Extensos corpos d’água como reservatórios hidrelétricos, aqui estudados, podem ser fontes consideráveis de gases de efeito estufa ('CH IND.4' e 'CO IND.2') devido à decomposição de parte da biomassa da floresta submersa e também pela biomassa alóctone e autóctone. Este trabalho apresenta concentrações e estimativas de fluxos difusivos e ebulitivos desses gases dissolvidos na coluna d’água, nos reservatórios hidrelétricos de Miranda (MG), Xingó (AL/SE), Ribeirão das Lages (RJ) e Represa do Lobo (SP) durante o período de outubro de 2001 a agosto de 2003. Utilizou-se, em perfis verticais, um sensor 'CH IND.4' de estado sólido comercial provido de detector de metano semicondutor, cuja superfície, ao adsorver o gás, varia sua resistência interna fornecendo sinal relacionado à concentração de gás. Foram usadas câmaras de troca difusiva na determinação de fluxos de troca de 'CH IND.4' e 'CO IND.2' na interface água-atmosfera e funis de captura de bolhas para processos ebulitivos. Mediram-se algumas variáveis físicas e químicas. Os perfis de gás metano dissolvido em água apresentaram elevadas concentrações, geralmente com valores crescentes desde próximo a superfície até a interface água-sedimento. Porém, sumidouros oxidativos presentes na coluna d’água, que consomem o gás metano no seu percurso até a superfície, juntamente com convecções impelidas pelo vento, foram responsáveis por perfis de diferentes tipos com concentrações alternadas, em conseqüência dessa ação. Fluxos difusivos também foram calculados a partir de experimentos de troca difusiva de gases dissolvidos na interface água-atmosfera resultando em emissões de 'CH IND.4' e 'CO IND.2' para atmosfera, e em alguns casos, absorção de 'CO IND.2' pelo reservatório / Extended water bodies such as the hydroelectric reservoirs here studied can be greenhouse gas sources ('CH IND.4' and 'CO IND.2') due to decay of part of submerged forest biomass and also due to allochtonous and autochtonous organic compounds. This work presents concentrations, ebullitive and diffusive fluxes of the gases dissolved in the water column in the following reservoirs : Miranda, Xingó, Ribeirão das Lages and Lobo, between October 2001 and August 2003. In the course of this work methane profiles were determined by a commercial methane sensor, a solid state device, the electrical resistance of which varies as a function of absorbed methane providing a signal related to dissolved gas concentration. Diffusion chambers were used to measure 'CH IND.4' and 'CO IND.2' exchange rates at the air-water interface; bubble capture funnels were used for ebullitive emission. Some physical and chemical variables were also measured. Dissolved methane profiles showed high concentrations, generally with increasing values from water surface to sediment. However, the oxidative methane sink in the water column consumes this gas in its upward migration path and together with wind-propelled convection produces different profile types. Diffusive flux was also calculated from diffusive exchange experiments of these gases at the air-water interface, which showed 'CH IND.4' and 'CO IND.2' emission, sometimes 'CO IND.2' absorption, by the reservoir

Verificando a importância da morfologia dos arcos dentários no tratamento ortodôntico, a proposta deste estudo foi avaliar e comparar as formas e dimensões de arcos de 30 indivíduos com oclusão normal e 30 com má-oclusão de Classe IIdivisão 1ª, geradas a partir de três categorias de pontos de referência. Foram demarcados nos modelos de estudo: os pontos médios das faces vestibulares dos dentes (1ª categoria de pontos); pontos no rebordo alveolar, perpendiculares aos anteriores e sobre a junção muco-gengival (2ª categoria de pontos); e pontos mesiais e distais das superfícies oclusais dos dentes. Todos os pontos foram digitalizados e convertidos automaticamente para o sistema de coordenadas x, y e z pela máquina de medidas tridimensional da Mitutoyo (modelo Crysta-Apex/C). Um software, especialmente desenvolvido para este trabalho, criou um conjunto de pontos de referência virtuais (3ª categoria de pontos) a partir dos pontos mesiais e distais das superfícies oclusais previamente demarcados nos modelos, que representou o fundo dos canais de encaixe de braquetes. Além disso, gerou curvaturas por meio de equações matemáticas (parábola, elipse, catenária e função beta) que se ajustaram, pelo método dos mínimos quadrados, às 3 diferentes categorias de pontos de referência, e mediu as dimensões transversais dentárias e dos rebordos alveolares. A seleção da equação matemática que melhor descreveu cada categoria de pontos de referência foi realizada por meio de avaliação do menor valor do erro médio. A curvatura do rebordo selecionada foi deslocada sobre o eixo y até tangenciar o ponto médio virtual do incisivo central mais anterior, simulando