Orientador: Fernando Alvarez / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T02:41:56Z (GMT). No. of bitstreams: 1 Figueroa_CarlosAlejandro_D.pdf: 23603712 bytes, checksum: 9d788dfc54dde973a5d614fc546e3311 (MD5) Previous issue date: 2004 / Resumo: A compreensão da radiação cósmica -a saber: os mecanismos de produção / aceleração e os processos de propagação - passa pela determinação de três grandezas: a energia dessa radiação, sua direção de chegada e sua composição química. Essas três "frentes de trabalho"desafiam a experiência, a capacidade e a responsabilidade de vários grupos de físicos de partículas do mundo todo. Este trabalho se refere à composição do primário da radiação cósmica no âmbito da Colaboração Auger. Ele não tem a ambição de encontrar uma técnica definitiva para a obtenção deste parâmetro. Aliás, determinar a composição química do primário é algo difícil, tendo em vista a dependência de modelos de interação hadrônica e a impossibilidade (atual) de sua caracterização evento a evento. Dos vários parâmetros usados para se estimar essa composição, tentamos analisar cinco deles: Xmax, tlO-50, t50-90, tlO-90, rlocal. Estes foram obtidos por meio de simulação de Monte Carlo, através dos códigos CORSIKA e AIRES. A rede de detectores de superfície foi simulada usando-se o programa SAMPLE. Os resultados das simulações foram comparados, quando possível, a dados experimentais fornecidos pelo Engineering Array do sítio sul do Observatório Auger / Abstract: The understanding of cosmic radiation -the production/ acceleration mechanism and the propagation processes -involves the determination of three parameters: the energy of this radiation, its arrival direction and the chemical composition. These three tasks have challenged the experience, the skill and responsibility of several groups of particle physicists over the whole world. This work refers to the primary cosmic ray composition in the scope of the Auger Collaboration. It does not intend to present a definite technique to obtain this parameter. As a matter of fact, to determine the primary composition is something difficult, considering the hadronic model dependence and the impossibi1ity (nowadays) of its description event by event. Among the several parameters used to estimate the composition, we attempted to investigate five of them: Xmax, tl0-50, t50-90, tl0-90, rlocal. They were obtained through Monte Carlo simu1ation with two different codes: CORSIKA and AIRES. The surface array was simulated by the SAMPLE program. The simu1ation results were compared, when possible, to experimental data from the Engineering Array of the Auger Observatory / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Ce travail de thèse est consacré à l'exploration de la dynamique d'espèces moléculaires confinées dans des réseaux nano-méso poreux. Pour caractériser le mouvement de diffusion, on a utilisé la diffusion quasi-élastique des neutrons. La dynamique rotationelle des espèces confinées a été suivie par RNM du deutérium à l'état solide. Plusieurs systèmes ont été étudiés : (i) la dynamique de l'eau dans des adsorbants sélectifs basés sur du chlorure de calcium déposé dans de la silice., (ii) la dynamique d'alcanes linéaires confinés dans les pores de la zéolithe 5A, (iii), la dynamique du butane dans la zéolithe ZSM-5, (iv) la dynamique des cycles benzéniques dans les réseaux de la MIL-53 et de la MIL-47, (v) la dynamique de l'hydrogène dans les MOFs MIL-53 et MIL-47. Dans tous les cas, la nature et la dynamique en milieu confiné dévie fortement de la dynamique à l'état condensé. / The work is dedicated to the investigation of dynamics of molecular species confined in nano-meso porous media. To investigate the translational diffusion, quasielastic neutron scattering technique was used. To characterize the rotational dynamics and intramolecular dynamics of the confined species, solid state 2H NMR was used. Several systems were studied : (i) dynamics of water in selective water sorbent SWS-1L based on CACL2 salt and porous silica ; (ii) dynamics of linear alkanes confined in zeolite 5A pores ; (iii) dynamics of linear butane in zeolite ZSM-5 ; (iv) dynamics of benzene rings in the metal-organic frameworks MIL-53 and MIL-47 ; (v) dynamics of hydrogen in MILs47 and 53. In all cases, the dynamics and the state of adsorbed species were characterized and it was shown that the dynamics in confinement strongly deviates from the dynamics in the usual bulk state.

