Práticas de manejo do solo afetam as emissões de N2O do solo, porém poucas são as informações disponíveis para ambientes tropicais e subtropicais. Dois estudos foram conduzidos com o objetivo de avaliar o efeito de práticas de manejo de solo nas emissões de N2O do solo nas condições subtropicais do Sul do Brasil. No Estudo I, num Argissolo vermelho, avaliou-se o efeito de longo prazo (22 anos) de sistemas de preparo do solo [plantio direto (PD) e preparo convencional (PC)], de sistemas de cultura [aveia/milho (A/M) e ervilhaca/milho (V/M)] e de fontes de N em PD [uréia e resíduo de ervilhaca]. No Estudo II, num Gleissolo, foi avaliado o efeito de curto prazo de sete fontes de N mineral aplicadas ao milho. Amostras de ar foram coletadas em câmaras estáticas e a concentração de N2O determinada por cromatografia gasosa. A emissão acumulada de N2O até 45 dias após o manejo das plantas de cobertura, no solo em PD, foi três vezes superior no sistema V/M (0,73±0,1 kg N ha-1) em relação ao sistema A/M (0,19±0,1 kg N ha-1). No solo em PC, entretanto, tais emissões foram equivalentes entre os sistemas: 0,51±0,1 kg N ha-1 no A/M e 0,55±0,1 kg N ha-1 no V/M. Essas emissões foram controladas principalmente pela disponibilidade de N-NO3- e de C orgânico dissolvido no solo, pela porosidade total do solo preenchida com água e pela atividade microbiana (fluxo de CO2). Ambas as fontes de N (uréia ou resíduo de ervilhaca) tiveram efeito semelhante, dobrando as emissões de N2O em comparação ao tratamento sem N Possivelmente, a emissão de N2O do solo com ervilhaca foi potencializada pelas chuvas abundantes após o manejo das plantas de cobertura, as quais atrasaram a semeadura do milho em 36 dias e mantiveram maiores teores de NO3- no solo em comparação ao tratamento com uréia em cobertura no milho no qual o fertilizante foi aplicado quando a cultura apresentava alta demanda do nutriente. Em relação as fontes de N mineral, as maiores taxas de emissão de N2O ocorreram no 3º dia após a aplicação, sendo mais intensas nas fontes com N nítrico (nitrato de amônio: 8587,4±1062,7; nitrato de cálcio: 3485,8±942,6 e uran: 2050,7±427,7 μg N m-2 h-1) em relação às fontes com N amoniacal (sulfato de amônio: 1435,3±172,3 μg N m-2 h-1) ou amídico (uréia: 859,1±197,6; uréia + inibidor de urease: 346,4±32,9 μg N m-2 h-1). A menor emissão de N2O ocorreu no solo adubado com N de liberação lenta (187,8±61,6 μg N m-2 h-1). A desnitrificação foi o principal processo envolvido na emissão de N2O no solo em ambos os estudos e sob estas condições a utilização de fontes amídicas de N apresentam potencial de mitigar a emissão de N2O. O potencial de mitigação das emissões de N2O por leguminosas de inverno em substituição ao N mineral depende das condições climáticas e, possivelmente, é restrito à anos em que o excesso de chuvas não determine atraso na semeadura do milho. / Soil management practices affect soil N2O emissions, but little is the information available to tropical and subtropical environments. Two studies were carried out aiming at assessing the effect of soil management practices on soil N2O emissions in the subtropical conditions of Southern Brazil. In Study I, in an Acrisol, we assessed the long-term effect (22 years) of soil tillage systems [no-tillage (NT) and conventional tillage (CT)], of cropping systems [oat/maize (O/M) and vetch/maize (V/M)] and of N sources [urea and vetch residues]. In Study II, in a Gleysol, we assessed the short-term effect of seven mineral N sources applied to maize. Air samples were collected in static chambers and N2O concentration was determined by gas chromatography. The accumulated N2O emission until 45 days after cover crops rolling, in NT soil, was three times greater in V/M system (0.73±0.1 kg N ha-1) than in O/M system (0.19±0.1 kg N ha-1). In CT soil, however, such emissions were similar in those two systems: 0.51±0.1 kg N ha-1 in O/M and 0.55±0.1 kg N ha-1 no V/M. These emissions were controlled mainly by NO3--N and dissolved organic C availability in soil, by water