Este trabalho descreve estudos eletroquímicos e espectroscópicos da eletrooxidação de etanol, acetaldeído e ácido acético sobre uma superfície de platina monocristalina de baixo índice de Miller 110 modificada por ósmio (Os). O eletrodo monocristalino de Pt(110) foi modificado por Os espontaneamente e pela aplicação de potencial. Os eletrodos foram caracterizados eletroquimicamente, de forma que foram obtidos valores baixos, intermediários e altos de Os sobre a superfície de Pt(110). A eletrooxidação de etanol sobre Pt(110) e Pt(110)/Os, analisada pelas técnicas de voltametria cíclica e cronoamperometria, mostrou que as densidades de corrente para essa reação foram maiores nos graus de recobrimento entre 0,51 – 0,61 ML. A partir dos resultados de FTIR in situ, verificou-se que a reação de oxidação de etanol difere em seus caminhos de acordo com o grau de recobrimento de Os. O caminho um sugere a quebra da ligação C—C com maior intensidade em graus de recobrimento entre 0,36 – 0,80 ML, formando espécies como COlinear, CHx e, posteriormente, CO2. O caminho dois mostra a formação de acetaldeído a partir de 0,4 V sobre os eletrodos Pt(110) e Pt(110)/Os, e que pode haver ainda a produção de CO e ácido acético a partir desse orgânico sobre eletrodos com HOs > 0,80 ML, a baixos potenciais. O estudo realizado com acetaldeído mostrou que o desempenho na oxidação desse orgânico foi sutilmente maior para os eletrodos modificados por Os. O caminho três apresenta a produção de CO2 proveniente da oxidação de etanol diretamente a ácido acético sobre eletrodos com alto grau de recobrimento. Durante a oxidação ocorre a formação a baixos potenciais de COlinear em grandes quantidades. Além disso, há produção de ácido acético e posteriormente de CO2. Ainda nos eletrodos espessos, a produção de CO2 ocorre sem que se observe a presença de COlinear, indicando a possibilidade da oxidação de ácido acético a CO2. A eletrooxidação de ácido acético sobre os diversos eletrodos de Pt(110)/Os mostra que ocorre a quebra dessa molécula para formar CO2, embora de forma menos expressiva que as demais moléculas estudadas. Sendo que parte do CO2 produzido provavelmente tem sua origem no grupo COO- que está adsorvido sobre a superfície do eletrodo. / This work reports the electrochemical and spectroscopic results of ethanol, acetaldehyde and acetic acid electrooxidation onto low index platinum single crystal surface (110) modified by osmium (Os). The Pt(110) electrode was modified by spontaneous and electroless Os deposition and checked electrochemically in order to obtain low, intermediate and high Os coverages on Pt(110). The ethanol electrooxidation on Pt(110) and Pt(110)/Os, which used voltammetric cycle and cronoamperometric techniques, showed higher currents toward this reaction on Os coverage between 0.51-0.61 ML. The FTIR results reveal that ethanol oxidation has different pathways according to Os coverage. The step one suggests that the cleavage of ethanol C—C bond occurs with major intensity forming species such as COlinaer and CHx when the reached coverage is 0.36 – 0.80 ML and further producing CO2. At the step two, acetaldehyde formation is improved above 0.4 V on Pt(110) and Pt(110)/Os, and at low potentials on HOs > 0.80 ML, this molecule can oxidize and form CO and acetic acid. Studies on acetaldehyde showed that the catalytic activity is slightly higher on electrodes modified by Os. The step three presents the CO2 production through acetic acid onto electrodes with high Os coverage. During the oxidation of this molecule, COlinear is produced in large quantities at low potentials; there is formation of acetic acid and thereupon CO2. Onto Os thick electrode, CO2 production occurs without the presence of COlinear, indicating the possibility of acetic acid oxidation directly to CO2. The acetic acid oxidation on various electrodes modified by Os is possible with cleavage of C—C bond to form CO2, though this process is less significant than others organic molecules studied. Since the amount of CO2 produced can arise through the acetate group once this specie is adsorbed onto the electrode surface.