a inserção de um arco ortodôntico, e foram medidas as distâncias entre esta curvatura e os pontos médios virtuais dos outros dentes. Todos os dados foram organizados em tabelas de acordo com a categoria dos pontos de referência, os arcos (superior ou inferior) e o tipo de oclusão. Verificou-se que todas as dimensões transversais dentárias e dos rebordos superiores, e posteriores inferiores são estatisticamente maiores nos indivíduos com oclusão normal do que nos indivíduos com má-oclusão de Classe II; e que as distâncias transversais dos rebordos alveolares são estatisticamente maiores do que as dentárias. Quanto às formas dos arcos, a catenária, seguida da elipse, foram as que melhor descreveram as suas curvaturas, independentemente da categoria de pontos e do tipo de oclusão. As outras formas, como a parábola e a gerada pela função beta, foram observadas com baixo percentual de ocorrência. As formas dos arcos não caracterizaram diferencialmente os tipos de oclusão e as 3 categorias de pontos de referência estudadas. Praticamente todos os pontos médios virtuais apresentaram-se internamente posicionados em relação à curvatura do rebordo alveolar quando esta foi deslocada até o ponto médio virtual do incisivo central mais vestibularizado, sendo encontrados valores estatisticamente maiores no arco superior dos indivíduos com má-oclusão de Classe II-divisão 1ª. Este dado revela maior tendência a vestibularização dos dentes superiores nestes indivíduos, quando o rebordo alveolar é utilizado como guia para a construção do arco ortodôntico, embora as diferenças entre os grupos não nos pareçam clinicamente importantes. / Given the importance of dental arch morphology in orthodontic treatment, we have evaluated and compared, based on three categories of reference points, the shapes and dimensions of the arches of 30 subjects with normal occlusion and 30 subjects with Class II, division 1 malocclusions. .The points marked on the study casts were: the middle points of the buccal surfaces of teeth (first category of points); points on the alveolar ridge, perpendicular to those of the first category and on the mucogingival junction (second category of points); and mesial and distal points of the occlusal surfaces of the teeth. All points were digitized and automatically converted to the x, y and z system of coordinates by a three-dimensional measurement machine (Mitutoyo - Crysta-Apex/C model). A computer software program especially developed for our study created a set of virtual reference points (third category of points) based on the distal and mesial points on the occlusal surfaces previously marked on the casts, which represented the most inner point of the bracket slot. In addition, the software generated curvatures using mathematical equations that were adjusted to the three categories of reference points by the method of minimum squares, and measured the transversal dimensions of teeth and alveolar ridges. Selection of the mathematical equation that best described each category of reference points was performed by evaluating the smallest value for the mean error. The selected ridge curvature was shifted on the y-axis until it became tangential to the virtual middle point of the most anterior central incisor, simulating the insertion of an orthodontic arch, and the distances between this curvature and the virtual middle point on the other teeth were measured. All data were tabulated according to reference point category, arch (upper or lower), and type of occlusion. We observed that all transversal dimensions of teeth, upper ridges and lower posterior ridges were statistically greater in subjects with normal occlusion than in subjects with Class II malocclusions; and that the transversal distances of the alveolar ridges were statistically greater than those of the teeth. As to arch shape, the catenary, followed by the ellipse, were the shapes that best described the arch curvatures, regardless of reference point category and occlusion type. The other shapes, such as the parabola and the shape generated by the Beta function, were observed at lower frequencies. The arch shapes did not differentially characterize the several types of occlusion or the 3 reference point categories studied. Practically all virtual middle points were located internally to the curvature of the alveolar ridge when this curvature was shifted up to the virtual middle point of the most buccaly projected central incisor, and the subjects with Class II division 1 malocclusion were found to have statistically greater values for the upper arch. This observation reveals a greater trend for buccally projected upper teeth in these subjects when the alveolar ridge is used as a guide to construct the orthodontic arch, although the differences observed between the groups do not seem to be clinically important.

