79 search hits
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"Smart" Hydrogels based on Trishydrophilic Triblock Terpolymers
(2010)
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Stefan Reinicke
- The work presented in this thesis focuses on the synthesis of double stimuli-responsive, trishydrophilic triblock terpolymers and their utilization for the construction of “smart” hydrogel systems, responding to a variety of external stimuli. The central focus was put on ABC triblock terpolymers composed of a pH-sensitive A block, a water soluble B block and a thermo-sensitive or multi-responsive C block. This concept was used for the construction of hydrogels responding independently to pH, temperature, and UV light. It was further applied to the formation of polymer/nanoparticle hybrid micelles suitable for the formation of magneto-responsive hydrogels (ferrogels). At first, a new route for the synthesis of block copolymers, containing ethylene oxide and glycidol derivatives, was developed. The crucial aspect of this procedure, based on sequential anionic polymerization, was the utilization of the phosphazene base t-BuP4, enabling the anionic polymerization of epoxide monomers in the presence of lithium counterions. It was shown, that ethoxyethyl glycidyl ether polymerizes easily under the established polymerization conditions without unwanted termination. Hence, we were able to synthesize well-defined block copolymers containing vinyl and epoxide monomers in a one-pot reaction, without performing additional intermediate steps. This new synthetic route was then utilized to synthesize a series of poly(2-vinylpyridine)-block-poly(ethylene oxide)-block-poly(glycidyl methyl ether-co-ethyl glycidyl ether) (P2VP-b-PEO-b-P(GME-co-EGE)) triblock terpolymers suitable for pH and temperature dependent hydrogel formation. The reversible gelation for this particular system relies on two distinct mechanisms. Under conditions, where only one outer block is insoluble, core-shell-corona (CSC) micelles are formed, resulting in gelation via close cubic packing of the micelles. On the other hand, the micelles are also able to crosslink through their corona when both outer blocks are insoluble. As a direct consequence, a temperature triggered gel-sol-gel transition occurred at pH = 7, accompanied by a unique gel strengthening. Solubility and gelation studies were performed by DLS, rheology and SANS. The influence of polymer concentrations and block lengths on the gelation behavior and gel properties was studied. In order to derive information about the exact structure of the cubic lattice formed in the low temperature gel phase (simple cubic or body centered cubic), a 19 wt% aqueous solution of a particular P2VP-b-PEO-b-P(GME-co-EGE) triblock terpolymer at pH = 7 was further investigated using SANS under steady shear. By application of shear stress, the irregularly arranged polydomains of the sample oriented macroscopically along a preferred direction, which led to highly defined, strongly anisotropic 2D scattering patterns. The interpretation of these patterns confirmed the presence of a body centered cubic packing. The gel-sol transition upon temperature increase can be explained by a shrinkage of the shell of the CSC micelles. To increase the versatility of the established hydrogel concept, we further synthesized ABC triblock terpolymers with different responsive polymers as C blocks. This required an alternative synthetic route, combining anionic polymerization and ATRP via “click” chemistry. After optimization of each synthetic step, exemplary poly(2-vinylpyridine)-block-poly(ethylene oxide)-block-poly(oligo(ethylene glycol) methacrylate) (P2VP-b-PEO-b-POEGMA) and poly(2-vinylpyridine)-block-poly(ethylene oxide)-block-poly(dimethyl- aminoethyl methacrylate) (P2VP-b-PEO-b-PDMAEMA) triblock terpolymers were synthesized, respectively, and characterized regarding their solubility and gelation behavior. At pH > 5, P2VP-b-PEO-b-PDMAEMA forms CSC micelles with a P2VP core, and a pH- as well as thermo-sensitive PDMAEMA corona. This particular structure represents a hydrogel, whose temperature dependent response can be easily changed from a gel-sol to a sol-gel transition by increasing the pH from 8 to 9. At pH = 7.5 on the other hand, gel formation is induced by the addition of hexacyanocobaltate(III) ions due to electrostatic interactions between the multivalent cobaltate ions and the charged DMAEMA units, causing a physical crosslinking of the CSC micelles. The gel can subsequently be disintegrated by an exposure to UV-light, based on a UV-catalyzed aquation of the trivalent hexacyanocobaltate(III) ions ions to divalent aquapentacyanocobaltate(III)-ions. In the last part, a new approach was developed to create a novel type of magnetic field-responsive hydrogels (ferrogels), in which the nanoparticles are tightly bound to the polymer matrix. The P2VP block of the previously synthesized P2VP-b-PEO-b-P(GME-co-EGE) triblock terpolymers was quaternized to a low extent and complexed with negatively charged, citrate stabilized maghemite (γ-Fe(III)-oxide) nanoparticles. Using different analytical methods it was shown that well-defined CSC hybrid micelles were obtained with cores formed by a complex of P2VP and 3-4 nanoparticles per core. Concentrated solutions of these micelles are able to form gels depending on temperature, as revealed by rheology measurements. Due to the presence of the maghemite particles, it is possible to induce gelation via remote heating using AC magnetic fields, which was demonstrated by high frequency magnetocalorimetry.
