A endotelina-1 (ET-1) é um peptídeo vasoconstritor que exerce um papel importante no controle do tônus do corpo cavernoso. No entanto, tem sido demonstrado que esse peptídeo também está envolvido na disfunção erétil (DE) associada ao diabetes mellitus e hipertensão. O consumo de etanol aumenta os níveis plasmáticos de ET-1 e a resposta contrátil a esse peptídeo em tecidos vasculares. Os objetivos deste trabalho foram o de estudar as consequências funcionais e celulares do consumo crônico de etanol sobre o sistema endotelinérgico no corpo cavernoso e identificar os mediadores envolvidos nessa resposta. Ratos Wistar foram divididos em dois grupos, os quais receberam água (controle) ou solução de etanol a 20% (vol./vol.) por seis semanas. Nossos resultados mostram que em tiras de tecido cavernoso, não houve alteração da resposta de relaxamento induzida pela adrenomedulina e nitroprussiato de sódio após tratamento com etanol. Com relação à acetilcolina, o consumo crônico de etanol reduziu o relaxamento induzido pelo referido agonista. Além disso, observou-se redução dos níveis plasmáticos e teciduais de nitrato no grupo etanol. Em conjunto, esses resultados sugerem que o tratamento crônico com etanol reduz a síntese/liberação do NO tecidual sem prejuízo em sua via de sinalização. O tratamento com etanol aumentou os níveis plasmáticos de ET-1 e a resposta contrátil induzida por esse peptídeo em corpo cavernoso de ratos. A contração induzida pela fenilefrina ou KCl 120 mmol/L não foi afetada pelo tratamento com etanol, sugerindo que os efeitos do tratamento sobre a reatividade do corpo cavernoso não são inespecíficos. O antagonista dos receptores ETB, o BQ788, não alterou a resposta de contração induzida pela ET-1 em corpo cavernoso de animais do grupo controle ou etanol. Não houve alteração da resposta de relaxamento induzida pelo IRL1620, um agonista seletivo dos receptores ETB. O tratamento com etanol não alterou os níveis de RNAm assim como a expressão protéica dos receptores ETB. Esses resultados mostram que o aumento da contração induzida pela ET-1 após tratamento com etanol não está relacionado à redução do relaxamento mediado pelos receptores ETB. Em nosso estudo o BQ123, antagonista seletivo dos receptores ETA, deslocou a curva cumulativa para ET-1 para direita em músculo cavernoso de ratos do grupo controle com consequente redução do valor de pD2. O mesmo não foi observado no tecido de animais do grupo etanol, indicando que a resposta mediada pelos receptores ETA está favorecida após o tratamento. O consumo de etanol não afetou os níveis de RNAm dos componentes do sistema endotelinérgico (ET-1, ECE-1, receptores ETA e ETB) e das isoformas da enzima óxido nítrico sintase (NOS) (eNOS, nNOS e iNOS), porém aumentou a expressão protéica do receptor ETA, da ET-1 e da iNOS no músculo cavernoso. O tratamento com etanol induziu aumento do estresse oxidativo sistêmico assim como dos níveis de ânions superóxido (O2-) no corpo cavernoso. As espécies reativas de oxigênio (ERO), os metabólitos derivados da NOS e da ciclooxigenase (COX) modulam negativamente a contração induzida por ET-1 e mostraram-se importantes no aumento da contração à ET-1 observada no corpo cavernoso de animais tratados com etanol. O Y27632, um inibidor da Rho-cinase, reduziu a resposta contrátil da ET-1 em corpo cavernoso de animais de ambos os grupos. Portanto, os resultados mostram que o tratamento com etanol aumenta a resposta contrátil da ET-1 por mecanismos que envolvem o aumento da expressão dos receptores ETA e das ERO e a via da Rho-cinase. / Endothelin-1 (ET-1) is a vasoconstrictor peptide that plays an important role in controlling the tone of the cavernosal smooth muscle (CSM). ET-1 is also involved in erectile dysfunction (ED) associated with diabetes mellitus and hypertension. Ethanol consumption increases plasma levels of ET-1 and the contractile response to this peptide in vascular tissues. This study aimed to investigate the cellular and functional consequences of chronic ethanol consumption on the endothelinergic system in CSM as well as the mediators involved in this response. Male Wistar rats were treated with ethanol 20% (vol./vol.) for 6 weeks. Reactivity experiments were performed on isolated CSM. Our findings show that adrenomedullin and sodium nitroprusside-induced relaxation was not altered after treatment with ethanol. On the other hand, acetylcholine-induced relaxation was reduced in CSM from ethanol-treated rats. Moreover, chronic ethanol consumption reduced plasma and CSM nitrate levels. These observations suggest that chronic ethanol consumption reduces NO synthesis/release but does not alter NO signaling pathway. Ethanol consumption increases plasma levels of ET-1 and the contractile response to this peptide in isolated CSM. Chronic ethanol consumption did not alter the contraction induced by phenylephrine or KCl 120mmol/L in isolated CSM strips. These observations suggest that the effects of chronic ethanol consumption on the CSM reactivity are nonspecific. BQ788, a selective ETB receptor antagonist, did not alter ET-1-induced contraction in CSM from both control and ethanol-treated rats. The relaxation induced by IRL1620, a selective ETB receptors agonist, was not affected by ethanol consumption. mRNA levels and protein expression for ETB receptor were not affected by ethanol consumption. We concluded that CSM hyper-reactivity to ET-1 is not related to reduction of ETB receptor-mediated relaxation. BQ123, a selective ETA receptor antagonist, shifted the concentration-response curve for ET-1 to the right in CSM from control rats. However, this response was not observed in CSM from ethanol group, indicating that the response mediated by the ETA receptor is favored after ethanol treatment. It was found that chronic ethanol consumption did not alter mRNA levels for the components of the endothelinergic system (ET-1, ECE-1, ETA and ETB receptors) and the isoforms of nitric oxide synthase (NOS) (eNOS, nNOS and iNOS), but increased protein expression for ETA receptor, ET-1 and iNOS. Ethanol induced systemic and cavernosal oxidative stress. Reactive oxygen species (ROS), metabolites derived from cyclooxygenase (COX) and NOS, modulate negatively ET-1-induced contraction and appear to be important mediators of ethanol-induced ET-1 hyper-reactivity in the isolated CSM. Y27632, a Rho-kinase inhibitor, reduced ET-1-induced contraction in CSM from both control and ethanol-treated rats. Our results show that chronic ethanol consumption increases ET-1 induced contraction in isolated CSM and that this response is mediated by the Rho-kinase pathway and an increase in ROS generation and ETA receptor expression.

