En prenant particulièrement appui sur le cas de la cité de maisons préfabriquées du Merlan à Noisy-le-Sec, cette thèse élabore une critique du processus de patrimonialisation. Elle en met en évidence les enjeux sociaux, architecturaux et historiques. La nature singulière des petites constructions de la cité qui date de la Reconstruction, amène à interroger les termes mêmes sous lesquels elles sont aujourd'hui considérées : s'agit-il d'un monument à considérer comme un ensemble ou de monuments historiques divers ? D'un patrimoine ou de patrimoines ? Le quartier, par son histoire et ses spécificités, oblige à reconsidérer des termes dont la définition, pour commune qu'elle semble, ne va pas sans histoire ni problèmes. La thèse l'établit à un certain niveau de généralité en évoquant d'autres cas, plus ou moins proches de ceux de la cité. Le but est d'esquisser des propositions qui tiennent compte du caractère habité, hier comme aujourd'hui, des cas considérés. Il s'agit d'abord de proposer des concepts aptes à déplacer le champ des perspectives et polémiques classiques (préserver, conserver, restaurer) : ceux de «traduction» et de «mises en récits». Il s'agit ensuite d'éprouver, de réaliser ou de mettre en œuvre ces concepts en mettant en jeu les techniques du «web-documentaire». L'objectif est d'exposer une forme alternative de recherche, théorique et pratique, susceptible de permettre à un public élargi de s'interroger sur la mémoire des lieux. Le travail concerne ainsi le design qu'il envisage lui-même comme élément méthodologique de recherche. / Focusing on the case of the prefabricated houses in the cité of Merlan in Noisy-le-Sec, this PhD analyses the process of patriomonialisation or cultural heritage. It underlines its social, architectural and historical aspects. The singularity of the small buildings of the cité which date back to the Reconstruction period makes us wonder about the terms to be used to refer to it: is it a monument on its own or a set or various historical monuments? Should we talk about a heritage or heritages in that case? Because of its history and specificities, the neighbourhood forces us to reconsider the definitions of supposedly-familiar words. This thesis aims at developing these definitions to a certain level of generality also using other cases, quite similar to those of the cité. The purpose is to suggest projects that take into account the fact that these buildings were lived in in the past and are still lived in today. First, it proposes some concepts able to move the perspectives and the conventional controversy (preserve, conserve, restore): those of "translating" and "putting into stories". Then it experiments, realizes and implements these concepts on a practical level by using "web-documentary" techniques. The aim is to expose an alternative research form, both theoretical and practical, potentially enabling a wider audience to question the memory of places. This work involves design and considers it a methodological research element.

La thèse porte sur l’industrialisation du logement en France (1885-1970), de la construction légère et démontable à la construction lourde et architecturale. L’objet de cette thèse se place à l’interface de quatre grands sujets : l’existence de l’industrialisation avant la seconde guerre mondiale, la politique technique du ministère de la Reconstruction et de l’Urbanisme (MRU), les projets réalisés après la seconde guerre mondiale dont on applique les méthodes d’industrialisation imposées par l’Etat, et les principes de la charte d’Athènes. La période d’étude s’étend de 1885, premier témoin européen de l’industrialisation du bâtiment, à 1970 année de remise en cause de ce type de construction. l’industrialisation du bâtiment a des racines très anciennes, elle croît d’abord parmi les militaires, pour les besoins de la conquête coloniale, des campagnes, des guerres qui enflamment l’Europe. La cabane de plage ou la baraque de villégiature, la tente de toile, l’auvent de marché, sont autant de figures constructives qui prolifèrent en fin du XIXe siècle. Surtout, les expéditions coloniales menées tambours battants exigent rapidité, sécurité, capacité : la baraque est la solution industrielle. L’industrialisation se poursuit, non plus légère mais lourde. Elle est pour l’Etat la principale voie car elle diminue le prix de revient de la construction, réduit les interventions et améliore le confort des logements. A partir de 1945, l’Etat français nouveau investit dans la partie la plus sinistrée, encourage les innovations basées sur l’emploi de matériaux et de techniques en instituant l’agrément technique des « matériaux nouveaux et des procédés non traditionnels de construction ». Dans la première partie de cette recherche, nous avons essayé de montrer qu’il y a bien une industrialisation du bâtiment avant la seconde guerre mondiale. L’industrialisation occupe « brutalement » la construction légère dans les années 1890. La baraque démontable et transportable, militaire, ambulante devient l’objet de compétitions, de confrontations, d’intérêts guerriers en Europe de l’ouest. Des dizaines de modèles sont préfabriqués et montés en arrière des champs de batailles ou en prévision des conquêtes territoriales. Dans un second temps nous avons choisi de continuer l’histoire de la construction lourde dans l’après guerre, spécifiquement la construction du logement. Par conséquent nous avons choisi d’étudier deux projets remarquables de la période juste après la seconde guerre mondiale. 