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3-Funktionalisierung von Tetron- und Tetramsäuren - Beiträge zur Totalsynthese von Bakkenolid-A und Macrocidin A
(2010)
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Bertram Barnickel
- Ziel des ersten Projekts dieser Arbeit war die Totalsynthese von Bakkenolid A. Der Schlüsselschritt hierfür war die Entwicklung einer regioselektiven Methode zur 3-Funktionalisierung von Tetronaten mittels Pentadienyl-Verbindungen. Bis zur Realisierung der Reaktion waren detaillierte Untersuchungen bezüglich deren Reaktionsmechanismus und der damit einhergehenden Regioisomere nötig. Durch die Synthese diverser Pentadien-Buildingblocks konnte letztlich der optimale Reaktionspartner für eine regioselektive Tsuji-Trost-Reaktion gefunden werden. Eine vollständige Synthese von Bakkenolid A scheiterte jedoch aufgrund unüberwindbarer, sterischer Hinderung bei der anschließenden Diels-Alder Reaktion. Im zweiten Teil dieser Arbeit wurde die Totalsynthese von Macrocidin A angestrebt. Ein zentraler Teil der Retrosynthese-Strategie beruhte auf der erfolgreichen 3-Acylierung von Tetramsäuren gemäß Yoshii et al. Da die Ausbeuten dieser Methode aufgrund des bis heute ungeklärten Mechanismuses sehr schwer vorherzusagen sind, wurden deren Möglichkeiten detailliert untersucht. Hierbei zeigte sich eine starke Abhängigkeit von der Kettenlänge und v.a. dem Verzweigungsgrad in α-Position der verwendeten Carbonsäure. Die so erhaltenen 3-Acyl-Tetramsäuren wurden in ihre partiell bzw. global entschützten Derivate überführt und somit eine Substanzbibliothek aufgebaut. Diese wurde bezüglich ihrer cytotoxischen bzw. antibakteriellen Wirksamkeit untersucht. Hierbei konnten einige Verbindungen mit IC50-Werten im einstelligen µM-Bereich identifiziert werden. Die Erstellung einer eindeutigen Struktur-Wirkungs-Beziehung gelang allerdings nicht. Der entscheidende nächste Schritt in Richtung Totalsynthese von Macrocidin A war der Ringschluss zum 17-gliedrigen Makrocyclus. Ursprünglich nur als Entschützung der Phenol-Funktion geplant, gelang durch Palladium-Katalyse der direkte Ringschluss eines Nor-Macrocidin A Precursors. Hierbei handelt es sich um eine bis dato unbekannte, mit einer Williamson-Ether-Synthese vergleichbaren Methode zur Synthese von Makrocyclen.