O acetaldeído é um comprovado agente mutagênico e carcinogênico, pode ser produzido endogenamente pela oxidação do álcool ingerido em bebidas alcoólicas e alimentos ou exogenamente, inalado como poluente, advindo da oxidação de combustíveis fósseis e etanol. O efeito do acetaldeído foi avaliado em modelos celulares e animais com o propósito de avaliarmos o aumento do estresse oxidativo, por lipoperoxidação, fragmentação do DNA, e a formação de adutos DNA, tais como 8-oxo-7,8-dihidro-2-desoxiguanosina, além de, 1,N2-eteno-2-desoxiguanosina e 1,N2-propano-2-desoxiguanosina que foram analisados por HPLC acoplado a espectrometria de massa com a utilização de metodologia ultra-sensível e reprodutiva. O tratamento de fibroblastos pulmonares humanos normais (IMR-90) com diversas concentrações de acetaldeído (58 µM a 711 µM) resultou em aumentos de morte celular, lipoperoxidação, fragmentação do DNA, cálcio intracelular e adutos de DNA. O efeito protetor do licopeno (20 µM) foi comprovado minimizando todos os efeitos deletérios promovidos pelo acetaldeído. O tratamento dos ratos Wistar por 8 e 30 dias com 150 mg/kg e 60 mg/kg via intra-peritoneal ou gavage, evidenciaram os efeitos tóxicos provocados pelo acetaldeído, como aumento significativo de lipoperoxidação, adutos e fragmentação de DNA no fígado e cérebro destes animais. A detecção dos adutos de DNA se mostrou uma ferramenta importante para a detecção dos efeitos provocados por exposição ao aldeído. No tratamento de animais por inalação com variadas concentrações de acetaldeído, que expôs os animais a quantidades do aldeído similares às encontradas em atmosferas poluídas, foi observado aumento de lipoperoxidação, sendo este dose dependente no fígado e pulmão. Já no cérebro, os níveis de MDA foram significativamente maiores em 10 ppb e 30 ppb em relação a 0 ppb e controle, e diminuíram significativamente em 90 ppb. Em relação aos níveis de fragmentação do DNA, observamos no pulmão aumento foi dose dependente em relação à concentração de aldeído. A quantificação de 1,N2-εdGuo e 1,N2-propanodGuo mostrou aumentos de ambos os adutos no pulmão de todos animais expostos ao acetaldeído . No fígado, também, foram detectados aumentos nos níveis de 1,N2-propanodGuo. A formação de 8-oxo-7,8-dihidro-2-desoxiguanosina, 1,N2-eteno-2-desoxiguanosina e 1,N2-propano-2-desoxiguanosina na urina de moradores da cidade de São Paulo, também foi investigada, com o desenvolvimento de metodologia ultra-sensível e reprodutiva por HPLC e espectrometria de massa, que indicou a presença dos três adutos nas urinas analisadas. A detecção do 1,N2-propanodGuo na urina é inédita. Nossos resultados comprovam que o acetaldeído é um forte agente citotóxico e genotóxico, mesmo em concentrações muito baixas, podendo contribuir para o esclarecimento dos mecanismos de desenvolvimento de doenças atribuídas ao aldeído, como o câncer. Além disso, o desenvolvimento de metodologias ultra-sensíveis para detecção e quantificação de adutos na urina e DNA isolado contribui para o emprego destes adutos, em especial o 1,N2-propano- 2-desoxiguanosina, como possível biomarcador de exposição ao acetaldeído presente em atmosferas poluídas e em patologias associadas ao estresse redox e abuso de bebidas alcoólicas. / Acetaldehyde is a known mutagen and carcinogen that can be produced endogenously by ethanol oxidation or directly inhaled as an air pollutant produced by fuel oxidation. The toxicity of acetaldehyde was evaluated in vitro and in vivo models, by means of oxidative stress parameters such as lipid peroxidation (measured as malonaldialdehyde -MDA), DNA fragmentation and DNA adducts such as 8-oxo-7,8-dihydro-2-desoxiguanosine, 1,N2-eteno-2-desoxiguanosine and 1,N2-propano-2-desoxiguanosine, this adducts were analyzed by an ultra-sensible and reproducible HPLC coupled to mass spectrometry assay. Treatment of human normal fibroblast (IMR-90) with a wide range of concentrations (58 µM to 711 