by Lee Hung Kay. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references. / Table of Contents --- p.i / Acknowledgements --- p.vi / Abstracts --- p.vii / Abbreviations --- p.ix / Chapter CHAPTER I. --- GENERAL INTRODUCTION / Chapter I.1 --- A Brief Review on the Background of Organometallic Chemistry --- p.1 / Chapter I.2 --- Stability of Organotransition Metal Complexes --- p.2 / Chapter I.3 --- Decomposition Pathways of Transition Metal σ Hydrocarbyls --- p.5 / Chapter I.4 --- Preparation of Transition Metal σ-Alkyl Complexes --- p.10 / Chapter I.5 --- A Survey on the Use of Functionalized Alkyl and Aryl Ligands in Synthesis of Transition Metal σ-Hydrocarbyls --- p.15 / Chapter I.6 --- 2-(Trimethylsilyl)methylpyridine (3) and 2-Bis(trimethylsilyl)- methylpyridine (4) as Ligand Precursors --- p.20 / Chapter I.7 --- A Brief Review of Previous Results on Synthesis of Metal Alkyl Complexes Using (1) and (2) as Ligands --- p.23 / Chapter I.8 --- Objective of This Work --- p.28 / Chapter I.9 --- References for Chapter I --- p.29 / Chapter CHAPTER II. --- "SYNTHESIS, STRUCTURES AND REACTIVITY OF IRON(n) AND COBALT(II) DIALKYL COMPLEXES" / Chapter II. 1 --- Introduction / Chapter II. 1.1 --- Synthesis of Iron(II) and Cobalt(II) Alkyl Complexes --- p.34 / Chapter IL1.1.1 --- Iron(II) Alkyl Complexes --- p.34 / Chapter II.1.1.2 --- Cobalt(II) Alkyl Complexes --- p.41 / Chapter II.1.2 --- Reactions of Transition Metal Alkyl Complexes with Protic Reagents and Halogens --- p.45 / Chapter II. 1.3 --- The Chemistry of Transition Metal Alkoxides and Thiolates 一 A Brief Review --- p.48 / Chapter II.2 --- Results and Discussion / Chapter II.2.1 --- "Synthesis of Homoleptic Iron(II) and Cobalt(II) Dialkyl Complexes [M {C(SiMe3)2C5H4N-2} 2] (M=Fe 55,Co 56)" --- p.51 / Chapter II.2.2 --- Attempted Reaction of [FeCl2(PPh3)2] with [{R2Li}2] --- p.52 / Chapter II.2.3 --- Attempted Synthesis of Monoalkyliron(II) Complexes --- p.53 / Chapter II.2.4 --- "Synthesis of Homoleptic Iron(II) and Cobalt(II) Dialkyl Complexes [M{(CHSiMe3)C9H6N-8}2] (M = Fe57, Co 58)" --- p.54 / Chapter II.2.5 --- Molecular Structures of [M{C(SiMe3)2C5H4N-2}2] (M =Fe 55.Co 56) and [Co{(CHSiMe3)C9H6N-8}2] (58) --- p.56 / Chapter II.2.6 --- Spectroscopic and Magnetic Properties of Compounds 55-58 --- p.63 / Chapter II.2.7 --- Electrochemistry of [Co(R2)2] (56) and [Co(R3)2] (58) --- p.66 / Chapter II.2.8 --- "Reactivities of [M{C(SiMe3)2C5H4N-2}2] (M = Fe55, Co 56)" --- p.70 / Chapter II.3 --- Experimentals for Chapter II --- p.83 / Chapter II.4 --- References for Chapter II --- p.86 / Chapter CHAPTER III. --- SYNTHESIS AND STRUCTURES OF DIALKYL COMPLEXES OF NICKEL(II) AND PALLADIUM(II) / Chapter III. 1 --- Introduction / Chapter III. 1.1 --- Nickel(II) Alkyl Complexes 一 A General Survey --- p.91 / Chapter III.1.1.1 --- η5-Cyclopentadienylnickel Alkyl and Aryl Complexes --- p.91 / Chapter III.1.1.2 --- Nickel Dialkyls --- p.96 / Chapter III. 1.2 --- Palladium(II) Alkyl Complexes ´ؤ A General Survey --- p.99 / Chapter III.1.2.1 --- Palladium Dialkyls --- p.99 / Chapter III. 1.2.2 --- Cyclopalladated Compounds --- p.101 / Chapter III.2 --- Results and Discussion / Chapter III.2.1 --- Synthesis of Nickel(II) Alkyl Complexes --- p.104 / Chapter III.2.1.1 --- Reactions of [{R1Li(Et2O)}2] and [{R2Li}2] with Nickelocenes ´ؤ Synthesis of η5 - Cyclopentadienylnickelalkyl Complexes (78-80) --- p.104 / Chapter III.2.1.2 --- Synthesis of the Substituted Nickelocene [Ni{{466}5- C5H3(SiMe3)2}2] (81) --- p.106 / Chapter III.2.1.3 --- Spectroscopic Properties of Compounds 78-80 --- p.107 / Chapter III.2.1.4 --- Molecular Structures of [(η5- C5H5)Ni{C(SiMe3)2C5H4N-2}] (78) and [{(η5- C5H5)Ni{CH(SiMe3)C5H4N-2}}2] (80) --- p.110 / Chapter III.2.1.5 --- "Reactions of [{R2Li}2] with NiCl2 and [NiCl2L2] (L2 = TMEDA, 2PPh3) ´ؤ Synthesis of Nickel Dialkyl Complex [Ni{C(SiMe3)2C5H4N-2}2] (82)" --- p.115 / Chapter III.2.1.6 --- Molecular Structure of [Ni{C(SiMe2)2C5H4N- 2}2] (82) --- p.118 / Chapter III.2.1.7 --- Spectroscopic Properties of [Ni{C(SiMe3)2C5H4N-2}2] (82) --- p.121 / Chapter III.2.1.8 --- Electrochemistry of [Ni{C(SiMe3)2C5H4N-2}2] (82) --- p.122 / Chapter III2.1.9 --- Reactivities of Ni[C(SiMe3)2C5H4N-2]2 (82) --- p.124 / Chapter III.2.1.10 --- "Reactions of [{R2Li}2] with [NiCl2(diphos)] [diphos = 1,2-bis(diphenylphosphino)ethane]" --- p.125 / Chapter III.2.1.11 --- Molecular Structure of [Ni{C(SiMe3)2C5H4N- 2}{5-(2'-C5H4NC(SiMe3)2C5H4N-2- CH(SiMe3)2}Cl] (83) --- p.127 / Chapter III.2.1.12 --- "Reactions of [{R1Li(Et2O)}2] and [R5Li] [-R5 = -CH2C5H4N-2] with NiCl2 and [NiCl2L2] (L2 = TMEDA, 2PPh3)" --- p.130 / Chapter III.2.1.13 --- Molecular Structure of [{CH(SiMe3)C5H4N- 2}2] (86) --- p.136 / Chapter III.2.2 --- Synthesis of Palladium(II) Alkyl Complexes --- p.139 / Chapter III.2.2.1 --- "Reactions of [{R2Li}2] with [PdX2L2] (L = PPh3, Et2S; X=Cl, Br) ´ؤ Synthesis of [Pd(R2)2] (88) and [Pd(R2)(PPh3)X] [X 二 Cl 89, Br 90]" --- p.139 / Chapter III.2.2.2 --- "Molecular Structures of Compounds [P'd{C(SiMe3)2C 5H 4N-2}2] (8 8), [Pd{C(SiMe3)2C5H4N-2}(PPh3)Cl] (89)，and [Pd{C(SiMe2)2C5H4N-2}(PPh3)Br] (90)" --- p.140 / Chapter III.2.2.3 --- Spectroscopic Properties of Compounds 88-90 --- p.146 / Chapter III.2 2.4 --- Electrochemistry of [Pd{C(SiMe3)2C5H4N-2}2] (88) --- p.147 / Chapter III.2.2.5 --- "Studies on Stereo specificity of the Reactions between [{R2Li}2] and [PdX2(PPh3)2] (X = Cl, Br)" --- p.150 / Chapter III.2.2.6 --- Attempted Synthesis of [Pd(R1)2] and [Pd(R1)(PPh3)Cll --- p.152 / Chapter III.2.2.7 --- Attempted Synthesis of [{Pd(R2)Cl}2]via Intramolecular C-H Activation --- p.153 / Chapter III.2.2.8 --- Molecular Structure of [{CH(SiMe3)2C5H4N- 2}2PdCl2} (91) --- p.154 / Chapter III.3 --- Experimentals for Chapter III --- p.157 / Chapter III.4 --- References for Chapter III --- p.165 / Chapter CHAPTER IV. --- SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF ZIRCONIUM(IV) AND HAFNIUM(IV) ALKYL COMPLEXES / Chapter IV. 1 --- Introduction --- p.169 / Chapter IV. 1.1 --- Homoleptic and Heteroleptic Complexes --- p.170 / Chapter IV. 1.2 --- Organo-Zirconium(IV) and -Hafnium(IV) Compounds Containing Functionalized Alkyl Ligands --- p.177 / Chapter IV.2 --- Results and Discussion / Chapter IV.2.1 --- "Synthesis of Zirconium(IV) and Hafnium(IV) Dialkyl Dichloride Compounds [M(R2)2C12] (M = Zr 103,Hf 104" --- p.181 / Chapter IV.2.2 --- Attempted Synthesis of Titanium(IV) Alkyl by the Reaction of TiCl4 with [{R2Li}2] --- p.182 / Chapter IV.2.3 --- Attempted Synthesis of Zirconium(IV) and Hafnium(IV) Alkyls with -R 1[= -CH(SiMe3)C5H4N-2] as Ligand --- p.182 / Chapter IV.2.4 --- Molecular Structure of [Zr{C(SiMe3)2C5H4N- 2}2C12] (103) --- p.183 / Chapter IV.2.5 --- Spectroscopic Properties of {C(SiMe3)2C5H4N- 2}2C12] (M = Zr 103，Hf 104) --- p.187 / Chapter IV.3 --- Experimentals for Chapter IV --- p.188 / Chapter IV.4 --- References for Chapter IV --- p.190 / Chapter CHAPTER V. --- COMPARISON OF BONDING PARAMETERS AMONG METAL ALKYL COMPLEXES WHICH CONTAIN ALKYL LIGANDS -R2 --- p.193 / References for Chapter V --- p.201 / APPENDIX I / Chapter A. --- General Procedures --- p.202 / Chapter B. --- Physical and Analytical Measurements --- p.202 / APPENDIX II / Magnetic Moment Measurements --- p.205 / APPENDIX III / "Table A-l. Selected Crystallographic Data for Compounds 55, 56, 58,and63" --- p.207 / "Table A-2. Selected Crystallographic Data for Compounds 78, 80，82 and83" --- p.208 / "Table A-3. Selected Crystallographic Data for Compounds 86, 88, 89 and90" --- p.209 / Table A-4. Selected Crystallographic Data for Compounds 91 and 103.… --- p.210

Neste trabalho foram realizadas sínteses do nitrosilo complexo trinuclear de rutênio de fórmula [Ru3O(CH3COO)6(NO)(py)2]PF6 (py = piridina) seguindo duas rotas sintéticas diferentes (convencional (a) e uma nova (b) ) a fim de verificar e comparar a eficiência de ambas. Além disso, foi feito o mapeamento da rota sintética convencional para analisar a melhor forma de conduzi-la em cada etapa para que a síntese fosse bem sucedida. Com isso, foi possível afirmar na rota (a) que é preciso purificar dois precursores: o precursor 1 [Ru3O(CH3COO)6(S)3]+ e 3 [Ru3O(CH3COO)6(CO)(L)2], não sendo necessário a purificação do produto final. As modificações vistas necessárias para a otimização da síntese (a) foram a utilização de uma solução recém preparada de bromo e a substituição do metanol seco no frasco lavador por diclorometano seco. Não se descarta a possibilidade da nova rota sintética (b), somada às modificações apontadas neste trabalho, apresentar bons resultados. As caracterizações foram feitas utilizando técnicas de espectroscopia na região UV-visível, infravermelho e RMN. Os estudos de