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Advanced Technologies in Education - Developing the Science Classroom of the Future
(2010)
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Sofoklis A. Sotiriou
- Information communication technology (ICT) nowadays provides innovative learning systems which although routinely available needs adjustment to real educational environments. Due to the complexity of the task an appropriate integration into everyday classrooms is an important global research challenges focusing on its utilization and effects in both, classroom and non-classroom settings. By rigorous collecting data on teaching methods, classroom characteristics and students learning effects needs analysis by concentrating on selected variables that may determine effectiveness as well as teachers characteristics such as teacherspreparation and professional development. Therefore, the aim of the four presented research papers focuses on envision the science classroom of the future, by constructing a framework for improving current educational practices and learning processes in science and mathematics through the effective implementation of advanced technological tools and applications. Overall this work presents a vision for the science classroom of the future: It will not be an island, a self-contained campus, a counter-world. The classroom of the future will be able to emit and absorb along different wavelengths, be immersed in contemporary culture, be open to the emotions, facts and news of its time. It will be permeated by society, but not unprotected: the relationship between school and society will be one of osmosis, where the pedagogical tools and applications act as a membrane and interface. For this purpose, four empirical studies were carried out in real school environments, based on the use of advanced educational systems. (i) The first system under study is the COSMOS Portal, which is an educational repository that offers access to a network of robotic telescopes across the world. At the same time it offers access to more than 85,000 educational resources. The behaviour of the teachers who are using this system was mapped through the log files of the system database for a period of one year. (ii) The second system, called Lab of Tomorrow, is a wearable device that allows high school students to use their every day life as the field where they will conduct sophisticated experiments and thus will deepen their understanding of the science concepts involved in the activities. The impact of the system on students learning and to the lesson profile was studied for a period of one school year. (iii) The third system, called CONNECT, is also a wearable device that includes an advanced visualization system that augments additional information to the optical view of the user. The system is used in the framework of educational visits in science centres and museums enriching the experiences of the visitors. The effectiveness of the system in supporting the students conceptual change was studied in this case. (iv) The fourth system, called EXPLOAR, evolved from the described CONNECT system to a much more user-friendly handheld device. Taking into account the school curriculum we have designed a series of scenarios of use of these tools. The scenarios of use include classroom activities, field trips in science centres and museums, informal learning activities, professional development opportunities and community building. In all four studies, students cognitive learning is analysed as well as selected teachers tasks on the job. By applying different assessment methods and tools (questionnaires, video captures of lessons, log files and web based data) we monitored the implementation procedure across different European countries. Our working hypothesis is that amending the traditional scientific methodology for experi¬mentation with visualization applications and model building tools will help students to articulate their mental models, make better predictions, and reflect more effectively. Additionally, working to reconcile the gaps and inconsistencies within their mental models, system models, predictions and results, will provide the learners with a powerful, explicit representation of their misconceptions and a means to repair them. Additionally our aim is to support teachers professional development. Apart from the purely technical training, in order for teachers to introduce ICT-enhanced learning methods into their everyday practice, they will have to perform a change in behaviour and to adapt a new culture and philosophy. The use of the new tools asks for systematic and detailed lesson planning procedures and use of student centred approaches. In our work we are demonstrating methods for involving teachers in this process but also tools to monitor this behavioural change.
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Advection at a forest site – an updated approach
(2010)
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Lukas Siebicke
- The exchange of carbon dioxide (CO2) across the vegetation-atmosphere interface of a spruce forest was investigated. Horizontal and vertical advection are recognized as important terms of the Net Ecosystem Exchange (NEE) budget in addition to the commonly measured turbulent flux and storage flux. Direct advection measurements are challenging because of the instrumental accuracy required to observe small concentration gradients and small wind velocities and because of the spatio-temporal measurement resolution required to observe complex 3-D flow phenomena. This work presents an experimental multi-analyzer setup for the observation of horizontal CO2 concentration gradients with high temporal resolution and good spatial resolution with no tradeoff between the two. A statistical approach was developed to correct for inter-instrument bias by applying a conditional time dependent bias correction. This approach relies on properties of probability density distributions of concentration differences between one sample point and the spatial average of the sample point field. Sub-canopy CO2 concentration gradients observed with the above presented system showed a high spatial variability which was dependent on vegetation structure. Local concentration perturbations correlated with statistical properties of coherent structures and were explained by vertical exchange between CO2 enriched sub-canopy air and low concentration above-canopy air. The small-scale variability of CO2 concentration gradients brings into question the representativity of horizontal advection measurements for the control volume if observed with a low spatial resolution. Vertical advection estimates rely on accurate measurements of vertical wind velocity (w). Different procedures were applied during coordinate rotation to align the coordinate system of the sonic anemometer with the long-term stream lines. Spatial variability of the wind field was addressed by a sector-wise coordinate rotation. An investigation of temporal aspects of vertical wind velocity showed significant contributions from low frequencies in the spectrum of w. The impact of the data set length used for coordinate rotation on w and on vertical advection was investigated and observed to be large. A sequential coordinate rotation with controlled window length was proposed. Advection contributed significantly to NEE during the night and during transition periods at the Waldstein-Weidenbrunnen (DE-Bay) FLUXNET site. Daily NEE budgets were more realistic, compared to NEE from turbulent flux and storage change alone, if direct advection measurements from continuous and bias corrected gradient sampling were included, reducing the estimated daily carbon sequestration of the forest by almost 50 %.