µM) resulted in an increase in citotoxicity, lipid peroxidation, DNA fragmentation, intracellular calcium release and DNA adducts. Furthermore, lycopene (20 µM) presented a protective effect against the cellular deleterious properties of acetaldehyde. Treatment of Wistar rats for 8 and 30 days with 150 mg/kg and 60 mg/kg intra-peritonially or by gavage resulted in increased toxicity, measured by lipid peroxidation and DNA damage in liver and brain. The detection of DNA adducts was shown an important tool for the identification of deleterious effects induced by exposure to the aldehyde. Animals treated by inhalation, of amounts commonly found in polluted air samples, presented increased levels of lipid peroxidation in a dose dependent manner in liver and lungs. Nevertheless, in the brain of those animals the higher concentration was devoid of toxic effect measured as MDA levels. Lung tissue presented increased levels of DNA fragmentation. Furthermore, increased levels of 1,N2-εdGuo and 1,N2-propanodGuo was also observed in lungs of all animals. In DNA from livers, 1,N2-propanodGuo presented increased levels. Formation of 8-oxo-7,8-dihydro-2-desoxiguanosine, 1,N2-eteno-2-desoxiguanosine and 1,N2-propano-2-desoxiguanosine in urine samples of people living in the city of São Paulo were also investigated using a newly developed and ultra-sensible methodology base in HPLC coupled to mass spectrometry. This methodology enabled us to detect, for the first time, the presence of 1,N2-propanodGuo in urine samples. In summary, our results demonstrate the acetaldehyde is a strong cytotoxic and genotoxic agent even at low concentrations, being able to contribute to the development of pathology such as cancer. Furthermore, the development of a very ultra-sensitive methodology for the detection of these adducts, mainly ,N2-propano- 2-desoxiguanosine, enables its use as a possible biomarker of acetaldehyde exposure in polluted air samples and in pathologies associated with redox unbalance and ethanol consumption.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The aim of this work was to evaluate the effect of post harvest ethanol or acetaldehyde application and to compare them with consolidated storage techniques on the quality maintenance of Royal Gala‟ apples. Also, we aimed to evaluate the effect of controlled atmosphere condition with ultra low oxygen partial pressures on the post storage quality maintenance of Royal Gala‟ apples. To reach such aims, three experiments were performed during 2008 and 2009. In the first experiment, carried out in 2008, the following treatments were evaluated: [1] control; [2] application of 0.5mL of ethanol month-1 kg-1; [3] application of 0.25mL acetaldehyde month-1 kg-1; [4] application of 625 ηL L-1 1-MCP; and [5] ethylene scrubbing (<0.02μL L-1). All fruits from the evaluated treatments were stored in CA with 1.0kPa O2 and 2.0kPa CO2. In the second experiment, carried out in 2009, the treatments were constituted in the following way: [1] control; [2] low relative air humidity (LRH); [3] LRH and application of 0.3mL of ethanol month-1 kg-1; and [4] application of 0.3mL of ethanol month-1 kg-1. All treatments were stored in CA with 1.2kPa O2 associated with 2.5kPa CO2. In the two experiments the fruits were stored at 0.5°C. In the third experiment, carried out in 2008, five CA conditions were evaluated: [1] 1.0kPa O2 and 2.0kPa CO2; [2] 0.8kPa O2 and 1.5kPa CO2; [3] 0.8kPa O2 and 1.0kPa CO2; [4] 0.6kPa O2 and 1.5kPa CO2; and [5] 0.6kPa O2 and 1.0kPa CO2. All conditions were stored in 0.0°C, 0.5°C and 1.0°C resulting in a factorial experiment. The application of 0.5mL ethanol month-1 kg-1 or 0.25mL acetaldehyde month-1 kg-1 cause increase in mealiness, flesh browning and rottenness incidence and decrease flesh firmness, resulting in decrease in the quality maintenance when compared with the application of 1-MCP and ethylene scrubbing. However, 0.3mL ethanol month-1 