<div><p>Nitrenes are reactive intermediates that are known to generate high interest organic molecules. Due to their inherent instability, nitrenes are often stabilized by introducing them to transition metal complexes. Many transition metal stabilized nitrenes (M=NR₂) have been reported and some of these complexes have been shown to control nitrene reactivity and selectivity. Transition metal nitrene reactivity can be categorized into two main groups: bond-insertion and group transfer reactions. In the reference to the former, chapter one of this dissertation highlights using unique dinuclear Nicatalysts to generate nitrenes from aromatic azides. These Ni₂ nitrenes are used towards selective C(sp²)−H bond amination in order to generate indole and carbazole derivatives. This work highlights the unique properties of the Ni₂ imide that enable a 1,2-addition pathway, which contrasts known bimetallic nitrene insertion reactions. A detailed mechanistic study, primarily using density functional theory (DFT) is the focus of this chapter.</p> <p>Chapter two of this dissertation focuses on nitrene group transfer. In particular, this chapter highlights the ability of the dinuclear Nicatalyst [<i>ⁱ</i>^-PrNDI]Ni₂(C₆H₆) to react with aromatic azides to perform N=N coupling. A large scope of functional groups are tolerated in high yield with short reaction times. Catalyst comparison studies, studies on relevant catalytic intermediates for N=N coupling and reaction kinetics are shown in this chapter. Lastly, chapter three showcases the expansion of the nitrene group transfer ability of [<i>ⁱ</i>^-PrNDI]Ni₂(C₆H₆) to generate high molecular weight azopolymers from aromatic diazides. These azopolymers are generated from monomers often used in organic semi-conducting materials. End group control and post polymer functionalization are highlighted in this chapter. Lastly, this work showcases a new polymer, polyazoisoindigo, as the first organic semiconducting material that reversibly transitions from a colored to colorless state upon reduction.</p><br></div>

Submitted by Jamile Barbosa da Cruz (jamile.cruz@ucsal.br) on 2016-09-29T18:15:34Z No. of bitstreams: 1 DISSERTACAOJOSEMARIOFERREIRA.pdf: 1284747 bytes, checksum: ab6959fdfc3d1836514da5bbb4553948 (MD5) / Approved for entry into archive by Maria Emília Carvalho Ribeiro (maria.ribeiro@ucsal.br) on 2016-11-22T21:28:49Z (GMT) No. of bitstreams: 1 DISSERTACAOJOSEMARIOFERREIRA.pdf: 1284747 bytes, checksum: ab6959fdfc3d1836514da5bbb4553948 (MD5) / Made available in DSpace on 2016-11-22T21:28:49Z (GMT). No. of bitstreams: 1 DISSERTACAOJOSEMARIOFERREIRA.pdf: 1284747 bytes, checksum: ab6959fdfc3d1836514da5bbb4553948 (MD5) Previous issue date: 2015-12-10 / O presente estudo busca explorar os cárias de Salvador, durante o processo de inserção no programa de aprendizagem e, apercursos juvenis no processo de formação e sua relação com os programas de aprendizagem no setor bancário de Salvador. Através de uma análise interdisciplinar das práticas laborais e de perspectivas futuras dos jovens, diante de um cenário social e econômico em profundas transformações, o estudo pôde verificar a aplicação na prática da lei pelas instituições bannalisar a relação entre o esperado-explicitado no Programa e com o acordo pela instituição formadora – e a prática vivenciada pelos jovens aprendizes durante a execução de suas atividades, e investiga em que medida a vivencia laboral dos jovens aprendizes inseridos no setor bancário, contribui para a sua formação cidadã. A trajetória dos jovens é avaliada mediante análise do Programa Nacional de Aprendizagem por meio da Lei 10.097/00 como Política Pública de inserção dos jovens no mercado de trabalho. A pesquisa base da dissertação tem caráter qualitativo, exploratório e compreensivo. O campo empírico é composto por cinco jovens ingressos no programa de aprendizagem, tendo-se como critério de participação na amostra, seis meses ou mais de contrato de trabalho com bancos da rede pública e privada, de modo a permitir visões distintas entre expectativas e o nível de realização durante a imersão no programa de aprendizagem. Sendo usados instrumentos de coleta de dados como entrevistas semiestruturadas aplicadas por meio da técnica de “Bola de Neve”, ou “cadeia de informantes”, focalizando construção de identidades com o mundo do trabalho e os desafios contemporâneos na formação profissional e transição para a vida adulta. / This study aims to explore the youth courses in the qualification process and its connection with the learning programs of the banking sector in Salvador. Via interdisciplinary analysis of the labor practices and of the future perspectives of the young, facing a social and economic scenery of deep transformations, the study could verify the practical law enforcement by the banking