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Os iodo-β-enaminoésteres cíclicos 13, 14, 15 e 16 (heterociclos nitrogenados de 5 membros) foram preparados pela iodociclização dos alquenil-β-enaminoésteres 7, 8, 9 e 10, respectivamente, com modificações na metodologia. Os tempos de reação foram diminuídos e o método de purificação foi modificado. Visando à extensão da metodologia para a obtenção de heterociclos nitrogenados de 6 membros, foi testada a iodociclização dos alquenil-S-enaminoésteres 11 e 12. O composto 11 forneceu o produto esperado 17 em 51% de rendimento enquanto que o composto 12 não sofreu ciclização nestas condições, porém ao modificá-las foi obtido composto 18\', via lactonização.As reações de desidroalogenação dos compostos 13, 14, 15 e 16 levaram aos produtos esperados 19, 20, 21 e 22, com rendimentos de 93, 99, 75 e 93%, respectivamente. O composto 17 não gerou nenhum produto nestas condições, mas ao modificá-las obteve-se o composto 23\', resultante de substituição nucleofilica interna, com 79% de rendimento. Nestas condições, os compostos 15 e 16 sofreram eliminação de HI gerando os compostos 21\' e 22\', respectivamente. / Cyclic iodo-β-enaminoesthers 13, 14, 15 e 16 (five-membered nitrogen heterocycles) were prepared by iodocyc1ization of alkenyl-β-enaminoesthers 7, 8, 9 e 10, respectively, with modifications in the method. The reaction times were diminished and the method of purification was changed. In order to extend this metodology to obtain six-membered nitrogen heterocycles, the iodocyclization of the alkenyl-β enaminoesthers 11 and 12 was tested. Compound 11 furnished the expected product 17 in 51% yield while compound 12 did not undergo cyclization in such conditions, however by changing them compound 18\' was obtained, via lactonization. The dehalogenation reaction of compounds 13, 14, 15 and 16 afforded the expected products 19, 20, 21 and 22, in 93, 99, 75 and 93% yield, respectively. Compound 17 did not furnish any products in these conditions, but modifying them compoud 23\' was obtained, resulting from a internal nucleophilic substitution, in 79% yield. In these conditions, compounds 15 and 16 underwent HI elimination giving compounds 21\' e 22\', respectively.

Les domaines millimétrique et submillimétrique sont des domaines qui permettent de caractériser la physico-chimie des atmosphères <br />planétaires par l'observation des molécules qui les composent. Le télescope spatial Herschel et l'interféromètre ALMA, qui <br />entreront prochainement en service, permettront d'améliorer considérablement notre connaissance des atmosphères planétaires.<br /><br />L'un des principaux objectifs de cette thèse est de développer un modèle d'analyse des observations millimétriques et submillimètriques qui seront effectuées avec Herschel et ALMA. C'est en ce sens que nous détaillons un modèle qui tient compte de la géométrie sphérique des corps observés et des spécificités instrumentales propres aux télescopes utilisés. <br /><br />Dans un premier temps, ce qui a permis notamment de valider notre modèle de transfert radiatif, nous avons étudié l'origine des <br />composés oxygénés dans les atmosphères des planètes géantes. Nous présentons l'analyse d'observations de Saturne et d'Uranus, effectuées avec les télescopes de l'IRAM et du JCMT, pour contraindre les sources de monoxyde de carbone dans ces atmosphères. Nous améliorons ainsi les limites supérieures précédemment publiées et réalisons la première observation du monoxyde de carbone dans l'atmosphère de Saturne dans <br />le domaine submillimètrique. Cette observation prouve l'existence d'une source externe pour ce composé. Nous analysons également des observations récentes de Jupiter, effectuées par le télescope spatial Odin, pour contraindre l'origine externe de l'eau dans la stratosphère de cette planète. Les observations confirment que la chute de la comète Shoemaker-Levy~9 est vraisemblablement la source principale d'eau. <br /><br />Dans un second temps, nous avons appliqué notre modèle à l'étude de la structure thermique et la dynamique de l'atmosphère de Mars, à partir d'observations du monoxyde de carbone. Ces observations sont comparées aux prédictions d'un modèle de circulation générale, ce qui permet de vérifier la validité de ses prédictions et de fournir de nouvelles contraintes observationnelles pour ce type de modélisations.<br /><br />Enfin, nous avons appliqué notre modèle à l'étude des planètes géantes avec le télescope spatial Herschel, dans le cadre du programme-clé de temps garanti du télescope spatial Herschel "Water and related chemistry in the Solar System''. Nous avons également identifié les améliorations à apporter à notre modèle pour analyser des observations ALMA.

