Submitted by Josimara Dias Brumatti (bcgdigital@ndc.uff.br) on 2017-03-29T13:14:59Z No. of bitstreams: 1 Tese completa.pdf: 1292437 bytes, checksum: 88c293c4232314645ea3dd00c6952f12 (MD5) / Approved for entry into archive by Josimara Dias Brumatti (bcgdigital@ndc.uff.br) on 2017-03-29T13:34:04Z (GMT) No. of bitstreams: 1 Tese completa.pdf: 1292437 bytes, checksum: 88c293c4232314645ea3dd00c6952f12 (MD5) / Made available in DSpace on 2017-03-29T13:34:04Z (GMT). No. of bitstreams: 1 Tese completa.pdf: 1292437 bytes, checksum: 88c293c4232314645ea3dd00c6952f12 (MD5) / A tese trata de narrativas que primaram por representar figurações extremas da infância, mais especificamente da infância sexualizada ou sedutora. O corpus inclui obras consagradas e conhecidas pelo tratamento polêmico da infância, como Lolita, de Vladimir Nabokov, A tragédia brasileira, de Sérgio Sant'Anna, Elogio da madrasta, de Mario Vargas Llosa, e O caderno rosa de Lori Lamby, de Hilda Hilst; assim como obras menos previsíveis como Teorema, de Pier Paolo Pasolini, e O bom crioulo de Adolfo Caminha. Nesses trabalhos, discuto o diálogo com as imagens tradicionais da infância, e igualmente a subversão polêmica dessas mesmas imagens, introduzindo uma concepção ou imagem sui generis daquele que conhecemos como o infante, ou aquele que se encontra no estágio infantil da sexualidade ou da psique. Vemos que o mito, como categoria supostamente a ser superada por essas narrativas (o mito da inocência infantil), retornará ao texto literário por vias insuspeitas e/ou alternativas, numa espécie de reconfiguração ou reatualização da infância mítica. / The thesis analyses narratives which present us extreme figurations of childhood, more specifically the figure of the sexual or seductive child. The literary corpus includes acclaimed works, known for their controversial treatment of childhood, such as Lolita, by Vladimir Nabokov, A tragédia brasileira, by Sérgio Sant'Anna, Elogio da madrasta, by Mario Vargas Llosa, and O caderno rosa de Lori Lamby, by Hilda Hilst. The analysis also considers less predictable works, such as Teorema, by Pier Paolo Pasolini, and O bom crioulo, by Adolfo Caminha. In the mentioned narratives, I will discuss their dialogue with traditional images of childhood, as well as a polemic subversion of those same images. The result would be a sui generis concept or image of the one we know as the infant, or the one who is in the infantile stages of psychosexual development. The myth as an allegedly overcome category in those narratives (the myth of childhood innocence) returns in unsuspected or alternative ways, reconfiguring or readapting the mythic childhood.

