The purpose of this study is to point to significant historical elements of James IV that appear to be characteristic of the plays of the late sixteenth century. One major characteristic of the plays of this period is the interest shown in historical events, current and. past. Other characteristics such as the use of allegory and didacticism appear in the plays of the period and are commented upon in this study. Standards of composition of this period that are relevant to James IV receive consideration also.

Made available in DSpace on 2016-06-02T20:21:35Z (GMT). No. of bitstreams: 1 6150.pdf: 1801179 bytes, checksum: d2366a6c320c54df184a270c81c7c653 (MD5) Previous issue date: 2014-02-27 / The present situation of energy and environmental setting in the world has favored the development of alternative energy sources, and has emerged as an option the use of biofuels, such as bioethanol. Besides ethanol produced from sugarcane, there is the alternative of to use plant biomass to get called second-generation ethanol. In Brazil, the major lignocellulosic material used to produce bioethanol is sugarcane bagasse, and this ethanol is obtained by fermentation of the hydrolyzate of the plant cell wall polysaccharides, this hydrolysis is performed normally by enzymes cellulolytic. Microorganisms, such as fungi of the genus Trichoderma, which are filamentous fungi present in the soil, have a variety of these enzymes that convert cellulose into glucose. In this context, the aim of this study was the recombinant production of Trichoderma harzianum IOC-3844 endoglucanase IV and its biochemical characterization. This Endo IV, which presents high similarity with Endo IV of other Thichoderma species, was expressed using the heterologous expression system of the yeast Pichia pastoris, and after be purified, assays were performed to test their activity. The recombinant enzyme hasn t show sign of degradation in any of the substrates used and can t be confirmed its hydrolytic action. However, the literature has been showed that these enzymes have capacity to increase the breaking of lignocellulose by cellulases (or a mix of them). Based on these data, a test was performed to evaluate the ability of endo IV supplemental activity in the cocktail Acellerase 1500 (Genencor) in the hydrolysis of biomass. In the experiment, copper was added as an electron donor and despite the increase in the hydrolysis of sugarcane bagasse the results showed that copper alone improves the cocktail performance. A circular dichroism analysis was performed and showed that the recombinant Endo IV is correctly coiled. The study showed that the enzyme produced at the laboratory has a high level of expression, but its activity couldn t be detected. The intention now is to perform tests with cocktails that don t contain expansins and isolated enzymes in order to verify that the Endo IV has effect upon them. / A atual situação do cenário energético e ambiental do mundo tem favorecido o desenvolvimento de fontes alternativas de energia, e como opção tem surgido a utilização de biocombustíveis, como o bioetanol. Além do etanol produzido a partir do caldo de cana, há a alternativa de utilizar a biomassa vegetal para obter o chamado etanol de segunda geração. No Brasil o principal material lignocelulósico utilizado para produção de bioetanol é o bagaço de cana-de-açúcar, e este etanol é obtido por meio da fermentação do hidrolisado dos polissacarídeos da parede celular dos vegetais, sendo esta hidrólise, realizada, normalmente, por enzimas celulolíticas. Microrganismos, como os fungos do gênero Trichoderma, que são fungos filamentosos presentes no solo, possuem uma variedade dessas enzimas capazes de converter a celulose em glicose. Nesse contexto, o objetivo deste trabalho foi a produção recombinante da enzima endoglucanase IV de Trichoderma harzianum IOC-3844 e sua caracterização bioquímica. Esta Endo IV, que apresenta alta similaridade com as Endo IV de outras espécies de Thichoderma, foi expressa utilizando-se o sistema de expressão heteróloga da levedura Pichia pastoris e, após ser purificada, foram realizados ensaios para testar sua atividade. A enzima recombinante não demonstrou sinal de degradação em nenhum dos substratos utilizados, não podendo ser comprovada sua ação hidrolítica. Porém, na literatura consta que essas enzimas têm a capacidade de aumentar a quebra de lignocelulose por celulases (ou uma mistura delas). Com base nesses dados, um teste foi realizado para avaliar a capacidade da endo IV de suplementar a atividade do coquetel Acellerase 1500 (Genencor) na hidrólise de biomassa. No experimento, foi adicionado cobre como doador de elétrons e apesar do aumento na hidrólise do bagaço-de-cana os resultados mostraram que o cobre sozinho melhora a performance do coquetel. Uma análise de dicroísmo circular foi realizada e revelou que a Endo IV recombinante se encontra corretamente enovelada. O estudo mostrou que a enzima produzida em laboratório possui alto nível de expressão, porém sua atividade não pôde ser constatada. Pretende-se agora realizar testes com coquetéis que não contêm expansinas e com enzimas isoladas, a fim de verificar se a Endo IV possui efeito sobre elas.

