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Made available in DSpace on 2014-10-09T12:34:20Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:10:33Z (GMT). No. of bitstreams: 0 / Em testes físicos de reatores que são realizados na criticalização, após uma troca de combustível, por exemplo, como ocorre nos reatores PWR, é muito importante monitorar continuamente a reatividade durante o processo de criticalização. Medir a reatividade utilizando o método da Cinética Inversa é um processo bastante utilizado durante a operação de um reator nuclear, e é possível determinar a reatividade em tempo real baseado nas equações de cinética pontual. Essa técnica é aplicada com sucesso a altas potências, ou em núcleos que trabalham sem a existência de uma fonte externa, já que nesse caso o Termo Fonte na equação de cinética pontual pode ser desprezado. Para operações a baixas potências, a contribuição da fonte de nêutrons precisa ser levada em consideração, e isso implica em conhecer um valor proporcional à intensidade da fonte e, portanto esse valor precisa ser determinado. O Método dos Mínimos Quadrados em Cinética Inversa (Least Square Inverse Kinetics Method LSIKM) foi testado com modelo teórico e aplicado em experimentos no Reator Nuclear IPEN/MB-01 para a determinação do Termo Fonte com a utilização de um reatímetro que ignora o Termo Fonte em primeira instância. Após a determinação da Fonte S de forma consistente, seu valor foi inserido ao algoritmo de Cinética Inversa, e utilizando dados de detectores durante a criticalização, o reatímetro com Termo Fonte foi usado para medir a reatividade no domínio subcrítico, nos passos de criticalização, após experimento. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Orientador: Oswaldo Luiz Alves / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-08T23:15:36Z (GMT). No. of bitstreams: 1 Rodrigues_CarolinaMartins_M.pdf: 50415494 bytes, checksum: b98d1323abe212ba30a7712dd028ce6f (MD5) Previous issue date: 2007 / Resumo: Esta dissertação visa à obtenção de nanoestruturas partindo do óxido misto Ti1-xZrxO2. O óxido precursor foi preparado pelo método de precipitação homogênea, via tetracloreto de titânio e oxicloreto de zircônio, usando uréia como reagente precipitante. Esses óxidos foram submetidos ao tratamento hidrotérmico em autoclave, em solução de NaOH, empregando temperatura de 140 e 170°C com intervalo de tempo de 2 a 7 dias. De acordo com as caracterizações físico-químicas feitas foi observado que os produtos obtidos via tratamento hidrotérmico com x < 0,50 apresentaram morfologia de nanotubos, nanoplacas e nanobastões. Entretanto, para x acima de 0,05 mostraram a existência de duas fases cristalinas, titanato de sódio e ZrO2 tetragonal. Para x > 0,50 não apresentaram mudanças morfológicas, tendo como fase formada o ZrO2 tetragonal. Quando o precursor com x = 0,50 (fase ZrTiO4) é observado no produto do tratamento hidrotérmico manutenção da estrutura cristalina e presença de nanotubos. Foi também mostrado, para x = 0,15, que o aumento de volume da solução na autoclave promove aumento da cristalinidade e destruição da organização das partículas. O aumento do tempo e da temperatura de reação proporcionou maior cristalinidade aos produtos hidrotérmicos com x = 0,15 e 0,50; para x = 0 aumento de nanotubos e para x = 0,15 diminuição das nanoplacas e para x = 0,80 e 1 não apresentaram mudanças nem na morfologia, nem na cristalinidade. Foi avaliada a reatividade dos nanotubos (x=0) e nanobastões/nanoplacas (x = 0,15) frente às moléculas orgânicas. Foi observado que os nanotubos interagem melhor com moléculas ácidas, e que tais moléculas promovem a destruição da morfologia e mudança da estrutura cristalina, sendo estas mais drásticas quando com aquecimento. Os nanobastões/nanoplacas interagem mais fortemente com as moléculas ácidas, porém sem perda de morfologia e estrutura cristalina / Abstract: The main of this Dissertation is the preparation of nanostructures from T1-xZrxO2 mixed oxide. The precursor oxide was prepared by the homogeneous precipitation method, from titanium tetrachloride and zirconium oxichloride, using urea as the precipitating agent. The oxides were hydrothermally treated in autoclave, in NaOH solution, at temperatures of 140 and 170 °C, for period of 2 to 7 days. According to the physical-chemical characterizations, it was observed that the products prepared by the hydrohermal treatment with x < 0.50 presented morphologies like nanotubes, nanosheets and nanorods. However, for x > 0.05, it was observed the presence of two crystalline phases, sodium titanate and tetragonal ZrO2. For x > 0.50, it was not observed morphological changes, being tetragonal ZrO2 the obtained phase. Starting from the mixed oxide with x = 0.50, ZrTiO4 phase, it was observed nanotubes with the same crystalline phase. For x = 0.15, it was also observed that the increase of solution volume in the autoclave causes a crystallinity increase and destruction of the particles organization. The increase in time and temperature of reaction caused an increase in the crystallinity of the hydrothermal products for x = 0.15 e 0. 