Orientadores: Edvaldo Sabadini, René Alfonso Nome Silva / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T10:23:43Z (GMT). No. of bitstreams: 1 Ito_ThiagoHeiji_D.pdf: 8761085 bytes, checksum: 521d52e10af7805f341661ecc562599c (MD5) Previous issue date: 2015 / Resumo: Micelas gigantes têm sido muito estudadas desde os anos de 1980 e suas propriedades têm atraído a atenção tanto do setor produtivo quanto acadêmico. Aumento de viscosidade, capacidade de reduzir o atrito hidrodinâmico, formação de fluidos viscoelásticos e do tipo gel, são alguns dos fenômenos que fazem deste, um sistema de interesse em ambos os setores. Na literatura, está relatada uma grande quantidade de sistemas com propriedades particulares, inclusive, responsivos a estímulos luminosos, elétricos ou mudança no pH, todas advindas de diversas combinações entre diferentes componentes. No entanto, pouco se conhece a respeito dos fatores que levam à formação (crescimento), à estabilidade e, consequentemente, aos diversos fenômenos que despertam tanto interesse desse tipo de sistema supramolecular. Neste trabalho, buscou-se compreender e sistematizar a influência da estrutura molecular de vários compostos aromáticos na capacidade de induzir a formação de micelas gigantes com surfactantes catiônicos, além de uma interpretação baseada na termodinâmica para compreender o processo de crescimento deste sistema supramolecular. Para isso foram utilizadas várias técnicas como reologia, espalhamento de luz e nêutrons, e calorimetria de titulação isotérmica, que demonstraram uma grande influência de fatores estruturais dos co-solutos aromáticos como a presença de carga, hidrofobicidade e, especialmente, a capacidade de empacotamento devido à planaridade da molécula, demostrado pela primeira vez. Além disso, os ensaios de calorimetria e espalhamento de luz elucidaram como se dá o processo de crescimento da micela, bem como, mostraram a importância que a carga superficial do agregado tem para transição entre micelas curtas e alongadas / Abstract: Giant micelles have been studied since the 1980s and their properties have attracted the attention of both the productive sector and the academic. Viscosity increase, the ability in promote hydrodynamic drag reduction, formation of viscoelastic and gel-like fluids, are some of the phenomena that turn interesting the system in both approaches. In the literature, it is reported a large number of systems showing particular properties, including light, electrical stimuli or pH responsive, resulting from combinations of several different components. However, little is known about the factors that lead to formation (growth), stability and, consequently, to many phenomena which arouse such interest on that kind of supramolecular system. In this study, we tried to understand the influence of the molecular structure of various aromatic compounds in the ability to induce the formation of wormlike micelles with cationic surfactants, and an interpretation based on thermodynamics to understand the growth process of such supramolecular system. Several techniques like rheology, light and neutrons scattering, and isothermal titration calorimetry, have been used in order to study the system, which showed the influence of structural factors of the aromatic co-solutes such as presence of electrostatic charge, hydrophobicity, and the packing capacity due the planarity of the molecule, demonstrated for the first time. Additionally, calorimetric and light scattering measurements elucidated the growth process of the micelle, and showed the importance of the surface charge in transition between small and elongated micelles / Doutorado / Físico-Química / Doutor em Ciências