Submitted by Jordan (jordanbiblio@gmail.com) on 2017-06-10T14:44:11Z No. of bitstreams: 1 DISS_2015_André Marinho de Oliveira.pdf: 817020 bytes, checksum: ecb72ce953134e0f66ee35184d03d982 (MD5) / Approved for entry into archive by Jordan (jordanbiblio@gmail.com) on 2017-06-10T16:42:54Z (GMT) No. of bitstreams: 1 DISS_2015_André Marinho de Oliveira.pdf: 817020 bytes, checksum: ecb72ce953134e0f66ee35184d03d982 (MD5) / Made available in DSpace on 2017-06-10T16:42:54Z (GMT). No. of bitstreams: 1 DISS_2015_André Marinho de Oliveira.pdf: 817020 bytes, checksum: ecb72ce953134e0f66ee35184d03d982 (MD5) Previous issue date: 2015-04-09 / CAPES / Este trabalho se propõe a analisar a Primeira Cruzada sob a trajetória senhorial de Raimundo IV de Toulouse. As marcações temporais adotadas acompanham o sujeito histórico selecionado do nascimento (1041) a conquista de Jerusalém (1099); abordando o percurso das relações políticas que o levaram da conquista do título de “conde de Toulouse” até a participação como cruzado. Para que consigamos dissertar sobre a maioria dos pontos, estabelecemos um quadro comparativo com a condição senhorial no Ocidente do século XI, incluindo da formação dos territórios de domínio à ação como combatente no Oriente. No decorrer das análises das fontes, consigamos estabelecer comparações metodológicas nas atitudes políticas de Raimundo. Em meio a tantos aparatos político, nos propomos a encontrar a utilização da espiritualidade na justificação da conquista, a discussão da autoridade e do poder para as cruzadas, bem como a multiplicidade de políticas estabelecidas pela grande diversidade de senhores que participaram do evento. A bibliografia, para abarcar todas essas questões, varia de relatos clássicos a discussões mais recentes: buscamos relatar os pontos nodais do poder senhorial desde as discussões de Marc Bloch e George Duby, até as recentes abordagens de Thomas N. Bisson e Dominique Barthélemy. Tal perspectiva foi aplicada sobre o estudo da cruzada, propondo uma abordagem crítica de trabalhos como os de Steven Runciman e Christopher Tyerman, relatam os detalhes junto com as fontes de Raimundo d’Aguilers, cronista do conde de Toulouse e Foucher de Chartres, ambos cronistas participantes da cruzada. Essas fontes, e algumas outras estão no compilado e excelente trabalho comparativo de August C. Krey; cujas notas elucidativas também se incluem na bibliográfica, ainda que como parte da obra. / This work propounds to analyze the Crusades by the politic vision of Raymond of Toulouse. This temporal marks follow the historical subject, starting with born of Raymond IV (1041) and end up to of the First Crusade (1099); account his lifetime including both the conquer of title of earl of Toulouse and his participation as crusade. For we could relate about this points, we established a common point for most of lords and their domains formations. While we make the analyses of sources, we could methodological measure on the politic behavior of Raymond. In the midst of so many political apparatus, we propose to find the use of the spiritualized in the justification of the conquest, the discussion of authority and power for the Crusades, as well as the multiplicity of policies established by the great diversity of lords of which attended the event. The bibliography to encompass all these issues, ranging from classical texts with more recent discussions: report the nodal points of landlord range from discussions of Marc Bloch and George Duby and include the recent one Thomas N. Bisson and Dominique Barthelemy. Steven Runciman and Christopher Tyerman are also report the details with Raymond d’Aguilers, the chronicler of the count, and Foucher de Chartres, both members of the crusades. These Sources and some others are in the compilation work of August C. Krey whose elucidative notes are included in this work, despite inside the Krey work.