filled porosity and by microbial activity (CO2 flux). Both N sources (urea and vetch residues) showed similar effects and doubled the N2O emissions in comparison to the treatment without N. The N2O emission derived from the addition of vetch residue was possibly potencialized by abundant rains after cover crops rolling. Rains delayed maize sowing by 36 days and maintained higher NO3- contents in soil in comparison to the treatment with sidedress urea, applied when crop had higher demand for nutrients. Regarding to mineral N sources, the highest N2O emission rates occurred three days after application, being more intensive in nitric N sources (ammonium nitrate: 8587,4±1062,7; calcium nitrate: 3485,8±942,6 and uran: 2050,7±427,7 μg N m-2 h-1) compared to ammoniacal N sources (ammonium sulfate: 1435,3±172,3 μg N m-2 h-1) or amidic (urea: 859,1±197,6; urea + urease inhibitor: 346,4±32,9 μg N m-2 h-1). The lowest N2O emission occurred in soil fertilized with slow release N source (187,8±61,6 μg N m-2 h-1). Denitrification was the major process in N2O emission in both studies and under these conditions the utilization of amidic N sources represents a potential to mitigate N2O emission. The potential of winter legumes in substitution to mineral N to mitigate N2O emissions depends upon climatic conditions and is possibly limited to years the rains do not delay maize sowing.

Made available in DSpace on 2014-06-12T18:07:41Z (GMT). No. of bitstreams: 2 arquivo7977_1.pdf: 566215 bytes, checksum: 8e7e2b51b740792c91b96bc496d9d01c (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2003 / A combustão de materiais orgânicos e particularmente do gás natural conduz à formação dos óxidos de nitrogênio (NO,, = NO e N02; N20) a partir de conteúdos de nitrogênio provenientes do ar de combustão e/ou de compostos derivados contidos no combustível. Os efeitos nocivos provocados pelas emissões de NOx, sobre a saúde humana e o meio ambiente, vêm contribuindo de forma alarmante para formação de ozônio na troposfera e destruição de ozônio na estratosfera. As implicações nos efeitos de serra e restrições nas regulamentações das emissões de NOx vêm conduzindo os pesquisadores a estudarem novas técnicas de tratamento destes efluentes gasosos industriais após a sua combustão. Adicionalmente, a reação do N02 com água, formando ácido nitroso, contribui de forma agressivo, provocando danos aos tecidos e vias respiratórias dos seres humanos e animais. Sob esta ótica, entendendo que o óxido nitroso está muitas vezes solubílizados em água, o presente trabalho propôs estudar seu processo de transformação através da avaliação da cinética de redução de ácido nitroso (HN02) por ácido amino suliramico (HS03N112) utilizando um reator mecanicamente agitado. Para este fim, leva em conta os seguintes parâmetros operacionais: velocidade de agitação, pH, temperatura, concentrações iniciais dos dois reagentes (ácido nitroso e ácido amino sulfamico) envolvidos no processo e suas razões estequíométricas. Segundo o estudo realizado, a transformação do ácido nitroso (XA= 98,54%) é favorecida em meio ácido (pH < 2,5) obedecendo-se uma lei cínética de Ia ordem em relação aos dois reagentes envolvidos na reação de redução. A avaliação do processo foi realizada a partir de dois métodos de análises verificando-se a diferença existente entre a concentração do nitrito, medida em fase líquida e calculada a partir da pressão relativa de nitrogênio em fase gasosa. As medidas em fase líquida permitiram a determinação de uma cinética mais representativa e intrínseca para o consumo de nitrito durante a reação de redução do ácido nitroso. Através do método manométrico constatou-se a influência da transferência de massa de nitrogênio da fase líquida para fase gasosa, permitindo assim o desenvolvimento de um modelo heterogêneo, relacionado à produção de nitrogênio, levando em conta os efeitos cinéticos associados aos da transferência de massa gás-líquído. Valores encontrados para a constante de velocidade de reação (0,03 IOs') e para o coeficiente de transferência de massa gás-líquido (0,0069s'), a partir dos experimentos, foram comparados com aqueles da literatura, tendo-se encontrado valores de mesmas ordens de grandeza