kg-1, performed on second experiment, resulted in higher flesh firmness retention, lower ACC oxidase activity and lower ethylene production. The lower relative air humidity is not efficient in maintain apple quality, however, it potentiated the effect of the application of 0.3mL ethanol month-1 kg-1. Royal Gala‟ apples stored in CA with O2 partial pressures below to 0.8kPa show lesser quality after storage. Temperature of 1.0ºC, compared with 0.0°C and 0.5°C, provided highest apple quality maintenance after eight months of storage and more seven days in shelf life at 20ºC. The best ULO condition for fruits stored at 1.0ºC is 1.0kPa O2 with 2.0kPa CO2. The interaction between ULO and storage temperature showed a necessity to increase O2 partial pressures when the storage temperature was increased. This behavior were verified especially when ACC oxidase activity and flesh browning incidence were analyzed. / O objetivo deste trabalho foi avaliar o efeito da aplicação pós-colheita de etanol e aldeído acético e comparar com tecnologias de armazenamento comprovadamente eficientes sobre a manutenção da qualidade de maçãs Royal Gala‟. Além disso, objetivou-se avaliar o efeito de condições de atmosfera controlada (AC) com pressões parciais ultrabaixas de oxigênio sobre a manutenção da qualidade de maçãs, Royal Gala‟ após o armazenamento. Para atingir tais objetivos foram conduzidos três experimentos no decorrer dos anos de 2008 e 2009. No primeiro experimento, realizado em 2008, foram testados os seguintes tratamentos: [1] controle; [2] aplicação de 0,5mL de etanol mês-1 kg-1; [3] aplicação de 0,25mL de aldeído acético mês-1 kg-1; [4] aplicação de 625 ηL L-1 de 1-MCP; e [5] absorção de etileno (<0,02μL L-1). Todos os frutos dos tratamentos avaliados foram armazenados em AC na condição de 1,0kPa O2 e 2,0kPa CO2. No segundo experimento, conduzido em 2009, os tratamentos avaliados foram constituídos da seguinte forma: [1] controle; [2] baixa umidade relativa do ar (BUR); [3] BUR com aplicação de etanol na dosagem de 0,3mL mês-1 kg-1; e [4] aplicação de etanol na dosagem de 0,3mL mês-1 kg-1. Todos os frutos dos tratamentos foram armazenados em AC com 1,2kPa O2 + 2,5kPa CO2. Nos dois experimentos os frutos foram armazenados na temperatura de 0,5°C. No terceiro experimento, conduzido em 2008, foram avaliadas cinco condições de AC: [1] 1,0kPa O2 e 2,0kPa CO2; [2] 0,8kPa O2 e 1,5kPa CO2; [3] 0,8kPa O2 e 1,0kPa CO2; [4] 0,6kPa O2 e 1,5kPa CO2; e [5] 0,6kPa O2 e 1,0kPa CO2, combinadas com temperaturas de 0,0°C, 0,5°C e 1,0°C, resultando em um experimento fatorial. A aplicação de 0,5mL de etanol mês-1 kg-1 ou 0,25mL de aldeído acético mês-1 kg-1, provocou aumento da incidência de polpa farinácea, degenerescência de polpa e podridões, assim como diminuição da firmeza de polpa, resultando em menor manutenção da qualidade comparada com a aplicação de 1-MCP e absorção de etileno. Entretanto, a dose de 0,3mL de etanol mês-1 kg-1, do segundo experimento, resultou na manutenção de maior firmeza de polpa, menor atividade da ACC oxidase e menor produção de etileno. A redução da umidade relativa do ar (BUR) não apresentou eficiência na manutenção da qualidade, porém, potencializou o efeito da aplicação de 0,3mL de etanol mês-1 kg-1. Maçãs Royal Gala‟ armazenadas em AC sob pressões parciais de O2 abaixo de 0,8kPa apresentaram inferior qualidade após o armazenamento. A temperatura de 1,0ºC, comparado a 0,0°C e 0,5°C, manteve a qualidade superior após oito meses de armazenamento e mais sete dias de exposição à temperatura de 20ºC. A melhor condição de ULO para frutos armazenados na temperatura de 1,0ºC é de 1,0kPa O2 combinado com 2,0kPa de CO2. A interação entre ULO e temperatura de armazenamento evidenciou a necessidade de elevação das pressões parciais de O2 quando a temperatura de armazenamento foi aumentada. Este comportamento foi verificado quando analisadas atividade da ACC oxidase e incidência de degenerescência de polpa.