50; for x = 0, it was observed more quantity of nanotubes; and for x = 0.15, fewer nanosheets; for x = 0.80 and 1, it was not observed either morphological neither crystalline changes. The reactivity of the nanotubes (x = 0) and nanorods/nanosheets (x = 0.15) with organic molecules, which promote the morphology destructions and changes in the crystalline structure. These effects were increased with heating. The nanorods/nanosheets strongly interact with acid molecules, without loosing of morphology or the original crystalline structures / Mestrado / Quimica Inorganica / Mestre em Química

Introdução: A hipertensão arterial sistêmica (HAS) é uma condição clínica multifatorial caracterizada por níveis elevados e sustentados de pressão arterial. Nos últimos anos, estudos demonstraram o efeito cardiovascular de diversos metabólitos originados de várias espécies de plantas. O diterpeno é um exemplo, o qual age por meio de diversos mecanismos farmacológicos. Sabendo que o Manool pertence a esta classe de compostos, isso o torna uma substância com potencial uso no tratamento da HAS, motivo pelo qual se propôs o desenvolvimento deste trabalho. Objetivos: 1) Avaliar in vivo o possível efeito vasodilatador de diferentes doses do Manool e o efeito sobre os níveis plasmáticos de óxido nítrico (NO), em animais normotensos e hipertensos e; 2) Verificar in vitro os mecanismos endoteliais envolvidos na resposta de relaxamento, em anéis de aorta de ratos. Material e métodos: Os animais foram divididos aleatoriamente em dois grupos: hipertenso e normotenso. Os animais do grupo hipertenso foram submetidos ao procedimento cirúrgico 2R1C para indução de hipertensão, enquanto os animais do grupo normotenso foram sham-operados. A pressão arterial (PA) não-invasiva, foi mensurada utilizando-se um manguito, conectado a um sensor para registro de PA, colocado em torno da cauda do animal. Para identificar os efeitos in vivo do composto, três doses do composto foram aplicadas nos animais, a monitorização invasiva da PA foi realizada por meio do MP System 100 A. Para a medida do óxido nítrico (NO) plasmático, foi utilizada a técnica de quimiluminescência NO/ozônio (O3). Com intuito de observar os mecanismos envolvidos no relaxamento induzido pelo composto, curvas concentração-resposta para o Manool, foram obtidas em anéis de aorta com e sem endotélio, na presença e ausência de L-NAME e ODQ. Resultados: Os resultados sobre a ?PAS mostrou que o Manool, promoveu redução da PAS tanto em normotensos quanto hipertensos. Os resultados das curvas dose-resposta mostraram que o manool promoveu relaxamento Resumo dependente do endotélio e este foi inibido na presença de L-NAME e ODQ. Não foi observado diferença na dosagem de NOx. Conclusão: Em resposta aos objetivos propostos para a presente investigação pode-se concluir que o Manool é uma droga hipotensora, possivelmente dependente em grande parte da função endotelial via NO/cGMP. / Introduction: Systemic hypertension (SH) is a multifactorial clinical condition characterized by high and sustained levels of blood pressure. In recent years, studies have demonstrated the cardiovascular effect of various metabolites derived from many plant species. The diterpene is an example, which acts through different pharmacological mechanisms. The Manool belongs to this class of compounds, that makes a substance with potential use in the treatment of SH, which let us to propose the development of this work. Objectives: 1) To evaluate in vivo the possible vasodilator effect of different doses of Manool and the effect on the plasma levels of nitric oxide (NO) in normotensive and hypertensive animals; 2) Evaluate in vitro endothelial mechanisms involved in the relaxation response in rat aortic rings. Material and methods: The animals were randomly divided in two groups: normotensive and hypertensive. The animals of the hypertensive group underwent the surgical procedure 2K1C for hypertension induction, while the animals of the normotensive group were sham-operated. The blood pressure (BP) non-invasive, was measured using a cuff, connected to a sensor for registration BP, placed around the animal\'s tail. To identify the in vivo effects of the compound, three doses of the compound were applied in animals, invasive BP monitoring was performed using the System MP 100 A. For the measurement of NO plasma, we used the technique of chemiluminescence NO/ozone (O3). In order to observe the