evaluated the possibilities for the future use of this technique in the development of high quality TlBr thin films to be used as high-energy radiation (such as X- and gamma rays) detectors. The total deposition time as well as the quality of the films were limited due to the formation of water droplets at the inner part of the top surface of the deposition chamber. These droplets would eventually fall over the substrates damaging the sample. This problem was solved by the use of an external heating system. The investigated deposition parameters were: nitrogen and solution flows, substrate position on top of the substrate holder, deposition temperature and composition of the solution. The crystalline and structural properties of the thin films were investigated by X-ray diffraction and Scanning Electron Microscopy. According to the results obtained from the diffraction experiments, the crystalline peaks increase with the saturation of the solution, low nitrogen flow and deposition temperatures close to 100oC. Nevertheless, the substrate position can also influence the crystallinity and amount of deposited material. In summary, we optimized the deposition parameters for the development of thick and high quality films that could be used for the development of sensors in the future.

Advances in protein topology mapping methods are urgently needed to complement the wealth of interactome data that is presently being generated at a rapid pace. Chemical crosslinking followed by mass spectrometry (MS) has evolved over the last decade as an attractive method for protein topology and interface mapping, and holds great promise as a counterpart to modern interactome studies in the field of proteomics. Furthermore, stabilization of proteins and protein complexes with crosslinking offers many advantages over high-resolution structural mapping methods, including the ability to study protein topologies in vivo. The reliance on direct detection of crosslinked peptides, however, continues to pose challenges to protein topology and interface mapping with chemical crosslinking plus MS. The present body of work aimed to develop a novel generic methodology that utilizes chemical crosslinking, cyanogen bromide (CNBr) cleavage and MS for the low-resolution mapping of protein topologies and interfaces. Through such low-resolution mapping of crosslinked regions, this novel strategy overcomes limitations associated with the direct detection of crosslinked peptides. Following optimization of various steps, the present method was validated with the bacterial DNA-directed RNA polymerase core complex and was subsequently applied to probe the tetrameric assembly of yeast Skp1p-Cdc4p heterodimers. Further improvements were made through the enrichment of crosslinked CNBr-cleaved protein fragments prior to their identification via MS. Two enrichment strategies were developed which depended upon the conjugation of tags to CNBr-cleaved peptide C-termini followed by either tandem affinity purification or tandem reversed-phase HPLC purification. These strategies were successfully applied for the efficient purification of disulfide-linked peptides from peptide mixtures. It is expected that the potential to achieve sensitive mapping of topologies and interfaces of multi-subunit protein complexes in vivo, in combination with further enhancements to permit studies on complex protein samples, will extend the utility of this method to complement large-scale interactome studies.

Advances in protein topology mapping methods are urgently needed to complement the wealth of interactome data that is presently being generated at a rapid pace. Chemical crosslinking followed by mass spectrometry (MS) has evolved over the last decade as an attractive method for protein topology and interface mapping, and holds great promise as a counterpart to modern interactome studies in the field of proteomics. Furthermore, stabilization of proteins and protein complexes with crosslinking offers many advantages over high-resolution structural mapping methods, including the ability to study protein topologies in vivo. The reliance on direct detection of crosslinked peptides, however, continues to pose challenges to protein topology and interface mapping with chemical crosslinking plus MS. The present body of work aimed to develop a novel generic methodology that utilizes chemical crosslinking, cyanogen bromide (CNBr) cleavage and MS for the low-resolution mapping of protein topologies and interfaces. Through such low-resolution mapping of crosslinked regions, this novel strategy overcomes limitations associated with the direct detection of crosslinked peptides. Following optimization of various steps, the present method was validated with the bacterial DNA-directed RNA polymerase core complex and was subsequently applied to probe the tetrameric assembly of yeast Skp1p-Cdc4p heterodimers. Further improvements were made through the enrichment of crosslinked CNBr-cleaved protein fragments prior to their identification via MS. Two enrichment strategies were developed which depended upon the conjugation of tags to CNBr-cleaved peptide C-termini followed by either tandem affinity purification or tandem reversed-phase HPLC purification. These strategies were successfully applied for the efficient purification of disulfide-linked peptides from peptide mixtures. It is expected that the potential to achieve sensitive mapping of topologies and interfaces of multi-subunit protein complexes in vivo, in combination with further enhancements to permit studies on complex protein samples, will extend the utility of this method to complement large-scale interactome studies.