Le chapitre 1 présente un résumé bibliographique des différentes façons de casser une liaison C-Hd'hydrocarbures, plus particulièrement du méthane, avec des complexes de métaux de transition tant de la gauche que de la droite du système périodique. Pour les métaux de transition de la gauche, notre attention a été principalement axée sur trois mécanismes: i) la métathèse de liaison sigma, ii) l’abstraction d’un hydrogène en position alpha couplée a l’addition-1,2 d’une liaison CH et iii) l’abstraction d’un hydrogène en position bêta couplée à l’addition-1,3 d’une liaison C-H.Le chapitre 2 aborde le problème de l'activation d'une liaison C-H du méthane par un complexe transitoire eta2-cyclopropène de niobium. Des études RMN à haute pression en solution, des études de marquage isotopiques ainsi que des analyses cinétiques sur l'échange dégénéré du méthane dans le complexe méthyle [TpMe2NbCH3(c-C3H5)(MeCCMe)] (1) sont décrits. L’activation stoechiométrique du méthane par le complexe mésitylène [TpMe2Nb(CH2-3,5-C6H3Me2)(c-C3H5)(MeCCMe)] (2) pour donner 1 est également réalisée. Les données montrent que ces réactions se déroulent via une abstraction intramoléculaire d'un hydrogène bêta du groupe cyclopropyle soit par un groupe méthyle soit par un groupe mésityle à partir du composé 1 ou 2, respectivement, ce qui donne l’intermédiaire réactif eta2-cyclopropène [TpMe2Nb(2-c-C3H4)(MeCCMe)] (A). Ceci est suivi par sa réaction inverse, l'addition-1,3 d’une liaison C-H du méthane pour donner le produit.Le chapitre 3 explore la réactivité du complexe 1 en vers des hétéroaromatiques, des hydrocarbures insaturés ainsi que le pentafluorobenzène et le ferrocène (FcH) via l’abstraction d’un hydrogène en position beta couplée à l’addition-1,3 d’une liaison C-H. Le compose 1 est en mesure d'activer de manière sélective la liaison C-H du furane, thiophène, 1-cyclopentène, phénylacétylène, pentafluorobenzène et ferrocène, donnant les produits correspondants [TpMe2NbX(c-C3H5)(MeCCMe)] (X = 2-C4H3O, 2-C4H3S, 1-C5H7, PhCC, C6F5, Fc) qui ont été isolés et caractérisés par spectroscopie RMN du 1H et 13C, des études électrochimiques ainsi que par des analyses de diffraction des rayons X. / Chapter 1 reports a literature summary of the different ways of cleaving a hydrocarbon C-H bond, mostparticularly methane, with both early and late transition metal complexes. For early transition metals ourattention is focused on three mechanisms: i) the σ-bond metathesis, ii) the α-H abstraction/1,2-CH bond addition and iii) the β-H abstraction/1,3-CH bond addition.Chapter 2 challenges the problem of the activation of a CH bond of methane by a transient η2-cyclopropene complex of niobium. High pressure solution NMR, isotopic labelling studies and kinetic analyses of the degenerate exchange of methane in the methyl complex [TpMe2NbCH3(c-C3H5)(MeCCMe)] (1) are reported. Stoichiometric methane activation by the mesitylene complex [TpMe2Nb(CH2-3,5-C6H3Me2)(c-C3H5)(MeCCMe)] (2) giving 1 is also realized. Evidence is provided that these reactions proceed via an intramolecular abstraction of a β-H of the cyclopropyl group from either methane or mesitylene from 1 or 2, respectively, yielding the transient unsaturated η2-cyclopropene intermediate [TpMe2Nb(η2-c-C3H4)(MeCCMe)] (A). This is followed by itsmechanistic reverse 1,3-CH bond addition of methane yielding the product.Chapter 3 explores the reactivity of complex 1 towards heteroaromatics, unsaturated hydrocarbons, pentafluorobenzene and ferrocene (FcH) via the β-H abstraction/1,3-CH bond activation mechanism. Compound 1 is able to selectively activate the C-H bond of furan, thiophene, 1-cyclopentene, phenylacetylene, pentafluorobenzene and ferrocene, yielding the corresponding products [TpMe2NbX(c-C3H5)(MeCCMe)] (X = 2-C4H3O, 2-C4H3S, 1-C5H7, PhC≡C C6F5, Fc) which have been isolated and characterized by 1H, 13C NMR spectroscopy, electrochemical studies and X-ray diffraction analysis.