La complexation des ions Th(IV), U(VI), Am(III) et Pu(IV) avec le ligand hydrophile SO3-Ph-BTP4- et des ions Th(IV) et Pu(IV) avec le ligand hydrophile SO3-Ph-BTBP4– a été étudiée. Ces nouveaux ligands ont été proposés dans le cadre du recyclage des combustibles nucléaires usés, pour la séparation sélective d’actinides(III) par rapport aux lanthanides(III) et aux produits de fission. L’objectif de ce travail était d’étudier la capacité de ces ligands à complexer les actinides de degré supérieur, soit IV et VI. Après des essais infructueux par spectroscopie directe, la méthode appliquée pour atteindre cet objectif est une étude par extraction liquide-liquide. Le système d'extraction est composé de deux ligands chélatants qui sont en compétition pour complexer les ions actinides: l’extractant tétraoctyldiglycolamide (TODGA), molécule neutre, lipophile, donneur oxygéné tridenté et le complexant anionique hydrophile tridenté (ou tétradenté) SO3-Ph-BT(B)P4–. La méthode consiste à mesurer l’évolution de l’extraction du cation par le TODGA (DM) lors de l’ajout de quantité croissante de complexant en phase aqueuse, tout en fixant une force ionique constante en phase aqueuse. Un modèle mathématique est établi en prenant en compte les équilibres d’extraction et de complexation, il permet d’évaluer la stœchiométrie des complexes formés et leurs constantes de stabilité relatives. Les expériences réalisées ont permis de conclure à la présence des complexes An:SO3-Ph-BTP4– 1:1 et 1:2 pour tous les actinides testés et du complexe 1:1 pour An(IV):SO3-Ph-BTBP4–.Deux séries de constantes conditionnelles de stabilité de ces complexes ont été déterminées dans nos expériences: des constantes de stabilité conditionnelles, αL,i, valables pour une solution 1 M en nitrate et faciles à évaluer et des constantes ßL,i, considérant de manière explicite la complexation des cations par les nitrates, toujours pour une force ionique I = 1 M. En considérant les constantes conditionnelles de stabilité ßL,i, des actinides pour les ligands SO3-Ph-BTP4- et SO3-Ph-BTBP4-, l'ordre suivant est observé: UO22+ < Am3+ < Th4+ < Pu(IV), conformément à l’augmentation du potentiel ionique z/r2, où z est la charge formelle et r est le rayon de l'ion métallique. L'analyse des valeurs ßL,i suggère que les effets électrostatiques jouent un rôle plus important dans la formation des complexes entre les ligands azotés polydentés et les ions actinide.Pour les complexes de Am3+ avec le ligand SO3-Ph-BTP4– tridenté, si on compare nos résultats avec l’étude menée par TRLFS (fluorescence laser à résolution temporelle) pour des complexes analogues de Cm3+, les constantes de stabilité de stoechiométrie 1:1 et 1:2, déterminées par extraction liquide-liquide sont plus faibles. En outre, la stœchiométrie 1:3 décrite pour Cm3+ n'a pas été détectée dans notre étude. Les constantes de stabilité des complexes SO3-Ph-BTP et SO3-Ph-BTBP avec les actinides(IV) n'ont pas été rapportées dans la littérature. Néanmoins les complexes supérieurs n’ont pas été observés: 1:3 avec le ligand tridenté SO3-Ph-BTP4– et 1:2 avec le ligand tétradenté SO3-Ph-BTBP4–. Ces observations surprenantes à priori peuvent provenir du traitement mathématique simplifié des équilibres chimiques et nécessiteraient des vérifications supplémentaires par des techniques permettant d’identifier les complexes en solution. Cependant, les données de partage obtenues ont permis de proposer des constantes de stabilité conditionnelles qui peuvent être exploitées pour modéliser le comportement des actinides (III), (IV) et (VI) dans un procédé de séparation. / The complexation of Th(IV), U(VI), Pu(IV) and Am(III) with the hydrophilic ligand SO3-Ph-BTP4–, and of Th(IV) and Pu(IV) with the hydrophilic SO3-Ph-BTBP4– ligand was studied. These new hydrophilic aromatic poly-N-dentate ligands are proposed, in the frame of recycling spent nuclear fuel, for a selective separation of actinides(III) from lanthanides(III) and from other fission products. The aim of this work was to compare the ability of the actinide ions to coordinate these N-dentate molecules. After some disappointing tests with classical spectroscopies, the method of liquid-liquid (solvent) extraction was applied to reach this goal. The extraction system consisted of two chelating ligands that competed for the actinide