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Algebraische Approximation von Kählermannigfaltigkeiten
(2010)
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Florian Schrack
- Eine kompakte komplexe Mannigfaltigkeit heißt algebraisch approximierbar, wenn sie beliebig kleine projektive Deformationen besitzt. Eine natürliche Fragestellung ist, ob jede kompakte Kählermannigfaltigkeit algebraisch approximierbar ist. Während dies in Dimension 2 nach den Arbeiten von Kodaira richtig ist, hat Voisin vierdimensionale Gegenbeispiele gefunden. In Dimension 3 ist die Frage noch offen. Ziel der vorliegenden Arbeit ist es, den dreidimensionalen Fall etwas näher zu beleuchten. Dazu wird algebraische Approximierbarkeit zunächst von einem allgemeinen Standpunkt aus betrachtet. Es werden Funktorialitätsfragen untersucht, also der Zusammenhang zwischen algebraischer Approximierbarkeit der Quelle und des Ziels gewisser holomorpher Abbildungen, und Ergebnisse für verschiedene Klassen von Abbildungen erzielt, wie etwa Aufblasungen, endliche Abbildungen, Faserungen und Morikontraktionen. Als Fallstudie einer konkreten Klasse von Kählerdreifaltigkeiten werden anschließend Konikbündel über Kählerflächen untersucht, die in natürlicher Weise in der Moritheorie auftreten. Nach dem Beweis einiger grundlegender Tatsachen über Konikbündel werden ihre Diskriminantenorte genauer untersucht und damit Chernklassenabschätzungen für Konikbündel mit relativer Picardzahl 1 über nichtalgebraischen kompakten Kählerflächen hergeleitet. Unter Verwendung dieser Abschätzungen wird die Existenz infinitesimaler Deformationen solcher Konikbündel gezeigt, was einen wichtigen ersten Schritt zum Beweis der algebraischen Approximierbarkeit darstellt. Ein spezieller Typ von Konikbündeln sind die projektivierten Rang-2-Bündel. Die Periodenabbildung verhilft zu einem guten Verständnis der Deformationstheorie solcher Bündel über K3-Flächen und zweidimensionalen Tori. Konkret werden Fortsetzungssätze für Geradenbündel und Rang-2-Bündel bewiesen, die implizieren, dass jedes projektivierte Rang-2-Bündel über einer K3-Fläche oder einem zweidimensionalen Torus algebraisch approximierbar ist. Durch Untersuchung von Aufblasungen solcher Flächen wird dieses Resultat auf projektivierte Rang-2-Bündel über beliebigen kompakten Kählerflächen mit Kodairadimension 0 ausgedehnt. Schließlich wird die zuvor entwickelte Deformationstheorie für Vektorbündel verwendet, um weitere Approximierbarkeitsergebnisse für Konikbündel über elliptischen Flächen und K3-Flächen zu bekommen.