1- Le projet de la cité expérimentale de Noisy-le-Sec : au travers de ce projet l’Etat a essayé de tester les procédés et matériaux nouveaux permettant d’utiliser moins de matières premières et d’énergie, de simplifier la mise en œuvre, de faire connaître ces nouveautés pour faire de la technique une technologie et contribuer à l’amélioration de l’habitat (confort intérieur, équipement). Pour ce faire, il importe des procédés et impose des changements de rythme et d’échelle. 2- le projet des Grands Terres : Le chantier des Grands Terres doit être considéré comme le premier chef d’œuvre de préfabrication lourde de logements. Ce projet affirme aussi une nouvelle façon de penser la ville et son rapport à l’habitat, il est une des applications réussies de la Charte d’Athènes, bible de l’urbanisme de Lods, et une référence pour les évolutions urbaines des décennies 60 et 70. Enfin, pour élaborer cette recherche académique j’ai pris le parti “chronologique” ” : 1885-1940 “la construction légère et démontable”, 1940-1970, “la préfabrication lourde et indémontable”, 1945-1953 “ la cité d’expérience de Noisy-le-Sec”, 1952-1956, “le modèle achevé le plus réussi des grands opérations, le projet des Grandes Terres”. / The thesis focuses on the industrialization of housing in France (1885-1970), from the lightweight and removable construction to the heavy construction and architecture. The purpose of this thesis is placed at the interface of four major topics: the existence of industrialization before the World War II, the technical policy of the Ministry of Reconstruction and Urbanism (MRU), projects after the Second World War that applied the methods of industrialization imposed by the State, and the principles of the Charter of Athens. The study period extends from 1885, the first witness of European industrialization of the building, to 1970ties of questioning of this type of construction. The industrialization of the building has very old roots; it grows primarily in the military, for the needs of the colonial conquest, campaigns, wars, which inflamed the Europe. The beach cabin or the shack resort, the canvas tent, canopy of market, are as much constructive figures which are proliferating at the end of the nineteenth century. Especially, the colonial expeditions conducted drums requiring speed, security, capacity: the shack is the industrial solution. Industrialization continues to be not light anymore but heavy. It is the main route for the State because it decreases the cost price of the construction, reduces the interventions and improves the comfort of the housing. From 1945, the French State newly invests in the most stricken, encourages innovation based on the employment of materials and techniques in establishing the technical approval of the "new materials and non-traditional methods of construction". In the first part of this research, i have tried to show that there is an industrialization of the building before the Second World War. Industrialization occupied "brutally" lightweight construction in the 1890s. The shack removable and transportable, military becomes the object of competitions, confrontations, of interest of warriors in Western Europe. Dozens of models are prefabricated and really mounted in the fields of battles or in anticipation of territorial conquest. In a second time i have chosen to continue the story in the heavy construction in the after war, specifically the construction of the housing. Therefore i chose to study two outstanding projects of the period just after the Second World War. First is the project of Noisy-le-Sec, through which the state tried to test the processes and new materials to use fewer the raw materials and energy, to simplify the implementation, to raise awareness of these innovations to advance technology and contribute to the improvement of the habitat (interior comfort and equipment). To do this, it imported new processes and imposed changes in pace and scale. Second is the project of Grandes Terres: The site of the project of Grandes Terres could be considered as the first masterpiece of heavy housing prefabrication. In addition the project of Grandes Terres affirms a new way of thinking about the city and its report to the habitat, it is one of the successful applications of the Charter of Athens, bible of the urbanism of Lods, and a reference for the urban development’s decades 60 and 70. Finally, to develop this academic research I have taken the party "chronologically":1885-1940 "the lightweight construction and demountable", 1940-1970, "the heavy prefabrication and Unremovable", 1945-1953 "the city of experience of Noisy-le-sec", 1952-1956, "the completed model which is the most successful of major operations, the project of Grandes Terres".