No description available.

<p dir="ltr">I conducted an in-depth analysis of the frequency and severity of external load accidents involving Chinook helicopters over a period of 30 years. The literature review encompassed General Aviation (GA) and ground-based safety organizations, while the data analysis predominantly relied on secondary data from the Army Combat Readiness Center (ACRC). In conducting this study, I aimed to identify key trends, causes, and effects of these accidents, particularly emphasizing material failures, human errors, and the substantial impact of rotor downwash as horizontal wind velocities in proximity to the ground. The study's goal was to improve safety and operational efficiency in Chinook external load operations by identifying frequency and severity of accidents over a 30-year period. The hope was that this would provide valuable insights for improvements in risk mitigation techniques.</p><p dir="ltr">By using an exploratory secondary data analysis of both publicly available U.S. Army accidents and accident data provided by the U.S. ACRC, I found that Chinook rotor downwash, which manifests as horizontal wind velocity when in close proximity to the ground, is the most significant and underreported factor. Based on the findings of this research, I recommend improved classification and documentation of such accidents. The findings highlighted the urgency of updating training and operational procedures to effectively address the unique challenges posed by rotor downwash and high gross weights in proximity to the ground, typical of Chinook external load Pickup and Landing Zone (PZ/LZ) operations. Implementing these recommendations is expected to enhance safety measures in both training and practical operations, ultimately reducing future accidents and improving safety standards in the aviation industry.</p>

Cyanoform (tricyanomethane) is one of the strongest carbon-based organic acids reported in text books of organic chemistry, which has evaded synthesis and isolation in its free state, since 120 years. In this dissertation, the acid-free synthesis of cyanoform by an absolutely new approach has been discussed. Generation of the elusive molecule, cyanoform from the photolysis and thermolysis of 2-(azidomethylidene)malononitrile, has been confirmed at very low temperatures by 1H NMR, 13C NMR, 15N NMR, and the relevant 2D NMR spectroscopic techniques. Moreover, it has been proved that cyanoform is relatively stable, but can be detected only below –85 oC, and not at high temperatures (at –45 oC, as has been reported in literature), because of a rapid equilibration with an another species. Furthermore, the chemistry of cyanoform in the ring enlargement reactions with various highly strained epoxides, azirines, and aziridines, via the highly reactive dicyanoketenimine intermediate, as well as its Michael addition reactions with different α,β-unsaturated carbonyl compounds has been well explored. In addition, the synthesis of N1-substituted 1,2,3-triazoles and study of their rearrangement to the corresponding N2-substituted 1,2,3-triazoles, under thermal and nucleophile-catalyzed reaction conditions, has been well investigated. / Cyanoform (Tricyanomethan) ist eine der stärksten in der Literatur beschriebenen organischen Kohlenstoffsäuren, welche sich seit 120 Jahren einer erfolgreichen Synthese und Isolierung entzogen hat. In dieser Arbeit wird die säurefreie Synthese des Cyanoforms mittels eines neuartigen Ansatzes diskutiert. Die Bildung des schwer fassbaren Moleküls durch Photolyse und Thermolyse von 2 (Azidomethyliden)malonitril ist bei tiefen Temperaturen durch 1H-NMR, 13C-NMR, 15N-NMR und relevante 2D-NMR-Methoden bestätigt worden. Es konnte bewiesen werden, dass Cyanoform relative stabil ist, aber erst unterhalb von –85 °C detektierbar ist und nicht bereits bei hӧherer Temperature (bei –45 °C, wie es in der Literatur beschrieben wurde) bedingt durch die rasche Äquilibrierung mit einer weiteren Species. Des Weiteren wurde die Reaktivität von Cyanoform in Ringerweiterungsreaktionen mit verschiedenen, stark gespannten Epoxiden, Azirinen und Aziridinen untersucht, wobei das hoch reaktive Dicyanoketenimin-Intermediat durchlaufen wird. Auch die Michael-Addition an α,β ungesättigte Carbonylverbindungen wurde ausführlich untersucht. Zusätzlich wurde die Synthese N1 substituierter 1,2,3-Triazole und deren Umlagerung in N2 substituierte 1,2,3-Triazole unter thermischen und nucleophil-katalysierten Bedingungen erforscht.