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Azobenzene-functionalized molecular glasses for holographic applications
(2010)
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Roland Walker
- Holography is an optical imaging technique, with which an authentic copy of the original object can be created, even in the absence of the object itself. This means, that in contrast to conventional photography, the information of depth is not lost. Holography is based on writing an interference grating in a photosensitive volume element. Hereby two light sources are generating an interference pattern, which causes chemical or physical changes in the photosensitive material. By illumination of the stored diffraction grating, the original information can be reconstructed. One of the most important classes of photoaddressable chromophores utilized in holography are azobenzene compounds. Owing to the rich photochemistry of these chromophores, materials incorporating azobenzenes can be used as photoswitches, allowing fast and reversible control over the chemical, physical or optical properties of the entire system. Therefore, azobenzene-containing compounds are envisioned as smart light-responsive materials for various holographic applications. This thesis describes the synthesis and characterization of azobenzene-containing molecular glasses as well as their application as functional materials in specific holographic experiments. By utilizing a modular design principle, we were able to fine-tune their physical and photo-physical properties and optimize the molecular structure in view of the formation of surface relief nanostructures as well as inscription of holographic volume gratings. Understanding the formation of surface relief nanostructures and discovering ways of controlling the process is of importance, as uniform surface relief gratings (SRGs) with adjustable spacing and amplitude are of interest. Therefore a new series of azobenzene-containing molecular glasses based on a triphenylamine core has been synthesized and photo-physically characterized. A clear relationship between the chemical structure of these molecules and SRG build-up was established: the rate of formation and the maximal achievable amplitude of SRGs strongly depend on the optical susceptibility at the wavelength of the writing laser. Furthermore, we found that different polarizations of the laser beams also have a major influence. With this knowledge we were able to efficiently form SRGs with amplitude heights of up to 600 nm by tailoring the molecular structure of the material and selecting specific experimental conditions. Furthermore, it has been demonstrated that these surface patterns are stable enough to be transferred to a polymer surface with replica molding techniques. This concept has the potential to be practically applied for holographic optical elements. Holography is a most promising solution for optical data storage, as in contrast to conventional optical storage media, the entire volume of the medium is used instead of only a few thin layers. Unfortunately, current rewritable materials still exhibit certain challenges, most important, sufficiently fast writing times. Therefore, material concepts especially for improving the recording time as well as the long-term stability of holographic volume gratings are presented. By employing azobenzene-containing molecular glasses in blends with photoaddressable polymers, we were able to merge the excellent long-term stability of the polymer systems with the higher photo-physical sensitivity of the molecular glasses, thus creating a superior holographic material which combines the advantages of both material classes. In order to find a suitable blending material, we synthesized series of photochromic azobenzene-containing molecular glasses and screened them with respect to their photo-physical properties. The best combination of structural variations was chosen for the blending experiments. Already a blend comprising as less as ten wt% of molecular glass allowed us to decrease the holographic writing time of a photoaddressable block copolymer system by a factor of three while increasing the recording sensitivity by the factor five. In addition to molecular glasses with ordinary azobenzene chromophores we also examined low molecular weight materials functionalized with bisazobenzene moieties. This enabled us to achieve higher maximum refractive index modulations. Liquid-crystalline behaviour could be introduced with the incorporation of substituents at the bisazobenzene moiety. Subsequent investigations of the photo-physical properties revealed a long-term stable photo-orientation solely based on small molecular compounds, making such materials an interesting alternative to established systems. In summary, this thesis demonstrates that azobenzene-containing molecular glasses are a worthwile focus for research, as they are an amazingly versatile and adaptable class of materials suitable for a large number of different applications.