A esterificação do sec-butanol com ácido acético, submetida à catálise homogênea, apresenta poucos resultados experimentais de cinética reacional e equilíbrio químico disponíveis na literatura. A presente dissertação visa determinar os parâmetros cinéticos e de equilíbrio químico desta reação de esterificação, empregando modelo cinético de 2ª ordem baseado em atividades. Os experimentos cinéticos foram realizados em reator batelada com auxílio da metodologia Karl Fischer para análise do teor de água e determinação do perfil de frações molares ao longo da reação. A principal dificuldade na modelagem desta esterificação consistiu em representar satisfatoriamente as não-idealidades da mistura em fase líquida, em espacial nas reações cuja fração molar inicial de ácido acético foi superior a 50%. Netas condições admitiu-se a ocorrência de dissociação do ácido acético levando ao surgimento de interações iônicas. O modelo empregado para obtenção das atividades, com base em frações molares, foi o NRTL. Este modelo representou bem as interações moleculares em condição de baixa acidez, mas apresentou desvios em condições de acidez e teores de água mais elevados. O estudo também visou o desenvolvimento de modelos de calibração para um método analítico on-line visando determinar o perfil de frações molares ao longo da reação. O método empregado foi a espectroscopia de infravermelho próximo (NIR), em vista à capacidade deste método analítico em determinar quantitativamente frações molares de água, além dos demais compostos envolvidos. Outro fator determinante ao emprego do NIR é a seu crescente uso no meio industrial, e o presente trabalho visou também contribuir para o uso futuro desta técnica de monitoramento no processo industrial. Modelos de calibração multivariável com conjuntos de calibração interna por validação cruzada se mostraram adequados ao sistema estudado. Calibrações externas resultaram em modelos imprecisos, não sendo possível determinar claramente os fatores responsáveis pela imprecisão. / There is a lack of literature data on the reaction kinetics and equilibrium of the homogeneously catalyzed esterification of sec-butanol with acetic acid. This work aims at obtaining the kinetic parameters and chemical equilibrium parameters of this esterification reaction by using a second order kinetic model based on activities. The kinetic experiments were performed in a batch reactor and the Karl Fischer analytical method was used to determine the molar fraction of water along the reaction progress. The main challenge of modeling this reaction was to represent the highly non-ideal mixture in liquid phase, specially for reactions runs starting with acetic acid mole fraction higher than 50%. In these conditions, it was assumed the occurrence of acetic acid dissociation that leads to ionic interactions. The thermodynamic model used to calculate the activities was the NRTL. This model predicted well the molecular interactions on low acidity conditions but presented deviations when molar fractions of acid and water were higher. The present study also aims to develop calibration models for analytical on-line method to obtain molar fraction profiles along the reaction. Near infrared spectroscopy (NIR) was used due to the possibility of quantitatively analyze water mole fraction, besides the mole fractions of the other components. Another important reason to choose NIR was its crescent use in industry, and the present work intended to contribute towards the future use of this on line monitoring technique in industrial applications. Multivariate calibration models using internal set of calibration and cross-validation seems to be suitable for this system. External set of calibration leads to less accurate models, and the causes of this lack of accuracy were not clearly identified.