Ph.D. (Chemistry) / Please refer to full text to view abstract

The redox behavior of a series of organometallic complexes containing Cp'M(NO) groups (Cp' = ƞ⁵-C₅H₅(Cp) or ƞ⁵-C₅Me₅(Cp*) ; M = Mo or W) has been investigated both by cyclic voltammetry and by chemical means. The neutral 16-electron Cp'Mo(N0)X₂ compounds (X = CL, Br or I) undergo a single, essentially reversible, one-electron reduction in CH₂CL₂/O.1M [n-Bu₄N]PF₆ at relatively low potentials (<-0.1 V vs SCE). The electrochemically observed reductions can be effected on a preparative scale by employing CP₂C0 as the chemical reductant. The isolable 17-electron [Cp'Mo (NO)X₂]•⁻ radical anions are cleanly reconverted to their 16-electron neutral precursors by treatment with [Cp₂Fe]BF₄. In contrast, the Cp'W(NO)I₂ compounds undergo rapid decomposition to their [Cp'W(NO)I]₂ monohalo dimers upon electrochemical reduction. Electrophiles NE⁺ (E = O or ϱ-O₂NC₆H₄N) undergo unprecedented insertions into the Cr-C ϭ-bonds of CpCr(NO)₂R complexes (R = Me, CH₂SiMe₃ or Ph) to afford [CpCr(N0)₂{N(E)R}]⁺ cationic complexes. Present evidence is consistent with these insertions occurring via charge-controlled, intermolecular attacks by NE⁺ at the Cr-R groups in classical SE2 processes. The newly-formed N(E)R ligands function as Lewis bases through nitrogen atoms toward the formally 16-electron [CpCr(NO)₂]⁺ cations and may be displaced from the chromium's coordination sphere by the more strongly coordinating CL⁻ anion. The resulting CpCr(NO)₂CL can be reconverted to CpCr(NO)₂R. thereby completing a cycle by regenerating the initial organometallic reactant. The entire sequence of stoichiometric reactions forming the cycle thus constitutes a selective method for the formation of new carbon-nitrogen bonds, the net organic conversions mediated by the CpCr(NO)₂ group being NE⁺ + R⁻ → N(E)R. The electrophilic [Cp'M(NO)₂]⁺ cations (Cp'=Cp or Cp* ; M = Cr, Mo or W) condense with methyl propiolate and 2,3-dimethyl-2-butene to afford cationic organometallic lactone complexes. These complexes undergo facile ⍜-dealkylation to yield the neutral Cp'M(NO)₂(ƞ¹-lactone) derivatives. Furthermore, the neutral Cp'W(NO)₂(ƞ¹-lactone) compounds decompose in air to their Cp'W(O)₂(ƞ¹-lactone) dioxo products. / Science, Faculty of / Chemistry, Department of / Graduate

Although hydrides of metal carbonyls are widely known, the number of hydrides in the related family of metal nitrosyls is extremely small. The preparation of a series of nitrosyl hydrides from the treatment of [CpW(NO)I₂]₂ (Cp=ƞ⁵-C₅H₅) with Na[H₂Al(OCH₂CH₂OCH₃)₂] is described. The addition of one or two equivalents of the aluminum reagent results in the formation of [CpW(NO)IH]₂ or [CpW(NO)H₂]₂ respectively. The reaction of [CpW(NO)IH]₂ with a Lewis base (L=P(OPh)₃, P(OMe)₃, PPh₃ or PMe₃) gives the monometallic CpW(NO)IHL, while [CpW(NO)H₂]₂ reacts with P(OPh)₃ or P(OMe)₃ to yield [CpW(NO)HL]₂ which undergoes further reaction to give CpW(NO)H₂L. Proton NMR spectroscopy shows that all bimetallic species contain bridging hydride ligands and are therefore best, formulated as [CpW(NO)1]₂(µ-H)₂, [CpW(NO)H]₂(µ-H)₂ and [CpW(NO)L]₂(µ-H)₂. The ¹H NMR spectrum of [CpW(NO)H]₂(µ-H)₂ shows that there is no hydride ligand exchange on the NMR time scale and that ¹jH(terminal)W ≃ ¹jH(bridging)w > ²jHW. From this finding, it is possible to develop new criteria for assessing the static or fluxional nature of hydride ligands for several families of organotungsten hydrides (Cp₂W, CpW(CO)₃, W(CO)₃ and CpW(NO)x (x=l or 2)). Within each family, the magnitude of ¹JHW strongly reflects the type of metal hydride bonding, i.e. [Formula Omitted] and suggests that bridge bonding involves all the atoms in the bridge and therefore the "fused" notation is introduced. Treatment of CpW(NO)(CH₂SiMe₃)₂ with low pressures of H₂ (60-80 