En France, 23 000 tonnes de graphites irradiés générés par le démantèlement des réacteurs nucléaires de première génération Uranium Naturel-Graphite-Gaz (UNGG) sont en attente d'une solution de gestion à long terme. Cette thèse porte sur le comportement du tritium, l'un des principaux contributeurs à l'inventaire radiologique des graphites à l'arrêt des réacteurs. Afin d'anticiper des rejets de tritium lors du démantèlement ou de la gestion des déchets, il est indispensable d'obtenir des données sur sa migration, sa localisation et son inventaire. Notre étude repose sur la simulation du tritium par implantation de l'ordre de 3 % at. de deutérium jusqu'à environ 3 μm dans un graphite nucléaire vierge. Celui-ci a ensuite subi des recuits jusqu'à 300 h et 1300 ° C sous atmosphère inerte, gaz caloporteur UNGG et gaz humide, dans le but de reproduire des conditions proches de celles rencontrées en réacteur et lors des opérations de gestion des déchets. Les profils et la répartition spatiale du deutérium ont été analysés via la réaction nucléaire 2H(3He,p)4He. Les principaux résultats montrent un relâchement thermique du deutérium se produisant selon trois régimes contrôlés par le dépiégeage de sites superficiels ou interstitiels. L'extrapolation des données au cas du tritium tend à montrer que son relâchement thermique en réacteur pourrait avoir été inférieur à 30 % et localisé à proximité des surfaces libres du graphite. L'essentiel de l'inventaire en tritium à l'arrêt des réacteurs serait retenu en profondeur dans les graphites irradiés, dont la décontamination nécessiterait alors des températures supérieures à 1300 °C, et serait plus efficace sous gaz inerte que sous gaz humide / In France, 23 000 t of irradiated graphite that will be generated by the decommissioning of the first generation Uranium Naturel-Graphite-Gaz (UNGG) nuclear reactors are waiting for a long term management solution. This work focuses on the behavior of tritium, which is one of the main contributors to the radiological inventory of graphite waste after reactor shutdown. In order to anticipate tritium release during dismantling or waste management, it is mandatory to collect data on its migration, location and inventory. Our study is based on the simulation of tritium by implantation of approximately 3 at. % of deuterium up to around 3 μm in a virgin nuclear graphite. This material was then annealed up to 300 h and 1300 °C in inert atmosphere, UNGG coolant gas and humid gas, aiming to reproduce thermal conditions close to those encountered in reactor and during waste management operations. The deuterium profiles and spatial distribution were analyzed using the nuclear reaction 2H(3He,p)4He. The main results evidence a thermal release of implanted deuterium occurring essentially through three regimes controlled by the detrapping of atomic deuterium located in superficial or interstitial sites. The extrapolation of our data to tritium suggests that its purely thermal release during reactor operations may have been lower than 30 % and would be located close to the graphite free surfaces. Consequently, most of the tritium inventory after reactor shutdown could be trapped deeply within the irradiated graphite structure. Decontamination of graphite waste should then require temperatures higher than 1300°C, and would be more efficient in dry inert gas than in humid gas

Ce travail de thèse porte sur développement de méthodes en spectrométrie de masse structurale pour l’analyse de protéines recombinantes et de leurs complexes associés. L’objectif central s’est porté sur des développements méthodologiques en échange hydrogène/deutérium couplé à la spectrométrie de masse (HDX-MS). Les techniques biophysiques de caractérisation structurale à haute résolution comme la cristallographie ou la RMN se heurtent régulièrement à des problèmes de productions de cristaux, de taille de complexes analysables ou encore de quantité de matériel nécessaire importante. Le développement de méthodes spécifiques HDX-MS a permis de réaliser une caractérisation structurale de systèmes protéiques variés, et réfractaires aux approches haute résolution. La combinaison de cette approche à différents outils de MS structurale est aussi illustrée, et montre tout son intérêt pour l’obtention d’informations à résolution augmentée. / This thesis work focuses on development of structural mass spectrometry methods for the analysis of recombinant proteins and their associated complex. The central objective has focused on the development of hydrogen/deuterium exchange coupled to mass spectrometry approaches (HDX-MS). The high resolution biophysical techniques for structural characterization such as crystallography or NMR regularly face problems of crystal productions, size analyzable complex or quantity of material required. The development of specific HDX-MS methods allowed the characterization of various, and refractory protein systems to high resolution approaches. The combination of this approach with complementary structural MS tools is also illustrated, and shows its interest to obtain increased resolution information.