O Grande Colisor de Hádrons (Large Hadron Collider - LHC) é um acelerador de prótons e íons pesados localizado no CERN (Conseil Européen pour la Recherche Nucléaire). Em um de seus experimentos, ALICE (A Large Ion Collider Experiment ), está sendo projetado um detector dedicado a explorar os aspectos únicos de colisões núcleo-núcleo. A principal finalidade do ALICE é estudar a formação de um novo estado da matéria, o plasma de quarks e glúon. Para isto devem-se ter medidas precisas de hádrons, elétrons, múons e fótons produzidos em colisões chumbo-chumbo. Assim está sendo proposto um calorímetro frontal (Foward Calorimeter - FoCal) como um upgrade para o ALICE. A função deste calorímetro é o estudo das funções de distribuição de pártons (Partons distribuction Functions - PDF) no regime de pequenos valores do x de Bjorken. Nesta região é esperado que estas PDFs tenham um comportamento não linear devido ao processo de saturação de glúons. Para o estudo desta região é necessária a medida de fótons diretos produzidos na colisão. Estes, por sua vez, ficam mascarados pelo fundo de fótons provenientes do decaimento de píon, o que leva a uma necessidade de suas identificações. Com isto surge a oportunidade para a utilização do método de clusterização que é uma ferramenta de mineração de dados. Este trabalho contribuiu para o desenvolvimento inicial de um algoritmo de clusterização para o calorímetro FoCal. / The Large Hadron Collider (LHC) is a CERN\'s accelerator that collides protons and heavy ions. One of its experiments, ALICE, is building a new detector to explore new aspects of heavy ions collisions. The Alice\'s main goal is to study the formation of quark-gluon plasma (QGP). To do that it\'s necessary to get accurate data on hadrons, electrons, muons and gammas created in lead-lead collision. So, to accomplish that a new calorimeter is in study to scan the foward region of experiment, the Foward Calorimeter (FoCal). It\'s proposed to study Parton Distribution Functions (PDFs) in a regime of very small Bjorken-x, where it is expected that the PDFs evolve non-linearly due to the high gluon densities, a phenomena referred to as gluon saturation.But to do that it\'s required to measure the direct gammas created on collision. These fotons are blended on by fotons descendant of pion. So there\'s a need to separate it from the direct gammas. One way to solve this problem is to use clustering methods (a type of mining data algorithm). This work helped on early stages of development that clustering algorithm.

[EN] For many years energy needs of ruminants have tried to be known to formulate rations adjusted, but it has been found that there are a variety of factors that affect them. Therefore, lots of studies are needed for evaluating the effect of these factors. Consequently, the main objective of this Thesis was to design and validate a respirometry system based on indirect calorimetry, which would allow assessing energy needs of small ruminants accurately. It was intended from the beginning it was a mobile system and of relatively low cost. Furthermore, a methane gas analyzer was incorporated to this system, which allowed the measurement of emissions of this greenhouse gas and quantification of energy losses in the form of methane. Initially the system had connected a mask, which was placed on the animal's face. A sample of exhaled gas was stored in a gas collection bag which was connected to the analyzer, and it measured the concentration of O2, CO2 and CH4 from the air. The proper functioning of the system was checked by a pilot experiment with dry Murciano-Granadina breed goats fed at maintenance level. Later this system was improved. Some of the most important changes were the replacement of the mask by a head hood in which the animal introduced the whole head, and the development of software that recorded and kept automatically concentrations of O2, CO2 and CH4 in exhaled air. This improvement allowed gas measurements during longer periods of time and recording more data. These changes were also validated through a pilot test with dry Manchega breed sheep. Subsequently, three experiments were performed. One of them with dry Guirra ewes and the other two with Murciano-Granadina goats during mid lactation. Diets were mixed rations that differed in the inclusion of cereal or fibrous by-products. In these experiments the effect of diet was studied on digestibility, energy balance and carbon-nitrogen, oxidation of nutrients, rumen parameters and methane production; in