An online, semi-continuous instrument to measure both total and gas phase atmospheric reactive oxygen species (ROS) and determine the concentration of ROS in the particle phase (ROS(p)) was developed. This instrument was based on a fluorescent probe for quantifying ambient ROS, specifically 2'7'-dichlorodihydrofluorescin, or DCFH probe. This probe was analyzed for sensitivity to a variety of offline and online parameters for efficient use in a field instrument. The ROS(p) instrument measures the peak light intensity at 530 nm to determine ambient ROS concentrations. ROS particles and gases are collected in a mist chamber in a nebulized mist. The instrument alternates measurements of ROS(p+g), or ROS(tot) by means of an inline filter. Fine (PM₂.₅) (ROS(p) is determined by subtraction of the ROS(g) concentration from the ROS(tot), as the ROS(g) signal could not be excluded. This instrument was tested during the summer (May-July) of 2012 at urban and rural sites in the metropolitan Atlanta and surrounding region. Concentrations of ROS(p) determined from this instrument were often below limit of detection. Average concentrations of ROS(p) were found to be 0.25 nmol/m³ in urban Atlanta (Jefferson St. and Georgia Tech), and 0.15 nmol/m³ in Yorkville, a rural site. A side by side comparison of this method with a filter collection method was made in July. The average ROS(p) offline concentrations were 0.15 nmol/m³. These concentrations were comparable to the online average concentrations of 0.21 nmol/m³ for the same period of time. This average and the majority of the measurements comprising it is dominated by the high limit of detection. The ROS instrument as constructed and operated is an efficient way to conduct ROS(p) measurements at the level of a filter study while reducing the labor intensive filter collection and extraction. In order for this instrument to be successful at measuring ambient ROS in the particle phase, the removal of the gas phase from the current sampling scheme is critical as the ROS(g) concentrations are over 90% of the measured ROS. The system as currently operable is best suited for source measurements, including biomass burning plumes or fresh exhaust to capture immediate formation.

Os iodo-&#946;-enaminoésteres cíclicos 13, 14, 15 e 16 (heterociclos nitrogenados de 5 membros) foram preparados pela iodociclização dos alquenil-&#946;-enaminoésteres 7, 8, 9 e 10, respectivamente, com modificações na metodologia. Os tempos de reação foram diminuídos e o método de purificação foi modificado. Visando à extensão da metodologia para a obtenção de heterociclos nitrogenados de 6 membros, foi testada a iodociclização dos alquenil-S-enaminoésteres 11 e 12. O composto 11 forneceu o produto esperado 17 em 51% de rendimento enquanto que o composto 12 não sofreu ciclização nestas condições, porém ao modificá-las foi obtido composto 18\', via lactonização.As reações de desidroalogenação dos compostos 13, 14, 15 e 16 levaram aos produtos esperados 19, 20, 21 e 22, com rendimentos de 93, 99, 75 e 93%, respectivamente. O composto 17 não gerou nenhum produto nestas condições, mas ao modificá-las obteve-se o composto 23\', resultante de substituição nucleofilica interna, com 79% de rendimento. Nestas condições, os compostos 15 e 16 sofreram eliminação de HI gerando os compostos 21\' e 22\', respectivamente. / Cyclic iodo-&#946;-enaminoesthers 13, 14, 15 e 16 (five-membered nitrogen heterocycles) were prepared by iodocyc1ization of alkenyl-&#946;-enaminoesthers 7, 8, 9 e 10, respectively, with modifications in the method. The reaction times were diminished and the method of purification was changed. In order to extend this metodology to obtain six-membered nitrogen heterocycles, the iodocyclization of the alkenyl-&#946; enaminoesthers 11 and 12 was tested. Compound 11 furnished the expected product 17 in 51% yield while compound 12 did not undergo cyclization in such conditions, however by changing them compound 18\' was obtained, via lactonization. The dehalogenation reaction of compounds 13, 14, 15 and 16 afforded the expected products 19, 20, 21 and 22, in 93, 99, 75 and 93% yield, respectively. Compound 17 did not furnish any products in these conditions, but modifying them compoud 23\' was obtained, resulting from a internal nucleophilic substitution, in 79% yield. In these conditions, compounds 15 and 16 underwent HI elimination giving compounds 21\' e 22\', respectively.

