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A range of substituted l,3-dithiol-2-ylidene systems have been prepared. These species have, subsequently, been converted to nitroso derivatives. The role of the 4-, 5- and ylidene subtituents in stabilising the nitroso-alkene moiety thus obtained has been investigated. X-ray molecular crystal data which show that these species are stabilised by intramolecular interactions are presented. Conversion of the nitroso derivatives to their thionitroso analogues has been attempted, but was unsuccessful. A selection of l-(l,3-dithiol-2-ylidene)-prop-2-ene systems have been prepared. These systems have been shown to be sufficiently activated to undergo nitrosation reactions at the 3-vinyl positon, though the nitroso-alkenes thus formed are unstable. A new route to 4,5-dicarbomethoxy-2-(tributylphosphino)-l,3-diselenolium tetrafluoroborate utilising hydrogen selenide as the source of selenium has been detailed. This Wittig reagent has been employed in the synthesis of various 1,3-diselenol-ylidene systems. Conversion to nitroso derivatives has been accomplised and X-ray data shows that the resultant nitroso-alkenes are stabilised by an intramolecular oxygen—selenium interaction.

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The novel bimetallic hydrides [(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)H₂]₂ can be prepared sequentially by the metathesis of [(n⁵-C₅H₅)W(N0)IH₂]₂ with Na[H₂Al(0CH₂CH₂0CH₃)₂]. Analyses of the ¹H NMR spectra of C[(n⁵-C₅H₅)W(N0)IH]₂ and [(n⁵-C₅H₅)W(N0)IH₂]₂ show the former contains hydride ligands bound to tungsten in a terminal fashion, while the latter possesses two terminal and two bridging hydrides. Addition of a Lewis base to [(n⁵-C₅H₅)W(N0)IH]₂ results in the formation of hydride species (n⁵-C₅H₅)W(N0)IHL (L = P(0Ph)₃, P(0Me)₃, PPh₃); in like manner, the dimer [(n⁵-C₅H₅)W(N0)IH₂]₂ is cleaved by triphenylphosphite to form the monomer cis or trans [(n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. A comparison is made of the reactivity of the tungsten-hydrogen link in the nitrosyl hydrides (n⁵-C₅H₅)- W(N0)IH[P(0Ph)₃], (n⁵-C₅H₅)W(N0)₂H, and (n⁵-C₅H₅)W(N0)IH₂[P(0Ph)₃]. The Mo(N0)₂²⁺ unit is obtained as the tetrakis-solvate via chloride abstraction from Mo(N0)₂Cl₂ by AgBF₄ or nitrosylation of Mo(C0)₆ by NOPF₆ in coordinating solvents such as nitromethane, acetonitrile, or tetrahydro-furan. The unsolvated complex [Mo(N0)₂(PF₆)₂][aub=n] is produced if the latter reaction is performed in dichloromethane; however, it readily converts to [Mo(N0)₂S₄](PF₆)₂ upon exposure to coordinating solvents (S). Hard Lewis bases (L = CH₃CN , 0PPh₃ or L₂ = 2 ,2-bipyridine replace the solvent molecules in [Mo(N0)₂S₄]X₂ (X = BF₄⁻, PF₆⁻) forming complexes [Mo(N0)₂L₄]²⁺ or [Mo(N0)₂L₂S₂]²⁺ depending upon the solvent employed. Reagents capable of being oxidized appear to reduce the dinitrosyl dication without permanent coordination to the molybdenum centre. Reduction of [Mo(NO)₂S₄](PF₆)₂ or [Mo(N0)₂(PF₆)₂][sub=b] is effected by sodium amalgam (one equivalent); addition of a ligand L₂ (L₂ = 2,2-bipyridyl, 3,4,7,8-tetramethyl-1,1O-phenanthroline) to the reaction mixture permits the isolation of [M(NO)₂L₂]₂(PF₆)₂. Addition of excess ligand results in the formation of non-nitrosyl containing species [Mp(L₂)₃]PF₆ (L = 0PPh₃ or L₂ = 3,4,7,8-tetramethyl-1 ,10-phenanthro- line). Decomposition of the nitrosyl species results from attempts to reduce [Mo(NO)₂S₄]²⁺ by two electrons. New complexes are identified by the aid of IR and ¹H, ¹⁹F, or ³¹P NMR spectroscopy and conductance measurements. Attempts to prepare thionitrosyl analogues of [Mo(N0)₂L₄]²⁺ have met with limited success; the only wel1-characterized thionitrosyls isolated in this study are the known (n⁵-C₅H₅)Cr(C0)₂NS and the new [(n⁵-C₅H₅)Mo-(N0)(NS)PPh₃]BF₄. Also discussed is the interaction of NOPF₆ with solvents. NOPF₆ has been found to react slowly with acetonitrile, a common solvent for nitro-sonium salts. / Science, Faculty of / Chemistry, Department of / Graduate