Depuis plus d’un siècle, la chimie hétérocyclique représente l’un des plus vastes domaines de recherche en chimie organique. En particulier, les hétérocycles bicycliques fusionnés à 5 chaînons, contenant à la fois des atomes de soufre et d’azote, présentent, de par leur rareté et leur potentiel biologique, un champ d’intérêt croissant pour les équipes de recherche et développement académiques ou des entreprises pharmaceutiques. Parmi les nombreux composés bicycliques [5-5], notre étude s’est focalisée sur le noyau imidazo[2,1-b][1,3,4]thiadiazole décrit sporadiquement dans la littérature et pour lequel les voies d’accès actuelles ne se limitent qu’à une seule méthode faisant intervenir une étape de cyclisation et des conditions drastiques. Ce verrou entraine inéluctablement une faible diversité fonctionnelle autour de cet hétérocycle, restreignant ainsi les domaines d’applications notamment biologiques. Afin de pallier à cette problématique, nous avons initié une étude de la réactivité de chacune des trois positions fonctionnalisables du bicycle imidazo[2,1-b][1,3,4]thiadiazole, développant ainsi diverses réactions pallado-catalysées (Suzuki-Miyaura, CH-arylation, Buchwald-Hartwig), de substitution nucléophile aromatique et de Pictet-Spengler. L’étude des propriétés biologiques des différents composés synthétisés et hautement valorisables durant ces travaux a abouti à la découverte de deux séries de molécules inhibant sélectivement les kinases DYRK-1A et CLK-1, deux protéines d’intérêt dans le traitement des affections du système nerveux central (neuropathies, Alzheimer…). / For more than a century, heterocyclic chemistry is one of the largest area in organic chemistry research. In particular, because of their rarity and their biological potential, [5-5] fused ring heterocycles containing both sulfur and nitrogen atoms are a large area of interest for both academic and industrial research and development teams. Among these numerous [5-5] bicycles, our study is focused on imidazo[2,1-b][1,3,4]thiadiazole scaffold, which is quite few described in the literature and whose pathways are limited to almost one method involving a cyclisation step and drastic conditions. This lock leads inevitably to low functional diversity around this heterocycle, thus restricting its applications, including biological. In order to overcome this problematic, we then initiated the reactivity study of each three positions of the bicycle imidazo[2,1-b][1,3,4]thiadiazole, developing thereby several palladium couplings (Suzuki-Miyaura, direct arylation, Buchwald-Hartwig), as well as aromatic nucleophilic substitution and Pictet-Spengler reaction. The study of the biological properties of the different compounds synthesized in this work and highly valuable led to the discovery of two series of molecules, inhibiting selectively DYRK-1A and CLK-1, two kinases of interest in the treatment of dysfunction of central nervous system (neuropathies, Alzheimer…).

Parmi la vingtaine de pathologies neurodégénératives recensées à ce jour, il a été retrouvé des caractéristiques communes telles que des lésions neuronales. Dans le cas de la Maladie d’Alzheimer, une dégénérescence neurofibrillaire a notamment été mise en évidence, ce qui se traduit par l’agrégation de protéines Tau anormalement modifiées. Bien que les mécanismes moléculaires impliqués demeurent encore mal compris, nous nous sommes intéressés, au cours de cette thèse, à la synthèse puis à l’évaluation biologique de nouveaux inhibiteurs de l’agrégation de la protéine TAU impliquée dans la Maladie d’Alzheimer. Les deux premières parties de ce travail sont basées sur la conception de dérivés imidazo[2,1-b]thiazoliques, sur lesquels sont greffés un ou plusieurs groupements (hétéro)aryles. La troisième partie est, quant à elle, consacrée à la formation d’entités thiazolo[3,2-b]triazoliques di- ou trisubstituées. Le choix de ces bicycles fusionnés à cinq chainons [5,5] découle de leurs propriétés biologiques dans des domaines très variés. L’obtention de ces composés a notamment été l’occasion de mettre en oeuvre de nouvelles méthodologies de synthèses. Ainsi, sur le motif imidazo[2,1-b]thiazolique, ont été développées des réactions de couplages de Suzuki-Miyaura, des réactions multicomposants, ainsi qu’une séquence réactionnelle de condensation d’électrophiles. Sur le bicycle thiazolo[3,2-b]triazole, un travail de CH activation