Made available in DSpace on 2016-03-15T19:32:52Z (GMT). No. of bitstreams: 1 Vinicius Jose Ribeiro de Carvalho.pdf: 508933 bytes, checksum: 35f5bc3268f8eb84a3d4d15678926b51 (MD5) Previous issue date: 2015-02-03 / This study seeks to understand the utilization of EBITDA by Brazilian market professionals. EBITDA, which emerged in the 1970s in the United States as a tool to measure the operating performance of companies with heavy capital investments and / or highly leveraged companies, due to its success quickly spread throughout the world as an important proxy for cash flows. However, over the years the academic and professional community, as well as regulators and standard-setting bodies, raised a number of criticisms and warnings on its use, possibly greater than its virtues. Thus, was born the motivation of this work: why and how highly skilled and qualified professionals continue utilizing EBITDA in their daily work, despite its conceptual weaknesses? Additionally, there was the motivation to discuss an issue lacking depth in Brazil. This is a qualitative and exploratory study, conducted through interviews with a sample of professionals selected by convenience and the data analyzed by the content analysis technique, with ATLAS.ti software support. The results show that the professionals of the sample continue using EBITDA mainly for ease of use and calculation, and deem it a good measure of operating performance. However, in addition to several criticisms, also showed us that they continue to utilize EBITDA due to the lack of a good proxy for cash flow that has a similar cost-benefit relation. Finally, we identified that one of the probable reasons for its mass utilization lies in Mimetic Isomorphism, as analyzed by the New Institutional Sociology, or Neo-institutionalism. / Este trabalho buscou entender a utilização do EBITDA por profissionais atuantes no mercado profissional brasileiro. O EBITDA, que despontou na década de 1970 nos Estados Unidos da América como uma ferramenta para medir o desempenho operacional de empresas com pesados investimentos em capital intensivo e/ou empresas altamente alavancadas, devido ao seu sucesso rapidamente se disseminou por todo o mundo como uma importante proxy para fluxos de caixa. No entanto, ao longo dos anos a comunidade acadêmica e profissional, assim como órgãos reguladores e normatizadores, levantaram uma série de críticas e ponderações quanto ao seu uso, possivelmente maiores que suas virtudes. Assim, nasceu a motivação deste trabalho: por que e como profissionais tão gabaritados continuam utilizando o EBITDA em seu dia a dia, apesar de suas fragilidades conceituais? Também teve-se a motivação de discutir um tema pouco aprofundado no Brasil. Trata-se de um trabalho de cunho qualitativo e exploratório, realizado através de entrevista com amostra de profissionais selecionados por conveniência e com os dados analisados pela técnica de análise de conteúdo, com suporte do software ATLAS.ti. Os resultados apontaram que os profissionais da amostra continuam utilizando o EBITDA principalmente pela facilidade de uso e de cálculo, além de entenderem ser uma boa medida de desempenho operacional. No entanto, além das diversas críticas tecidas, apontam também que o utilizam devido a falta de uma boa proxy para fluxo de caixa que tenha custo benefício de utilização semelhante. Por fim, identificamos que uma das razões para sua utilização reside no Isomorfismo Mimético, conforme analisado pela Nova Sociologia Institucional, ou Neo-institucionalismo.

La présence d'hétéroatomes et métaux dans des fractions lourdes de pétrole brut peuvent entraîner la désactivation des catalyseurs d’hydrotraitement et d’hydrocraquage. Les composés contenant ces éléments sont connus pour être inclus dans des agrégats macromoléculaires d’asphaltènes, qui sont considérées comme les composants les plus problématiques des produits pétroliers. Ces travaux ont pour objectif d’apporter une meilleure compréhension de l’environnement chimique de ces espèces et des phénomènes d’agrégation pour optimiser les processus de raffinage. Des techniques de séparation comme la chromatographie de perméation de gel ou Gel Permeation Chromatography (GPC), Advanced Polymer chromatographie (APC) et la chromatographie sur couche mince d’haute performance ou High Performance Thin Layer Chromatography (HPTLC) ont été combinées avec des techniques d’analyse élémentaire comme la spectrométrie de masse à plasma à couplage inductif ou Inductively Coupled Plasma Mass Spectrometry (ICP-MS) et la spectrométrie de masse moléculaire d’haute résolution pour la caractérisation des fractions pétrolières lourdes. Les profils de distribution en taille d’espèces qui contiennent du vanadium, du nickel et du soufre, les hétéroatomes et métaux les plus abondants dans les produits pétroliers, ont été déterminés par GPC couplé à une détection élémentaire par ICP MS. Les paramètres ayant le plus