psig) in the presence of Lewis bases (L=P(0Ph)₃, PMePh₂) gives the unusually stable alkyl hydride compounds CpW(NO)(H)(CH₂SiMe₃)L. This chemistry is then extended to the Cp* (Cp*=ƞ⁵ -C₅Me₅) analogues, including the preparation of the appropriate starting materials. Upon thermolysis of Cp*W(NO)(H)(CH₂SiMe₃)(PMe₃) in C₆H₆, the intermolecular C-H activation product Cp*W(N0)(H)(C₆H₅)(PMe₃) is cleanly formed. However, intermolecular activation of CH₄, C₆H₁₂ or n-C₆H₁₄ does not occur under similar experimental conditions. Hydrogenolysis of Cp*W(NO)(CH₂SiMe₃)₂ at high pressures (≃920 psig) with no Lewis base present results in the formation of isolable [Cp*W(NO)H]₂(µ-H)₂ and [Cp*W(N0)H](µ-H)₂[Cp*W(N0)(CH₂SiMe₃)]. The latter is a new example of the rare class of dinuclear alkyl hydride complexes. Proton NMR spin tickling experiments on this compound allow the complete assignment of all couplings in the spectrum and show that ¹jH(terminal)W' ¹JH(bridging)W and ²jHW have the same sign. / Science, Faculty of / Chemistry, Department of / Graduate

The nitrosyl complex CpW(NO)R₂ (R = CH₂SiMe₃) forms 1:1 adducts via isonitrosyl linkages to Lewis acids such as AlMe₃ and Cp₃Er, i.e. CpWR₂(NO→A) (A = AlMe₃, ErCp₃). These adducts regenerate the starting dialkyl complex when treated with water. Protonation of CpW(NO)R₂ by HBF₄⋅0Me₂ can also be effected. Whether the site of protonation is the nitrogen or the oxygen atom of the nitrosyl ligand is not known with certainty, although O-protonation is postulated by analogy with the other Lewis-acid adducts of CpW(NO)R₂. In these adducts, the nitrosyl stretching frequency is shifted to lower wavenumbers relative to that of the parent dialkyl, to an extent which increases as harder Lewis acids are employed. The colour of the adducts also ranges from red to orange to yellow as progressively harder acids are used. Treatment of CpW(NO) (CH₂SiMe₃)₂ with [Ph₃C]⁺ PF₆⁻ in Ch₂CL₂ results in electrophilic cleavage of a carbon-silicon bond to yield the mixed dialkyl CpW(NO)(CH₂SiMe₃)(CH₂CPh₃), which has been fully characterized by spectroscopic methods and by a single-crystal X-ray crystallographic study. The formation of Me₃SiF and PF₅ (coordinated to Lewis bases in the reaction mixture) as by-products of this reaction has been confirmed by ³¹P and ¹⁹F NMR spectroscopy of the reaction mixture in CD₂CL₂. Preliminary attempts to extend this novel reaction of a silicon-containing ligand by using other carbocations were unsuccessful. This is attributed to the high reactivity of the required carbocations and the large number of possible reaction sites on the metal complex. Some reactions of the mixed dialkyl CpW(NO)RR¹ (R = CH₂SiMe₃ R¹ = CH₂CPh₃) were found to be analogous to those of the parent CpW(NO)R₂, while other reactions followed a different course because of the ability of the CH₂CPh₃ ligand to orthometallate. Thus, CpW(NO)RR¹ is much less thermally stable than CpW(NO)R₂. As a solid or a solution in non-coordinating solvents, it decomposes in a matter of days at room temperatures to a mixture of products which were not identified. In acetonitrile solution, an orthometallated complex derived from CpW(NO)RR¹ can be trapped by coordination of solvent. The product CpW(NO)(CH₂C(C₆H₄)Ph₂)(NCMe) has been isolated and crystallographically characterized. Cyclic voltammograms of CpW(NO)R₂ and CpW(NO)RR¹ show that both complexes undergo an apparently chemically reversible reduction and an irreversible oxidation. The mixed dialkyl CpW(NO)RR¹ is somewhat easier both to reduce and to oxidize than CpW(NO)R₂. Like CpW(NO)R₂, CpW(NO)RR¹ reversibly forms a 1:1 adduct with PMe₃. Also analogously to CpW(NO)R₂, it reacts with 0₂ to form a 5:1 mixture of dioxoalkyl complexes CpW(0)₂R and CpW(0)₂R¹, and with NO(g) to form 2 CpW(NO)R¹(ƞ² -0₂N₂R). In this product, insertion of NO has occurred exclusively in the W-CH₂SiMe₃ bond. Upon photolysis, both complexes CpW(NO)R¹¹(ƞ²-0₂N₂R) (R¹¹ = CH₂SiMe₃ or CH₂CPh₃) form dioxo alkyls CpW(O)₂R¹¹ in an unprecedented reaction. The ability of CpW(NO)RR¹ to orthometallate also results in the formation, when this complex is treated with sulphur, of CpW(O)(CH₂C(C₆H₄)Ph₂)-(SR). No analogue to this compound can be obtained from reaction of CpW(NO)R₂ with sulphur. The sequence of reactions leading to the formation of this product is not known. / Science, Faculty of / Chemistry, Department of / Graduate