Volatile organic compounds (VOCs) in the indoor air have adverse effects on the dwellers residing in a building or a vehicle. One of these effects is called sick building syndrome (SBS). SBS refers to situations in which the users of a building develop acute health effects and discomfort depending on the time they spend inside some buildings without having any specific illness. Furthermore, monitoring volatile organic compounds could lead to early diagnosis of specific illnesses through breath analysis. Among those VOCs formaldehyde, acetaldehyde can be listed. In this thesis, VOC detecting thin film sensors have been investigated. Such sensors have been manufactured using semiconducting metal oxides, ligand activated gold nanoparticles and Graphene/TiO2 mixtures. Advanced gas deposition unit, have been used to produce NiO thin films and Au nanoparticles. DC magnetron sputtering has been used to produce InSnO and VO2 thin film sensors. Graphene/TiO2 sensors have been manufactured using doctor-blading. While presenting the results, first, material characterization details are presented for each sensor, then, gas sensing results are presented. Morphologies, crystalline structures and chemical properties have been analyzed using scanning electron microscopy, X-ray diffraction and X-ray photo electron spectroscopy. Furthermore, more detailed analyses have been performed on NiO samples using extended X-ray absorption fine structure method and N2 adsorption measurements. Gas sensing measurements were focused on monitoring formaldehyde and acetaldehyde. However, responses ethanol and methane were measured in some cases to monitor selectivity. Graphene/TiO2 samples were used to monitor NO2 and NH3. For NiO thin film sensors and Au nano particles, fluctuation enhanced gas sensing is also presented in addition to conductometric measurements.

No description available.

Also aged bottles are safer to use than new bottles because their chemical leaching was found to be lower than that of new bottles. This study recommends the reassessment of the absence of international guidelines for acetaldehyde in water and foods. The study also recommends that the amount of acetaldehyde that can be added to soft drinks as flavouring agent should be below the specific migration limit (SML) for migration of acetaldehyde from PET bottle into bottle contents. This is essential since the SML was designed to ensure that exposure to acetaldehyde, as a result of intake of bottled water and soft drinks in PET bottles, is below the tolerable daily intake (TDI) for acetaldehyde. As antimony was reported to go beyond the safe limits in some Nigerian bottled water and soft drinks after 11 months of storage this study discourages the use of bottle contents stored for a very long time.

L'objectif de ce travail était d'une part d'étudier la dégradation du phénol en milieu aqueux par un plasma GlidArc d'air humide et d'autre part d'étudier la conversion de l'acétaldéhyde dans des gaz atmosphériques par un plasma DBD généré par une haute tension impulsionnelle. Les résultats de l'étude paramétrique de la dégradation du phénol ont montré une augmentation de l'efficacité en fonction de la concentration initiale et du débit d'air humide. L'augmentation du gap entre les électrodes à occasionné celle de la concentration des ions nitrates. La majeur parie des nombreux produits de réactions est constituée d'acides carboxyliques mais aussi d'hydroquinone, de para-nitrophénol et de para-nitrosophénol. Cette identification a permis de dresser un schéma réactionnel de la dégradation du phénol. La conversion de l'acétaldéhyde a été effectuée dans des conditions de température allant de l'ambiante jusqu'à 300°C et dans deux types de mélanges: CH3CHO/N2 et CH3CHO/N2/O2 (jusqu'à 10% O2). Les résultats ont montré que le coût énergétique baisse en présence d'oxygène dans le mélange et également lorsque la température augmente. Les principaux sous-produits identifiés dans CH3CHO/N2 sont CO, H2, CH4, HCN, C2H6, CH3CN tandis que dans les mélanges