d’impact sur la distribution en taille et l’évolution des agrégats dans les solutions de différentes coupes pétrolières ont été optimisés. Cela nous a permis de faire différentes comparaisons, entre de nombreuses charges et effluents de procédés, ainsi que d’autres séries d’échantillons ou de mélanges provenant d’unités-pilotes d’hydrotraitement. Les résultats obtenus ont pu être mis en regard de caractéristiques macroscopiques comme la viscosité. Le couplage du nouveau système APC avec l’ICP MS a été mis au point avec succès. Cette technique a permis de réaliser des cartographies d’échantillons pétroliers plus rapides qu’en GPC tout en consommant moins de solvant. Cependant, les différences des chromatogrammes APC obtenus par rapport aux profils GPC suggèrent des interactions indésirables avec la phase stationnaire, qui ont été l’objet d’une évaluation approfondie.Enfin, un dernier type de séparation a été évaluée. L’HPTLC, qui utilise des plaques à usage unique, peut être appliquée à la séparation de produits lourds par polarité, et ce sans étapes de déasphaltage préalable, contrairement aux colonnes de chromatographie liquide qui peuvent être détériorées à cause de l'adsorption irréversible et de la précipitation des asphaltènes. Différents types de plaques et éluants ont été testés afin de développer une méthode simple pour la séparation des fractions SAR (Saturés, Aromatiques et Résines) des échantillons de distillat sous vide ou Vacuum Gas Oil (VGO). Ce travail avait pour but des migrations en une seule étape et analyse UV qui pourrait être mis en œuvre pour l’analyse de routine dans les laboratoires de contrôle avec une adsorption irréversible réduite. Des résultats très prometteurs ont été obtenus avec l’utilisation de plaques de cellulose pour la séparation des familles de polarité différentes au sein des agrégats d’asphaltènes. Des tests sur l'analyse directe des plaques par Désorption-Ionisation par Électronébulisation (DESI) MS, l'analyse directe en temps réel ou Direct Analysis in Real Time (DART) MS et Ablation Laser (LA) ICP MS ont été effectués. / The presence of heteroatoms and metals in heavy fractions of crude oil can cause the deactivation of hydrotreatment and hydrocracking catalysts. Compounds containing these elements are known to be included in macromolecular asphaltene aggregates, which are considered the most problematic components of heavy oil. This thesis aimed for a better understanding of the chemical environment of these species and on the aggregation phenomenon to optimize refining processes. Separation techniques such as Gel Permeation Chromatography (GPC), Advanced Polymer Chromatography (APC) and High Performance Thin Layer Chromatography (HPTLC) were combined with elementary analysis techniques such as Inductively Coupled Plasma Mass Spectrometry (ICP MS) or high-resolution molecular mass spectrometry for the characterization of heavy fractions of crude oil. Here, the size profiles of species that contain vanadium, nickel and sulfur, the most abundant heteroatoms and metals present in petroleum products, were determined by GPC online with elemental detection by ICP MS. The parameters having the most significant impact on size distribution and the evolution over time of aggregates from solutions of different petroleum cuts were optimized. This allowed the comparison between various feeds and effluents and other series of samples and mixtures from pilot units of refining processes by GPC ICP MS. Results obtained could be related to macroscopic characteristics such as viscosity. Hyphenation of the new APC System to ICP MS has been successfully completed. It allowed the mapping of petroleum samples faster than GPC, therefore with less solvent consumption. However, the differences of the APC chromatograms obtained with respect to the GPC profiles suggested significant unwanted interactions of the highly polar compounds of the petroleum samples with the stationary phase, which have been thoroughly studied. Finally, another type of separation was evaluated. HPTLC, of single-use plates, can be applied to the analysis of heavy petroleum products by polarity without prior deasphalting steps while chromatography columns can be deteriorated because of the irreversible adsorption and asphaltene precipitation. To this end, various types of plates and eluents were tested to develop straightforward SAR (Saturates, Aromatics and Resins) separations of Vacuum Gas Oil (VGO) samples. This method, based on single-step migrations with reduced irreversible adsorption and UV monitoring, could be implemented for routine analysis in control laboratories. Very promising results were obtained by the use of cellulose plates for the separation of different families within asphaltene aggregates. Tests on Desorption ElectroSpray Ionization (DESI) MS, Direct Analysis in Real Time (DART) MS and Laser Ablation (LA) ICP MS analyses of the plates have been performed.