the case of lactating goats, also on milk performance. The determination of the calibration factor for O2 (1.005 ± 0.0101) confirmed the proper functioning of equipment. Moreover, small differences between the heat production obtained by indirect calorimetry and the carbon-nitrogen balance (2% in sheep and 1% in goats) demonstrated that this system allows determining the heat production of the animals reliably and accurately. In the experiments of this Thesis have been estimated maintenance energy needs of two Spanish native sheep breeds, such as the sheep from the Guirra and Manchega breeds; net maintenance requirements were 270 kJ/kg BW0.75, on average. In the case of Murciano-Granadina breed goats, in the middle of lactation, the average utilization efficiency of metabolizable energy for lactation was 0.61. / [ES] Desde hace años se ha tratado de conocer las necesidades energéticas de los rumiantes con el fin de formular raciones ajustadas, pero se ha comprobado que hay una gran variedad de factores que les afectan; por ello son necesarios estudios que evalúen el efecto de estos factores. Como consecuencia, el principal objetivo de esta tesis fue diseñar y validar un equipo de respirometría, basado en calorimetría indirecta, que permitiese evaluar las necesidades en energía de pequeños rumiantes de forma precisa. Se pretendió desde el inicio que fuese un sistema móvil y de relativo bajo coste. Además, a este sistema también se le incorporó un analizador de gas metano, que permitía la medición de las emisiones de este gas de efecto invernadero y la cuantificación de las pérdidas energéticas en forma de metano. Inicialmente el equipo tenía conectada una máscara que se colocaba en la cara del animal. Una muestra del gas espirado era almacenada en una bolsa de recogida de gases que era conectada al analizador, el cual medía la concentración de O2, CO2 y CH4 del aire. Se comprobó el correcto funcionamiento del sistema mediante una prueba piloto con cabras de raza Murciano-Granadina secas, alimentadas a nivel de mantenimiento. Posteriormente este sistema fue mejorado. Algunos de los cambios más importantes fueron la sustitución de la máscara por una urna en la que el animal introducía la cabeza entera, y el desarrollo de un software que registraba y guardaba de forma automática las concentraciones de O2, CO2 y CH4 del aire espirado. Esta mejora permitía medidas de gases durante periodos de tiempo más largos y el registro de muchos más datos. Estas modificaciones también fueron validadas mediante una prueba piloto con ovejas de raza Manchega secas. Posteriormente se realizaron tres experimentos. Uno de ellos con ovejas de raza Guirra secas y los otros dos con cabras Murciano-Granadinas en mitad de lactación. Las dietas fueron raciones mixtas que diferían en la inclusión de cereal o subproductos fibrosos. En estos experimentos se estudió el efecto de la dieta sobre la digestibilidad, balances de energía y carbono-nitrógeno, oxidación de los nutrientes, parámetros del rumen y producción de metano; en el caso de las cabras en lactación, también sobre los rendimientos productivos. La determinación del factor de calibrado para el O2 (1,005 ± 0,0101) confirmó el buen funcionamiento del equipo. Por otro lado, las pequeñas diferencias entre la producción de calor obtenida mediante calorimetría indirecta y el balance de carbono-nitrógeno (2% en ovejas y 1% en cabras) demostraron que este sistema permite determinar la producción de calor de los animales de forma fiable y precisa. En los trabajos de esta Tesis se han estimado las necesidades energéticas de mantenimiento en dos razas de ovejas autóctonas españolas, como son las razas Guirra y Manchega; las necesidades netas de mantenimiento fueron 270 kJ/kg PV0,75, de media. En el caso del ganado caprino de raza Murciano-Granadina, en mitad de lactación, la eficacia media de utilización de la energía metabolizable para la lactación fue de 0,61. / [CAT] Des de fa anys s'ha tractat de conèixer les necessitats energètiques dels remugants a fi de formular racions ajustades, però s'ha comprovat que hi ha una gran varietat de