oxygénés, CO2 et CO, CH2O, CH3OH sont les sous-produits les plus importants. L'étude cinétique menée à la suite de cette analyse grâce à un modèle 0D simplifié a permis de mettre en évidence le rôle primordial de la dissociation par quenching des états métastables d'azote et de l'oxydation notamment par O et OH dans la conversion de l'acétaldéhyde. La modélisation a aussi permis de comprendre les processus de formation des sous-produits majoritaires. Des catalyseurs à base de MnO2 ont été placés en aval de la zone de décharge pour décomposer l'ozone qui se forme abondamment dans les mélanges oxygénés surtout à basse température. L'oxygène atomique produit lors de cette décomposition oxyde l'acétaldéhyde résiduel et ses sous-produits. Le coût énergétique a ainsi été diminué et les concentrations des sous-produits comme CH2O et CH3OH ont été réduites. / This work aimed to study the degradation of aqueous phenol by humid air GlidArc plasma and to study the removal of acetaldehyde in atmospheric gas by pulsed DBD plasma. The parametric study of phenol degradation showed an increase in efficiency as a function of the initial concentration and humid air flow. The increase of the inter-electrodes gap has increased nitrate ions concentration. The numerous reaction products formed consist mostly of carboxylic acids. Other byproducts identified are hydroquinone, para-nitrophenol and para-nitrosophenol. By-products identification enabled drawing a reaction scheme of phenol degradation. The acetaldehyde removal has been achieved in temperature conditions ranging from ambient to 300°C and in two types of mixtures: CH3CHO/N2 and CH3CHO/N2/O2 (up to 10 % O2). The results showed that the energy cost decreases in the presence of oxygen in the mixture as well as when the temperature increases. In CH3CHO/N2, the main by-products are CO, H2, CH4, HCN, C2H6, CH3CN whereas in oxygenated mixtures, CO2 and CO, CH2O, CH3OH are the most important by-products. The kinetic study following this analysis, by using a simplified 0D model has highlighted the key role of the quenching of nitrogen metastables states and that of the oxidation of acetaldehyde, caused in particular by O and OH. The modeling also helped understanding the formation processes of major by-products. A MnO2 based catalyst was placed downstream of plasma zone in order to decompose ozone that is abundantly formed in oxygenated mixtures especially at low temperature. The atomic oxygen produced during this decomposition is used to oxidize the residual acetaldehyde and its by-products. The energy cost was thus decreased and the concentrations of certain by-products such as CH2O and CH3OH have been reduced as well.

Cette thèse a pour objet l’analyse de la cinétique de la conversion de l’acétaldéhyde, CH₃CHO, à des concentrations initiales inférieures ou égale à 5000 ppm dans un mélange de gaz à base d’azote et contenant jusqu’à 20% d’oxygène, à température ambiante. L’étude a été réalisée en utilisant trois réacteurs mettant en œuvre des décharges de qualités spatiales différentes. Il s’agit d’un réacteur (UV510) à décharge pré-ionisée (photo-déclenchée) par rayonnement UV produisant un plasma homogène, et de deux réacteurs à décharge à barrière diélectrique (DBD), de géométrie plane (plan-plan) et de géométrie cylindrique (tige-tube) alimentés par impulsion HT et produisant des plasmas non homogènes à faible (plan) ou forte (cylindre) filamentation ; un diagnostic d’imagerie rapide (ns) de la DBD de géométrie plane montre que le plasma peut être considéré quasi-homogène. En s’appuyant sur une modélisation 0D auto-cohérente de la décharge photo-déclenchée, l’étude de la cinétique du mélange N₂/CH₃CHO montre l’importance des états métastables de la molécule d’azote, triplet A³Σu⁺, et singlets (groupe a' ¹∑⁻u, a ¹∏g, et w ¹Δu) dans la dissociation de l’acétaldéhyde. Un coefficient minimum de 6.5×10⁻¹¹ cm³.s⁻¹ est estimé pour le quenching des singlets par l’acétaldéhyde. Le coefficient du triplet est estimé entre 4.2×10⁻¹¹ cm³.s⁻¹ et 6.5×10⁻¹¹ cm³.s⁻¹. Cette dissociation