ions: a lipophilic tri-O-dentate neutral molecule of dioctylamide (TODGA) and a hydrophilic tri(or tetra)-N-dentate anion SO3-Ph-BT(B)P4–. The simple model we applied, well known in literature, considered chemical equilibria resulting in accumulation of the metal complexes with the lipophilic ligand in the organic phase, and those with the hydrophilic ligand – in the aqueous phase. With increasing concentration of the hydrophilic ligand (the concentration of the lipophilic ligand being constant) the equilibrium shifted towards the complexes with the hydrophilic ligand, and the distribution ratio of the metal decreased.The results have been interpreted in terms of the formation of 1:1 and 1:2 actinide complexes with tridentate SO3-Ph-BTP4– and only single 1:1 An(IV) complexes with tetradentate SO3-Ph-BTBP4– ligands in the two-phase systems studied. Two series of conditional stability constants of the complexes have been determined in our experiments: one set of the conditional stability constants, αL,i, related to 1 M nitrate media, whereas the other, βL,i, – to aqueous solutions of ionic strength I = 1 M, where the complexation by nitrates was taken into account. In the latter case, when the effect of the actinide complexation by nitrates was deducted, the conditional stability constants, βL,1, of the actinide complexes with SO3-Ph-BTP4– increase in the order UO22+ < Am3+ < Th4+ < Pu(IV), in accordance with the increasing z/r2 ratio (where z is the formal charge and r is the radius of the metal ion). The analysis of the βL,i values suggests that the electrostatic effects play the major role in the formation of the complexes between the poly-N-dentate ligands and actinides ions.Concerning the complexation of Am3+ with the tri-N-dentate SO3-Ph-BTP4– ligand, if we compare our results with the literature values for the analogous Cm3+ complexes studied by a spectroscopic (TRLFS) technique, the stability constants of 1:1 and 1:2 complexes of Am3+ are much lower, and its 1:3 complex has not been found by the solvent extraction method. The stability constants of the SO3-Ph-BTP and SO3-Ph-BTBP complexes with the actinides(IV) have not been reported yet in literature, therefore such comparison was impossible in this case. However, the expected 1:3 complexes of Pu(IV) and Th(IV) with the SO3-Ph-BTP4– ligand have not been found in our solvent extraction experiments as well. Similarly, only 1:1 Pu and Th complexes with the tetra-N-dentate SO3-Ph-BTBP4– ligand have been found by solvent extraction, in spite of that the 1:2 complexes were also expected. These surprising results could be a result of oversimplification of the used model of extraction, and should be completed by further spectroscopic studies to identify all the complexes formed in the two-phase system studied. Nevertheless, the stability constants determined in the solvent extraction experiments (“practical” stability constants) allow us to correctly describe and to predict the behaviour of metal ions in such two-phase systems.

Dipeptidyl peptidase-IV (DPP-IV) is a multifunctional transmembrane glycoprotein removing X-Pro dipeptide from the amino-terminus of the peptide chain. This evolutionary conserved sequence protects a number of biologically active peptides against the unspecific proteolytic cleavage. DPP-IV belongs into the group of "Dipeptidyl peptidase-IV Activity and/or Structure Homologues" (DASH), which, except the canonical DPP-IV, comprises fibroblast activation protein-α/seprase (FAP), and several other molecules. However several of DASH molecules are the enzymes, they execute at least some of their biological functions by non-proteolytic protein-protein interactions. DASH molecules, their substrates and binding partners are parts of "DASH system" which is affected in several pathological process including a cancer. Specifically DPP-IV and its closest structural relative FAP are among others expected to be involved in the development and progression of malignant glioma. In this study we showed the expression and colocalization of DPP-IV and FAP in glioma cells in vitro and in human high grade gliomas. In addition to the DPP-IV/FAP double positive transformed glial cells, we also identified a subpopulation of FAP positive mesenchymal cells located in the perivascular compartment. Moreover we described the...

