SYNTHESIS OF FERROCENYL CYCLOHEPTADIENONES A&ccedil / ikg&ouml / z, Canet M.S., Department of Chemistry Supervisor: Assoc. Prof. Dr. Metin Zora August 2005, 85 pages Synthesis of seven-membered ring systems such as cycloheptadienones has attracted a great deal of attention in organic chemistry since they are present in a variety of biologically important molecules. Incorporation of the essential structures of such compounds with a ferrocene moiety instead of an aryl group could provide subtances with enhanced antitumor activities since some ferrocene derivatives have already proved to be active against a number of tumors. To develop a ferrocenyl-substituted seven-membered ring forming reaction, we have investigated the reaction of cyclopropylcarbene-molybdenum complex with ferrocenyl-substituted alkynes. As ferrocenyl-substituted alkyne, ferrocenyl&not / propyne (25B), (2-ferrocenylethynyl)trimethylsilane (25C), 1-ferrocenyl-3-phenylprop-1-yne (25D), 1-ferrocenyl-2-phenylethyne (25E), diferrocenylethyne (25F), ferrocenyl(formyl)acetylene (25G) were synthesized starting from ethynylferrocene (25A). The reaction between cyclopropylcarbene-molybdenum complex and ferrocenyl alkynes produced ferrocenyl-substituted cycloheptadienones 26, hydrolysis product of cycloheptadienones, 27, &amp / #61537 / -hydroxycycloheptadienones 28 and cyclobutenones 29, depending on the substitution pattern of the alkyne moiety. Interestingly, &amp / #61537 / -hydroxycycloheptadienone product 28B was isolated from these types of reactions for the first time. Terminal alkynes, trimethyl- and formyl-substituted alkynes did not produce any expected product, possibly depending on the steric and electronic effects, and/or the polymerization of the alkyne. Proposed mechanism for the formation of cycloheptadienones involves metallacyclobutene formation, electrocyclic ring opening, electrocyclic ring closure, CO insertion, reductive elimination.

The analysis of the immensity of data in space and time is a challenging task. For this thesis, the time-dependent data has been explored in various directions. The studies focused on data visualization, feature extraction, and data classification. The data that has been used in the studies comes from various well-recognized archives and has been the basis of numerous researches. The data characteristics ranged from the univariate time series to multivariate time series, from hand gestures to unconstrained views of general human movements. The experiments covered more than one hundred datasets. In addition, we also discussed the applications of visual analytics to video data. Two approaches were proposed to create a feature vector for time-dependent data classification. One is designed especially for a bio-inspired model for human motion recognition and the other is a subspace-based approach for arbitrary data characteristics. The extracted feature vectors of the proposed approaches can be easily visualized in two-dimensional space. For the classification, we experimented with various known models and offered a simple model using data in subspaces for light-weight computation. Furthermore, this method allows a data analyst to inspect feature vectors and detect an anomaly from a large collection of data simultaneously. Various classification techniques were compared and the findings were summarized. Hence, the studies can assist a researcher in picking an appropriate technique when setting up a corresponding model for a given characteristic of temporal data, and offer a new perspective for analyzing the time series data. This thesis is comprised of two parts. The first part gives an overview of time-dependent data and of this thesis with its focus on classification; the second part covers the collection of seven publications.

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Applicable image-based reconstruction of three-dimensional (3D) objects offers many interesting industrial as well as private use cases, such as augmented reality, reverse engineering, 3D printing and simulation tasks. Unfortunately, image-based 3D reconstruction is not yet applicable to these quite complex tasks, since the resulting 3D models are single, monolithic objects without any division into logical or functional subparts. This thesis aims at making image-based 3D reconstruction feasible such that captures of standard cameras can be used for creating functional 3D models. The research presented in the following does not focus on the fine-tuning of algorithms to achieve minor improvements, but evaluates the entire processing pipeline of image-based 3D reconstruction and tries to contribute at four critical points, where significant improvement can be achieved by advanced human-computer interaction: (i) As the starting point of any 3D reconstruction process, the object of interest (OOI) that should be reconstructed needs to be annotated. For this task, novel pixel-accurate OOI annotation as an interactive process is presented, and an appropriate software solution is released. (ii) To improve the interactive annotation process, traditional interface devices, like mouse and keyboard, are supplemented with human sensory data to achieve closer user interaction. (iii) In practice, a major obstacle is the so far missing standard for file formats for annotation, which leads to numerous proprietary solutions. Therefore, a uniform standard file format is implemented and used for prototyping the first gaze-improved computer vision algorithms. As a sideline of this research, analogies between the close interaction of humans and computer vision systems and 3D perception are identified and evaluated. (iv) Finally, to reduce the processing time of the underlying algorithms used for 3D reconstruction, the ability of artificial neural networks to reconstruct 3D models of unknown OOIs is investigated. Summarizing, the gained improvements show that applicable image-based 3D reconstruction is within reach but nowadays only feasible by supporting human-computer interaction. Two software solutions, one for visual video analytics and one for spare part reconstruction are implemented. In the future, automated 3D reconstruction that produces functional 3D models can be reached only when algorithms become capable of acquiring semantic knowledge. Until then, the world knowledge provided to the 3D reconstruction pipeline by human computer interaction is indispensable.