This thesis consists of two different research problems. In the first one, the aim is to model and simulate a solar-powered, single-effect, absorption refrigeration system using a flat-plate solar collector and LiBr-H2O mixture as the working fluid. The cooling capacity and the coefficient of performance of the system are analyzed by varying all independent parameters, namely: evaporator pressure, condenser pressure, mass flow rate, LiBr concentration, and inlet generator temperature. The cooling performance of the system is compared with conventional vapor-compression systems for different refrigerants (R-134a, R-32, and R-22). The cooling performance is also assessed for a typical year in Tampa, Florida. Higher COP values are obtained for a lower LiBr concentration in the solution. The effects of evaporator and condenser pressures on the cooling capacity and cooling performance are found to be negligible. The LiBr-H2O solution shows higher cooling performance compared to other mixtures under the same absorption cooling cycle conditions. For typical year in Tampa, Florida, the model shows a constant coefficient of performance of 0.94. In the second problem, a numerical model is developed for a typical food retail store refrigeration/HVAC system to study the effects of indoor space conditions on supermarket energy consumption. Refrigerated display cases are normally rated at a store environment of 24ºC (75ºF) and a relative humidity of 55%. If the store can be maintained at lower relative humidity, significant quantities of refrigeration energy, defrost energy and anti-sweat heater energy can be saved. The numerical simulation is performed for a typical day in a standard store for each month of the year using the climate data for Tampa, Florida. This results in a 24 hour variation in the store relative humidity. Using these calculated hourly values of relative humidity for a typical 24 hour day, the store relative humidity distribution is calculated for a full year. The annual average supermarket relative humidity is found to be 51.1%. It is shown that for a 5% reduction in store relative humidity that the display case refrigeration load is reduced by 9.25%, and that results in total store energy load reduction of 4.84%. The results show good agreement with available experimental data.

Dissociation of gas hydrates has been the primary concern of the oil and gas industry for flow assurance, mainly in an offshore environment. There is also a growing interest in the rapid formation of gas hydrates for gas storage, transport of natural gas and carbon sequestration. In this thesis, we experimentally measure the kinetics of formation and dissociation of methane hydrates and the effect of various anionic and cationic surfactants such as sodium dodecyl sulfate (SDS), cetyl trimethylammonium bromide (CTAB) and alpha olefin sulfonate (AOS) on the association/dissociation rate constants. The importance and necessity of micelle formation in these surfactants has been studied. The effect of foam generation on the rate of formation of these hydrates has also been measured. SDS was found to significantly decrease the induction time for hydrate formation. There was an added decrease in the induction time when a foamed mixture of water and SDS was used. On the other hand CTAB and AOS had an inhibiting effect. The contribution of micelles towards promoting hydrate formation was demonstrated with a series of experiments using SDS. The micelles formed by these surfactants appear to serve as nucleation sites for the association of hydrates. New experimental data is presented to show that some surfactants and the use of foam can significantly increase the rate of hydrate formation. Other surfactants are shown to act as inhibitors. A new experimental setup is presented that allows us to distinguish between surfactants that act as promoters and inhibitors for hydrate formation. / text

Tetra-n-Butyl Ammonium Bromide (TBAB) forms semi-clathrate hydrates which can incorporate small gas molecules, such as methane and nitrogen at ambient temperatures and atmospheric pressure. Such favourable stability conditions, combined with ease of formation could make semi-clathrates particularly attractive for a large variety of applications. These hydrates have recently been investigated for their use in the separation of gases, and it is proposed that the same technology could potentially be used for storage and transportation of gases. To evaluate the feasibility of using TBAB hydrates for separation and storage purposes, an extensive test programme was conducted to determine: phase stability of the semi-clathrates, gas storage capacity, and composition of the stored gas. The results show that TBAB semi-clathrates have very favourable stability conditions. They can store considerable quantities of gas, and favour small molecules in their structures. These experiments suggest that semi-clathrate hydrates, such as TBAB, could have a significant potential as an alternative for industrial separation, storage, and transportation of natural gas.