produit des radicaux (CH₃, CH₃CO, HCO, H, O) et des molécules (CH₄, CH₂CO, C₂H₄, C₂H₂, H₂, CO). Ainsi les sous-produits majoritaires mesurés à la fin de la post décharge temporelle sont le méthane, le dihydrogène, le monoxyde de carbone et l’éthane. Les minoritaires sont l’acétylène, l’éthène, l’acétone et l’acétonitrile. Dans les mélanges contenant de l’oxygène, l’importance de la dissociation de CH₃CHO par quenching des états métastables de N₂ diminue au profit des processus d’oxydation par le radical hydroxyle, OH, et l’oxygène atomique, O (³P). La mesure résolue en temps du radical OH dans la post-décharge du réacteur UV510 montre une très forte réactivité de ce radical avec les sous-produits de conversion de l’acétaldéhyde. Une densité maximum de OH égale à 3.5×10¹⁴ cm⁻³ a été mesurée pour 10 % d’oxygène et 5000 ppm d’acétaldéhyde. Le schéma cinétique adopté pour ces mélanges donne, par la modélisation auto-cohérente, une valeur de densité plus élevée. Toutefois, la conversion de l’acétaldéhyde dans N₂/O₂/CH₃CHO est bien expliquée par le modèle, de même que les concentrations produites de méthane et d’éthane. Enfin, la comparaison de l’efficacité énergétique des trois réacteurs étudiés montre que l’homogénéité de la décharge favorise, pour des milieux pauvres en oxygène (moins de 2 %), la conversion de l’acétaldéhyde. / The present study deals with the kinetics analysis of acetaldehyde (CH₃CHO) conversion in electrical discharges with different spatial qualities et at room temperature. Acetaldehyde concentrations up to 5000 ppm in nitrogen-based gas mixture containing up to 20% of oxygen have been investigated. Three different plasma reactors were used: an UV510 reactor producing a homogeneous plasma thanks to a pre-ionization by UV radiation (photo-triggered), a plane-to-plane and a rod-tube dielectric barrier discharges (DBDs) reactors, In both DBDs reactors discharges were driven by high voltage pulses allowing the production of weakly inhomogeneous plasma in the plane geometry and highly filamentary discharges in the cylindrical one. A high speed imaging diagnostic (ns range) of the plane-to-plane DBD shows that the plasma can be considered quasi-homogeneous. Based on a self-consistent 0D model, the kinetics study of the N₂/CH₃CHO mixture conversion in the photo-triggered discharge shows the importance of nitrogen molecule metastable states , i.e. the triplet A³Σu⁺ and the singlets group a' ¹∑⁻u, a ¹∏g, et w ¹Δu, in the acetaldehyde dissociation process. A minimum coefficient of 6.5×10⁻¹¹ cm³.s⁻¹ has been estimated for the quenching of N₂ singlets state by acetaldehyde. For the triplet states quenching the coefficient of has been evaluated between 4.2×10⁻¹¹ cm³.s⁻¹ and 6.5×10⁻¹¹ cm³.s⁻¹. This dissociation process produces radicals as CH₃, CH₃CO, HCO, H, O, and molecules like CH₄, CH₂CO, C₂H₄, C₂H₂, H₂, CO. Thus, the major by-products detected at the end of the post-discharge time are methane, hydrogen, carbon monoxide and ethane; smaller amounts of acetylene, ethene, acetone and acetonitrile were also detected. In containing oxygen mixtures, the importance of the CH3CHO dissociation processes due to N₂ metastable states quenching of decreases in favor of oxidation processes promoted by the hydroxyl radical, OH, and atomic oxygen, O (³P). Time-resolved measurements of the OH radical in the photo-triggered post-discharge show a very high reactivity of this radical with the by-products of acetaldehyde conversion. A maximum density of OH radical equal to 3.5×10¹⁴ cm⁻³ was measured for 10% oxygen and 5000 ppm of acetaldehyde. The kinetic scheme adopted in the self-consistent model for the same gas mixture gives a higher density value; by the way the model is in good agreement with the acetaldehyde conversion in N₂/O₂/CH₃CHO mixtures, as well as with the methane and ethane produced concentrations. Finally, the comparison of the three studied reactors energy efficiency shows that, for low oxygen content (less than 2%), the homogeneity of the discharge promotes the acetaldehyde conversion.