Die vorliegende Arbeit beschäftigt sich mit der Entwicklung eines UAV-basierten Systems und der zugehörigen Methodenentwicklung zur automatisierten Rehkitzsuche in Feldern. Jedes Jahr sterben sehr viele Wildtiere -- vor allem Rehkitze -- während dem Mähen von landwirtschaftlich genutzten Wiesen. Mit herkömmlichen Methoden ist es unter vertretbarem Aufwand bisher nicht gelungen, die Zahl der Mähopfer auf ein erträgliches Maß zu reduzieren. Mit der Entwicklung des in dieser Arbeit beschriebenen "Fliegenden Wildretters" könnte sich das in Zukunft ändern. Mit Hilfe einer Wärmebildkamera aus der Vogelperspektive lässt sich ein warmes Tier, wie ein Rehkitz, wesentlich leichter aufspüren, als mit herkömmlichen Methoden. Auslegung und Aufbau des Systems orientieren sich speziell an dem Aspekt, wie eine möglichst hohe Flächenleistung erreicht werden kann, ohne dabei Tiere zu übersehen. Drei Faktoren sind besonders wichtig, um dieses Ziel zu erreichen: Eine hohe Geschwindigkeit des gesamten Suchprozesses, eine zuverlässige Detektion und eine präzise Lokalisierung der Tiere. Durch Automatisierung lassen sich viele Teilaspekte dieser Aufgabe beschleunigen. Deshalb werden im Rahmen dieser Arbeit verschiedene Methoden entwickelt und validiert, unter anderem zur Flugplanung, Flugsteuerung, Bilddaten-Auswertung, Objekt-Detektion und Georeferenzierung. Die Kenntnis der Rehkitz-Merkmale und der Einflussgrößen bei der Thermalbilderfassung helfen, die Qualität der Detektion zu erhöhen, weshalb sie in dieser Arbeit besondere Berücksichtigung finden. Auch die Präzision der Lokalisierung lässt sich durch Kenntnis der Einflussgrößen auf die Positions- und Lagemessung des UAVs erhöhen. Anhand von umfangreichen Messkampagnen wird die Funktion und Qualität des Systems unter realen Bedingungen belegt.

Die salzhaltigen Abwässer des Kalibergbaues führen in natürlichen Süßwassersystemen zu Ionenimbalanzen und einer sekundären Versalzung der Werra in Deutschland. Die Auswirkungen dieser Ionenungleichgewichte auf die Reproduktion von Süßwasserfischen wurden unter Verwendung der Modellfischart Danio rerio untersucht. Angepasst an die aktuellen Grenzwerte für die Einleitung der Abwässer aus dem Kalibergbau wurden fünf verschiedene Kombinationen erhöhter Ionenkonzentrationen getestet. Während eines partiellen Lebenszyklustests wurden adulte Fische 35 Tage lang in den Salzkombinationen exponiert. Anschließend wurden die Nachkommen dieser Fische bis zum 8. Tag nach der Befruchtung den gleichen Salzkonzentrationen ausgesetzt. Zusätzlich wurden Early-Life-Stage-Tests (ELST) mit den Nachkommen von nicht exponierten Eltern durchgeführt. Im Vergleich zu natürlich vorkommenden Ionenkonzentrationen und -verhältnissen in Süßwassersystemen war die Befruchtungsrate der Eier für alle Ionenkombinationen signifikant niedriger, die Koagulations- und Deformationsrate jedoch signifikant höher. Die ELST ergaben bei den Embryonen und Larven u.a. vorzeitige und verlängerte Schlupfzeiten, verringerte Überlebensraten, erhöhte Deformationsraten und Herzschlagfrequenzen sowie Unregelmäßigkeiten des Ganzkörpergehalts von K, Mg, Na und Ca und des Ganzkörper-Ionenverhältnisses von Ca:Mg bei erhöhten Ionenkonzentrationen und Ionenimbalanzen. Im Vergleich zu den Effekten auf die Fortpflanzung und Entwicklung der Nachkommen waren die Effekte auf die adulten Tiere moderat. Die Ergebnisse dieser Dissertation zeigen, dass Teillebenszyklus-Tests besser als Fischeitests oder ELST geeignet sind, die Effekte von durch Abwasser verursachten Ionenimbalanzen, auf die Fortpflanzung und frühe Entwicklung von Süßwasserfischen, zu untersuchen. Weder die momentan gültigen noch die zukünftig herabgesetzten Grenzwerte bis 2027 sind danach als unschädlich, für die Reproduktion von Süßwasserfischen, zu betrachten. / The potash mining industry discharges saline effluents which generate ion imbalances in natural freshwater systems and cause severe secondary salinization in the river Werra in Germany. The effects of these ion imbalances on reproduction of freshwater fish were investigated using the fish model species Danio rerio. Five different combinations of elevated ion concentrations adjusted to the current threshold values for the discharge of potash mining effluents in Germany were tested. During a partial life cycle test, adult fish were exposed to the salt combinations for 35 days. Subsequently, the offspring were exposed to the same concentrations until hatch, and the larvae were further reared at the exposure concentrations from hatch until the 8th day post fertilization. Additionally, a standard early life stage test with offspring from unexposed parents was performed. Compared to naturally occurring ion concentrations and ratios in freshwater systems, the fertilization rate of the eggs was significantly lower for all ion combinations, while coagulation and deformation rates were significantly higher. Early life stage tests on embryos and larvae revealed premature and prolonged hatching times, reduced survival rates, increased deformation and heart rates and irregularities in whole body content of K, Mg, Na and Ca and whole body Ca:Mg ratios at elevated ion concentrations and imbalances of ion ratios. Compared to effects on reproduction and development of the offspring, effects on the parental generation were moderate. The results of this dissertation indicate that partial life cycle tests instead of fish egg tests or ELST are needed to examine most sensitively the effects of ion imbalances caused by potash mining effluents on reproduction and early development of freshwater fish. Neither the recent German threshold values nor the future reduced values until 2027 are safe for the reproduction of freshwater fish.