Malignant gliomas belong to a highly aggressive class of tumours. Average patient survival time generally does not exceed 15 months. Despite intensive research, no therapeutic strategies capable of significantly extending the lives of those affected by the disease have been established to date. One potentially viable area of research into possible therapeutic targets in cancer therapy focuses on cell surface proteases. This group of proteins includes dipeptidyl peptidase IV (DPP-IV). Changes to DPP-IV expression have been established in the case of various cancer types including malignant gliomas. Understanding the role of DPP-IV in the biological processes of this malignant disease may thus contribute to the development of new therapeutic modalities. This thesis is therefore dedicated to establishing an orthotopic xenograft model as well as a genetically engineered model (GEM) of the glioma. The effects of DPP-IV on the growth of an experimental glioma were subsequently examined, as was the ratio of catalytic and non- catalytic mechanisms in this process. The GEM model was used for monitoring enzymatic activity and DPP-IV distribution. Non-invasive fluorescence imaging was employed in order to monitor the intraexperimental dynamics of experimental gliomas. The results indicated that DPP-IV...

El descubrimient o del mayor efecto hipoglicémic o del bis(maltolato)oxovanadio (IV) (BMOV) con respecto a las salesde vanadio, propició el diseño, síntesis y evaluación in vitro e in vivo de una amplia variedad de complejos de oxovanadio(IV) con diversos ligandos orgánicos para su potencial uso como fármacos antidiabéticos que reemplacen , parcial ototalmente , las incómodas inyecciones de insulina en el tratamiento de la diabetes mellitus tipo 1 o los fármacos oraleshipoglicemiante s empleados generalment e en terapias combinadas para la tipo 2.Recientemente , un complejo etil sustituido , análogo al BMOV, ha completado favorablemente la fase clínica I deensayos en humanos. El diseño de nuevos tipos de complejos y el desarrollo de nuevos modos de administración constituyenactualmente un activo campo de investigación / Design of Vanadium Antidiabetic Agents: Development and Recent AdvancesThe discovery of the enhanced hypoglycemic activity of bis(maltolate)oxovanadiu m (IV) (BMOV) compared to simplevanadium salts stimulated the design, synthesis and both in vitro and in vivo evaluation of a large variety of oxovanadium (IV)complexes with different organic ligands for their potential use as antidiabetic drugs that may be able to substitute, either partially or totally, the daily insulin injections used in the treatment of type 1 diabetes mellitus or the orally available hypoglycemic drugs usually used in combined therapy for type 2 diabetes.Recently, a close BMOV analogue, an ethyl substitute, has already successfully completed the phase 1 clinical trial in humans. The design of new types of complexes and the development of alternative delivery methods represent an active research field today.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A Riparina IV, uma alcamida sintetizada de Aniba riparia, foi testada em modelos animais padronizados de dor, bem como os possÃveis mecanismos de aÃÃo envolvidos. Foram utilizados camundongos Swiss (20-30g), e a Riparina IV foi administrada de forma aguda em todos os testes, nas doses de 25 e 50 mg/kg, por via oral. Foram utilizados os testes de contorÃÃes abdominais induzidas por Ãcido acÃtico; placa quente; teste da formalina; hipernocicepÃÃo mecÃnica induzida pela carragenina; teste da nocicepÃÃo induzida por capsaicina, cinamaldeÃdo, mentol; teste da nocicepÃÃo induzida por glutamato, bem como em modelos comportamentais que permitam excluir a possibilidade de uma atividade relaxante muscular ou induzir resultados falso-positivos nos modelos anteriores, tais como testes do campo aberto e rota Rod. Os resultados demonstraram que a Riparina IV possui uma atividade antinociceptiva no modelo de nocicepÃÃo visceral induzida por Ãcido acÃtico. A Riparina IV nÃo demonstrou atividade no modelo de nocicepÃÃo tÃrmica da placa quente. O prÃ-tratamento com a Riparina IV reduziu significativamente a nocicepÃÃo inflamatÃria induzida pela segunda fase da formalina, porÃm nÃo alterou a nocicepÃÃo neurogÃnica induzida pela primeira fase do teste da formalina. Os animais prÃ-tratados com a Riparina IV tambÃm exibiram uma reduÃÃo