institutions of Salvador, during the insertion process in the qualification program, and analyze the relationship between the expected-explicit in the Program and the accord by the teaching institution – and the practices experienced by the young apprentices during the execution of their activities. It also investigates to what point the labor experience of the young apprentices in the banking sector contributes to their citizen qualification. The trajectory of the young people is evaluated through analysis of the National Learning Program, according to the Law 10.097/00 as a public policy to introduce the young into the labor market. The research, which serves as a basis to the dissertation, has a qualitative, exploratory and comprehensive nature. The empirical field is composed by five young people inside the learning program, having at least six months of work contract in banks of the public or private area as the criteria for participation in the sample. In this sense, distinct views came forward among the expectations and the level of satisfaction during the immersion in the learning program. The instruments to collect data were semi-structured interviews, applied with the “Snowball” technique, or “chain of informants”, focusing on the construction of identities with the labor world and the contemporary challenges in the professional qualification and transition to adult life.

L’analyse des processus de création de l’écrivain américain William Burroughs et de l’artiste brésilien Cildo Meireles construit deux figures exemplaires de l’artiste en tant que sujet politique. Les choix faits par ces deux artistes pendant le processus de réalisation de leurs œuvres déclarent en effet leur position face à la littérature, à l’art et à la réalité. Ils les construisent en tant que sujets-artistes et produisent des rencontres qui (re) configurent l’espace artistique. Ils renouvellent les pratiques de création. Nous étudions ces processus avec pour outils différentes notions théoriques. Outre celle de la politique, qui, selon Jacques Rancière, est le processus de l’égalité ; celle du sujet, définie par Alain Badiou, comme une construction qui se produit quand un événement arrive ; et celle de choix qui, selon Slavoj Zizek, ne laisse pas intacte la subjectivité du sujet. Nous essayons ainsi de définir le caractère politique des choix faits par ces deux artistes et de mettre en évidence l’idée de l’art et de la politique que leurs œuvres mobilisent.Nous étudions le processus de création de Burroughs, de son premier roman jusqu’à la découverte du cut-up et l’écriture de son texte Last Words. Nous analysons le processus de création des œuvres de Meireles : Insertions dans les circuits idéologiques, œuvre qui se constitue dans un processus en marche ; et Le sermon sur la montagne : Fiat lux. Construction d’une situation : transformation d’un espace en une bombe potentielle.Malgré leurs différences, ces œuvres ont une procédure de réalisation similaire, une sorte de travail tabulaire, de collage d’éléments hétérogènes. / The analysis of the creation process of both Americain writer Willam Burroughs and Brazilian artist Cildo Meireles construct two exemplary figures of the artist as political subject. The choices made by these artistes during the process of realization of their works declare indeed their position on literature, art and reality. Their choices construct them as artists-subjects and produce encounters that (re) configure the art space. They renew the creative practices. We study these processes with some theoretical tools: such as the notion of politics which according to Jacques Rancière, is the process of equality; the notion of subject, defined by Alain Badiou as a construction that is produced when an event happens; and the notions of choice which, according to Slavoj Zizek, does not leave intact the subjectivity of the subject. Thus we try to define the political nature of the choices made by these artists and to highlight the idea of art and politics that their works mobilize. We study the process of creation of Burroughs, from his first novel until his discovery of cut-up technique and the writing of his text Last Words. We analyze the process of creation of Meireles’s works: Insertions into Ideological Circuits, a work that is established as a running process and The Sermon on the Mount: Fiat Lux that is the construction of a situation. It is the transformation of a space into a potential bomb. Despite their differences these works have a similar implementations procedures a kind of a tabular work, a collage of heterogeneous elements.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Apparaît au XIIIe s. un nouveau type de roman français qui intercale dans sa matière des poésies empruntées au répertoire de la lyrique médiévale. Nous avons voulu démontrer que la lecture de ces romans hybrides consistait en une réduction des hétérogénéités selon trois mouvements. 