O consumo de álcool vem sendo associado a um aumento do risco de câncer e a uma situação de estresse oxidativo. Os metabólitos responsáveis por tais processos permanecem em discussão. Neste trabalho, caracterizamos novos metabólitos radicalares do etanol e examinamos suas interações com ácidos nucléicos. Primeiramente, demonstramos que os radicais 1-hidroxietila e 2-hidroxietila produzidos durante a oxidação do etanol por sistemas Fenton alquilam DNA e RNA in vitro produzindo os adutos 8-(1-HE)Gua e 8-(2-HE)Gua, respectivamente. Esses adutos foram sintetizados e caracterizados quimicamente. Também, demonstramos que acetaldeído, o principal metabólito do etanol, é oxidado por sistemas Fenton, peroxinitrito, xantina oxidase, partículas submitocondriais e ratos a radicais acetila e metila. Esses radicais foram caracterizados e seus mecanismos de formação elucidados, pelo menos in vitro. A possibilidade do radical 1-hidroxietila alquilar ácidos nucléicos in vivo foi também examinada. Inesperadamente, o aduto 8-(1-HE)Gua foi detectado em RNA e DNA do fígado de ratos controle e seus níveis não foram significativamente alterados após administração aguda de etanol. Esses resultados sugerem que os radicais 1-hidroxietila, acetila e metila são importantes metabólitos do etanol in vivo mas atacam preferencialmente outras biomoléculas que não ácidos nucléicos. / Alcohol consumption has been associated with increased cancer risk and an oxidative stress condition. Ethanol metabolites responsible for these processes remain debatable. Here, we characterized novel radical metabolites of ethanol and examined their interactions with nucleic acids. First, we demonstrated that the 1-hydroxyethyl and 2-hydroxyethyl radical produced from ethanol oxidation by Fenton systems alkylated DNA and RNA in vitro to produce 8-(1HE)Gua and 8-(2-HE)Gua, respectively. Both adducts were synthesized and structurally characterized. Next, we demonstrated that acetaldehyde, the main ethanol metabolite, is oxidized by Fenton systems, peroxynitrite, xanthine oxidase, submitochondrial particles and whole rats to acetyl and methyl radicals. These radicals were characterized and their production mechanisms in vitro elucidated. The possibility of the 1-hydroxyethyl radical alkylating nucleic acids in vivo was also examined. Unexpectedly, the adduct 8-(1-HE)Gua was detected in RNA and DNA from liver of control rats and their levels were not increased by acute ethanol treatment. Overall, the results suggest that the radicals 1-hydroxyethyl, acetyl and methyl are important ethanol metabolites in vivo but they preferentially attack biomolecules other than nucleic acids.

O carcinoma epidermóide é uma neoplasia que pode ter origem do revestimento mucoso de vários sítios das vias aerodigestivas superiores, sendo a língua o sítio primário com maior incidência. Entre os fatores de risco para a doença estão a idade, as mutações genômicas, o hábito tabagista e principalmente o consumo de etanol. O etanol é considerado um agente cocarcinogênico no processo de desenvolvimento do câncer de boca. Por outro lado, o acetaldeído, subproduto da oxidação do etanol, é tóxico e participa diretamente na carcinogênese. Assim, polimorfismos genéticos que alteram a oxidação de etanol para acetaldeído promovendo seu acúmulo podem alterar o risco de câncer oral. Os resultados sugerem que pacientes portadores do polimorfismo do gene ADH1C Ile350Val possuem maior risco de tornarem-se etilistas crônicos (OR=2,0199), mas o risco de desenvolverem câncer não é alterado quando comparado aos não portadores. Já os portadores dos polimorfismos nos genes ADH1B Arg47His (OR=0,3445), CY2E1 (ins) (OR=0,3261) e ALDH2 (GA) (OR=0,4811) apresentaram menores riscos de desenvolverem câncer oral, mas estes polimorfismos não estavam associados ao risco de tornarem-se etilistas crônicos. Observou-se também uma possível interação entre a baixa atividade da enzima ALDH2 e a expressão do gene CYP2E1 como um fator protetor no desenvolvimento do câncer de boca. Entretanto, há necessidade de mais estudos para comprovar esses achados / Squamous cell carcinoma is a neoplasm that may originate from the mucosal tissue from various sites of the upper aerodigestive tract, the tongue being the primary site with the highest incidence. Among the risk factors for the disease are age, genomic mutations, smoking habit, and especially the consumption of ethanol. Ethanol is considered a co-carcinogenic agent in the development of oral cancer. Moreover, acetaldehyde, ethanol oxidation product, is toxic and is directly involved in carcinogenesis. Thus, genetic polymorphisms that alter the oxidation of ethanol to acetaldehyde by promoting its accumulation can alter the risk of oral cancer. The results suggest that patients with the ADH1C Ile350Val polymorphism have increased risk of becoming chronic drinkers (OR = 2.0199), but the risk of developing cancer is not changed when compared to non carriers. Since the carriers of polymorphisms in genes ADH1B Arg47His (OR = 0.3445), CY2E1 (ins) (OR =0.3261) and ALDH2 (GA) (OR = 0.4811) lower risk of developing oral cancer, but these polymorphisms were not associated with risk of becoming chronic drinkers .There was also a possible interaction between the low activity of the enzymeALDH2 and CYP2E1 gene expression as a protective factor in the development of oral cancer. However, we need more studies to confirm these findings