reatividade mostraram que, para ambos os complexos analisados ([RuIII,III,III3O(CH3COO)6(NO)(py)2]PF6 e [RuIII,III,III3O(CH3COO)6(4-acpy)2(NO)]PF6), sugere-se a formação da espécie [RuIII,III,II3O(CH3COO)6(NO2-)(L)2]- onde L = 4-acpy ou py - sendo esta reação dependente da concentração de íons hidroxila do meio. Estudos da reatividade e redução do [Ru3O(CH3COO)6(NO)(py)2]PF6 com o redutor de interesse biológico ácido ascórbico na presença de íons OH-, permitiram sugerir uma hipótese para o mecanismo de liberação de NO0 com estímulo redox, na ausência de luz. Propõe-se que primeiramente o ligante NO0 coordenado sofra um ataque nucleofílico dos íons hidroxila presentes no meio, concomitante a uma transferência eletrônica intra-molecular que gera a espécie [RuIII,III,II3O(CH3COO)6(NO2-)(py)2]-. Este último é reduzido pelo ácido ascórbico, restaurando o ligante NO0 que, agora coordenado à unidade metálica reduzida [RuIII,III,II3O], finalmente é labilizado, gerando o complexo [Ru3O(CH3COO)6(S)(py)2]0 / In this work, the synthesis of the trinuclear ruthenium complex [Ru3O(CH3COO)6(NO)(py)2]PF6 (py = pyridine) was performed following two different synthetic routes (conventional (a) and a new one (b)) in order to verify and to compare the efficiency of both. In addition, the mapping of the conventional synthetic route was done to analyze the best way to conduct it at each step for the synthesis to be successful. It was possible to state in route (a) that two precursors must be purified: precursor 1 [Ru3O(CH3COO)6(S)3]+ and 3 [Ru3O(CH3COO)6(CO)(L)2], no purification of the final product being necessary. The modifications required for the optimization of synthesis (a) were the use of a freshly prepared solution of bromine and the substitution of the dry methanol in the washing flask by dry dichloromethane. We can not rule out the possibility of the new synthetic route (b), added to the modifications pointed out in this work, to present good results. The characterizations were made using UV-visible, infrared and NMR spectroscopy techniques. Reactivity studies for both complexes analyzed ([RuIII,III,III3O(CH3COO)6(NO)(py)2]PF6 and [RuIII,III,III3O(CH3COO)6(4-acpy)NO)]PF6), suggested the formation of the species [RuIII,III,II3O(CH3COO)6(NO2-)(L)2]- - where L = 4-acpy or py - this reaction being dependent on the concentration of hydroxyl ions in the medium. Studies of the reactivity and reduction of compound [Ru3O(CH3COO)6(NO)(py)2]PF6 with the biological reductant ascorbic acid, in the presence of OH- ions, allowed to suggest a hypothesis for the NO0 release mechanism with redox stimulus, in the absence of light. It is proposed that the coordinated NO0 ligand undergoes a nucleophilic attack of the hydroxyl ions present in the medium, concomitant to an intra-molecular electron transfer that generates the species [RuIII,III,II3O(CH3COO)6(NO2-)(py)2]-. The latter is reduced by ascorbic acid, restoring the ligand NO0 which, now coordinated to the reduced metal unit [RuIII,III,II3O], is finally labilized, generating the complex [Ru3O(CH3COO)6(S)(py)2]0

Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2018-08-08T16:43:38Z No. of bitstreams: 1 Ana Júlia Maciel Marinho Fernandes_.pdf: 24903248 bytes, checksum: e58f36fcc0799fa5830bd2beede0f0ac (MD5) / Made available in DSpace on 2018-08-08T16:43:38Z (GMT). No. of bitstreams: 1 Ana Júlia Maciel Marinho Fernandes_.pdf: 24903248 bytes, checksum: e58f36fcc0799fa5830bd2beede0f0ac (MD5) Previous issue date: 2018-05-28 / Nenhuma / A utilização de materiais cimentícios suplementares (MCS) na produção de cimento é uma estratégia bastante difundida para diminuição de custos de produção, e pode contribuir para a minimização da emissão de CO2. Estes materiais, ao reagirem com o hidróxido de cálcio (CH), gerado na hidratação do cimento, formam silicatos de cálcio e aluminatos de cálcio hidratados adicionais, contribuindo para o ganho de resistência. Segundo a normativa brasileira, para ser considerado um material pozolânico, o somatório de óxidos de Si, Al e Fe deve ser maior do que 70%. No entanto este requisito deve ser tomado com restrições, pois evidências indicam que somente a fração amorfa dos óxidos pozolânicos é que consomem CH. Diante disto, este trabalho teve por objetivo geral avaliar de forma comparativa a influência da composição química e da fração amorfa dos