1. Interprétation. Le rôle du lecteur consiste à construire des isotopies dans le texte à partir du contenu inséré. Ces isotopies relèvent de deux catégories sémantiques : la thématique et la dialectique. 2. Interprétant. Différents indices disséminés dans le texte d'accueil rendent pertinentes les relations entre énoncés et orientent le parcours interprétatif. Une modélisation permet alors d'illustrer la tension interprétative générée entre une immanence, associée à la construction des isotopies par le lecteur (interprétation), et une manifestation, liée aux consignes de connexion dispensées par le texte (interprétant). 3. Prémisses et rythmes. La réduction des hétérogénéités est aussi le fait d'une anticipation de l'insertion. Cette appréhension du contenu lyrique repose sur des prescriptions génériques assurant au registre inséré d'être corrélé à une configuration narrative adaptée. Le rapport entre cette configuration d'accueil et le poème constitue tendanciellement le support d'un sens en relation avec une sémiotique de l'événement. Un autre élément permettant au lecteur de saisir " intuitivement " la présence du morceau à venir relève de la périodicité des contenus textuels (dimension tactique de l'interprétation). Ce travail propose une exploration technique des insertions lyriques grâce à trois outils de l'analyse textuelle : la sémantique, la sémiotique, et l'informatique.

[Truncated abstract] Polymorphic Alu insertions (POALINs) are known to contribute to the variation and genetic diversity of the human genome. In this report specific POALINs of the Major Histocompatibility Complex (MHC) were studied. Previous population studies on the MHC POALINs have focused on individuals of African, European and Asian descent. In this study, we expand the research by studying a new and previously uncharacterised population, focusing on the Bedouin from the Middle East. Specifically we report on the individual insertion frequencies of four POALINs within the MHC class I region of this population. POALINs are members of a young Alu subfamily that have only recently been inserted into the human genome. POALINs are either present or absent at particular sites. Individuals that share the inserted (or deleted) polymorphism inherited the insertion (or deletion) from a common ancestor, making Alu alleles identical by decent. In population genetics a comparison of the resulting products from each population can then be done by comparing the lengths of the PCR products in a series of unrelated individuals and may also detect polymorphisms with regard to the presence or absence of the Alu repeats. As a direct result of their abundance and sequence identity, they promote genetic recombination events that are responsible for large-scale deletions, duplication and translocations. The deletions occur mostly in the A-T rich regions and have found to be unlikely to have been created independently of the insertions of the Alu elements (Callinan et al, 2005) The easy genotyping of the POALINs has proven to be very valuable as lineage markers for the study of human population genetics, pedigree and forensics as well as genomic diversity and evolution. POALINs have been used in a range of applications, primarily focusing on anthropological analysis of human populations. As a result of its ease of use and its utility as a marker in human evolutions studies, combining the POALINs along with other markers used in forensics could lead to improved identity testing in forensic science. More specifically, in combination with more traditional markers, race specific genotypes and haplotypes could be used for profiling crime scene samples. ... This is supported by previously reported molecular data using various types of genetic markers. In a study using six separate Alu genes, Antunez-de-Mayolo et al were able to generate a phylogenetic tree, in which the biogeographical groups followed a pattern. The biogeographical groups started with African populations that were found to relate closely to the hypothetical ancestral African population. The African populations were then followed in order by Southwest Asian populations, European populations which include Middle Eastern groups (Antunez-de-Mayolo et al, 2002). This study shows the similarities and differences between the frequencies of the Middle Eastern Bedouin and the rest of the compared populations. Though no clear results were determined, the information from the POALINs along with information provided from other genetic markers can lead to further research on the Bedouin population and the improvement of the forensic population database in order to accurately test individual ethnic background of samples to be analysed.