Vapor absorption systems offer advantages over vapor compression systems for air-conditioning systems in some applications. They use heat as their primary energy input and hence provide opportunities to use solar energy or waste heat to drive these systems. The absorber is the most crucial component of the vapor absorption system and has the largest impact on its performance. Absorber design requires a keen understanding of the underlying heat and mass transfer processes in the absorber. The horizontal tube geometry is by far the most popular absorber geometry, due to the high absorption efficiencies achievable without incurring commensurate pressure drops. Several models have been proposed in the literature to model the heat and mass transfer during absorption over horizontal tube banks. However all of them make very simplistic assumptions about the flow profiles in the absorber. High speed flow visualization studies in the literature have shown that the flow occurs in the form of droplets and the formation and the detachment of these droplets and their impact on the tube has significant effects on the heat and mass transfer. Most absorption models in the literature neglect these flow modes and assume the solution to flow as a uniform film. The present study attempts to numerically model the heat and mass transfer in the absorber taking the realistic drop-wise and wavy film flow patterns into consideration. The impact of the fall of these droplets on the tube causes the lithium bromide solution present on the film on the tube to mix and present newer regions of the solution for vapor absorption. The impact of the droplets also causes waves that propagate axially over the liquid film on the tube. The mixing effect and the waves caused due to droplet impact play a very important role in the heat and mass transfer. Results obtained from this study will aid in better understanding of the vapor absorption process, and in the design of more efficient absorbers.

Orientador: Elaine Maria Cardoso / Resumo: Sistemas de refrigeração são indispensáveis para o modo de vida do homem atual, porém o grande gasto energético, de fontes não renováveis, e os impactos ambientais, levam-nos a estudar e a pensar em outras fontes de energia, de preferência renováveis, e em outros ciclos de refrigeração com gasto energético menor. Este trabalho tem como objetivo a modelagem de um sistema de refrigeração por absorção de vapor para o conforto térmico de ambientes, verificando a viabilidade desse sistema de refrigeração para aplicação em salas de aula. No presente trabalho mostra-se o sistema de refrigeração como sendo umas das alternativas ao sistema de refrigeração por compressão de vapor, o qual possui um alto gasto energético. Para o funcionamento do sistema de refrigeração por absorção de vapor foi proposto a energia solar como fonte de energia térmica do gerador, pois em regiões como Rio Verde – GO (localizada na região de latitude 17°47’S e longitude 50°58’W, onde o clima tropical predomina em quase todos os meses do ano, com temperatura mínima de ~20 ° C e máxima de ~30 °C) o condicionamento do ambiente é imprescindível. Foi utilizado o software EES para a simulação e modelagem do sistema de absorção de vapor, baseado nas trocas de calor entre os componentes desse sistema, desprezando perdas energéticas e de pressões que ocorrem em um ciclo real de absorção de vapor. As simulações e resultados mostraram que, nessa região tropical, o clima é propício para o uso de energia solar e que sua t... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Cooling systems are indispensable for today's man's way of life, but the high energy expenditure from non-renewable sources and environmental impacts lead us to study and think about other sources of energy, preferably renewable, and in other refrigeration cycles with lower energy expenditure. The objective of this work is the modeling of a vapor absorption refrigeration system for the thermal comfort of environments, verifying the viability of this refrigeration system for application in classrooms. In the present work is shown the refrigeration system as one of the alternatives to the system of refrigeration by compression of steam, which has high energy expenditure. For the operation of the vapor absorption refrigeration system, solar energy was proposed as the generator's thermal energy source, since in regions such as Rio Verde - GO (located in latitude 17° 47' S and longitude 50° 58' W, where the tropical climate prevails in almost every month of the year, with a minimum temperature of ~ 20° C and maximum of ~ 30° C), the ambient air-conditioning is essential. EES software was used for the simulation and modeling of the vapor absorption system based on the heat exchanges between the components of this system, disregarding energy and pressures losses that occur in a real vapor absorption cycle. The simulations and results showed that, in this tropical region, the climate is favorable to use solar energy and its transformation into thermal energy is sufficient for the ope... (Complete abstract click electronic access below) / Mestre