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Bedeutung der Baumart für die Aktivität, Diversität und Abundanz methanoxidierender Bakterien in temperaten Waldböden
(2010)
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Daniela Degelmann
- Die mikrobielle Oxidation atmosphärischen Methans ist in Nadelwaldböden bis zu drei Mal niedriger als in Laubwaldböden. Ziel dieser Dissertation war es, anhand von drei deutschen Waldstandorten (Solling, Steigerwald und Unterlüß) mit jeweils benachbarten Beständen der Rotbuche (Fagus sylvatica L.) und der Gemeinen Fichte (Picea abies L.), die Umweltparameter zu identifizieren, die diese unterschiedlichen Methanoxidationsraten hervorrufen, und deren Auswirkungen auf die Diversität und Abundanz der methanotrophen Lebensgemeinschaft zu bestimmen. Die Aufnahme von Michaelis-Menten-Kinetiken an intakten Bodenkernen bei konstanter Methankonzentration, Temperatur sowie konstantem Matrixpotenzial ergab, dass die kinetischen Parameter Vmax(app) und KM(app) in Fichtenwaldböden bis zu 65% niedriger waren als in entsprechenden Buchenwaldböden. In situ Methanaufnahmeraten und atmosphärische Methanoxidationsraten gestörter Bodenproben waren in Böden unter Fichte ebenfalls niedriger. Die maximale methanotrophe Aktivität war im Oa-Horizont (Buche) oder in den ersten fünf Zentimetern des Mineralbodens lokalisiert. Unter Fichte wurde im Oa-Horizont keine Methanoxidation detektiert. Im Oi- und Oe-Horizont wurde in keinem der beiden Waldbodentypen methanotrophe Aktivität verzeichnet. Die Gasdiffusion durch die organische Auflage der Böden, der pH-Wert und die Ammoniumkonzentration waren in beiden Waldbodentypen ähnlich und schieden somit als regulierende Faktoren für die atmosphärische Methanoxidation in Laub- und Nadelwaldböden aus. Die Produktion von Ethylen unter oxischen Bedingungen war vernachlässigbar, so dass Ethylen ebenfalls ausgeschlossen werden konnte. β-Pinen, welches in Fichtennadeln und -wurzeln vorkommt und eine sehr hohe inhibitorische Wirkung auf die Methanoxidation zeigt, inhibierte die Oxidation von Methan in Bodenaufschlämmungen des Steigerwalds vollständig bei einer Konzentration, die dem Fünffachen der in situ Konzentration entsprach. Die von Fichten freigesetzten Monoterpene können die verminderte Methanaufnahme in Fichtenwaldböden erklären. Der Einfluss der Baumart auf die Zusammensetzung der methanotrophen Lebensgemeinschaft wurde durch vergleichende Analyse der Gene der partikulären Methanmonooxygenase (pmoA) untersucht. Von den insgesamt 366 analysierten pmoA-Genen waren 82% Upland Soil Cluster alpha (USCα) zuzuordnen, dem global am häufigsten detektierten pmoA-Genotyp in Waldböden. Durch Vergleich der PmoA-Sequenzen mit den entsprechenden 16S rRNA-Gensequenzen bekannter methanotropher Isolate wurde ein distanzbasierter „Cut-off“ von 7% auf Proteinebene zur Differenzierung methanotropher OTUs auf Artenebene kalkuliert. Unter Anwendung dieses „Cut-offs“ konnten in Buchenwaldböden sieben OTUs innerhalb von USCα unterschieden werden. Außerdem wurden zwei tiefabzweigende Genotypen (Cluster 6 und Cluster 7) detektiert, die nur entfernt verwandt zu bekannten PmoA-/AmoA-Sequenzen waren. In Fichtenwaldböden waren dagegen nur vier USCα-OTUs sowie Cluster 6 detektierbar. Die erniedrigte Diversität Methanotropher in Fichtenwaldböden wurde durch statistische Analysen bestätigt. Genfragmente von mmoX und der pmoA von methanotrophen Verrucomicrobia wurden nicht detektiert. amoA-Gene mit hoher Verwandtschaft zur amoA von Nitrosospira briensis wurden gelegentlich kodetektiert. Die Abundanz der pmoA-Gene von USCα, der Anteil von USCα an der bakteriellen Gemeinschaft sowie die zellspezifische Aktivität von USCα waren in Böden unter Fichte niedriger als unter Buche. Die ermittelten Werte für die zellspezifische Aktivität von USCα lagen unterhalb des theoretischen Mindestwerts, der für das Überleben einer methanotrophen Zelle bei Oxidation von atmosphärischem Methan notwendig ist. Dies lässt vermuten, dass USCα neben atmosphärischem Methan auf alternative Kohlenstoff- und Energiequellen angewiesen sein könnte. Zusammenfassend lassen die Ergebnisse dieser Disseration den Schluss zu, dass von Fichten freigesetzte Monoterpene die Aktivität, Diversität und Abundanz atmosphärischer Methanoxidierer reduzieren und so die atmospherische Methanaufnahme von Fichtenwaldböden verringern.