factors que els afecten; per això són necessaris estudis que avaluen l'efecte d'estos factors. Com a conseqüència, el principal objectiu d'aquesta Tesi va ser dissenyar i validar un equip de respirometría, basat en calorimetria indirecta, que permetera avaluar les necessitats en energia de menuts remugants de forma precisa. Es va pretendre des de l'inici que fóra un sistema mòbil i de relatiu baix cost. A més, a este sistema també se li va incorporar un analitzador de gas metà, que permetia el mesurament de les emissions d'este gas d'efecte hivernacle i la quantificació de les pèrdues energètiques en forma de metà. Inicialment l'equip tenia connectada una màscara que es col·locava en la cara de l'animal. Una mostra del gas expirat era emmagatzemada en una bossa d'arreplega de gasos que era connectada a l'analitzador, el qual mesurava la concentració d'O2, CO2 i CH4 de l'aire. Es va comprovar el funcionament correcte del sistema per mitjà d'una prova pilot amb cabres de raça Murciano-Granadina seques, alimentades a nivell de manteniment. Posteriorment este sistema va ser millorat. Alguns dels canvis més importants van ser la substitució de la màscara per una urna en què l'animal introduïa el cap sencera, i el desenrotllament d'un programari que registrava i guardava de forma automàtica les concentracions d'O2, CO2 i CH4 de l'aire expirat. Esta millora permetia mesures de gasos durant períodes de temps més llargs i el registre de moltes més dades. Estes modificacions també van ser validades per mitjà d'una prova pilot amb ovelles de raça Manxega seques. Després es van realitzar tres experiments. Un d'ells amb ovelles de raça Guirra seques i els altres dos amb cabres Murciano-Granadinas en mitat de lactació. Les dietes van ser racions mixtes que diferien en la inclusió de cereal o subproductes fibrosos. En estos experiments es va estudiar l'efecte de la dieta sobre la digestibilitat, balanços d'energia i carboni-nitrogen, oxidació dels nutrients, paràmetres del rumen i producció de metà; en el cas de les cabres en lactació, també sobre els rendiments productius. La determinació del factor de calibrat per a l'O2 (1,005 ± 0,0101) va confirmar el bon funcionament de l'equip. D'altra banda, les xicotetes diferències entre la producció de calor obtinguda per mitjà de calorimetria indirecta i el balanç de carboni-nitrogen (2% en ovelles i 1% en cabres) van demostrar que este sistema permet determinar la producció de calor dels animals de forma fiable i precisa. En els treballs d'esta Tesi s'han estimat les necessitats energètiques de manteniment en dos races d'ovelles autòctones espanyoles, com són les races Guirra i Manxega; les necessitats netes de manteniment van ser 270 kJ/kg PV0,75, de mitja. En el cas del bestiar caprí de raça Murciano-Granadina, en mitat de lactació, l'eficàcia mitjana d'utilització de l'energia metabolitzable per a la lactació va ser de 0,61. / López Luján, MDC. (2015). Development of a mobile open-circuit system based on indirect calorimetry for energetic metabolism studies in small ruminants [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/50430 / TESIS

Small ligand diffusion in heme proteins is not fully understood. To help better understand CO diffusion, three systems were investigated: L29H/F43H site-directed sperm whale myoglobin, horse heart myoglobin in a heavy water buffer, and calix[4]resorcinarene. Binding of copper to calix[4]resorcinarene was photophysically characterized to unravel transient binding of small molecules in heme-copper proteins. Copper binding was found to have a low dissociation constant of approximately 8.6 micrometers.. Reaction profiles using photoacoustic calorimetry were constructed for the myoglobin systems. In deuterium oxide, ligand escape is not rate limited by water entry. Large enthalpy differences arise from the thermodynamic properties of deuterium oxide and the extensive hydrogen bonding network in myoglobin. In the mutant, CO rebinds primarily to the heme and is exothermic with a large volume contraction because of altered electrostatics within the binding pocket and higher water occupancy.