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.

Orientador : Felix Guilhermo Reyes Reyes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-07-15T12:44:40Z (GMT). No. of bitstreams: 1 MendonzaCampos_NestorFernando_M.pdf: 2768192 bytes, checksum: 4891f31255e89c29b5c43a433eb646ca (MD5) Previous issue date: 1986 / Resumo: No presente trabalho foi desenvolvido um procedimento analítico para a identificação e quantificação de N-nitrosaminas voláteis em bacon e lingüiça, utilizando-se cromatografia gasosa acoplada a um detector termoiônico sem chama - nitrogênio-fósforo específico (CG-DNP). Características de resposta deste detector, tais como: linearidade, reprodutibilidade e limite de detecção, foram determinadas para nitrosodimetilamina (NDMA), nitrosodietilamina (NDEA), nitrosodipropilamina (NDPA) e nitrosopirrolidina (NPIR). As nitrosaminas foram extraídas por diclorometano a partir de amostras de bacon e lingüiça, colocadas em coluna de celite. Os extratos obtidos desta coluna, em ambos os tipos de amostras, foram de pureza insuficiente para o detector DNP sendo, portanto, necessária a sua purificação prévia à injeção no cromatógrafo. Com esta finalidade, colunas de sílica gel e alumina foram testadas, sendo que a efetividade da primeira coluna foi superior á de alumina. Com o propósito de diferenciar nitrosocompostos de outros compostos presentes nas amostras, foi estudada a velocidade de decomposição fotoquímica, das nitrosaminas, por irradiação com luz ultravioleta. Isso também permitiu a confirmação destes nitrosocompostos. Cromatografia gasosa ¿ DNP foi utilizada no estudo da fotodecomposição. Um método alternativo utilizado para a identificação dos mesmos compostos foi cromatografia em camada delgada. A recuperação e reprodutibilidade do método na quantificação de NDMA e NPIR foram determinadas utilizando-se como padrões internos NDEA e NDPA. Os teores de NDMA e NPIR determinados em quatro amostras de bacon variaram na faixa de 19 a 5l µg/kg (ppb), teores estes frequentemente encontrados neste tipo de amostra. / Abstract: The information presented in this thesis covers research findings on the development of an analytical procedure for the analysis of volatile nitrosamines in bacon and sausage, using gas chromatography equiped with a Nitrogen.Phosphorous Thermoionic Detector (GC-NPD). Characteristics of the detector such as: re¬producibility, linearity and limit of detection were determined for N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodipropylamine (NDPA) and N-nitrosopyrrolidine (NPYR). The nitrosamines from bacon and sausage were extracted from a celite column using dichloromethane. Since the extracts from this column were hot sufficiently pure for the NPD detector, they were purified using silica gel or alumina columns. The effectively of the silica gel column was superior to that of the alumina column. In order to differentiate Nitrosocompounds from other compounds present in the samples the velocity of photodecomposi¬tion of the nitrosamines using UV light was studied. This also allowed us to confirm the identity of these nitrosocompounds. GC-NPD was used in this study. Thin layer chromatography was used as an alternative method for the identification of the nitrosamines. NDEA and NPYR were used as internal standards in the evaluation of the recovery and reproducibility of the method for the quantitation of the NDMA and NPYR. The concentrations of NDMA and NPYR determined in four samples of bacon were within those values frequently found for this type of samples, and varied from 19 to 51 µg /kg (ppb). / Mestrado / Mestre em Ciência de Alimentos

No description available.