<p> 1-nitropyrene and 1,8-dinitropyrene are environmental pollutants and direct-acting mutagens in bacteria. Studies have shown that reduction of the nitro group is essential for the expression of the mutageneity of these compounds and the formation of covalent DNA adducts in Salmonella typhimurium. It has also been shown that the corresponding amino compounds are only slightly mutagenic. Since the reduction of nitro compounds to amino compounds must proceed via the nitroso and hydroxylamino intermediates, it has been proposed that the hydroxylamines derived from 1-nitropyrene and 1,8-dinitropyrene are the ultimate mutagens.</p> <p> 1-nitrosopyrene and 1-nitroso-8-nitropyrene were synthesized and reduced to their corresponding hydroxylamines with ascorbic acid. While 1-nitrosopyrene (50,226 rev/nmole) was 50X more potent than 1-nitropyrene (985 rev/nmole) in the Ames Test, 1-nitroso-8-nitropyrene (8,000 rev/nmole) was 10X less potent than 1,8-dinitropyrene (85,830 rev/nmole). The hydroxylamines derived from these compounds proved to be very labile species and could not be characterized.</p> / Thesis / Master of Science (MSc)

Orientador: Newton Nunes / Coorientador: Patricia Cristina Ferro Lopes / Banca: Roberta Carareto / Banca: Vivian Fernanda Barbosa / Banc: Bruno Watanabe Minto / Resumo: Compararam-se os efeitos de diferentes frações inspiradas de oxigênio (FiO2) associado ao óxido nitroso (N2O) ou ao ar comprimido sobre a hematose, parâmetros cardiorrespiratórios, intracranianos e o índice biespectral (BIS), em leitões mantidos em ventilação espontânea ou controlada a pressão, associada ou não à PEEP (5 cmH2O). Foram utilizados 48 leitões, distribuídos em 6 grupos, submetidos à 10, 30 e 50% de ar comprimido (GA10, GA30 e GA50) ou N2O (GN10, GN30 e GN50), associadas às FiO2 de 0,9, 0,7 e 0,5, respectivamente. O GA30 mostrou maior proximidade do intervalo fisiológico da pressão parcial de oxigênio no sangue arterial. A PEEP não foi eficaz na pressão parcial de dióxido de carbono no sangue arterial, independente da FiO2, quando se utilizou o N2O. O pH, déficit base e bicarbonato no sangue arterial foram influenciados pela FiO2 e N2O. As alterações do volume corrente e volume minuto parecem correlacionadas à introdução da ventilação mecânica (VM) e PEEP. Na diferença alvéolo-arterial de oxigênio, a PEEP influenciou negativamente o GA30 e GN30 e não foi adequada para manutenção do shunt pulmonar. Já a pressão média da artéria pulmonar e pressão média capilar pulmonar apresentaram acréscimos após introdução da PEEP. A associação da PEEP com N2O (50%) ou ar comprimido (50%) parece ser a receita para desempenho inferior da variação de pressão de pulso. Para a pressão intracraniana, apenas o GN30 apresentou valor menor ao se instituir a VM quando comparado com o mome... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The effects of different fractions of inspired oxygen (FiO2) associated with compressed air or nitrous oxide (N2O) on lung oxygenation, cardiorespiratory parameters, intracranial parameters and the bispectral index (BIS) were compared in piglets maintained under spontaneous or controlled ventilation, with or without PEEP (5 cmH2O). Forty-eight piglets, distributed in six groups, were submitted to 10, 30 and 50% of compressed air (GA10, GA30 and GA50) or N2O (GN10, GN30 and GN50), associated with FiO2 of 0.9, 0.7 and 0.5, respectively. GA30 showed greater proximity to the physiological range of partial oxygen pressure in the arterial blood. When N2O was used, PEEP was ineffective in maintaining partial carbon dioxide pressure in the arterial blood, independent of FiO2. Arterial blood pH, base deficit and bicarbonate were influenced by FiO2 and N2O. Changes in tidal and minute volumes seem to correlate with the introduction of mechanical ventilation (MV) and PEEP. The difference in alveolar-arterial oxygen under PEEP negatively influenced GA30 and GN30 and was inadequate for pulmonary shunt maintenance. Mean pulmonary artery pressure and mean capillary pulmonary pressure increased following the initiation of PEEP. The association of PEEP with N2O (50%) or compressed air (50%) seems to result in lower performance of pulse pressure variation. Regarding intracranial pressure, only GN30 presented a lower value when MV was established compared with the time point when PEEP was initi... (Complete abstract click electronic access below) / Doutor

