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Als Datengrundlage für die Erhebung von Flächennutzungsparametern, wie sie in geografischen Informationssystemen (GIS) abgelegt und verwaltet werden, dienen oft Bilddaten aus der Erdfernerkundung. Die zur Erkennung und Unterscheidung der Objekte notwendige hohe Pixelauflösung führt bei der Erfassung eines Zielgebiets wie beispielsweise einer Stadt zu enormen Datenmengen. Aus diesen Bilddaten gilt es, möglichst schnell und preiswert die für ein GIS notwendigen Informationen, wie Umrissvektoren und Objektattribute, zu extrahieren. Diese Arbeit ist ein Beitrag zur Automatisierung dieses Schritts mit besonderem Schwerpunkt auf der Gebäudeextraktion. Datengrundlage sind hochauflösende multispektrale Orthobilder und ein digitales Oberflächenmodell (DOM) der digitalen Luftbildkamera HRSC-A bzw. HRSC-AX zum Einsatz. Deswegen werden das Aufnahmeprinzip sowie die Datenverarbeitung der HRSC überblicksartig vorgestellt. Auf Basis dieser HRSC-Standarddatenprodukte wird ein Vorgehen zur Extraktion von Objekten entwickelt. In einer hierarchisch geordneten Abfolge an Segmentierungsschritten werden aus der Pixelinformation bedeutungstragende Einheiten extrahiert. Dieser Segmentierungsansatz lässt sich auf mehrere Objektkategorien, wie Straßen oder Ackerflächen, erweitern. So werden in der aktuellen Entwicklungsstufe neben Gebäuden auch Baumregionen detektiert. Anhand des Oberflächenmodells werden erhöhte Regionen erkannt. Dazu wird das DOM durch Berechnung eines Terrainmodells auf Grundhöhe normiert. Für erhöhte Objekte wird die Grundhöhe aus umliegenden Grundregionen abgeleitet. Die erhöhten Regionen werden anschließend in Bäume und Gebäude unterteilt. Dazu werden aus den Multispektraldaten Vegetationscharakteristika bestimmt und entsprechende Baumsegmente ermittelt. Die Gebäuderegionen resultieren aus einer Nachverarbeitung der verbleibenden Segmente. Um Gebäudekomplexe in einzelne Häuser aufzuteilen, wird ein gradientenbasierter Ansatz entwickelt. Anhand der für Brandmauern typischen Gradienteninformation werden Linienhypothesen zur Unterteilung der Gebäudesegmente generiert. Diese werden schrittweise anhand geometrischer und radiometrischer Kriterien auf ihre Plausibilität überprüft. Schließlich werden die ursprünglich aus dem DOM stammenden Konturen der Gebäudesegmente und deren Übereinstimung mit Bildkanten eines Orthobildes betrachtet. In einem adaptiven Ansatz wird das Konturpolygon durch die Gradienteninformation an angrenzende Bildkanten angepasst. Zur Umsetzung typischer Gebäudegeometrien wie rechter Winkel oder Parallelität werden innerhalb des Adaptionsprozesses entsprechende Nebenbedingungen formuliert. Die Extraktion erhöhter Objekte wie auch deren Unterteilung in Bäume und Gebäude erfolgt mit hoher Genauigkeit, z.B. liegen die Detektionsraten bei Gebäuden über 90%. Der neuartige Ansatz zur Unterteilung in einzelne Häuser ohne explizite Liniendetektion führt bereits in der vorgestellten Entwicklungsstufe zur Beschleunigung einer manuellen Interpretation. Die adaptive Verbesserung der Gebäudekontur führt zu gebäudetypischeren Umrissen ohne Beeinträchtigung der hohen Detektionsraten. / Remote sensing image data are often used as a basis for determining land use parameters, as they are stored and managed in geographic information systems (GIS). Covering a target area leads to an enormous amount of data due to the high pixel resolution required for recognizing and discriminating objects. To effectively derive GIS information like contour vectors or object attributes from these data, the extraction process has to be fast and cost-effective. This thesis is a contribution to the automization of this step with a focus on building extraction. High resolution multispectral ortho-images and a digital surface model (DSM), generated by the digital aerial camera HRSC-A or HRSC-AX, are used as data basis. Therefore, the HRSC imaging principle and data processing are summarized. Based on these HRSC standard data products, an object extraction scheme is developed. In a hierarchically ordered sequence of segmentation steps, meaningful units are extracted from pixel information. This segmentation approach is extendable to several object categories like streets or fields. Thus, tree regions, as well as buildings are detected in the current stage of implementation. Elevated regions are recognized using the digital surface model. For that purpose the DSM is normalized by calculating a terrain model. For elevated objects the terrain height is derived from surrounding ground regions. Subsequently, the elevated regions are separated into trees and buildings. Determining spectral characteristics of vegetation from the multispectral data leads to corresponding tree segments. The building regions result from post-processing the remaining segments. In order to split the building segments into single houses, a gradient based approach is developed. By means of the gradient information associated with firewalls, line hypotheses for subdividing the building segments are generated. Their plausibility is checked by gradually applying geometric and spectral criteria. Finally, the building contours, originally derived from the DSM, and their correspondence to image edges in an ortho-image, are considered. In an adaptive approach, the contour polygon is adjusted to neighboring image edges using the gradient information. Typical building geometries like right angles or parallelism are enforced by applying corresponding constraints in the adaption process. The extraction of elevated objects, as well as the separation into trees and buildings, is carried out with high accuracy, e.g. the building detection rates are over 90%. In the current development stage the novel approach for separating building segments into single houses without an explicit line detection already leads to a speeding-up of a manual interpretation. The adaptive improvement of building contours leads to building typical contours without affecting the high detection rates.

Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a,b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b–d, orthoesters 4a–c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl) acetylenedicarboxylate (1c) with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

O objetivo deste trabalho e a determinação dos coeficientes de viscosidade de cisalhamento e condutividade térmica de gases ideais quânticos. No cálculo dos coeficientes de transporte foram considerados dois aspectos: uma estatística quântica com seções transversais quânticas e uma estatística quântica com seções transversais quânticas. No primeiro caso, e utilizado um método alternativo para a determinação das aproximações sucessivas (ate a quinta ordem) para os coeficientes de transporte dos gases Helio 4, Helio 3, para-hidrogênio e orto-hidrogênio. No caso de estatística quântica desenvolvida uma teoria com base no método dos momentos de Grad e na equação de Uehling- Uhlenbeck, com a finalidade de determinar as express6es algébricas para os coeficientes de transporte. Esta teoria e baseada em 13 momentos, de densidade, velocidade, tensor pressão e fluxo de calor. Do conhecimento da função de distribuição em termos dos momentos, as equações constitutivas são determinadas e os coeficientes de transporte seguem de um método iterativo semelhante ao procedimento Maxwelliano. / The aim of this work is the determination of the coefficients of shear viscosity and thermal conductivity of quantum ideal gases. In the calculation of the transport coefficients two aspects have been taken into account: a classical statistical with quantum cross-sections and a quantum statistical with quantum cross-sections. In the first case, an alternative method is used for the determination of the successive approximations (up to the fifth order) to the transport coefficients of the gases helium 4, helium 3, para-hydrogen, ortho-hidrogen. In the case of quantum statistical a theory based on method of moments of Grad and on the Uehling-Uhlenbeck equation is developed in order to determine the algebraic expressions to the transport coefficients. This theory is based on 13 moments of density, velocity, pressure tensor and heat flux. From the knowledge of the distribution function the constitutive equations are determinate and the transport coefficients follow from an iterative method akin to the 11axwellian procedure.

Formaldehyde is a chemical used widely in the manufacture of building materials. A remarkable example is represented by the Lucite two-step Alpha technology for the large scale production of methyl methacrylate (MMA), the essential building block of all acrylic-based products. Esters and ketones are important intermediates in the manufacture of acrylate esters therefore α-hydroxymethylenation of carbonyl compounds using formaldehyde as a one carbon alkylating agent and subsequent dehydration to the corresponding methylenated derivatives has been explored in the current work. We report a novel catalytic approach for the synthesis of methyl methacrylate (MMA) via one-pot α-methylenation of methyl propanoate (a chemical intermediate of the ALPHA process) with formaldehyde, generated in situ by Ru-catalysed dehydrogenation of methanol. Elucidation of the mechanism involved in the catalytic dehydrogenation of methanol along with the collateral alcohol decarbonylation reaction was gained through a combined experimental and DFT study. The development of an alternative process where anhydrous formaldehyde is produced in situ would provide a simplification over the current second step of the ALPHA technology where the formaldehyde is initially produced as formalin, subsequently dehydrated to afford anhydrous formaldehyde in order to ensure high selectivity to MMA. As an alternative approach, ketones, in particular 3-pentanone and 2-butanone, were targeted as potential substrates in order to overcome some of the problems related to competing reactions that occur at the ester group. Hydroxymethylenation, followed by dehydration and Baeyer-Villager oxidation, possibly catalysed by enzymes to reverse the normal selectivity, leads to the formation of acrylate esters. The catalytic reaction is enabled by a gold carbene hydroxide complex in such a way that the substrate undergoes C-H activation and the nascent metal alkyl acts as a nucleophile towards the electrophilic formaldehyde, supplied in the form of alcoform* (solution of paraformaldehyde in methanol).