The scope of this masters thesis is the preparation of a model mucin system and its utilization as an artificial model of the native mucus system. The creation of this model system, according to several designed methods was a part of experimental part of the thesis. The preparation of mucin system comprised of physical and chemical methods of hydrogel formation, screening and characterisation of the various physical conditions of the mucin properties on its molecular level, and the preparation of sorbent with sorption surface containing mucin. Methods of light scattering, namely dynamic light scattering (DLS), used for mucin particles size change monitoring, and electroforetic light scattering (ELS), used for Zeta potential change monitoring, were used for the screening of the impact of physical factors on the properties of mucin.For the characterisation of impact of the temperature on changes in mucin sctructure was, apart from monitoring of light scattering, used also a diferential scanning calorimetry (DSC), which registered temperature value, at which mucin thermal denaturation occurs. In the next part of the thesis we subdued the created sorption surfaces to various physical-chemical analyses, which task is the characterisation and projection of surface and confirmation of mucin presence.Substancial part in monitoring and characterisation of changes in surface sctructure of sorption surface was accomplished by Fourier transform infrared spectroscopy (FTIR). Scanning electron microscophy (SEM) was used for the final, more detailed, projection of the mucin enriched, sorbent surface structure. Suggested methods of mucin hydrogel, didnt prove sufficient results for the possibility of application of hydrogel as a artificial model of real mucus system, but the sorbent application was indicated as a suitable alternative and an instrument for the further mucin behaviour research and possibly subsequent bacterial adhesion, which represents the first step in the formation of the bacterial biofilm.

This diploma thesis deals with non-traditional binder, which is strontium aluminate, with his preparation and hydration. The behaviour of binary and ternary mixtures of strontium-calcium-barium aluminates was also studied. These aluminates were prepared by firing an equimolar mixture of aluminum oxide and the appropriate carbonate. Samples prepared this way, including their mixtures, were characterized by analytical methods such as X-ray diffraction analysis (XRD), thermal analysis with evolved gas analysis (TG-DTA and EGA), scanning electron microscopy (SEM), infrared spectroscopy (IR) and calorimetry, with the greatest importance for the study of the hydration process.

VLIV VZTAHU DÉLKY DOLNÍ KONČETINY A VELIKOSTI RÁFKU NA PSYCHOFZIOLOGICKOU ODEZVU ORGANISMU Cíle: Cílem této práce je posoudit vliv délky dolní končetiny (DK) na psychofyziologickou odezvu organismu při jízdě na horském kole s odlišnými velikostmi ráfků. Metody: Soubor probandů tvořilo 20 mužů ve věku 26,4 ± 4,2 let. Jednalo se o experiment. Psychofyziologická odezva byla stanovena na základě výkonu (zajetého času), tepové frekvence a subjektivním hodnocení jízdních vlastností horského kola a vlastního vynaloženého úsilí hodnoceného na Borgově škále. Ke kontrolní analýze při testování byl použit přístroj MetaMax 3B. Testovány byly tři velikosti ráfků o stejné šíři plášťů. Jízdy byly realizovány na 800 m dlouhém okruhu. Testované osoby absolvovali každou jízdu s individuálně zvoleným fixním převodem v poloze v sedle s maximálním možným úsilím. Výsledky: Při jízdě na různě velkých ráfcích jsme u skupiny č. 2 (85 -90 cm DK) shledali velký rozdíl (P = 0,016) v dosažených časech při jízdě na různě velkých ráfcích. U skupiny č. 1 jsme shledali významné rozdíly v průměrné tepové frekvenci (P = 0,010), který činil 3 tepy a u subjektivního hodnocení vlastního vynaloženého úsilí pomocí Borgovy škály jsme se pohybovali na hranici významnosti (P = 0,060). Skupina č. 3 (97 - 101 cm DK) se pohybovala na hranici...