significativa na hipernocicepÃÃo mecÃnica induzida pela carragenina. Em relaÃÃo à participaÃÃo dos receptores de potencial transitÃrio (TRP), a Riparina IV demonstrou atividade nos modelos de nocicepÃÃo induzida pela administraÃÃo de capsaicina e mentol, porÃm nÃo apresentou atividade na nocicepÃÃo induzida por cinamaldeÃdo. TambÃm reduziu a nocicepÃÃo induzida pela administraÃÃo intraplantar de glutamato. Para o estudo dos mecanismos de aÃÃo da Riparina IV foi utilizada somente a dose de 50 mg/kg da substÃncia. Na avaliaÃÃo da participaÃÃo dos canais de potÃssio ATP-dependentes, o prÃ-tratamento com glibenclamida nÃo foi capaz de reverter a aÃÃo antinociceptiva da Riparina IV, descartando-se o seu envolvimento; da mesma forma, o prÃ-tratamento com ioimbina, um antagonista &#945;2-adrenÃrgico, e pCPA, um depletor das reservas de serotonina, tambÃm nÃo foram capazes de reverter tal aÃÃo, nÃo havendo envolvimento com o mecanismo de aÃÃo da Riparina IV. O prÃ-tratamento com L-arginina, um precursor do Ãxido nÃtrico, reverteu a aÃÃo antinociceptiva da Riparina IV, sugerindo, em parte, a participaÃÃo da via do Ãxido nÃtrico no seu mecanismo de aÃÃo. Os resultados mostraram que essa substÃncia nÃo alterou a atividade locomotora no teste do campo aberto, nem diminuiu o nÃmero de quedas no teste do rota Rod, descartando a possibilidade de haver sedaÃÃo ou incoordenaÃÃo motora por parte da Riparina IV. Em sÃntese, os resultados demonstraram que a Riparina IV possui uma atividade em modelos animais de nocicepÃÃo, possivelmente envolvendo os receptores TRPV1, TRPM8, glutamatÃrgicos e a via do Ãxido nÃtrico. / Riparin IV, an alkamide synthesized from Aniba riparia, was tested in standard animal models of pain, as well as the possible mechanisms of action involved. It was used Swiss mice (20-30g), and Riparin IV was administred acutely in all tests, at the doses of 25 and 50 mg/kg, by gavage. It was used the tests of abdominal writhing induced by acetic acid, hot plate test, formalin test, mechanical hypernociception induced by carrageenan, nociception test induced by capsaicin, cinnamaldehyde and menthol, nociception test induced by glutamate, as well as models of behavior that ruled out the possibility of a muscle relaxing activity or induce false-positive results in previous models, such as the open field test and the rota Rod test. The results showed that Riparin IV has an antinociceptive activity at the model of visceral nociception induced by acetic acid. Riparin IV did not show any activity at the hot plate thermal nociception model. Pretreatment with Riparin IV reduced significantly the inflammatory nociception induced at the second phase of formalin test, but did not alter the neurogenic nociception induced at the first phase of formalin test. The animals pretreated with Riparin IV also exhibited a significant reduction at the mechanical hypernociception induced by carrageenan. Related to the participation of the Transient Potential Receptors (TRP), Riparin IV showed an activity at the models of nociception induced by capsaicin and menthol, but did not show any activity at the nociception induced by cinnamaldehyde. Also reduced the nociception induced by administration of glutamate at the rind paw. To study the mechanisms of action of Riparin IV, it was used only the dose of 50 mg/kg of the substance. At the evaluation of participation of the ATP-dependent potassium channels, pretreatment with glibenclamide was not able to reverse the antinociceptive action of Riparin IV, discharging its involvment; at the same way, pretreatment with yohimbine, an a2-adrenergic antagonist, and pCPA, a depletor of the serotonin reservations, were not able of reverse such action, not having any involvement with the mechanism of action of Riparin IV. Pretreatment with L-arginine, a precursor of Nitric Oxide, reversed the antinociceptive action of Riparin IV, suggesting, in part, the participation of nitric oxide pathway at the mechanism of action. The results showed that this substance did not alter the locomotor activity at the open field test, neither diminished the number of falls at the rota Rod test, discharging the possibility of sedation or incoordination by Riparin IV. In summary, the results showed that Riparin IV has an action in animal models of nociception, possibly involving the receptors TRPV1, TRPM8, glutamatergic receptors and the nitric oxide pathway.