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-17T17:51:24Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-17T17:51:24Z (GMT). No. of bitstreams: 0 / Atualmente, uns dos grandes desafios para a indústria automobilística é aumentar o desempenho do conjunto mecânico responsável por selar a câmara de combustão interna de motores automotivos e também reduzir os seus custos de obtenção. O objetivo deste trabalho foi o de tratar termicamente insertos de assentos de válvulas (do inglês valve seat insert, VSI) obtidos pela rota de metalurgia do pó. Esta técnica possibilitou a substituição do cobalto e do chumbo, devido ao seu elevado custo e efeito toxicológico, respectivamente. Ao longo do trabalho foram avaliados VSI obtidos com três misturas de pós diferentes, sendo que os elementos comuns nestas três misturas foram os pós de ferro, sulfeto de manganês, carboneto de nióbio, grafite, estearato de zinco e cobre. Em cada uma destas misturas variou-se apenas os tipos de pós de aços rápidos e aço ferramenta utilizado, sendo estes o aço rápido AISI M3:2 (Mistura 1), aço rápido AISI M2 (Mistura 2) e aço ferramenta AISI D2 (Mistura 3). Os tratamentos térmicos aplicados aos VSI consistiram em têmpera ao ar e têmpera ao óleo, ambas seguidas de duplo revenimento em sete temperaturas equidistantemente diferentes, variando de 100 °C a 700 °C. Os ciclos dos tratamentos térmicos foram determinados por meio da utilização de termopares do tipo k acoplados à um sistema de aquisição de dados. As propriedades físicas e mecânicas dos VSI foram determinadas através da dureza aparente, densidade aparente e resistência à ruptura radial. A caracterização microestrutural foi realizada utilizando-se a microscopia óptica e microscopia eletrônica de varredura. A composição química foi determinada por meio da análise elementar e por espectrometria de fluorescência de energia dispersiva de raios X. Os melhores resultados em relação às propriedades mecânicas dos VSI foram obtidas para os insertos temperados ao ar e duplamente revenido a 600 °C para a Mistura 1 e Mistura 2, e a 500 °C para Mistura 3. Já para a têmpera ao óleo, as melhores respostas foram para os VSI obtidos com a Mistura 1 duplamente revenida a 400 °C e a, 300 °C para os componentes obtidos com a Mistura 2 e Mistura 3. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Le nombre de génomes bactériens et archées complètement séquencés augmentant sans cesse plus, une telle augmentation rend possible le développement de nouveaux types d’approches large échelle, afin de comprendre l’évolution de la structure des génomes au cours du temps. La prédiction du contenu en gènes et la comparaison des génomes ont évolué de telle sorte qu’il est dorénavant possible d’extraire un certain nombre de nouvelles information permettant de comprendre l’évolution des procaryotes. Des séquences importantes dans la compréhension des opérations de réarrangements au sein des génomes de au cours du temps sont les éléments transposables, qui sont des fragments d’ADN ayant la possibilité de se mouvoir d’un lieu à l’autre, et peuvent se dupliquer au cours de ces transpositions. Les éléments transposables chez les procaryotes sont les séquences d’insertion, qui suivent un processus de couper-coller à l’intérieur des séquences ADN. Cependant, les outils ayant pour but de découvrir de telles séquences d’insertions d’une manière efficace et de développer une manière algorithmique originale pour découvrir les séquences d’insertions dans des génomes bactériens, et de constituer une base de données pour découvrir les séquences d’insertion dans des génomes bactériens, et de constituer une base de données les insérant. A l’aide de ces données, nous devons déduire un modèle d’évolution de ces éléments transposables, qui doit être relié à l’évolution de la séquence hôte (le génome procaryote). En particulier, nous devons déterminer si les séquences d’insertion et les génomes hôtes ont évolué de la même manière, et si ces séquences sont responsables, au moins jusqu’à une certaine mesure, de recombinaisons génomiques telles que les inversions. / The number of completely sequenced bacterial and archaeal genomes are rising steadily, such an increasingmakes it possible to develop novel kind of large scale approaches to understand genomes structureand evolution over time. Gene content prediction and genome comparison have both provided newmajor information and deciphering keys to understand evolution of prokaryotes. Important sequencesin understanding rearrangement operations inside genome sequences during evolution are the so-calledtransposable elements (TEs), which are DNA fragments or segments that have the ability to insert themselvesinto new chromosomal locations, and often make duplicate copies of themselves during transposition process.The transposable elements involved in such a move are the insertion sequences (ISs) in prokaryotes, theyfollow a cut-and-paste process inside the host DNA sequence. But the tools that deal with discovering ISs inan efficient way and that relate them to genome rearrangements are still too few and not totally accurate.The aim of this thesis is to develop an accurate algorithmic way to discover insertion sequences (ISs) inbacterial genomes and to constitute a database with these discoveries. Using these data, we must deduce amodel of evolution of these transposable elements, which must be related to the evolution of the host sequence(the prokaryotic genome). In particular, wemust ask whether insertion sequences and host genomes haveevolved in a similar way, and if ISs are responsible, at least to some extent, for genomic recombinationlike inversions.