Title: Movement economy and physiological response during differing climbing speeds in sport climbers. Aims: The work aims to evaluace climbing economy and physiological responses of intermediate and advanced climbers in different climbing speeds. Methodology: 32 climbers (11 advanced men, 11 intermediate men, 10 intermediate women) performed 3 submaximal tests in treadwall at slope of 90ř at speeds 4, 6 and 9 m.min-1 . Each of the tests lasted exactly 4 minutes. Oxygen consumption (VO2), heart rate (HR), ventilation (VE), respiratory ratio (RER) and energy expenditure were monitored. Results: Advanced men reported lower energy expenditure than intermediate men in all climbing speeds (4 m.min-1 : -0,06 kcal.kg-1 , P = 0,007; 6 m.min-1 : -0,06 kcal.kg-1 P = 0,048; 9 m.min-1 : -0,07 kcal.kg-1 P = 0,022). Intermediate women reported only slightly lower energy expenditure than intermediate men (4 m.min-1 : -0,01 kcal.kg-1 P = 0,051; 6 m.min-1 : 0,06 kcal.kg-1 P = 0,091; 9 m.min-1 : -0,03 kcal.kg-1 P = 0,115). Energy expenditure was significantly lower at 4 m.min-1 than at 6 m.min-1 (-9,82 kcal, p = 0,001) and also signicantly lower at 6 m.min-1 than at 9 m.min-1 (-8,3 kcal, p = 0,001). Advanced men reported significantly lower VO2 at speeds 4 a 6 m.min-1 (- 2,2 ml.kg- 1 .min-1, P = 0,022; -3,9 ml.kg-1...

Les réseaux métallo-organiques (MOF) sont une nouvelle classe de matériaux poreux hybrides. Néanmoins leurs propriétés uniques introduisent également des difficultés significatives dans la caractérisation par adsorption de gaz. Dans cette thèse, la création d'un code source libre est détaillé, pour standardiser le traitement des isothermes. En utilisant ce code, un traitement à haut débit de plus de 18 000 isothermes est utilisé pour explorer l'échelle d'incertitude présente dans les données publiées sur l'adsorption dans les matériaux poreux. De plus, la mesure directe de l'enthalpie différentielle de l'adsorption en utilisant la microcalorimétrie s'avère être un excellent moyen d'obtenir la contribution des interactions particulières sur l'énergie d'adsorption. Ensemble, ces méthodes peuvent être utilisées pour étudier les sources d'incertitude des MOF. On étudie d’abord l’impact des défauts structurels au moyen d’une méthode post-synthétique alternative de génération de linker/cluster manquants dans l'UiO-66(Zr). Le traitement des matériaux pour leurs utilisations dans un environnement industriel par façonnage est étudié ici sous l’effet de la granulation par voie humide sur trois MOF topiques (UiO-66(Zr), MIL-100(Fe) et MIL-127(Fe)). Enfin, les comportements contre-intuitifs intrinsèques aux cristaux poreux «souples» sont étudiés, où la structure elle-même est responsable de la fluctuation dans les isothermes d'adsorption. Ici, une étude fondamentale sur un matériau flexible DUT-49 (Cu), apporte des informations sur la source de flexibilité induite par adsorption et sa changeabilité par modification structurelle / Metal organic frameworks (MOF) are novel adsorption materials with unique and desirable properties. However, structural defects, processing and structural compliance can lead to irreproducibility in adorption measurements. In this thesis, the creation of an open-source codebase is detailed, which is intended to standardize the processing of isotherms. Using this framework, high throughput processing of over 18 000 isotherms is used to explore the scale of uncertainty present in published adsorption data. Then, direct measurement of the differential enthalpy of adsorption using microcalorimetry is shown to be an excellent avenue of obtaining further insight into the contribution of guest-host and host-host interactions to the overall energetics of adsorption. Together, these methods are used to study some of the sources of the variability of MOFs, and quantify their effect. First, the impact of structural defects is investigated, through an alternative post-synthetic method of missing linker/cluster generation in the prototypical UiO-66(Zr) MOF. The processing of materials for their use in an industrial environment through shaping is another potential source of performance modification, which is here studied as the effect of wet granulation on three topical MOFs (UiO-66(Zr), MIL-100(Fe) and MIL-127(Fe)). Finally, counterintuitive behaviours intrinsic to ``soft'' porous crystals are investigated, where the structure itself is responsible for fluctuation in adsorption isotherms. A fundamental study on a copper paddlewheel based material, DUT-49(Cu) yields know-how on the source of adsorption induced compliance and its tunability through structural modification

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