Abstract The subjects of this thesis are the dynamics of liquid crystals in external electric and magnetic fields as well as the magnetic properties of small molecules, both studied by liquid crystal nuclear magnetic resonance (LC NMR) spectroscopy. Director dynamics of a liquid crystal 5CB in external magnetic and electric fields was studied by deuterium NMR and spectral simulations. A new theory was developed to explain the peculiar oscillations observed in the experimental spectra collected during fast director rotation. A spectral simulation program based on this new theory was developed and the outcome of the simulations was compared with the experimental results to verify the tenability of the theory. In the studies on the properties of small solute molecules, LC NMR was utilised to obtain information about anisotropic nuclear magnetic interaction tensors. The nuclear magnetic shielding tensor was studied in methyl halides, the spin-spin coupling tensor in methyl mercury halides and the quadrupolar coupling tensor in deuterated benzenes. The effects of small-amplitude molecular motions and solvent interactions on the obtained parameters were considered in each case. Finally, the experimental results were compared to the corresponding computational NMR parameters calculated in parallel with the experimental work.

In part one, betulinic acid (1) was isolated from the American Sycamore (Platanus occidentalis) in 1.6% yield, while ursolic acid (3) was isolated from Fuji and McIntosh apple peels in 1.0% and 0.8% crude yields, respectively. Oleanolic (4) and dehydrocanophyllic (6) acids were previously available, along with several analogs. Additional analogs of 1, 3 and 4 were prepared, including 9 new compounds, for a total of 51 compounds. Compounds were initially screened for cortisol lowering properties in vitro using a fish head kidney cell assay. Platanic acid (43) was selected for in vivo study in rats, along with 1 and a blend of Platanus occidentalis and Souroubea sympetela. No significant cortisol lowering was observed in vivo. In part two, β-ionone-d6 (75) was synthesized in 6.5% yield from ethyl 2-oxo-cyclohexane carboxylate (77). Total deuterium incorporation was 99.85%, with 0.03% d0 analog. 75 was converted to retinoic acid-d6 (93) in 2.2% yield.

O aumento de massa muscular (hipertrofia muscular), é uma das principais adaptações promovidas pelo treinamento de força (TF), contudo, como a hipertrofia é modulada e os mecanismos que a regulam ainda são curiosamente obscuros. Para investigar como a hipertrofia muscular é modulada durante o TF e os processos fisiológicos relacionados, medimos em 10 homens jovens (27[1] anos; 24[1] kg·m-2) no início (T1), na terceira (T2) e décima semanas (T3) de TF: 1) a área de secção transversa (AST) do vasto lateral (VL) e intensidade-eco por imagens de ultrassom; 2) a taxa de síntese proteica miofibrilar (SPMio) integrada dia-a-dia (24h e 48h) após sessões de TF máximas utilizando a ingestão de óxido de deutério e biópsias musculares; 3) o dano muscular induzido por sessões de TF máximas por meio de análises de integridade de linhas-Z sarcomerais e marcadores indiretos; 4) a AST de fibras (ASTf) tipo I e II, a modulação na quantidade de células satélites (CS), número e domínio mionuclear por meio de análise de imunofluorescência; 5) a expressão gênica global por meio de análise de microarray. Os principais resultados demonstram que houve hipertrofia muscular (aumento na AST do VL e ASTf tipo II) significante (P<0,04) somente em T3 (aumentos na AST do VL em T2 foram considerados edema, por meio da intensidade-eco); as alterações na SPMio pós-sessão em T1, T2 e T3 foram maiores em T1 (P<0,03) do que em T2 e T3 (valores semelhantes entre T2 e T3). O dano muscular foi maior pós-sessão em T1, foi atenuado em T2 e ainda mais atenuado em T3. A alteração na SPMio pós-sessão tanto em T2 quanto em T3, mas não em T1, foi fortemente correlacionada (r~0,9; P<0,04) com a hipertrofia muscular (T3-T1). A quantidade de CS aumentou 48h após o exercício somente em T1, e se manteve elevada cronicamente (P<0,05). Não houve