Made available in DSpace on 2014-10-09T12:50:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:54Z (GMT). No. of bitstreams: 1 10891.pdf: 10297564 bytes, checksum: e2cbc8792530f432498c2945ee2cc670 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/12269-7

Made available in DSpace on 2014-10-09T12:50:22Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:54Z (GMT). No. of bitstreams: 1 10891.pdf: 10297564 bytes, checksum: e2cbc8792530f432498c2945ee2cc670 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:01/12269-7

Biomass is a renewable source of energy and represents an acceptable alternative to fosil fuels. Usable methods of energetic use of biomass are combustion and gasification. Main interest is focused on gasification in last years. Gasification is based on conversion of organic material to usable gaseous product called syngas, which can be used as a fuel for energy production. Large amount of tar is formed as a by-product of incineration and gasification of biomass. Tar is composed by various mixture of organic substances, has a negative effect on operating conditions and is a potential threat to environment. Experimental part of this study was focused on analysis of tar obtained by gasification of various kind of biomass. Selected groups of hydrocarbons and oxygen compounds were identified in analysed samples. Individual biomass samples were compared regarding to determined relative content of selected substances. Analysis was done by complete twodimensional gas chromatography with mass spectrometric detection (GCxGC/TOF-MS).

Les domaines millimétrique et submillimétrique sont des domaines qui permettent de caractériser la physico-chimie des atmosphères planétaires par l'observation des molécules qui les composent. Le télescope spatial Herschel et l'interféromètre ALMA, qui entreront prochainement en service, permettront d'améliorer considérablement notre connaissance des atmosphères planétaires. L'un des principaux objectifs de cette thèse est de développer un modèle d'analyse des observations millimétriques et submillimétriques qui seront effectuées avec Herschel et ALMA. C'est en ce sens que nous détaillons un modèle qui tient compte de la géométrie sphérique des corps observés et des spécificités instrumentales propres aux télescopes utilisés. Dans un premier temps, ce qui a permis notamment de valider notre modèle de transfert radiatif, nous avons étudié l'origine des composés oxygénés dans les atmosphères des planètes géantes. Nous présentons l'analyse d'observations de Saturne et d'Uranus, effectuées avec les télescopes de l'IRAM et du JCMT, pour contraindre les sources de monoxyde de carbone dans ces atmosphères. Nous améliorons ainsi les limites supérieures précédemment publiées et réalisons la première observation du monoxyde de carbone dans l'atmosphère de Saturne dans le domaine submillimétrique. Cette observation prouve l'existence d'une source externe pour ce composé. Nous analysons également des observations récentes de Jupiter, effectuées par le télescope spatial Odin, pour contraindre l'origine externe de l'eau dans la stratosphère de cette planète. Les observations confirment que la chute de la comète Shoemaker-Levy~9 est vraisemblablement la source principale d'eau. Dans un second temps, nous avons appliqué notre modèle à l'étude de la structure thermique et la dynamique de l'atmosphère de Mars, à partir d'observations du monoxyde de carbone. Ces observations sont comparées aux prédictions d'un modèle de circulation générale, ce qui permet de vérifier la validité de ses prédictions et de fournir de nouvelles contraintes observationnelles pour ce type de modélisations. Enfin, nous avons appliqué notre modèle à l'étude des planètes géantes avec le télescope spatial Herschel, dans le cadre du programme-clé de temps garanti du télescope spatial Herschel ``Water and related chemistry in the Solar System''. Nous avons également identifié les améliorations à apporter à notre modèle pour analyser des observations ALMA. / The planetary atmospheres can be characterized by observations carried out in the millimeter and submillimeter wavelength ranges. In a near future, the Herschel Space Observatory as well as the ALMA interferometer will increase our knowledge of the planet atmospheres. One of the main goals of this thesis work consists in developping an analysis tool for millimeter and submillimeter observations, which will be carried out with Herschel and ALMA. The model we have developped takes into account the spherical geometry of the planets and the properties of the telescopes. First, we have studied the origin of oxygen compounds in the atmospheres of the giant planets. We have validated our radiative transfer model from this study. We present the analysis of observations of carbon monoxide in the atmospheres of Saturn and Uranus, which have been carried out with the IRAM and JCMT telescopes, in order to constrain the origin of this compound. We improve existing upper limits and prove the existence of an external source of carbon monoxide in the atmosphere of Saturn from the first observation of this compound at submillimeter wavelengths. We also analyse recent observations from the Odin space telescope of water vapor in the stratosphere of Jupiter to constrain its external source. We confirm that the observed water is probably mostly due to the collision of comet Shoemaker-Levy~9 with the planet. Then, we have used our model in order to study the thermal structure as well as the dynamics of the atmosphere of Mars from carbon monoxide observations. These observations are compared to predictions of a general circulation model to check the consistency of the predictions. They also provide new observational constraints to general circulation models. Finally, we have used our model to study the atmospheres of the giant planets in the frame of the Herschel garanteed time key-program ``Water and related chemistry in the Solar System''. We have also determined the upgrades to implement in our model to analyse ALMA observational data.