óxidos pozolânicos na reatividade de materiais cimentícios suplementares. Foram estudados uma cinza volante da combustão do carvão (CV); de um resíduo de cerâmica vermelha (RCV); e de um metacaulim (MK). Os materiais tiveram a granulometria ajustada a fim de se obter um D50 de 4 ± 2 µm, buscando uma menor diferença entre a distribuição granulométrica dos MCS e o pó de quartzo (PQ), empregado para compor um padrão secundário de referência, o que permite isolar o fator consumo de cimento nas análises. Os MCS foram caracterizados por FRX, por granulometria à laser, por adsorção de nitrogênio, por picnometria de gás hélio, e microscopia eletrônica de varredura. Empregou-se também DRX em conjunto com o refinamento de Rietveld, utilizando-se o método do padrão interno para a quantificação de fases. A reatividade dos MCS foi medida pelo método de Fratini, por TG/DTG e por resistência à compressão, em pastas e argamassas. Constatou-se que todos os MCS são reativos. O teor de amorfos totais em geral não explica o consumo de CaO, nem as resistências de argamassas. O teor de alumina amorfa apresenta considerável influência sobre consumo de CH, medido em análise térmica, em relação à pasta com PQ. O emprego de pastas para ensaios de resistência, e o padrão com PQ, permitiu avaliar a contribuição da reação dos MCS para as resistências, e, neste caso o teor de amorfos totais e de Al2O3 amorfa apresentam a mesma tendência de comportamento, quanto maior o teor, maior a resistência. No entanto, esta tendência não foi observada quando o teor de SiO2 é isolado, pois o RCV não segue o mesmo comportamento. Foi observado também que o teor elevado de Fe2O3 do RCV pode ser o responsável pela baixa redução de CaO observada no ensaio de Fratini deste MCS. / The use of supplementary cementitious materials (SCM) in the cement production is an usually strategy to reduce costs, and it can promote the reduce of the CO2 emissions. These materials react with the calcium hydroxide (CH), generated in the cement hydration, forming hydrated calcium silicates and aluminates, contributing for the compressive strength. A pozzolanic material has to have, according the Brazilian Standards, a sum of Si, Al and Fe oxides above 70%. However, this requirement have to be taken in account with caution, as evidences indicate that only the amorphous fraction of the pozzolanic oxides consume CH. The aim of this work is to evaluate in a comparative way the influence of the chemical composition and of the amorphous fase of pozzolanic oxides in the reactivity of supplementary cementitious materials. It was studied a fly ash from coal burning (FA), a fired-clay brick powder (FCP) and a comercial metacaulim (MK). The size distribution of the material was adjusted in order to obtain a D50 of 4 ± 2 µm, in order to adjust the granulometry of the materials with the quartz powder (QP), that was employed in a secondary reference composition. The use of this secondary reference allows to compare the pozzolanic materials mixtures with a reference with the same cement consumption. The SCM were characterized by XRF, by laser granulometry, by nitrogen adsorption method, helium gas pycnometry, and by scanning electronic microscopy. It was also employed XRD associated with Rietveld refinement, using the internal pattern method for phase quantifying. The SCM reactivity was measured by Fratini Method, by TG/DTG and by compressive strength, in cement pastes and mortars. It was found that all SCM are reactions. The total amorphous content in general does not explain the CaO consumption, neither the mortars strength. The amorphous alumina content shows a considerable influence on the CH consume measured by TG, taking as reference the pastes with QP. The use of cement paste for compressive strength tests, as well the reference with QP, allowed to evaluate the contribution of the reactivity of SCM for the strength, and, in this case, the total amorphous content and the amorphous Al2O3 content presented the same tendency of behaviour: as big is the content, as big is the strength. However, this tendency it was not observed when the amorphous SiO2 is isolated, because the FCP does not have the same behaviour. It also was observed that the high content of Fe2O3 in the FCP can be responsable for the low tax of CaO consumption observed in the Fratini method of this SCM.