alteração significante no número de mionúcleos ou no domínio mionuclear durante o TF. A análise de microarray indicou melhora na eficiência metabólica e na resposta ao estresse/dano muscular, e fortalecimento de estruturas musculares envolvendo proteínas miofibrilares e matriz extracelular. A SPMio após a primeira sessão de TF não é direcionada para suportar a hipertrofia muscular, mas sim para regenerar o dano muscular desta sessão. No entanto, a SPMio integrada é rapidamente \"refinada\", e, com a progressiva atenuação do dano muscular já em T2, ela passa a ser direcionada para suportar a hipertrofia muscular (também encontrado em T3). Portanto, a hipertrofia muscular é o resultado do acúmulo de proteínas miofibrilares provenientes de aumentos intermitentes da SPMio pós-sessões de TF com a progressiva atenuação do dano muscular. A ausência do aumento no número de mionúcleos cronicamente indica que os mionúcleos pré-existentes foram capazes de expandir a SPMio pósexercício induzindo hipertrofia muscular. A expansão inicial das CS, mantida cronicamente, favorece uma função envolvendo reparo em resposta ao dano muscular e um estado de \"prontidão\" antecipatório ao invés de um papel direto na hipertrofia muscular, pelo menos durante as primeiras 10-semanas de TF em homens jovens / Skeletal muscle hypertrophy is one of the main outcomes of resistance training (RT), but how hypertrophy is modulated and the mechanisms regulating it are not fully understood. To investigate how muscle hypertrophy is modulated during RT and the mechanisms that underpin it, we measured in 10 young men (27[1] years, 24[1] kg·m-2) at the beginning (T1), at the third week (T2), and tenth week (T3) of RT: 1) vastus lateralis cross-sectional area (CSA) and the echo intensity by ultrasound; 2) day-to-day (24h and 48h) integrated myofibrillar protein synthesis (MPS), after maximal resistance exercise (RE) using deuterium-oxide ingestion and muscle biopsies; 3) RE-induced muscle damage by analyzing Z-line streaming and indirect markers; 4) type I and II fiber CSA (fCSA), modulations in satellite cells pool and in myonuclear number and domain by immunohistological analyses; 5) global gene expression by microarray. Main results show that there was significant (P<0.04) muscle hypertrophy (increase in muscle CSA and type II fCSA) only in T3 (increases in muscle CSA in T2 were considered edema through echo intensity analyses). Changes in MPS post-RE at T1, T2 and T3 were greater at T1 (P<0.03) than at T2 and T3 (similar values between T2 and T3). Muscle damage was the highest during post-RE recovery at T1, attenuated at T2 and further attenuated at T3. Changes in MPS post-RE at both T2 and T3, but not at T1, were strongly correlated (r~0.9, P<0.04) with muscle hypertrophy (T3-T1). Satellite cells pool markedly increased 48h post-RE only in T1, and remained chronically elevated (P<0.05). There was no significant change in myonuclear number or domain during RT. The microarray analysis indicated improved metabolic efficiency, improved stress response and attenuated muscle damage, and strengthening of muscle structures involving myofibrillar proteins and extracellular matrix. Initial MPS response post-RE in a RT program is not directed to support muscle hypertrophy, coinciding with the highest magnitude of muscle damage. However, integrated MyoPS is quickly \'refined\', and with the progressive attenuation on muscle damage by 3wk of RT (T2), MPS is related to muscle hypertrophy (also at T3). We conclude that muscle hypertrophy is the result of accumulated intermittent changes in MPS post-RE in RT, which coincides with progressive muscle damage attenuation. The absence of change in myonuclei number indicates that preexisting myonuclei were able to expand post-RE MPS to promote muscle hypertrophy. Initial expansion in satellite cells pool, chronically maintained, favors a regeneration purpose of satellite cells in response to muscle damage and an anticipatory \"readiness\" state rather than a direct role in muscle hypertrophy, at least for the first 10 weeks of RT in young men

No description available.