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Beiträge zur Chemie von Übergangsmetallkomplexen mit Alkenylcarbenen, Phosphoryliden und bioaktiven Hydroxyverbindungen als Liganden
(2010)
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Alexander Gmeiner
- Ein Schwerpunkt dieser Arbeit waren Versuche, Alkin-Insertions-Cyclopropanierungs-sequenzen mit Tetracarbonyl-eta2-Allylamino-Carben-Chelat-Komplexen für die Synthese von oligocyclischen organischen Verbindungen zu verwenden. Die Umsetzungen mit symmetrischen Alkinen wie 3-Hexin bzw. Tolan führte ich unter verschiedensten Be-dingungen in verschiedenen Lösungsmitteln durch. Hier war entweder kaum Umsatz zu beobachten oder die Reaktionen führten zu einer Vielzahl nicht weiter charakterisierter Zer-setzungsprodukte Es wurden auch Versuche zur Darstellung von bis dato unbekannten kationischen Eta3-Allyl-Amino-(Oxo)-Chrom(0)-Carben-Komplexen unternommen. Diese Verbindungen könnten als vielseitige Vorstufen zur enantioselektiven Synthese von Tetracarbonyl-eta2-(Oxo)Aminoalkenyl-Carben-Chelat-Komplexen dienen. Die Absicht war, durch Alkin-Insertions-Cyclopropanierungssequenzen mit enantiomerenreinen Tetracarbonyl-eta2-(Oxo)Aminoalkenyl-Carben-Chelat-Komplexen, enantioselektiv cyclopropanierte sechs-gliedrige (Oxo)Azacyclen aufzubauen. Zur Herstellung solcher Eta3-Komplexe wurden Ausgangskomplexe mit geeigneten Abgangsgruppen in der Alken-Seitenkette benötigt. Diverse Versuche diese Komplexe darzustellen, schlugen jedoch fehl. Ein weiterer Teil dieser Arbeit beschäftigte sich mit titanierten Phosphoryliden. Durch Reaktion von Methylentriphenylphophoran mit den Bis-phenoxy-dichlor-titan(IV)-Ver-bindungen konnten monomere titanierte Phosphorylide erhalten werden. Durch Umsetzung eines titanierten Phosphorylids mit diversen aromatischen Aldehyden, unter verschiedenen Bedingungen, konnten keine 1,3-Diarylallene erhalten werden. Basierend auf dem cytotoxischen Potential von Titanocendichlorid, war ein Primärziel dieser Arbeit die Synthese von antitumoraktiven Titanocenderivaten. Im Gegensatz zu den etablierten, in der Tumortherapie häufig verwendeten Platinverbindungen, würden Titanocen-derivate, aufgrund anderer Wirkmechanismen, eventuell auch bei Nierenkarzinom- und Cisplatin-resistenten Zelllinien wirksam sein. Der Schwerpunkt dieser Arbeit war die Synthese von Titanocenkomplexen mit bioaktiven Hydroxyliganden, ausgehend von Titanocendichlorid bzw. Dimethyltitanocen. Als Liganden dienten unter anderem Combretastatin-analoge Chalkone und Oxazole. Unter wasserfreien Bedingungen konnten auch die Ferrocenylchalkone dargestellt werden. Durch Reaktion von Dimethyltitanocen mit dem sterisch anspruchsvollen Naturstoff Schisandrol A wurde ein stabiler Methyl-Titanocen-Schisandrol A-Komplex gebildet. Nie zuvor war ein Titanocen-Methyl-Komplex, welcher einen derart sperrigen Alkoxyliganden trägt, synthetisiert worden. Ein weiters Themengebiet dieser Arbeit war die Darstellung von Tricarbonyl-Chrom(0)-Komplexen des Schisandrol A. Es konnte eine saubere Verbindung isoliert werden. Laut NMR-Daten handelte es sich eindeutig um einen Tricarbonyl-Chrom(0)-Komplex. Jedoch war nicht feststellbar, welches Isomer vorlag. Dies müsste durch Herstellung größerer Mengen, Züchtung eines Einkristalls und anschließender Röntgenstrukturanalyse endgültig geklärt werden. Unter anderem wurde vom mir auch ein aussergewöhnlicher Tricarbonyl-Eisen(0)-Dien-Komplex des cytotoxisch hochwirksamen Naturstoffs Illudin M hergestellt.
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Bogoliubov Excitations of Inhomogeneous Bose-Einstein Condensates
(2010)
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Christopher Gaul
- In this thesis, different aspects of interacting ultracold bosons in presence of inhomogeneous external potentials are studied. The first part deals with repulsively interacting Bose-Einstein condensates in speckle disorder potentials. In the Bogoliubov approach, the many-body problem is split into the Gross-Pitaevskii condensate (mean-field) and the Bogoliubov excitations, which are bosonic quasiparticles. The disorder potential causes an imprint in the condensate, which makes the Hamiltonian for the Bogoliubov excitations inhomogeneous. The inhomogeneous Bogoliubov Hamiltonian is the starting point for a diagrammatic perturbation theory that leads to the renormalized Bogoliubov dispersion relation. From this effective dispersion relation, physical quantities are derived, e.g. the mean free path and disorder corrections to the speed of sound and the density of states. The analytical results are supported by a numerical integration of the Gross-Pitaevskii equation and by an exact diagonalization of the disordered Bogoliubov problem. In the second part, Bloch oscillations of Bose-Einstein condensates in presence of time-dependent interactions are considered. In general, the interaction leads to dephasing and destroys the Bloch oscillation. Feshbach resonances allow the atom-atom interaction to be manipulated as function of time. In particular, modulations around zero are considered. Different modulations lead to very different behavior: either the wave packet evolves periodically with time or it decays rapidly. The former is explained by a periodic time-reversal argument. The decay in the other cases can be described by a dynamical instability with respect to small perturbations, which are similar to the Bogoliubov excitations in the first part.