As cucurbiturilas são moléculas versáteis empregadas em diversos ramos da química, essas gaiolas moleculares formam uma família de homólogos oriundos da condensação da glicolurila e do formaldeído em meio ácido. As aplicações se estendem para campos como catálise, fotoquímica, sínteses orgânica e inorgânica, química de materiais e supramolecular. Particularmente a cucurbit[6]urila, comumente chamada apenas de CB[6], uma molécula bastante simétrica, têm em seus opérculos, sítios propícios à coordenação, especialmente com espécies pequenas e pouco polarizáveis. Aproveitando o caráter dos portais, foi possível sintetizar um complexo inédito, com um sítio catalítico proveniente de íons vanadila, VO2+, ligados às extremidades do cavitando. O acesso ao centro catalítico desta molécula, seria determinado pela captura do substrato no interior do macrociclo, limitado pelo volume do substrato e pelas relações de solvofobicidade, pois a cavidade possui um caráter hidrofóbico. A estrutura desse complexo ainda não foi completamente elucidada, pois não foi possível obter um cristal único e determiná-la através de difração de raios-x. As técnicas de caracterização no estado sólido empregadas indicaram que esse novo complexo teria o seu centro metálico provavelmente numa configuração piramidal de base retangular, isso é evidenciado pelas medidas espectroscópicas que remetem a uma simetria C2V. Foram feitas tentativas de coordenação mono e binuclear, mas algumas técnicas apontam para a formação apenas da espécie mononuclear. Os primeiros testes catalíticos, em condições brandas para a conversão de hidrocarbonetos apresentaram bons resultados frente a substratos lineares e inatividade frente a substratos cíclicos mais volumosos. Os resultados obtidos nos levam a crer que as reações de oxidação de alcanos, com estas espécies, se dão pelo interior da cavidade, ao longo do orbital dz2 do íon (V=O)2+, e não pela parte superior através do átomo de oxigênio ligado ao vanádio. / Cucurbiturils are versatile molecules used in several branches of chemistry. These molecular cages form a family of homologues from the condensation of glycoluril and formaldehyde in acidic medium. Their applications range from catalysis, photochemistry, organic and inorganic synthesis, materials and supramolecular chemistry. Particularly cucurbit[6]uril, or simply CB[6], is a very symmetrical molecule, which posesses coordination points on its portals, especially with hard acids. Due to this characteristic, it was possible to synthesize a new complex, with a vanadyl, VO2+, catalytic center bonded to the extremity of the cavitand. The access to the catalytic center of this molecule should be determined by the entrance of the substrate inside the macrocycle, which is limited by its volume and by solvophobicity, because the cavity is strongly hydrophobic. The structure of this new complex could not be completely solved yet, because it was impossible to obtain a single crystal for X-rays diffraction analysis. The solid state characterization techniques indicated that this new complex has its metallic center in a rectangular-base pyramid configuration. This was shown by the spectroscopic evidences which point to a d1 ion in a C2V symmetry. Attempts were made to synthesize both mono and binuclear species, but all the techniques we have used have demonstrated that only the former one was obtained. The first catalytic tests for hydrocarbons convertion in mild conditions have shown good results towards for linear substrates and no activity at all towards more volumous cyclic molecules. The results we have obtained indicate that the alkane oxidation reactions with these complexes occur inside the cavity along the (V=O)2+ ion dz2 orbital , and not on its superior moiety on the vanadyl oxygen atom.

Este trabalho propõe a tradução do discurso Panegírico, de autoria do ateniense Isócrates. A versão vem acompanhada de notas, que visam a fornecer um breve comentário das passagens mais importantes do texto. Um estudo introdutório, cujo primeiro capítulo pretende discutir algumas questões propostas pelo texto, tratando de sua composição, do tratamento dos fatos históricos e um breve relato das principais interpretações modernas do Panegírico. O capítulo seguinte aborda o problema dos bárbaros no Panegírico e como o retrato de Isócrates dos povos não gregos visa a reforçar as propostas feitas pelo autor em seu texto. Na parte final do estudo, examina-se a relação desse texto com obras precedentes tratando das mesmas questões que o Panegírico. / This work proposes to translate the Panegyricus, a speech by the Athenian Isocrates. Endnotes have been added, in order to comment the most important passages in the text. In addition, an introductory study is included to clarify the some points of the text, such as the problems posed by the composition of the text, its treatment of the historical facts and a brief review of the main modern interpretations of the Panegyricus. The next chapter discusses the role which the barbarians play in the Panegyricus and how Isocrates portrait of the non-Greek peoples serves the propositions advanced by the author in his text. The final part of the study examines the relation of the Panegyricus with texts treating the same questions.