mechanisms involved in the relaxation induced by compound concentration-response curves for Manool were obtained in the aorta rings with and without endothelium in the presence and absence of L-NAME and ODQ. Results: The results on variation of systolic blood pressure (?SBP) showed that Manool, decreases the SBP in both normotensive as hypertensive. The results of the dose-response curves showed that the Manool promoted endothelium dependent relaxation and this was inhibited in the presence of L-NAME and ODQ. There was no difference in NOx dosage. Conclusion: In response to the proposed Abstract objectives for the present investigation may conclude that the Manool is a hypotensive drug, possibly dependent in large part on endothelial function NO / cGMP pathway.

Ce travail de thèse est axé sur la synthèse et la réactivité d'un nouveau germylène P,N-hétérocyclique stabilisé par un fragment phosphanylidène-phosphorane. Le premier chapitre constitue un état de l'art des études portant sur la réactivité des espèces dérivées du groupe principal vis-à-vis de petites molécules (H2, NH3, éthylène, etc.). Une emphase particulière a été apportée à la description des différents mécanismes impliqués dans l'activation des liaisons de hautes énergies et à leur comparaison avec ceux rencontrés dans le cas des métaux de transitions. Le deuxième chapitre présente la synthèse et la caractérisation complète de germylene-phosphacétènes stabilisés par différents ligands phosphine fonctionnalisés. Ces dérivés sont thermiquement labiles et leur décarbonylation à diverse températures conduit au germylène-phosphinidène transitoire correspondant. L'évolution de ces intermédiaires est étroitement liée à la nature du ligand phosphine coordinné au Ge(II) central et, dans le cas du germylène stabilisé par un ligand diaminophosphine à quatre chaînons très volumineux, une migration intramoléculaire conduisant à un nouveau germylène cyclique à six chaînons est observée. L'étude de ce germylène P,N-hétérocyclique fait l'objet du troisième chapitre de ce manuscrit. Ce germylène présente un écart énergétique HOMO-LUMO faible du fait de sa stabilisation par le fragment phosphanilidène-phosphorane. En conséquence, sa réactivité est accrue en comparaison des germylènes N-hétérocycliques classiques pour qui l'écart d'énergie singulet-triplet est supérieur. La réactivité de ce nouveau germylène, incluant une étude en chimie de coordination vers acides de Lewis, est présentée. Dans le quatrième chapitre, un adduit réactif du germylène P,N-hétérocyclique avec un borane a été étudié expérimental et théoriquement. Du fait de l'existence de plusieurs sites réactifs de différentes natures au sein de ce composé, il se comporte comme un système "multi-activation" vis-à-vis de petites molécules. Son utilisation en tant que catalyseur dans des transformations organiques sera également présentée. / The synthesis and reactivity of a new P,N-heterocyclic germylene, stabilized by a phosphanylidene-phosphorane moiety, are the subjects of this work. In the first chapter, a bibliographic study resumes the state of the art of principal main-group systems capable to activate small molecules, such as H2, NH3, ethylene, etc. following similar activation mechanism that those of transition metal complexes. The second chapter present the synthesis and full characterization of stable phosphaketenes functionalized germylenes supported by different phosphine ligands. These derivatives are thermally labile and easily undergo thermal decarbonylation, affording the corresponding transient germylene-phosphinidene. The evolution of these intermediates is strongly related to the nature of the phosphine ligand coordinated to the Ge(II) centre and, in the case of the germylene stabilized by the bulkier four-membered cyclic diamino-phosphine, the phosphine ligand migrates from the germanium to the phosphorus atom to form a new six-membered cyclic germylene. The study of this P,N-heterocyclic germylene is the main subject in the thirds chapter. This germylene presents a small HOMO-LUMO energy gap due to the stabilization provided by the phosphanilidene-phosphorane fragment. As a consequence, it presents an enhanced reactivity compared to that of classical N-heterocyclic germylenes, where the singlet-triplet energy gap is larger. The reactivity of this new germylene, as well as its coordination ability towards Lewis acids, will be discussed. In the fourth chapter, a stable adduct of the P,N-heterocyclic germylene with a bulky borane will be experimental and theoretically studied. Due to the presence of multiple reactive sites in this germylene-borane complex, it behaves as a multiple-activation system towards small molecules. Its use as catalyst in some organic transformations will be also presented.