A presente tese relata o estudo conformacional e das interações eletrônicas de algumas &#945;-feniltio-acetatos de etila para-substituídos e suas formas mono- e di-oxigenadas EtOC(O)CH2SOn-&#934;-X (p) (I) e de alguns &#945;-feniltio-tioacetatos de etila para-substituídos e sua forma mono-oxigenada EtSC(O)CH2SOn-&#934;-X (p) (II), [ n =0 (a), 1 (b) e 2 (c) para (I)] e [n= 0 (a) e 1 (b) para (II)], sendo X substituintes atraentes, hidrogênio e doadores de elétrons. Este estudo foi realizado através da espectroscopia no infravermelho e cálculos ab initio HF/6-31G**. Nos &#945;-ester-sulfetos (Ia) e &#945;-tioester-sulfetos (IIa) as conformações gauche são fortemente estabilizadas pelas interações orbitalares &#960;*co/ &#963;c-s (hiperconjugativa) e &#960;*co/ns. Nos &#946;-ester-sulfóxidos (Ib) e &#946;-tioester-sulfóxidos (IIb) enquanto a s conformações gauche são estabilizadas pela interação orbitalar &#960;co/ &#963;*c-so, a conformação cis é estabilizada pela interação no(co)&#8594;&#960;*SO. Nas &#946;-ester-sulfonas (Ic) o confôrmero menos polar e mais estável gauche é fortemente estabilizado pelas interações Coulombicas e orbitalares O&#948;-(CO) &#8594; S&#948;+(SO2) e O&#948;-(SO2) &#8594; C&#948;+(CO), enquanto que o confôrmero gauche 1 é estabilizado por esta ultima interação e desestabilizado pela interação repulsiva entre os oxigênios negativamente carregados dos grupos C(O)OEt e SO2Et. / This thesis reports the conformational and electronic interaction studies of some ethyl &#945;-phenylthio-acetates and their mono-and di-oxygenated derivatives EtOC(O)CH2SOn-&#934;-X (I) [for n=0 (a), l(b), and 2 (c)] and some ethyl &#945;-phenylthio-thioacetates and their mono-oxygenated derivatives EtSC(O)CH2SOn-&#934;-X (II) [for n= 0 (a) and 1 (b)], bearing at the para position electron-attracting, hydrogen and electron-donating substituents. This study was performed by means of infrared spectroscopy and HF/6-31G** ab initio calculations. For the &#946;-ester-sulfides (Ia) and &#946;-thioester-sulfides (IIa) the more stable gauche conformers are strongly stabilised by the &#960;*co/ &#963;c-s and &#960;*co / ns orbital interactions. As for the &#946;-ester-sulfoxides (Ib) and &#946;-thioester-sulfoxides (IIb) while the gauche conformers are stabilised by the &#960;co/ &#963;*c-s orbital interaction, the cis conformer is stabilised by the no(co) &#8594; &#960;&#8727;co interaction. For the &#946;-ester-sulfones (Ic) the least polar and most stable gauche rotamer is strongly stabilised by the crossed O&#948;-(CO)&#8594; S&#948;+(SO2) and O&#948;-(SO2)&#8594; C&#948;+(CO) Coulombic and orbital interactions, while the least stable gauche1 rotamer is stabilised by this latter interaction and destabilised by the repulsive interaction between the negatively charged oxygen atoms of the C(O)OEt and SO2Et groups.