A agricultura é uma importante fonte de gases de efeito estufa (GEE). Porém, ela também tem grande capacidade de mitigá-los, através do uso de práticas de manejo que resultem no sequestro do CO2 atmosferico na matéria orgânica do solo (MOS) e que diminuam as emissões de oxido nitroso (N2O) e de metano (CH4). A pesquisa foi desenvolvida em experimento de longa duração (18 anos), em Paysandu, Uruguai, e teve os seguintes objetivos: i) avaliar o efeito de rotações de culturas contínuas e culturas-pastagens sob preparo convencional (PC) e plantio direto (PD) sobre a emissão e balanço de GEE; ii) identificar as principais variáveis de solo e meteorologicas controladoras dos fluxos de N2O e CH4 do solo. Avaliou-se uma sequência de culturas contínuas (trigo-soja) (CC) e uma sequencia de cultura-pastagem (três anos de trigo-soja e três anos de pastagem perene) (CP), ambas sob PC e PD, sendo que no sistema de PD avaliou-se também uma sequencia de trigo-milho (CCPDC4). Durante dois anos foram avaliados os fluxos de N2O e de CH4 do solo utilizando a metodologia de câmaras estáticas e analise da concentração dos gases por cromatografia gasosa. No caso do CO2, o fluxo liquido deste gas foi avaliado através da variação dos estoques de C na MOS (0-18 cm), entre os anos 2003 e 2011. Os sistemas de manejo não se diferenciaram (P<0.1) nas emissões de N2O nem nas quantidades de CH4 oxidado pelo solo, com magnitudes anuais entre 1,89 e 3,98 kg N-N2O ha-1 ano-1 e entre -1,00 e -0,39 kg de C-CH4 ha-1 respectivamente. As emissões de N2O concentraram-se principalmente no inverno e as principais variáveis controladoras dos fluxos foram a porosidade preenchida por agua e os teores de NO3 no solo. Os fluxos de CH4 não foram claramente explicados por nenhuma das variáveis de solo e meteorológicas avaliadas e também não apresentaram sazonalidade. O CCPC foi o único sistema que apresentou queda dos estoques de C no solo, liberando CO2 para à atmosfera. Em termos de balanço das emissões, em CO2 equivalente, este sistema apresentou o maior potencial de aquecimento global (PAG) por unidade de área (581 kg C equivalente ha-1 ano-1) e também por unidade de energia bruta produzida (47,9 kg C equivalente Gcal-1). Neste sentido, a emissão foi quase duas vezes a mais que nos sistemas em rotação com pastagens e quase três vezes mais que os sistemas de agricultura contínua sob PD, que foram os mais eficientes. Assim, os sistemas de manejo de solo considerados conservacionistas, desde o ponto de vista de manter ou aumentar os níveis de C na MOS, também foram capazes de mitigar as emissões de GEE em comparação a sistemas de agricultura contínua sob PC. / Agriculture is a major source of greenhouse gases (GHG). However, this problem is considerably mitigated through the use of soil management practices that result in the sequestration of atmospheric CO2 in soil organic matter (SOM), and reduce emissions of nitrous oxide (N2O) and methane (CH4). This research was conducted in a long-term experiment (18 years) in Paysandú, Uruguay, with the following objectives: i) to evaluate the effect of continuous cropping rotations and crop-pastures rotations under both conventional tillage (CT) and no tillage (NT) on GHG fluxes and balance; and ii) to identify key soil and meteorological variables controlling the fluxes of N2O and CH4 of the soil. We evaluated a sequence of continuous cropping (wheat - soybean) (CC) and crop-pasture (three years of wheat - soybean followed by three years of perennial pasture) (CP), under both CT and NT; and a wheat - corn sequence (CCPDC4) under NT. Soil N2O and CH4 fluxes were evaluated over a period of two years using the closed chambers method, and gas analysis was performed by gas chromatography. Liquid flux of CO2 was evaluated in terms of the change in stocks of C in SOM (0 -18cm), between 2003 and 2011. Management systems did not differ (P<0,1) in N2O emissions or quantities of methane oxidized by the soil. Annual magnitudes ranged from 1,89 to 3,98 kg N2O-N ha-1 yr-1; and from -1,00 to -0,39 kg CH4-C ha-1 yr-1, respectively. N2O emissions were mainly concentrated during the winter; the main variables controlling fluxes were water-filled porosity and NO3 tenors in the soil. CH4 fluxes were not clearly explained by either soil or weather evaluated variables and nor showed seasonality. CCCT was the only system which decreased in soil C stocks, releasing CO2 to the atmosphere. In terms of the balance of emissions of CO2 equivalent, this system displayed the highest global warming potential (GWP) per unit area (581 kg C equivalent ha-1 yr-1); and per unit of gross energy produced (47,9 kg C equivalent Gcal-1): the emissions were nearly twice of that observed in crop-pasture rotation systems; and almost three times more than in the continuous cropping systems under NT, which were the most efficient systems. Thus, soil conservation management systems, which are able to maintain or increase levels of C in SOM, also mitigated GHG emissions when compared to continuous cropping systems under CT.

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Thesis (Ph. D.)--University of Missouri-Columbia, 2002. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.