a également été mise au point. Une collection de deux cents moléculesoriginales a ainsi pu être constituée, et plus de la moitié des nouveaux produits ont été évalués in vitro. Unetechnique de fluorescence permettant de déterminer l’inhibition de l’agrégation des protéines TAU a été miseau point, utilisant notamment la protéine K18 comme modèle tronqué de protéine TAU. / TAU pathology is a brain lesion common to more than twenty neurodegeneratives diseases. It consists of the abnormal aggregation of the microtubule-associated protein TAU into neurofibrillary tangles. While mechanisms underlying TAU aggregation are not fully understood yet, we have been investigated the synthesis and the biological evaluations of novel class of TAU aggregation inhibitors involved in Alzheimer’s disease. The first two parts of this work reports the synthesis of various imidazo[2,1-b]thiazoles molecules, on which are substituted (het)aryles groups. The third and last part is devoted to the formation of some di-/trisubstituted novel N-fused ring system such as thiazolo[3,2-b]triazoles. In order to provide a functional diversity and generate a therapeutic effect, the peaks C-2, C-3, C-5 and C-6 were functionalized on the imidazo[2,1-b]thiazole ring. It was also the opportunity to develop news synthetic methodologies such as a new Suzuki-Miyaura reaction, a multicomponent reaction, and an electrophilic condensation. On the thiazolotriazole core, an effective procedure of CH activation was performed. More than two hundred original molecules were synthesized, and more than half were evaluated in vitro. A fluorescence technique allowed us to determine the inhibition of TAU aggregation, using the particular K18 protein as a truncated model of normal TAU protein.

Cyanoform (tricyanomethane) is one of the strongest carbon-based organic acids reported in text books of organic chemistry, which has evaded synthesis and isolation in its free state, since 120 years. In this dissertation, the acid-free synthesis of cyanoform by an absolutely new approach has been discussed. Generation of the elusive molecule, cyanoform from the photolysis and thermolysis of 2-(azidomethylidene)malononitrile, has been confirmed at very low temperatures by 1H NMR, 13C NMR, 15N NMR, and the relevant 2D NMR spectroscopic techniques. Moreover, it has been proved that cyanoform is relatively stable, but can be detected only below –85 oC, and not at high temperatures (at –45 oC, as has been reported in literature), because of a rapid equilibration with an another species. Furthermore, the chemistry of cyanoform in the ring enlargement reactions with various highly strained epoxides, azirines, and aziridines, via the highly reactive dicyanoketenimine intermediate, as well as its Michael addition reactions with different α,β-unsaturated carbonyl compounds has been well explored. In addition, the synthesis of N1-substituted 1,2,3-triazoles and study of their rearrangement to the corresponding N2-substituted 1,2,3-triazoles, under thermal and nucleophile-catalyzed reaction conditions, has been well investigated. / Cyanoform (Tricyanomethan) ist eine der stärksten in der Literatur beschriebenen organischen Kohlenstoffsäuren, welche sich seit 120 Jahren einer erfolgreichen Synthese und Isolierung entzogen hat. In dieser Arbeit wird die säurefreie Synthese des Cyanoforms mittels eines neuartigen Ansatzes diskutiert. Die Bildung des schwer fassbaren Moleküls durch Photolyse und Thermolyse von 2 (Azidomethyliden)malonitril ist bei tiefen Temperaturen durch 1H-NMR, 13C-NMR, 15N-NMR und relevante 2D-NMR-Methoden bestätigt worden. Es konnte bewiesen werden, dass Cyanoform relative stabil ist, aber erst unterhalb von –85 °C detektierbar ist und nicht bereits bei hӧherer Temperature (bei –45 °C, wie es in der Literatur beschrieben wurde) bedingt durch die rasche Äquilibrierung mit einer weiteren Species. Des Weiteren wurde die Reaktivität von Cyanoform in Ringerweiterungsreaktionen mit verschiedenen, stark gespannten Epoxiden, Azirinen und Aziridinen untersucht, wobei das hoch reaktive Dicyanoketenimin-Intermediat durchlaufen wird. Auch die Michael-Addition an α,β ungesättigte Carbonylverbindungen wurde ausführlich untersucht. Zusätzlich wurde die Synthese N1 substituierter 1,2,3-Triazole und deren Umlagerung in N2 substituierte 1,2,3-Triazole unter thermischen und nucleophil-katalysierten Bedingungen erforscht.