In this work, 22-pole ion trap machines have been applied to investigate protonated water clusters H+(H2O)n (n=4..10) and ionic hydrocarbons CHn+ (n=2..5) at low temperatures. Protonated water clusters H+(H2O)n play an important role in atmospheric chemistry and in interstellar space. The Taipei 22-pole ion trap machine has been applied to kinetic and spectroscopic investigations of these clusters produced from a supersonic expansion in a corona discharge source. Using low-pressure He buffer gas for collisional thermalization, refrigeration of the ion trap by liquid nitrogen allows a good control of the cluster temperature over the range 80K-350K. This method provides an accurate means of determining the dissociation energies of the cluster ions by measuring their dissociation rates as a function of temperature and calculating their internal energies from vibrational frequencies provided by density functional theory. Results of the thermochemical measurements at well-defined cluster temperatures have been given for H+(H2O)n, n=4..10. The feasibility of using the ion trap to acquire temperature-dependent infrared spectra is presented. The deuteration and abstraction reactions of small ionic hydrocarbons CHn+ (n=2..5) with H2, HD and D2 and the subsequent association processes have been explored at temperatures down to 15K in the Chemnitz 22-pole apparatus. The reactions of the investigated ionic species and their isotopic variants are important for understanding ion-molecule processes in the interstellar medium. One of the starting points of the research program was the question whether protonated methane, CH5+, is subject to H-D-exchange in collisions with HD at low temperatures. It turns out that the rate coefficient for this deuteration process is very small, whereas CH3+ deuterates with HD by three subsequent fast exchange reactions to CD3+ at a temperature of 15K. The latter process is very efficient and happens close to the collision limit. The methane cation, CH4+, on the other hand, shows also some interesting features in collisions with H2, HD and D2. It exhibits an inverse temperature dependence with the rate coefficient increasing at least one order of magnitude going from 300K to 15K. Furthermore, reacting with HD at the temperature of 15K, the reaction channel leading to CH5+ is preferred over the D-atom abstraction channel (isotope effect). / Im Rahmen dieser Arbeit wurden zwei Apparaturen mit 22-Pol-Ionenfallen benutzt, um protonierte Wassercluster H+(H2O)n (n=4..10) und kleine ionische Kohlenwasserstoffe CHn+ (n=2..5) bei tiefen Temperaturen zu untersuchen. Die in einer Koronaentladungsquelle erzeugten Cluster H+(H2O)n wurden kinetisch und spektroskopisch untersucht. Dazu wurden sie in einem 22-Pol-Speicher mithilfe eines He-Puffergases auf einer Temperatur zwischen 80K und 350K thermalisiert. Die Bestimmung der Bindungsenergien fuer Cluster der Groesse n=4..10 wird ermoeglicht durch die Messung der temperaturabhaengigen Dissoziationsraten und durch die Ermittlung der inneren Energien mittels berechneter Schwingungsfrequenzen. Temperaturabhaengige IR-Spektren im Bereich der freien OH-Streckschwingung wurden aufgenommen. Die Austausch- und Abstreifreaktionen von ionischen Kohlenwasserstoffen CHn+ (n=2..5) mit H2, HD und D2 und die darauffolgenden Assoziationsprozesse wurden im Temperaturbereich 15K bis 300K untersucht. Es stellt sich z.B. heraus, dass der H-D-Austauschprozess zwischen CH5+ und HD bei 15K sehr langsam ist, wogegen CH3+ mit jeder Kollision einen Austausch ausfuehrt. In der Abstreifreaktion von CH4+ mit Wasserstoffmolekuelen beobachtet man eine inverse Temperaturabhaengigkeit. Dies wird vorlaeufig mit einer laengeren Komplexlebensdauer bei tiefen Temperaturen erklaert.

Bacterial protein WrbA from E. coli is the founding member of a new family of FMN-dependent NAD(P)H oxidoreductases, forming a functional and structural bridge between bacterial flavodoxin and certain mammalian NAD(P)H:quinone oxidoreductase. For these reasons, protein WrbA is recently intensively studied using various analytical and computing methods. Protein WrbA participates in the protection of cells against oxidative stress, but precise function of the protein WrbA in vivo is still unknown. Protein WrbA forms multimers in solutions. In μM concentrations and at low temperature (4 řC) the protein is in the form of a dimer, with increasing temperature becomes tetrameric. Available three-dimensional crystal structure contains the information about the tetrameric form of the protein, the dimeric form has not been structurally characterized. This thesis was focused on the study of the dynamic behavior of protein WrbA in solution using methods of hydrogen-deuterium exchange and chemical cross-linking followed by mass spectrometric analysis with high resolution (FT-ICR). Behavior of the protein was monitored according to the presence of cofactor FMN. Effect of temperature and protein concentration was also studied. Hydrogen-deuterium exchange provided information about solvent accessibility and...