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This thesis presents electronic structure calculations on problems related to the bonding in inorganic coordination compounds and clusters. A wide range of molecules with the ability to exist in different structural forms or electronic states has been selected and density functional theory is systematically applied in order to gain detailed insight into their characteristics and reactivity at the electronic level. First, we address the question of redox non-innocent behaviour of bipyridine in a series of 1st row transition metal complexes. Complexes of the type [M(2,2'-bipyridine)(mes)₂]⁰ (M = Cr, Mn, Fe, Co, Ni; mes = 2,4,6-Me₃C6H₂) and their one-electron reduced forms have been explored. The results clearly show that the anions are best described as complexes of the monoanionic bipyridine radical (S_bpy = 1/2), giving a rationale for the observed structural changes within the ligand. Likewise, we have identified dianionic bipyridine in both the complexes [Zn2(4,4'-bpy)(mes)₄]²⁻ and [Fe(2,2'-bpy)₂]²⁻. In no case have we found evidence for significant metal-to-ligand backbonding. The subject of redox-noninnocence is further revisited in a comparative study of the two complexes [M(o-Clpap)₃] (M = Cr, Mo; o-Clpap = 2-[(2-chloro-phenyl)azo]-pyridine), and their associated electron transfer series. The results indicate that all electron transfer processes are primarily ligand-based, although in the case of the Mo analogue these are coupled to substantial electron density changes at the metal. The ability of pap to form radical anions finds a contrasting case in the di- nuclear Rh complex [Rh₂(μ-p-Clpap)₂ (cod)Cl₂], where the two ligand bridges act as acceptors of strong dπ∗ backbonding from a formally Rh^–I centre. We then direct our attention to the endohedral Zintl clusters [Fe@Ge₁₀]³⁻ and [Mn@Pb₁₂]³⁻, which reveal peculiar topologies. We have probed the electronic factors that influence their geometric preferences, and propose a model based on the shift of electron density from the endo- hedral metal to the cage to account for the observed geometries. Subsequently, we reassess the electronic structure of the xenophilic clusters Mn₂(thf)₄(Fe(CO)₄)₂ and [Mn(Mn(thf)₂)₃(Mn(CO)₄)₃]^–. We conclude that these are best viewed as exchange coupled Mn^II centres bridged by closed- shell carbonylate fragments. In the closing chapter the reduction of NO₂^– to NO by the complex [Cu(tct)(NO₂)]⁺ (tct = cis,cis-1,3,5-tris(cinnamylideneamino)cyclohexane) is studied, a process that mimics the enzyme-catalysed reaction. Two viable pathways for the reaction have been traced and key inter-mediates identified. Both direct release of NO or via decomposition of a Cu-NO complex are kinetically and thermodynamically feasible.

Master of Music / Department of Music, Theatre, and Dance / Frank C. Tracz / Three essential components of wind band conducting are as follows: music selection, score study, and rehearsal planning. This report contains an analysis and rehearsal plan for two band works and a discussion on quality literature selection for band as well as a personal philosophy of music education and student learning. The two works presented are Dances of Innocence by Jan van der Roost and Air for Band by Frank Erickson.

O reconhecimento da presunção de inocência não se mostra incompatível com a admissão da prisão e de outras medidas de caráter pessoal no curso da persecução penal. Assim como os demais direitos fundamentais, a presunção de inocência não se mostra absoluta ou insuscetível de restrições. O ordenamento jurídico brasileiro admite intervenções legítimas no âmbito de proteção da presunção de inocência, submetendo-as ao controle da proporcionalidade e do conteúdo essencial dos direitos fundamentais. A proporcionalidade serve como limite das intervenções e desdobra-se nos pressupostos, requisitos extrínsecos e requisitos intrínsecos já explorados. O descumprimento de qualquer destes pontos revela a desobediência à regra da proporcionalidade e, com isto, o caráter ilegítimo da intervenção no âmbito de proteção da presunção de inocência. Esta análise pode ocorrer tanto da perspectiva abstrata, examinando-se a previsão normativa, como da perspectiva concreta, analisando a aplicação e a execução da norma / The recognition of the presumption of innocence is inconsistent with the admission of the prison and other measures of personal character in the course of criminal prosecution. Like other fundamental rights, the presumption of innocence does not show absolute and subject to no restrictions. The Brazilian legal system admits intervention legitimate in the context of protection of the presumption of innocence, places them under the control of proportionality and the essential content of fundamental rights. Proportionality serves as a limit of interventions and unfolds in the assumptions, requirements extrinsic and intrinsic requirements already explored. The breach of any of these seven elements reveals the disobedience to the rule of proportionality and, thus, the illegitimate nature of the intervention under protection of the presumption of innocence. This analysis can occur from both the abstract perspective, examining the legislative provision, as the concrete perspective, examining the implementation and enforcement of the standard.