Der erste Teil der Aktivitäten dieser Arbeit bestand in der Entwicklung einer modernen Ionenspeicher Apparatur zur Untersuchung chemischer Prozesse mit atomarem Wasserstoff. Die Integration eines differentiell gepumpten Radikalenstrahls in eine vorhandene temperaturvariable 22-Pol Speicherapparatur erforderte größere Änderungen an dieser. Da astrophysikalische Fragestellungen im Vordergrund standen, führt die Einleitung zunächst in das Gebiet der Astrophysik und -chemie ein. Die Grundlagen der Ionenspeicherung in temperaturvariablen Hf-Speichern sind ausführlich in der Literatur dokumentiert. Daher ist die Beschreibung der Apparatur (Kapitel 2) relativ kurz gehalten. Viel Mühe wurde in die Entwicklung einer intensiven und stabilen Quelle für Wasserstoffatome aufgewandt, deren kinetische Energie variiert werden kann. Das Kapitel 3 beschreibt dieses Modul in vielen Details, wobei der Einsatz von magnetischen Hexapolen zum Führen der Atome und die chemische Behandlung der Oberflächen zur Reduzierung der H-H Rekombination einen wesentlichen Platz einnimmt. Durch die außergewöhnliche Empfindlichkeit der Speichertechnik kann das neue Instrument zur Untersuchung von vielen Reaktionen eingesetzt werden, die von astrochemischer und fundamentaler Bedeutung sind. Die Ergebnisse dieser Arbeit sind im Kapitel 4 zusammengestellt, einige Reprints und Entwürfe von Publikationen findet man im Anhang. Die Reaktionen von CO2+ mit Wasserstoffatomen und -molekülen erwiesen sich als sehr geeignet, um in situ H and H2 Dichten über den gesamten Temperaturbereich der Apparatur zu bestimmen (10 K - 300 K). Zum ersten mal wurden Reaktionen von H- and D-Atomen mit den Kohlenwasserstoffionen CH+, CH2+, and CH4+ bei Temperaturen des interstellaren Raums untersucht. Ein sehr interessantes, noch nicht ganz verstandenes Stoßsystem ist die Wechselwirkung von protoniertem Methan mit H-Atomen. Im Ausblick der Arbeit werden einige Ideen aufgezeigt, wie man das Instrument verbessern kann, und es werden einige Reaktionen erwähnt, die man als nächste untersuchen könnte. Diese Dissertation ist einen Beitrag zum Projekt 5 der Forschergruppe Laboratory Astrophysics: Structure, Dynamics and Properties of Molecules and Grains in Space, die von der DFG im Zeitraum von 2000 bis 2006 unterstützt wurde. / The first part of the activities of this thesis was to develop a sophisticated ion storage apparatus dedicated to study chemical processes with atomic hydrogen. The integration of a differentially pumped radical beam source into an existing temperature variable 22-pole trapping machine has required major modifications. Since astrophysical questions have been in the center of our interest, the introduction first gives a short overview of astrophysics and -chemistry. The basics of ion trapping in temperature variable rf traps is well-documented in the literature; therefore, the description of the basic instrument (Chapter 2) is kept rather short. Much effort has been put into the development of an intense and stable source for hydrogen atoms the kinetic energy of which can be changed. Chapter 3 describes this module in detail with emphasis on the integration of magnetic hexapoles for guiding the atoms and special treatments of the surfaces for reducing H-H recombination. Due to the unique sensitivity of the rf ion trapping technique, this instrument allows one to study a variety of reactions of astrochemical and fundamental interest. The results of this work are summarized in Chapter 4, some reprints and drafts are reproduced in the appendix. Reactions of CO2+ with hydrogen atoms and molecules have been established as calibration standard for in situ determination of H and H2 densities over the full temperature range of the apparatus (10 K - 300 K). For the first time, reactions of H- and D-atoms with the ionic hydrocarbons CH+, CH2+, and CH4+ have been studied at temperatures of interstellar space. A very interesting, not yet fully understood collision system is the interaction of protonated methane with H. The outlook presents some ideas, how to improve the new instrument and a few reaction systems are mentioned which may be studied next. This thesis is a contribution to the project 5 of the research unit Laboratory Astrophysics: Structure, Dynamics and Properties of Molecules and Grains in Space which has been supported by the DFG from 2000 to 2006.