La distillation dite « charentaise » est une méthode de distillation discontinue permettant la production d’eaux-de-vie de cognac à partir de vin. La distillation est effectuée dans des alambics en cuivre avec un chauffage à feu nu qui peut être favorable à la génération de composés volatils. Or, les précurseurs et les mécanismes de réactions formant ces composés, pendant la distillation, restent mal connus. La première partie de l’étude consiste à identifier les composés volatils formés au cours de la distillation charentaise. Le bilan matière effectué sur de nombreux composés lors du procédé de distillation a révélé que 2 esters, 3 aldéhydes, 3 terpènes et 12 norisoprénoïdes étaient générés. Par la suite, deux distillations utilisant un mode de chauffe différent (feu nu et vapeur) ont été menées sur un alambic pilote. Le but était d’évaluer l’impact du mode de chauffe sur la génération en composés volatils. L’étude a montré que le mode de chauffe a peu d’effet sur la génération en composés volatils. De plus, les composés formés sont similaires à ceux formés lors de la distillation en alambic traditionnel. Enfin, le troisième axe de l’étude porte sur la caractérisation de l’hydrolyse acide de l’α- terpenyl-O-β-glucopyranoside, précurseur impliqué dans la formation de l’α-terpineol, identifié comme étant généré lors de la distillation charentaise ainsi qu’en alambic pilote. Le suivi de la dégradation dans un réacteur hermétiquement fermé de l’α-terpenyl-O-β-glucopyranoside et dans des conditions représentatives du vin durant la distillation montre l’hydrolyse pour former l’α- terpineol, le trans-terpin et son isomère. Cette étude a révélé que l’hydrolyse du précurseur est favorisée en milieu aqueux et suit une cinétique d’ordre 1 / The « charentaise » distillation is a batch distillation method that allows the production of cognac spirits from wine. The distillation is performed in copper alembics through a direct open flame heating that could favor the formation of volatile compounds. The first part of this study consists in identifying the volatile compounds formed during the distillation of cognac spirits. The mass balance performed on volatile compounds revealed that 2 esters, 3 aldehydes, 3 terpenes and 12 norisoprenoids were generated. Thereafter, two distillations using a different heating mode (direct open flame and steam) were conducted on a small-scale alembic. The goal was to assess the impact of the heating mode on the formation of volatile compounds. The study showed that the mode of heating has little effect on volatile compounds’ generation. Moreover, the compounds formed are similar to the ones during the traditional distillation of cognac spirit. Finally, the third part of the study focuses on the characterization of the acid hydrolysis of α-terpenyl-O-β-glucopyranoside which is the suspected precursor to be involved in the formation of α-terpineol, identified as generated during the charentaise distillation and in small-scale distillations. α-terpenyl-O-β- glucopyranoside was placed in two representative model solutions corresponding to the initial wine and the stillage. Both solutions were exposed to 100 °C in a closed reactor system. Results showed that the hydrolysis of the precurseur formed α- terpineol, trans-terpin and its isomere that seems to be 4-(2-hydroxypropan-2-yl)-1- methylcyclohexan-2-ol). Data also revealed that the hydrolysis of the precursor follows a first order reaction model ant that an aqueous media promotes the formation of trans-terpin.

Este trabalho apresenta um estudo sobre o efeito de sombreamento em detectores de nêutrons, quando estes são utilizados em medidas de reatividade com a técnica de rod drop. O sombreamento pode ser entendido como uma mudança na eciência dos detectores, quando esta é dada em nêutrons detectados/ssão ocorrida no reator, sendo mais evidente nos detectores mais próximos ao banco sendo inserido. O método de análise, fundamentalmente teórica, baseou-se em simulações do reator IPEN/MB-01 utilizando o código CITATION e o programa MCNP. Em ambos os casos, os resultados são estáticos, mostrando os uxos neutrônicos apenas em duas situações: antes da inserção do banco, e após sua inserção. A reatividade, neste caso, é obtida utilizandose a expressão derivada da técnica de source jerk. Em adição ao estudo teórico, os dados de um experimento de rod drop realizado no reator IPEN/MB-01 também foram utilizados. Neste caso, a reatividade foi obtida com o método de cinética inversa, já que os dados experimentais são constituídos de valores que variam no tempo. Em todos os casos, fatores de correção para o efeito de sombreamento são propostos. / This work presents a study on the eect of shading in neutron detectors, when used in measures of reactivity with the rod drop technique. Shading can be understood as a change in the eciency of the detectors, when it is given in detected neutrons / ssion occurred in the reactor, more evident in the detectors closest to the bank being inserted. The method of analysis was based on simulations of reactor IPEN/MB-01, using the code CITATION and MCNP program. In both cases, the results were static, showing Neutronic ows in only two situations: before insertion of the control rod and after insertion. The measure of reactivity in this case was achieved using the expression derived from the source jerk technique. In addition to theoretical study, data from a rod drop experiment conducted in the reactor IPEN/MB-01 were also used. In this case, the reactivity was obtained using inverse kinetic method, since experimental data were set of values that vary with time. In all cases, correction factors for the shadowing eect have been proposed.