This study expanded the current literature by assessing PTSD in relation to reactivity and recovery from negative emotional arousal among OEF/OIF/OND Veterans. Cardiac impedance was employed during a speech task and a trauma imagery procedure. Those in the PTSD-S group displayed lower SBP and higher TPR reactivity relative to the PTSD- and PTSD+ groups; lower CO reactivity relative to the PTSD+ group; and more CO recovery than those in the PTSD+ group to the trauma task. For speech task, Veterans in the PTSD-S group exhibited lower HR reactivity for both speech preparation and delivery than those in the PTSD- group. Depression was not a significant mediator in the relation between PTSD and reactivity. However, further analyses revealed that it served as a moderator between PTSD and reactivity during speech preparation (SBP, HR, and PEP reactivity), and speech delivery (HR, PEP, and CO reactivity). Simple slopes analysis revealed that depression was positively associated with HR and SBP (speech preparation) and HR (speech delivery) for those in the PTSD-S group. For those in the PTSD- group, depression was positively associated with PEP during the speech task (to include preparation) and negatively associated with SBP and CO (speech preparation) and HR and CO (speech delivery). For those in the PTSD+ group, depression was negatively associated with CO and positively associated with PEP. For the most part, Veterans in the PTSD-S group exhibited lower reactivity to both tasks than Veterans in the PTSD+ group or combat-exposed controls without PTSD. In light of the emerging evidence relating blunted reactivity to unhealthy behaviors and negative health outcomes (e.g., depression, obesity), it would appear that both extremes, exaggerated and diminished reactivity are maladaptive responses to stress and that the most optimally response to stress is a moderate reaction.

Major depressive disorder (MDD) is primarily characterized by prevalent sadness and anhedonia. Laboratory studies find that depression is characterized by reduced reactivity across emotional contexts, while a few studies using naturalistic designs find that depressed people show normative reactivity to negative life events and mood brightening in response to positive events. The current study was an investigation of emotional reactivity in depression through the use of experimental and naturalistic designs. This allowed for an investigation of sources of lab-life discrepancies in emotional functioning in depression, including negative affect (NA) regulation. We examined experiential reactivity across contexts and types of stimuli in 41 currently depressed (MDD) and 33 healthy controls. Results showed that overall, our groups were largely indistinguishable in NA and PA reactivity magnitude across contexts and types of stimuli, with some exceptions. When looking at sadness reactivity specifically, despite higher sadness at baseline, MDDs reported in the lab similar decreases in sadness to a humorous film as controls. In daily life, MDDs reported larger decreases in sadness in response to positive daily events, yet indistinguishable reactivity to a structured humorous film relative to controls. Analyses using HLM showed that NA response to the happy film in the acceptance condition was marginally predictive of overall NA in daily life but not of NA reactivity to positive events. Findings suggest group differences in emotional reactivity vary across contexts and stimuli, however these variations are dependent on specificity of emotion. Current results possibly highlight increased flexibility during experience of positive events in daily life in depression. Acceptance of NA may have implications for the experience of overall negative mood in depression.