Characterization of cellulose by its molecular weight distribution is afforded after polymeranalogeous dissolution. Additionally, a molecular dispersion of the polymer is a prerequisite. Common processes are dissolution of cellulose in dimethylacetamide-lithiumchloride, nitration and carbanilation. Degradation of the polysaccharide chains can occur in each of the mentioned processes. It is shown that degradation in pyridine occurs via beta-elimination at carbonyl groups along the cellulose chains. Carbanilierung in DMSO is much more pronounced. It comprises oxidation along the Pfitzner-Moffatt-mechanism and subsequent beta-elimination at the thus formed carbonyl-groups. This was elucidated with model systems and by investigation of the carbanilation in different media. Carbonyl groups of cellulose are masked through reaction with phenylisocyanate. This was shown with model. Therefore, the determination of carbonyl groups in cellulose-tricarbanilates is not possible. The separation of low-molecular weight byproducts was optimised. The influence of pretreatment and preactivation of cellulose-samples on the completeness of the conversion was studied. A standard protocol for the carbanilation of cellulose is provided. / Cellulose wird u.a. durch ihre Molmassenverteilung charakterisiert, deren Ermittlung ein polymeranaloges Verfahren zur molekulardispersen Auflösung des Polymers erfordert. Hierfür sind die Direktlösung, die Nitrierung und die Carbanilierung in Gebrauch. Bei allen Prozessen kann es zum Abbau der Polysaccharidketten kommen, wobei diesen Prozessen wenig Beachtung geschenkt wurde. In der Arbeit wird gezeigt, daß der Abbau bei der Carbanilierung in Pyridin durch Beta-Eliminierung an vorhandenen Carbonylgruppen erfolgt. Die Carbanilierung in DMSO fällt stets stärker aus als bei Einsatz von Pyridin und umfasst die Prozesse Oxidation nach dem Pfitzner-Moffatt-Mechanismus und anschließende Beta-Eliminierung an den neu gebildeten Carbonylgruppen. Dies wird durch Untersuchungen an Modellsystemen und am Polymer herausgearbeitet. Carbonylgruppen an Cellulose werden durch die Umsetzung mit Phenylisocyanat maskiert, was an Modellverbindungen gezeigt wurde (Bildung von Endioldicarbanilaten und carbanilierten Halbacetalen). Ihre Bestimmung in Cellulosecarbanilaten ist daher nicht möglich. Die Abtrennung von niedermolekularen Nebenprodukten der Umsetzung wurde optimiert. Der Einfluss der Vorbehandlung und Voraktivierung von Celluloseproben auf die Vollständigkeit der Umsetzung wurde eingehend untersucht. Es wird ein Standardverfahren zur Carbanilierung von Cellulose angegeben.

[pt] Uma das formas de detectar a contaminação ambiental é pela análise de respostas bioquímicas, ou biomarcadores, de tecidos de organismos-sentinela, como os mamíferos marinhos, uma vez que estes atuam como bioindicadores da saúde dos oceanos e de suas respectivas cadeias tróficas. A toninha (Pontoporia blainvilei) e o golfinho-de-dentes-rugosos (Steno bredanensis) são animais com longa expectativa de vida e estão no topo da cadeia alimentar, sendo, portanto, considerados indicadores adequados de contaminação ambiental. Neste trabalho foram estudadas as concentrações de metais e metalóides, tanto não-essenciais quanto essenciais, em amostras de fígado, rim e músculo de indivíduos de P. blainvilei e S. bredanensis coletados na Região dos Lagos e Norte Fluminense do estado do Rio de Janeiro, através da técnica de espectrometria de massas com plasma indutivamente acoplado (ICP-MS). Além das concentrações totais, foram avaliados como estes se distribuem nas diferentes frações subcelulares, obtidas a partir de processos de extração diferencial. Além disso, foi avaliada também a indução de metalotioneína (MT) e glutationa reduzida (GSH), consideradas proteínas de resposta a este tipo de contaminação, por espectrofotometria na região do UV-visível. Não houve diferença significativa entre as concentrações de MT encontradas nos três tecidos analisados para ambas as espécies, nem para GSH em P. blainvilei. No entanto, foi verificada uma diferença significativa entre GSH de fígado e músculo em S. bredanensis. Como esperado, a concentração no fígado foi mais elevada, por este ser um órgão metabolicamente ativo, além do principal órgão de destoxificação. Em P. blainvilei, elementos como Al, As, Cd, Cr, Mn, Pb e Ti, apresentaram altas concentrações nas frações termolábil e termoestável de todos os tecidos avaliados, indicando que grande parte