A number of theories have attempted to explicate mechanisms underpinning the transition from recreational drug use to substance dependence. A highly reliable correlate of dependence is the value ascribed to the drug. However, supernormal drug valuation may be insufficient to fully account for a subgroup of dependent individuals for whom the course of dependence is chronic and relapsing and who persist in drug use in the face of devastating costs. Three candidate secondary mechanisms for dependence are considered in this thesis: cue reactivity, cost discounting, and sensitivity to negative affect. Neither cue reactivity nor cost discounting were found to be significantly associated with severity of alcohol dependence in samples of young adult drinkers. By contrast, induced negative affect was found to be reliably associated with augmented alcohol motivation, and sensitivity to this effect was related to symptoms of depression and self-reported drinking to cope with negative affect: both risk factors for the development of dependence. These findings delineate a particular subset of dependent individuals for whom negative affect may represent a substantial trigger to continued drug use. There are a lack of brief interventions to abolish or limit negative affect driven drug motivation. This thesis trialled three potential interventions. A natural walk intervention in hazardous drinkers showed no evidence of limiting this effect in two experiments. Brief instruction in acceptance-based coping showed no evidence of limiting annoyance in response to an aversive noise induction procedure in an alcohol dependent population, and was therefore also eliminated as a potential intervention. However, engagement with pleasant environmental images, as a proxy for environmental enrichment, significantly reduced negative affect driven alcohol choice in student drinkers who reported a desire to visit the locations shown (high liking), compared to low-liking individuals and controls. This provides preliminary evidence for the efficacy of environmental enrichment type interventions, justifying further trials. In treatment of dependence more generally, interventions to increase access to healthy, non-drug sources of positive reinforcement may prove effective.

Made available in DSpace on 2014-06-11T19:22:15Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-09Bitstream added on 2014-06-13T19:27:19Z : No. of bitstreams: 1 deus_acf_me_botfca.pdf: 1380017 bytes, checksum: 6e4d5e1437947fadf9a4d182d77580da (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A eficiência dos corretivos de acidez do solo, e, sua qualidade depende da taxa de reatividade (RE), e do poder de neutralização (PN), sendo esta eficiência indicada pelo poder relativo de neutralização total (PRNT). Para os silicatos existem poucos estudos que estabeleça taxas de reatividade para suas frações granulométricas e, portanto, utilizam-se as mesmas taxas de reatividade do calcário. Foram desenvolvidos três experimentos no período de julho/2008 a outubro/2009 em casa de vegetação na Faculdade de Ciências Agronômicas/UNESP – Botucatu-SP, com o objetivo de comparar valores de reatividade das frações granulométricas para materiais silicatados em três solos de diferentes classes texturais cultivados com plantas de alfafa. Utilizou-se seis materiais corretivos: escória, silicato de cálcio, silicato de cálcio e magnésio, wollastonita, calcário dolomítico e calcário calcítico os quais no experimento 1 e 2 foram separados em quatro frações granulométricas, peneiras: nº 10 (Ø = 2 mm), nº 20 (Ø = 0,84 mm), nº 50 (Ø = 0,30 mm) e fundo (Ø<0,30 mm), exceto a wollastonita que possui apenas a granulometria < 0,30 mm. Os tratamentos foram aplicados em três solos: Latossolo Vermelho distrófico, Nitossolo Vermelho eutrófico e Neossolo Quartzarênico. No 1° experimento aplicou-se quatro doses (1, 2, 4 e 8 t ha-1) afim de obter a curva de neutralização dos solos, para determinar a dose a ser aplicada de cada fração granulométrica para atingir o pH 5,5. O 2° experimento constou da aplicação das doses ecomendadas no primeiro experimento e com o valor de pH obtido aos 90 dias de incubação calculou-se a eficiência relativa de reatividade para cada fração granulométrica, tomando-se como referência o pH obtido com a aplicação do calcário dolomítico na peneira... / The efficiency and quality of materials for soil acidity correction are based on the reactivity rate (RR) and neutralization power (NP), and it is indicated by the effective calcium carbonate (ECC). Considering that there are few studies establishing reactivity rates of silicate particle-size fractions, lime values are used as reference. Three experiments were carried in the period July/2008 to October/2009 out in greenhouse in College of Agricultural Sciences, UNESP, Botucatu – SP, aiming to compare reactivity rates of silicate particle-size fractions in three soils with distinct textures cultivated with alfalfa plants. Slag, calcium silicate, calcium+magnesium silicate, wollastonite, dolomitic and calcitic lime were the materials evaluated. The first and second experiments consisted of four particlesize fractions obtained from each material, separated by the sieves no. 10 (Ø = 2 mm), no. 20 (Ø = 0.84 mm), no. 50 (Ø = 0.30 mm) and bottom (Ø < 0.30 mm), except that the wollastonite has the particle-size fraction < 0,30 mm. Treatments were applied in three soils: Oxisol, Hapludox and Quartzipsamment. In the first study, four doses were applied (1, 2, 4 and 8 t ha- 1) to obtain soil neutralization curve and thus determine which one was to be applied for each particle-size fraction to reach pH 5.5. The second study consisted of the application of the recommended doses from the first experiment. Then, with the pH values obtained 90 days after incubation, the relative efficiency of reactivity was calculated for each particle-size fraction based on the pH of dolomitic lime from the last sieve. Afterwards, RR and ECC were calculated. In the third study, the doses to increase soil base saturation up to 80% were calculated based on both the PRNT reported in the laboratory and in the experiment. Treatments were incubated... (Complete abstract click electronic access below)

