Submitted by Joana Azevedo (joanad@id.uff.br) on 2017-08-31T18:36:13Z No. of bitstreams: 1 Dissert Daniel de Almeida Silva.pdf: 6579620 bytes, checksum: 22b71ae4b113d212a7f446e42047cc50 (MD5) / Approved for entry into archive by Biblioteca da Escola de Engenharia (bee@ndc.uff.br) on 2017-09-01T13:48:01Z (GMT) No. of bitstreams: 1 Dissert Daniel de Almeida Silva.pdf: 6579620 bytes, checksum: 22b71ae4b113d212a7f446e42047cc50 (MD5) / Made available in DSpace on 2017-09-01T13:48:01Z (GMT). No. of bitstreams: 1 Dissert Daniel de Almeida Silva.pdf: 6579620 bytes, checksum: 22b71ae4b113d212a7f446e42047cc50 (MD5) Previous issue date: 2017-06-23 / A pesquisa procura realizar propostas de ações para melhoria do desempenho sustentável de edificações de ensino superior federal, utilizando como modelo exploratório duas edificações modelos, como objeto de estudo de caso. Em virtude da existência de duas gerações de edificações bastante semelhantes, devido ao padrão conceitual e projetual utilizado também busca-se verificar avanços para sustentabilidade que tenham ocorrido no interstício de aproximadamente 30 anos entre os projetos analisados. Como marco temporal, tem-se duas fases de grande expansão universitária proporcionada pelo governo federal, o MEC-BID III e o REUNI. Como método de pesquisa foi utilizado uma revisão bibliográfica, uma pesquisa documental e uma pesquisa de campo para mapear a percepção dos especialistas que trabalham e gerencias os projetos, obras, operação e manutenção das edificações objetos do estudo. Como resultado, espera-se comprovar as questões iniciais buscando relacionar os projetos verificados, com os indicadores de sustentabilidade de certificações reconhecidas pela sociedade, registrando as boas práticas de projeto para potencializar os critérios de avaliação de sustentabilidade. / The research seeks to make proposals for actions to improve the sustainable performance of federal higher education buildings, using as an exploratory model two model buildings, as object of case study. Due to the existence of two generations of very similar buildings, due to the conceptual and design standard used, it is also sought to verify advances for sustainability that have occurred in the intersection of approximately 30 years between the projects analyzed. As a time frame, there are two phases of great federal university expansion provided by the federal government, MEC-BID III and REUNI. As a research method, a bibliographical review, a documentary research and a survey were used to map the perception of the specialists who work and manage the projects, works, operation and maintenance of the object objects of the study. As a result, it is expected to prove the initial questions seeking to relate the verified projects, with the sustainability indicators of certifications recognized by the company, recording good project practices to enhance the criteria for sustainability assessment.

Made available in DSpace on 2016-04-04T18:31:45Z (GMT). No. of bitstreams: 1 Jose Roberto Paim Neto.pdf: 12512704 bytes, checksum: 6bcf82095a1d2623487ef1d1c987b7f0 (MD5) Previous issue date: 2015-02-03 / The Brazilian electric sector has already presented signs of exhaustion that culminated in power rationing. It is estimated that the Brazilian population shows an increase by 2050 about 50%, so the generation and distribution of more energy becomes a concern. There is a great evolution on the process of evaluating equipment and buildings for their energy efficiency, however it is known that human behavior and consumer habits have huge influence on the energy efficiency of a building. Energy efficiency provided by the deployment of smart grids, suggests an intelligent and efficient city, which depend more and more on human behavior to improve the rational use of electricity. This paper presents a proposal for classification of individual energy efficiency, based on the Brazilian Labeling Program, the research of equipment possession and usage habits in the residential class, held by Eletrobras, and the application of fuzzy logic. / O setor el?trico brasileiro j? apresentou sinais de esgotamento que culminaram em racionamento de energia. Estima-se que popula??o brasileira apresente um crescimento at? 2050 de cerca de 50%, dessa forma a gera??o e a distribui??o de mais energia el?trica torna-se uma preocupa??o. Verifica-se um grande avan?o na avalia??o de equipamentos e constru??es quanto ? sua efici?ncia energ?tica, entretanto sabe-se que o comportamento humano e os h?bitos de consumo t?m grande influ?ncia no resultado final da efici?ncia energ?tica de uma edifica??o. A efici?ncia energ?tica proporcionada pela implanta??o das redes inteligentes, sugere uma cidade inteligente e eficiente, a qual depender? cada vez mais do comportamento do ser humano para melhorar o uso racional da energia el?trica. Este trabalho apresenta uma proposta de classifica??o da efici?ncia energ?tica individual, tendo como base o Programa Brasileiro de etiquetagem, a pesquisa de posse de equipamentos e h?bitos de uso na classe residencial, realizada pela Eletrobras, e a aplica??o da l?gica nebulosa.