destes analitos está sendo destoxificado por complexação com MT ou outras proteínas e compostos não enzimáticos. Outros elementos, como Ag, Cu, Fe, Hg, Ni, Se, Sn e Zn, embora presentes nos indivíduos, apresentaram a maior parte de sua concentração na fração insolúvel, indicando que, provavelmente, as vias preferenciais de destoxificação destes elementos nesta espécie não sejam realizadas através de MT. Em S. bredanensis, os metais Al e Cr também foram encontrados majoritariamente na fração insolúvel. Com relação às concentrações totais desses metais, níveis elevados para a maioria dos analitos foram observados em fígado, rim e músculo na espécie S. bredanensis. Diversas correlações estatisticamente significativas foram observadas entre elementos não-essenciais e essenciais em todas as frações subcelulares, no fígado e músculo de ambas espécies, através de uma análise de componentes principais. Além disso, alguns efeitos protetivos foram postulados contra elementos não-essenciais, avaliados a partir de cálculos de razões molares. Diferentes perfis foram observados para metaloproteínas contidas na fração termoestável destes indivíduos, através da técnica de cromatografia de alta eficiência acoplada a ICP-MS (HPLC-ICP-MS), indicando acúmulo dos metais e metalóides nos tecidos analisados, possível perturbação da homeostase dos elementos essenciais e tentativas de desintoxicação de metais não-essenciais por diversas metaloproteínas. / [en] One of the ways to detect environmental contamination is by analyzing biochemical responses, or biomarkers, in sentinel species tissues, such as marine mammals, as these animals act as bioindicators of ocean health and their respective trophic chains. Porpoises (Pontoporia blainvilei) and rough-toothed dolphins (Steno bredanensis) present long-life expectancy and are at the top of the food chain and are, therefore, considered appropriate environmental contamination indicators. In this study, environmental contamination by metals and metalloids, both non essential and essential, was assessed by means of inductively coupled plasma mass spectrometry (ICP-MS), as well as their distribution in different subcellular fractions, obtained from differential extraction processes analysis, in P. blainvilei and S. bredanensis liver, kidney and muscle samples of individuals sampled from in the Lakes and Northern Fluminense regions, in the state of Rio de Janeiro. In addition, the induction of both metallothionein (MT) and reduced glutathione (GSH) considered response proteins to this type of contamination, were also assessed by spectrophotometry in the UV-visible region. No significant difference between MT concentrations in the three analyzed tissues were noted for both species. This was also observed for GSH in P. blainvilei. However, a significant difference was observed between liver and muscle GSH in S. bredanensis, and, as expected, liver concentrations were higher as this is a metabolically active and main detoxification organ. In P. blainvilei, metals like as Al, As, Cd, Cr, Mn, Pb e Ti were present in high concentrations in the thermolabile and thermostable fractions of all evaluated tissues, indicating that a significant portion of these analytes is being detoxified by complexation with MT or other proteins and non-enzymatic compounds. Some metals, such as Ag, Cu, Fe, Hg, Ni, Se, Sn e Zn although detected, were present mostly in the insoluble fraction, indicating that the preferred detoxification pathways of these elements in this species are probably not performed through MT. In S. bredanensis, Al and Cr were also detected in the insoluble fraction. Regarding the total concentrations of these metals, high levels for most analytes were observed in S. bredanensis liver, kidney and muscle. Several statistically significant correlations between toxic and essential elements were observed in the liver and muscle of both species for all subcellular fractions, through a principal component analysis. In addition, some protective effects were postulated against toxic elements, evaluated from molar ratios calculations. Different profiles were observed for metalloproteins contained in the thermostable fraction of these individuals, using high efficiency chromatography coupled to ICP-MS (HPLC- ICP-MS), indicating metal and metalloid accumulation in the analyzed tissues, possible disturbance of elemental homeostasis and attempts to detoxify toxic metals by several metalloproteins.