O reconhecimento da presunção de inocência não se mostra incompatível com a admissão da prisão e de outras medidas de caráter pessoal no curso da persecução penal. Assim como os demais direitos fundamentais, a presunção de inocência não se mostra absoluta ou insuscetível de restrições. O ordenamento jurídico brasileiro admite intervenções legítimas no âmbito de proteção da presunção de inocência, submetendo-as ao controle da proporcionalidade e do conteúdo essencial dos direitos fundamentais. A proporcionalidade serve como limite das intervenções e desdobra-se nos pressupostos, requisitos extrínsecos e requisitos intrínsecos já explorados. O descumprimento de qualquer destes pontos revela a desobediência à regra da proporcionalidade e, com isto, o caráter ilegítimo da intervenção no âmbito de proteção da presunção de inocência. Esta análise pode ocorrer tanto da perspectiva abstrata, examinando-se a previsão normativa, como da perspectiva concreta, analisando a aplicação e a execução da norma / The recognition of the presumption of innocence is inconsistent with the admission of the prison and other measures of personal character in the course of criminal prosecution. Like other fundamental rights, the presumption of innocence does not show absolute and subject to no restrictions. The Brazilian legal system admits intervention legitimate in the context of protection of the presumption of innocence, places them under the control of proportionality and the essential content of fundamental rights. Proportionality serves as a limit of interventions and unfolds in the assumptions, requirements extrinsic and intrinsic requirements already explored. The breach of any of these seven elements reveals the disobedience to the rule of proportionality and, thus, the illegitimate nature of the intervention under protection of the presumption of innocence. This analysis can occur from both the abstract perspective, examining the legislative provision, as the concrete perspective, examining the implementation and enforcement of the standard.

The goal of my thesis is to analyze physical and moral survival in three novels from King's oeuvre. Scholars have attributed survival in King's universe to factors such as innocence, imaginative capacity, and career choice. Although their arguments are convincing, I believe that physical and moral survival ultimately depends on a character's knowledge of the dark side of human nature and an understanding of moral agency. I have chosen three novels that span several decades of Kings work-'Salem's Lot, Needful Things, and Desperation-to illustrate the relationship between knowledge and survival. In 'Salem's Lot, King uses the main character's interest in the horror genre to emphasize the importance of an exposure to the dark side of human nature. In Needful Things, King vividly shows the dire consequences of naiveté, or in other words, uneducated innocence. Desperation represents a culmination of King's ideas. The final novel in my analysis shows the power of youth tempered by knowledge of human nature and informed by religious conviction. King links religion and horror to show the power of both in religious survival and to show the ultimate morality of horror.

Asymmetric catalysis is one of the most effective ways to control a target molecule’s stereochemistry. Through the development of a wide variety of chiral transition metal complexes, synthetic chemists are given the tools they need to synthesize the desired enantiomer of numerous compounds. This work focuses on exploiting the non-innocent ligand reactivity of metal bis-dithiolenes with multiple conjugated π systems in order to synthesize chiral ligands. Recent work has shown that platinum bis-dithiolene reacts with dienes stereoselectively to form a racemic mix of C2 -chiral thioether ligands. The present contribution will show approaches to synthesizing chiral dienes and organometallic complexes with potential applications for asymmetric allylic substitution reactions. Dienes with various chiral auxiliaries were reacted with platinum dithiolene and monitored through NMR spectroscopy. Attempts to synthesis palladium bis-dithiolene complexes, not previously seen in the literature were made, and the reaction of α-β unsaturated ketones with metal bis-dithiolenes was explored.

Asymmetric catalysis is one of the most effective ways to control a target molecule’s stereochemistry. Through the development of a wide variety of chiral transition metal complexes, synthetic chemists are given the tools they need to synthesize the desired enantiomer of numerous compounds. This work focuses on exploiting the non-innocent ligand reactivity of metal bis-dithiolenes with multiple conjugated π systems in order to synthesize chiral ligands. Recent work has shown that platinum bis-dithiolene reacts with dienes stereoselectively to form a racemic mix of C2 -chiral thioether ligands. The present contribution will show approaches to synthesizing chiral dienes and organometallic complexes with potential applications for asymmetric allylic substitution reactions. Dienes with various chiral auxiliaries were reacted with platinum dithiolene and monitored through NMR spectroscopy. Attempts to synthesis palladium bis-dithiolene complexes, not previously seen in the literature were made, and the reaction of α-β unsaturated ketones with metal bis-dithiolenes was explored.