Submitted by Fabiano Vassallo (fabianovassallo2127@gmail.com) on 2017-05-17T19:08:57Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Renata Valente dos Santos.pdf: 1455505 bytes, checksum: 81eebf4936c09e70bcba7f903b9b7d50 (MD5) / Approved for entry into archive by Josimara Dias Brumatti (bcgdigital@ndc.uff.br) on 2017-05-17T20:45:02Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Renata Valente dos Santos.pdf: 1455505 bytes, checksum: 81eebf4936c09e70bcba7f903b9b7d50 (MD5) / Made available in DSpace on 2017-05-17T20:45:02Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Renata Valente dos Santos.pdf: 1455505 bytes, checksum: 81eebf4936c09e70bcba7f903b9b7d50 (MD5) / Com a expansão, nas duas últimas décadas, das políticas e ações voltadas para a internacionalização da língua portuguesa, cresceu também a produção de materiais didáticos destinados ao ensino de Português do Brasil a estrangeiros (PBE). Contudo, nos textos desses materiais, as amostras da variedade brasileira oferecidas aos aprendizes nem sempre são representativas de nossa fala e escrita. Nesta pesquisa, analisamos - em diálogos impressos em livro didático de PBE contemporâneo e de ampla circulação, que declara enfatizar a comunicação no português como é falado no Brasil - se o uso dos pronomes pessoais, demonstrativos, possessivos e relativos é consistente com essa proposta. Analisamos as ocorrências de pronomes desses tipos nos diálogos da obra selecionada, à luz de descrições presentes em gramáticas e estudos recentes sobre o português brasileiro, que contemplam a fala, e também de descrições contidas em gramáticas com base na tradição escrita. Concluímos que, nos diálogos do livro didático analisado, no que se refere ao uso desses pronomes, sobretudo os pessoais e demonstrativos, ainda são frequentes as representações da fala inadequadas, ou seja, distanciadas das descrições contemporâneas do português do Brasil falado e influenciadas pela descrição com base na tradição gramatical escrita / As a result of an development of politics and activities regarding the internationalization of the Portuguese language, an increase on the production of didactic material has happened with the purpose of teaching foreigners the Portuguese of Brazil (PBE). Nevertheless in the set texts of these materials, the examples that are presented to the learners in order to demonstrate the wide scope of the Brazilian linguistic diversity, not always represent the way we speak and write. In this research we analyse the consistancy of the usage of Personal Pronoun, Demonstrative Pronoun, Possessive Pronoun, and Relative Pronoun according to this proposal by means of examining written dialogues on contemporary book for the Teaching of Brazilian Portuguese For Foreigners (PBE) with broad circulation and that it emphasizes communication in the Portuguese language as people speak it in Brazil. We analysed these pronouns as they appeared in the set texts, bearing in mind up to date grammatical studies on Brazilian Portuguese which deal with the Brazilian Portuguese speach as well as structures and rules on grammars based on written tradition. We come to the conclusion that the dialogues on the analysed book in reference to these pronouns, mainly Demonstrative and Personal Pronoun, are to some extent inadequate concerning the speach, meaning that, they are rather distant from the contemporary structures of the Brazilian Portuguese the way it is spoken and as they are influenced by the description based on the written grammatical tradition

Catalytic amination reactions are a powerful tool in organic synthesis. They aim to introduce nitrogen atom to alkane, alkene or thioether moieties, giving rise to amine products that have various medical and industrial applications. The Lebel group has developed catalytic amination reactions in the presence of rhodium dimers using N-sulfonyloxycarbamates as nitrene precursors. In the presence of a base, N-sulfonyloxycarbamates presumably afforded rhodium nitrenes which underwent C-H insertions, C=C additions or reactions with the sulfur atom of thioethers resulting in acyclic and cyclic carbamates, aziridines and sulfilimines respectively. In addition, good diastereoselectivities were observed in the presence of a chiral N-sulfonyloxycarbamate reagent and a chiral rhodium dimer for all three reactions. In this dissertation, we are interested in the mechanistic aspects of these amination reactions. Given the absence of experimental proofs of in-situ generated rhodium nitrene species, playing the role of the amination agent, nor of its precomplex, the rhodium nitrenoid, the different amination reactions mechanisms remain uncertain. Our approach is based on the scan of the potential energy surfaces of different mechanistic paths, for each of the amination reactions, well established on the experimental level, by resorting to the Functional Theory of Density (DFT). The Ernzerhof research group is expert on the development of exchange-correlation functionals, therefore relevant strict criteria have been considered when choosing and validating the theoretical model used during the mechanistic studies. The correlation exchange functional developed by Perdew-Burke-Ernzerhof (PBE) was established as the best to study reactions involving rhodium dimers where the electronic correlation is strong. We studied the formation and reactivity of rhodium nitrene species considering their two lower energy spin states. Singlet rhodium nitrenes appeared to be the most reactive intermediates for the C-H amination reaction. In addition, singlet