Cette thèse présente la réactivité de diènes polyfonctionnalisés incorporant un atome de bore (diènes borylés) en présence de composés de type nitroso. La première partie est une étude de la réactivité des diènes borylés en présence de dérivés arylnitroso. Le produit formé ainsi que l'efficacité de la réaction est dépendant de la substitution sur l'atome de bore ainsi que du solvant utilisé pour la réaction. Suivant les conditions employées, la formation de composés avec différentes structures; pyrroles, oxazines substitués par un atome de bore, ou nitrones a été obtenue. Une stratégie one-pot a ensuite été développée pour la synthèse d'oxazolines utilisant la formation des nitrones en tant qu'intermédiaire. Des investigations théoriques et pratiques concernant le mécanisme de la formation du pyrrole ont été réalisées. La séquence expliquant la synthèse de cette structure est basée sur la cascade suivante; cycloaddition régiosélective (Nitroso Diels-Alder)/réarrangement/élimination du borate. La formation des composés de type nitrone n'a pas été totalement explicité. Des recherches sont actuellement en cours dans le but d'obtenir plus de détails sur le mécanisme mis en jeu. La deuxième partie de l'étude est orientée sur la réactivité des diènes borylés en présence de dérivés carbonylnitroso. Au contraire des dérivés arylnitroso, la nature du composé carbonylnitroso joue un rôle majeur sur la réactivité. Si le même type de réactivité engendrant la formation de pyrroles et d'oxazines substitués par un atome de bore a été observé dans certains cas, l'utilisation d'un composé carbonylnitroso étant assez pauvre en électrons génère la formation du produit issu d'une réaction nitroso-ène. Ce produit, issu de la réaction nitrosoène, a été utilisé comme intermédiaire clé pour la synthèse de différents produits polycycliques. Une séquence one-pot, multicomposants, Diels-Alder/allylboration a été optimisée donnant différentes structures suivant le dienophile et l'aldehyde employé. Dans le but de diversifier la chimie du produit résultant de la réaction nitroso-ène, une autre séquence a été mise au point utilisant la synthèse des pyrroles. Une voie multi-étape a permis la synthèse de nouvelles structures bicycliques incorporant une oxazine et un pyrrole. / This thesis presents the reactivity of dienylboronated compounds towards arylnitroso and carbonylnitroso derivatives and its use in the synthesis of heterocyclic and polycyclics compounds. The first study focused on the reactivity of dienylboronate compounds with arylnitroso derivatives resulting in pyrrole or furan products. The outcome and efficiency of the reaction is related to the boron on the dienyl moiety and the solvent used. Using the certain conditions, pyrroles, boronated MIDA ester oxazines or nitrones could be obtained. A one-pot strategy was then applied to synthesise oxazoline derivatives using nitrones as an intermediate. Theoretical, as well as experimental, work has supported that the formation of the pyrrole was obtained by a regioselective nitroso Diels-Alder reaction/rearrangement/borate elimination cascade process. Details on the nitrone formation have not been clarified, but further investigations are on-going. Secondly, attention was focused on the reactivity of dienylboronate compounds with carbonylnitroso derivatives. Contrary to the arylnitroso species, the nature of the carbonylnitroso had a dramatic impact on reactivity. On the one hand, similar reactivity towards the formation of pyrroles and boronated MIDA ester oxazines was observed, however, by employing a higher electron-deficient carbonylnitroso species, the product resulting from a nitroso-ene reaction was obtained. Ene-product was used as the key intermediate for the synthesis of different polycyclic compounds. A multicomponent, one-pot, Diels-Alder/allylboration procedure was optimised to yield various structures depending on the nature of the dienophile and the aldehyde. To diversify the chemistry of the ene-product another sequence was designed using the pyrrole synthesis. A multi-step pathway was optimised to afford novel fused bicylic oxazine-pyrrole products.