O objetivo deste trabalho e a determinação dos coeficientes de viscosidade de cisalhamento e condutividade térmica de gases ideais quânticos. No cálculo dos coeficientes de transporte foram considerados dois aspectos: uma estatística quântica com seções transversais quânticas e uma estatística quântica com seções transversais quânticas. No primeiro caso, e utilizado um método alternativo para a determinação das aproximações sucessivas (ate a quinta ordem) para os coeficientes de transporte dos gases Helio 4, Helio 3, para-hidrogênio e orto-hidrogênio. No caso de estatística quântica desenvolvida uma teoria com base no método dos momentos de Grad e na equação de Uehling- Uhlenbeck, com a finalidade de determinar as express6es algébricas para os coeficientes de transporte. Esta teoria e baseada em 13 momentos, de densidade, velocidade, tensor pressão e fluxo de calor. Do conhecimento da função de distribuição em termos dos momentos, as equações constitutivas são determinadas e os coeficientes de transporte seguem de um método iterativo semelhante ao procedimento Maxwelliano. / The aim of this work is the determination of the coefficients of shear viscosity and thermal conductivity of quantum ideal gases. In the calculation of the transport coefficients two aspects have been taken into account: a classical statistical with quantum cross-sections and a quantum statistical with quantum cross-sections. In the first case, an alternative method is used for the determination of the successive approximations (up to the fifth order) to the transport coefficients of the gases helium 4, helium 3, para-hydrogen, ortho-hidrogen. In the case of quantum statistical a theory based on method of moments of Grad and on the Uehling-Uhlenbeck equation is developed in order to determine the algebraic expressions to the transport coefficients. This theory is based on 13 moments of density, velocity, pressure tensor and heat flux. From the knowledge of the distribution function the constitutive equations are determinate and the transport coefficients follow from an iterative method akin to the 11axwellian procedure.

Ce manuscrit décrit la synthèse et la caractérisation de nouvelles molécules incluant un cœur organophosphoré, le phosphole. Certaines de ces molécules ont été utilisées pour la fabrication de dispositifs OLEDs ou de cellules photovoltaïques organiques. Le premier chapitre fait un état de l'art de la chimie du phosphole dans le domaine des matériaux organiques entre 2010 et 2013. Le second chapitre décrit la synthèse et l'étude physico-chimique de molécules qui permettent de moduler l'angle de torsion dans les systèmes π conjugués pour faire varier les propriétés optiques et rédox. Une de ces molécules a permis la fabrication d'une diode blanche organique. Le troisième chapitre de ce manuscrit présente une structure tridimensionnelle intéressante, le 1,1-biphosphole. En plus de posséder une structure tridimensionnelle, ces structures présentent un mode de conjugaison original, la conjugaison σ-π, qui permet de réduire l'écart HO-BV de nos systèmes. Une de ces molécules a permis la fabrication de la première cellule photovoltaïque organique avec un dérivé du phosphole inséré dans la couche active. Dans une deuxième partie, ce chapitre traite également de la réactivité originale du 1,1'-biphosphole qui permet de fonctionnaliser l'atome de phosphore par une simple substitution nucléophile, permettant d'insérer une grande variété de substituants pour moduler les propriétés des molécules. Pour finir, ce manuscrit présente un quatrième chapitre qui implique le phosphole comme unité coordinante afin de réaliser des nouveaux complexes qui permettent de réaliser une ortho-métallation par activation C-H. De nouveaux complexes ortho-métallés d'Ir(III) et de Rh(III) ont été synthétisés et caractérisés. / This thesis describes the synthesis and the characterization of new molecules including an organophosphorous unit, the phosphole ring. Some molecules have been used to build devices like organic light emitting diodes or organic photovoltaic cells.The first chapter describes the state of the art of the phosphole chemistry in organic materials between 2010 and 2013. The second chapter describes molecules having a tuneable twist angle allowing a fine control of the properties of the molecules like the HOMO-LUMO gap. One of those molecules has been used to build a white organic light emitting diode. The third chapter of this thesis presents an interesting three dimensional structure, the 1,1'-biphosphole. Beside this three dimensional structure, the molecules possess an original conjugation mode, the σ-π conjugation which allows a decrease of the HOMO-LUMO gap. One molecule from this chapter was used as absorber in organic photovoltaic cell. In the second part of this chapter, the 1,1'-biphosphole structure shows an interesting reactivity toward nucleophilic attack in order to functionalize the phosphorus center. This reactivity has been used to make new molecules and offer the opportunity to attach a wide range of substituents to the phosphorus atom in order to tune the properties of the molecules. The fourth chapter deals with the coordination chemistry of the phosphole in order to realize new ortho-metalated complexes. New Ir(III) and Rh(III) complexes have been synthesized and characterized.