rhodium nitrenes were shown responsible for the formation of secondary products such as carbonyls and primary carbamates derived from the corresponding N-mesyloxycarbamates. In sharp contrast, in the aziridination reaction, both singlet and triplet rhodium nitrene species acted as aminating agents in a process involving an intersystem spin crossover. To further rationalize the asymmetric induction of catalytic aziridination reactions, we have undertaken the calculation of the diastereoselectivity ratios in the presence of the chiral catalyst Rh2[(S)-nttl]4. An exhaustive study was performed and it revealed that the asymmetric induction was due to a reactive conformation of rhodium nitrene species in which the ligand adopts C4 symmetry. Up to now, no mechanistic study involving DFT calculations have been reported in the literature for the amination of thioethers, no matter what catalytic system is used. To study catalytic sulfimidation reactions, we calculated the different mechanistic paths of rhodium catalyzed thioanisole imidation with and without DMAP and bis(DMAP)CH2Cl2 additives. The study showed a 'classical' insertion mechanism of rhodium nitrene species into the thioether in absence of bis(DMAP)CH2Cl2. In the presence of the latter, the mechanism diverged to a thioether insertion/salt (bis(DMAP)CH2Cl-OMs) elimination reaction where the rhodium nitrenoid complex was, henceforth, the imidation reagent. / Les réactions d’amination catalytiques sont un outil très efficace en synthèse organique. Elles consistent à introduire un azote sur différents composés organiques, permettant de synthétiser des produits aminés qui peuvent être utilisés pour différentes applications médicales et industrielles. Le groupe de recherche du Pr Lebel a développé des réactions d’amination faisant appel aux dimères de rhodium comme catalyseurs et en utilisant les Nsulfonyloxycarbamates, comme précurseurs de nitrènes métalliques. En effet, en présence d’une base, les N-sulfonyloxycarbamates forment possiblement un intermédiaire de type nitrène de rhodium qui peuvent s’insérer dans un lien C-H, s’additionner sur un lien C=C ou réagir avec un atome de soufre d’un thioéther. On peut ainsi préparer des carbamates cycliques et acycliques, des aziridines et des sulfilimines respectivement. Dans le cas où les réactions d’amination sont catalysées par des dimères de rhodium chiraux, on obtient de bonnes diastéréosélectivités en présence d’un réactif N-sulfonyloxycarbamate chiral. Dans cette dissertation, nous nous sommes intéressés aux aspects mécanistiques de ces réactions d’amination. À défaut de preuves expérimentales solides pour prouver la génération in-situ des espèces nitrènes de rhodium, lesquelles sont les agents d’amination clés, ni de celle du pré-complexe, nitrénoïde de rhodium, des incertitudes subsistaient toujours concernant les mécanismes des différentes réactions d’amination. Notre approche se base sur l’étude des surfaces d’énergies potentielles de différents chemins mécanistiques possibles pour chacune des réactions d’amination, bien établie sur le plan expérimental, en faisant recours à la Théorie des Fonctionnelles de la Densité (DFT). Le groupe de recherche du Pr Ernzerhof est expert dans le développement des fonctionnelles d’échange-corrélation. Pour ce, des critères strictes et pertinents ont été pris en compte lors du choix et de la validation du modèle théorique utilisé dans ces études mécanistiques. La fonctionnelle d’échange corrélation développée par Perdew–Burke– Ernzerhof (PBE) s’est révélé être la meilleure pour décrire ces systèmes réactionnels faisant intervenir les dimères de rhodium dont la corrélation électronique est forte. À l’aide de cette fonctionnelle pure, nous avons étudié la formation et la réactivité des espèces nitrènes de rhodium en fonction de leurs deux états de spin de plus basse énergie. Les nitrènes de rhodium singulet se sont révélés être les intermédiaires les plus réactifs dans l`amination de liens C-H. De plus, les nitrènes de rhodium à l’état singulet sont responsables de la formation des produits secondaires tels que les carbonyles et les carbamates primaires dérivés des Nmésyloxycarbamates correspondants. Dans la réaction d’aziridination, les espèces nitrènes de rhodium à l’état singulet et triplet peuvent toutes les deux agir comme agents d'amination et les processus font intervenir un croisement intersystème de spin. Afin de rationaliser l’induction asymétrique des réactions d’aziridination catalytiques, nous avons entrepris le calcul des ratios de diastéréosélectivités en présence du catalyseur chiral Rh2[(S)-nttl]4. L’étude exhaustive de cette réaction a permis de déterminer que l’induction asymétrique provient d’une conformation réactive de l’espèce nitrène de rhodium de symétrie C4. Aucune étude mécanistique s’appuyant sur la chimie computationnelle n’a été rapportée dans la littérature pour la réaction d’amination de thioéthers et ce peu importe le système catalytique. Afin d’étudier les réactions de sulfimidation catalytiques, nous avons calculé les différents chemins mécanistiques de l’imidation du thioanisole catalysée par un complexe de rhodium avec et sans les additifs DMAP et bis(DMAP)CH2Cl2. L’étude montre que le mécanisme procède via une insertion ‘classique’ des espèces nitrènes de rhodium dans le thioéther en absence de bis(DMAP)CH2Cl2. En présence de ce dernier, le mécanisme diverge vers une réaction d’insertion du thioéther/élimination d’un sel (bis(DMAP)CH2Cl-OMs) où le complexe nitrénoïde de rhodium devient, désormais, l’agent d’imidation.