A presente discussão e uma extensão do modelo de cinética pontual de nêutrons, onde a reatividade e decomposta em termos de contribuição de curtas e longas escalas de tempo. A primeira representa o controle operacional do reator, enquanto a segunda e devido a alteração da composição química do combustível nuclear, como consequência do burn-up. E um primeiro passo em uma nova direção, uma vez que considera os efeitos dos principais venenos na cinética de nêutrons, ou seja, Xenônio-135 e Sam ario-149. O modelo proposto consiste em um sistema de equações não-lineares acoplado para a densidade de nêutrons, para os precursores de nêutrons atrasados e para as cadeias de decaimento dos venenos produtos de fissão. O sistema de equações e resolvido através de um método de decomposição, que expande os termos não-lineares em uma série infinita, obtendo um sistema recursivo, onde a inicialização da recursão e uma equação linear homogênea e os passos de recursão subsequentes consideram contribuições não-lineares como termo fonte constru dos em passos de recursão anteriores. A construção hierárquica do modelo também e realizada, onde graus espaciais de liberdade são considerados. São apresentados casos de estudos com várias estruturas temporais afim de mostrar a robustez da abordagem atual para este tipo de problema. / The present discussion is an extension to Neutron point kinetics models, where the reactivity is decomposed in a short and a long term contribution. The rst one represents operational reactor control, whereas the second one is due to the change of the chemical composition of the nuclear fuel as a consequence of burn-up. This is a rst step into a new direction where we consider only the e ects of the principal neutron poisons on neutron kinetics, i.e, Xenon-135 and Samarium-149. The proposed model consists in a system of coupled nonlinear equations for the neutron density, the delayed neutron precursors and the neutron poison decay chains. The equation system is solved using a decomposition method, which expands the non-linear terms in an in nit series, obtaining a recursive system, where the recursion initialization is a homogeneous linear equation and the subsequent recursion steps consider the non-linear contributions as source terms constructed from previous recursion steps. A hierarchical construction of the model is also performed, where spatial degrees of freedom are considered. We present case studies with severe time structure in order to show the robustness of the present approach for this kind of problems.

Estudos epidemiológicos têm demonstrado que a exposição à fumaça de cigarro - ativa ou passiva - está altamente correlacionada ao agravamento e severidade do quadro asmático, que inclui inflamação, hiperresponsividade e remodelamento pulmonar. Os modelos experimentais que conjugam asma e tabagismo, em geral, abordam apenas alguns aspectos isolados desta complexa relação, e carecem de elucidação sobre as possíveis interrelações existentes. Neste modelo experimental, a proposta foi analisar os efeitos da coexposição de curta duração à fumaça de cigarro - do tipo \"mainstream\" - e alérgeno em camundongos previamente sensibilizados, focando as características fisiopatológicas e funcionais da asma ao final de três semanas. Os resultados demonstraram que o grupo coexposto à OVA e fumaça de cigarro (OF) apresentou diminuição do número total e diferencial de todas as células no lavado broncoalveolar, bem como da expressão celular de INF-gama e IL-4 quando comparados ao grupo OVA. Por outro lado, os parâmetros relativos ao remodelamento pulmonar parecem ser afetados de maneira oposta, demonstrado pelo aumento substancial do conteúdo de colágeno e pela expressão celular de MMP9 e TGF-? no grupo OF. A responsividade pulmonar, por sua vez, apresentou elastância aumentada nos animais com inflamação pulmonar alérgica crônica em comparação aos demais grupos, sugerindo uma correlação entre o número de eosinófilos e a resposta mecânica observada. A atividade de certos componentes específicos da fumaça de cigarro parece influenciar o comportamento das alças regulatórias no processo de inflamação, como sugerido pela expressão celular aumentada de IL-10 nos grupos expostos ao fumo. Conclui-se, portanto, que neste modelo experimental, a variedade de elementos químicos presentes na fumaça do cigarro pode afetar de maneira diferenciada os aspectos da inflamação pulmonar alérgica crônica em camundongos. / Several epidemiologic studies have shown that active as well passive smoking is positively associated with asthma severity, including inflammation, hiperresponsiveness and lung remodeling. Experimental models that conjugate asthma and smoking usually approach isolated aspects of this complex relation and more elucidation is needed about possible mechanisms involved. In this experimental model, the proposal was analyze the effects of short-term cigarette smoke - mainstream - on animals previously sensitized, pointing on physiological and functional characteristics of asthma during three weeks. Results demonstrated coexposed group to allergen and cigarette smoke (OVA+CS group) showed a decrease of total and differential number of all cells of bronchoalveolar lavage, as well cellular expression of INF-gamma and IL-4 when compared to OVA group. On the other hand, parameters related to lung remodeling seemed to be affected in opposite way, demonstrated by an increase of collagen content and cellular expression of MMP9 and TGF-beta of OVA+CS group. Pulmonary responsiveness was increased in tissue elastance in animals with chronic allergic pulmonary inflammation when compared to all groups, suggesting a correlation between eosinophils number and mechanical response observed. The activity of specific cigarette smoke components may influence the behavior of regulatory loops in inflammatory process, as showed by increased cellular expression of IL-10 in cigarette smoke exposed groups. In conclusion, in this experimental model the variety of chemical elements of cigarette smoke may affect in distinct ways aspects related to chronic allergic pulmonary inflammation in mice.