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Characterization of reactive and non reactive trace gas fluxes in and above soil
(2010)
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Anika Bargsten
- Nitrogen is one of the most important compounds on earth. All organisms need nitrogen to live and grow. Even the majority (78.08%) of the atmosphere (and so the air we breathe) is dinitrogen. Over the last century, human activities have dramatically increased emissions and removal of nitrogen to the global atmosphere by as much as three to five fold. Nitrous oxide is the fourth largest single contributor to positive radiative forcing, and serves as the only long-lived atmospheric tracer of human perturbations of the global nitrogen cycle. Nitrogen oxides belong to the so called indirect greenhouse gases. These indirect greenhouse gases control the abundances of direct greenhouse gases through atmospheric chemistry and contribute on this way to the greenhouse effect. For a better understanding of these feedback mechanisms it is necessary to know the source strength of nitric oxide and nitrous oxide. Thus, the knowledge about exchange processes of nitrogen is of interest and importance for scientist and policy makers, likewise. This thesis contributes the understanding of processes in the nitrogen cycle. The thesis is addressed on nitric and nitrous oxide emissions. Nitric oxide emissions were measured on soil samples using an automated laboratory system. Nitrous oxide emissions were measured directly on the field site using a closed chamber technique. The laboratory measurements were compared with field measurements of NO (modified Bowen ratio method) at a grass land site. The field NO fluxes were always around 1.8 ng m 2 s-1 while the laboratory derived NO fluxes were between 2.1 and 5,2 ng m-2 s-1. The agreement between the two data sets is considered to be quite good. The laboratory derived NO fluxes exceeded the field NO fluxes by a factor of 1.5 to 2.5. Most studies of nitric oxide (NO) emission potentials up to now have investigated mineral soil layers only. In this thesis soil organic matter was sampled for laboratory measurements under different understory types (moss, grass, spruce, blueberries) in a humid mountainous Norway spruce forest plantation in the Fichtelgebirge (Germany). In this thesis the response of net potential NO fluxes on physical and chemical soil conditions (water content and temperature, bulk density, particle density, pH, C/N ratio, organic C, soil ammonium, soil nitrate) was determined. Net potential NO fluxes (in terms of mass of N) from soil samples taken under the different understories ranged from 1.7 - 9.8 ng m 2 s-1 (soil sampled under grass and moss cover), 55.4 - 59.3 ng m-2 s-1 (soil sampled under spruce cover), and 43.7 - 114.6 ng m 2 s-1 (soil sampled under blueberry cover) at optimum water content and a soil temperature of 10°C. Effects of soil physical and chemical characteristics on the net potential NO flux were statistically significant (0.01 probability level) only for NH4+. Therefore, as an alternative explanation for the differences in soil biogenic NO emission we consider more biological factors like understory vegetation type, amount of roots, and degree of mycorrhization; they provide a potential explanation of the observed differences of net potential NO fluxes. Also, soil nitrous oxide (N2O) emissions in an unmanaged, old growth beech forest in the Hainich National Park, Germany, were measured at 15 plots over a one-year period (November 2005 to November 2006). The annual field N2O flux rate was 0.46±0.32 kg ha 1 yr 1. The N2O emissions showed a background emission pattern with two event based N2O peaks. A correlation analysis showed that the distance between plots (up to 380 m) was secondary for their flux correlations. Annual N2O fluxes obtained from a standard model (Forest-DNDC) parameterized with soil parameters as well as daily temperature and precipitation substantially overestimated the actual field N2O fluxes and also did not describe their actual temporal and spatial variabilities. Temporal variability was described well by the model only at plots with higher soil organic carbon and the modelled N2O fluxes increased during freezing periods only were soil organic carbon was larger than 0.06 kg-1 C kg. The results indicate that the natural background of nitrous oxide emissions may be lower than previously thought and also lower than assumed in standard modelling. This suggests a higher anthropogenic contribution to N2O emissions.