The issue of the criminalization of prostitution raises all kinds of legal questions, especially in South African law. Governments have adopted different positions regarding prostitution. South Africa has tried, by means of law, to crack down on prostitution. This dissertation discusses the question of prostitution as provided by s 20 (1)(aA) of the Sexual Offences Act 23 of 1957. Whether criminalization is the indicated way to lessen or eliminate prostitution determines the focus of the discussion. It seemed necessary to understand the topic, to present the most important systems for addressing prostitution, the South African model and its evaluation. A legal comparison is presented. The discussion looks also at international instruments, which place the emphasis on forced prostitution. There is, in South African law, a pressing need to enact laws in accordance with the Bill of Rights, and with the international norms to which South Africa is party. / Criminal & Procedural Law / LL. D. (Criminal Law and Criminal Procedure)

RNA interference (RNAi) is a gene regulation mechanism conserved among eukaryotes. To silence gene expression, RNAi relies on a short single-stranded guide RNA to steer the RNA-induced Silencing Complex (RISC) to mRNAs with guide strand-complementary sequences. RNAi is a highly membrane-associated process. The RISC complex is likely loaded at the rough Endoplasmic Reticulum, where it can bind to and degrade mRNAs. Components of the RISC complex also colocalize to late endosomes, and the efficiency of RNAi-mediated silencing is affected by changes in late endosome to lysosome fusion. RNAi can be systemic and inherited, effecting gene silencing in distal tissues and in the offspring. In this thesis, the model organism Caenorhabditis elegans was used to identify and characterize factors connecting systemic and inherited RNAi to the endomembrane system. We identify two SNARE proteins, SEC-22 and SYX-6, that both act as negative regulators of RNAi. SNAREs are necessary for vesicle fusion. Both SEC-22 and SYX-6 localize to late endosomes, and both interact with systemic RNAi protein SID-5 in a yeast two-hybrid (Y2H) screen. We find that in addition to its function in systemic RNAi, SID-5 is required for proper maturation of late endosomes. Furthermore, we identify the putative RNA-binding protein C12D8.1 as a novel regulator of RNAi inheritance. Mutant C12D8.1 animals will have enhanced inheritance of RNAi silencing, which negatively affects the ability of the progeny to silence new targets using RNAi. Finally, we describe a novel, object-based method for estimating significance in colocalization studies. This method helped us describe and quantify spatial relations between fluorophore-labeled proteins in situations where such analyses would otherwise be impossible. In conclusion, the work presented here further elucidates the connection between cellular RNAi, the endomembrane system, and the outside world.

O objetivo principal de nossa pesquisa é o exame da questão da representação no interior da obra política de Jean-Jaques Rousseau. Isso se fará sob três pontos distintos: Em um primeiro momento, buscaremos compreender a noção de representação no desenvolvimento das paixões, da história e das instituições. Guiados pela dicotomia existente entre ser e parecer, abarcaremos as principais características desta noção sob o ponto de vista do paradoxo entre realidade e aparência, elucidando sua significação, apontando sua gênese e compreendendo sua relação com os demais processos de expansão cultural do homem. Na segunda parte de nossa pesquisa, procuraremos compreender as relações existentes entre representação e linguagem, o efeito direto da representação na constituição das línguas, as diferenças entre a língua escrita e a língua falada e sua relação com o processo de corrupção humano. Buscaremos evidenciar o papel da linguagem no desenvolvimento moral do homem, bem como sua inseparabilidade do aprofundamento das paixões humanas e do desenvolvimento de suas instituições. Finalmente, nos aprofundaremos nas relações existentes entre representação e política propriamente dita, salientando o efeito nefasto que a representação possui neste âmbito. Nossas preocupações aqui limitam-se a compreender a denúncia feita por nosso autor à teatralização do poder, compreender o caráter de ilegitimidade da representação no interior do corpo político, a partir da doutrina do contrato social, sobretudo a concepção de vontade geral. / The main purpose of our research is the examination of the matter of representation in the depth of the Jean-Jaques Russeau s work. It will be taken under three different points: At first time we will try to comprehend the notion of representation upon the development of passions, history and institutions. Guided by the dichotomy that is between be and realize, we will forestall to the main characteristics of this notion under the point of view of paradox between reality and appearance, elucidating its meaning, pointing out its genesis and understanding its relation to other process of mans culture expansion. In the second part of our research, we will try to understand the relation between representation and language, the direct effect of representation on the constitution of languages, the discrepancies between spoken language and written language and its relation to the humans corruption process. We will try to highlight the purpose of language in the mans moral development such as its indivisibility from deepness of humans passions and the development of its institutions. Finally, we will go deeper to the relation presented between representation and polity as itself, pointing out the disgraceful that the representation has in this ambit. Our preoccupation here covers the comprehension of the deletion done by our author toward the theatricalization of the power, understand the character of illegitimacy of the representation in the interior of the politic body from the doctrines of the social contract, overall the conception of the general will.