No description available.

Cette thèse décrit le développement et la méthodologie pour la synthèse de 2-pyrazolo[1,5-a]pyridines à partir d’ylures de N-iminopyridinium et d’halogénures de styryle. Des dérivés de chaque ylure de N-iminopyridinium et d’halogénures de styryle ont été utilisés pour la synthèse de plusieurs composés avec un intérêt pharmaceutique. Le premier chapitre présente les précédents littéraires pour la synthèse de pyrazolopyridines. Spécifiquement trois types différents de synthèse seront présentés en détail. L’importance biologique de ces composés sera discutée. La vue d’ensemble des travaux développés dans notre groupe de recherche pour la synthèse des produits de départ sera présentée brièvement. Finalement, la science intéressante qui a apporté cette idée de recherche sera révélée. Le deuxième chapitre décrit les résultats des optimisations étudiées pour la synthèse des 2-phénylpyrazolo[1,5-a]pyridines à partir d’ylures de N-benzoyl-iminopyridinium et d’iodure de styryle. Chaque substrat de la réaction a été étudié individuellement afin d’être optimisé; les ratios, les solvants, la température du milieu réactionnel et le temps optimal de la réaction ont aussi été explorés. Le troisième chapitre présente l’étendue de la synthèse des pyrazolopyridines. L’étendue de la réaction inclut les dérivés des halogénures de styryle. L’étendue de la réaction a été élargie aux dérivés d’ylures de N-iminopyridinium et ils incluent des groupements donneurs d’électrons ainsi que des groupements pauvres en électrons. Des groupements exotiques d’iodure et de bromure de vinyle ont aussi été explorés. Le quatrième chapitre démontre les études mécanistiques que l’on a faites pour mieux comprendre les cycles catalytiques qui ont lieu durant la réaction. Des études de cyclisation avec les ylures de N-iminopyridinium ont été explorées pour les produits de départ suivants : iodure de styryle et phényl acetylène. / This thesis describes the development of a methodology for the one-pot synthesis of 2-pyrazolo[1,5-a]pyridines from N-iminopyridinium ylide and styryl-halide starting materials. Both N-iminopyridinium ylide derivatives and styryl-halide derivatives were employed for the synthesis of various pharmaceutically interesting pyrazolo[1,5-a]pyridines. The first chapter presents the literature precedents for the synthesis of pyrazolopyridines. More specifically, three different types of syntheses will be shown in detail. Furthermore, the biological importance of these compounds will be discussed. An overview of the developed methodologies previously carried out in our research group for the synthesis of the starting materials will be presented. Finally, the copper-catalyzed direct alkenylation of N-iminopyridinium ylides that brought about this research idea will be discussed. The second chapter describes the results of the optimization studies for the synthesis of 2-phenyl pyrazolo[1,5-a]pyridines from N-benzoyliminopyridinium ylides and styryl iodides. Each component of the reaction was individually screened and the loading ratios were optimized: e.g., solvent and temperature. The third chapter presents the scope of the pyrazolopyridine synthesis. The scope includes styryl iodide, –bromide and –chloride derivatives. The scope of the reaction was extended to N-iminopyridinium ylide derivatives and included electron donating and electron withdrawing groups. Substituted vinyl iodides and bromides were also investigated. The fourth chapter demonstrates the mechanistic studies conducted in order to obtain an accurate understanding of the catalytic cycles taking place during the reaction. Cyclization studies were explored for both styryl iodides and phenyl acetylene starting materials reacted with N-iminopyridinium ylides.