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In this thesis, we give two constructions for Riemannian metrics on Seiberg-Witten moduli spaces. Both these constructions are naturally induced from the L2-metric on the configuration space. The construction of the so called quotient L2-metric is very similar to the one construction of an L2-metric on Yang-Mills moduli spaces as given by Groisser and Parker. To construct a Riemannian metric on the total space of the Seiberg-Witten bundle in a similar way, we define the reduced gauge group as a subgroup of the gauge group. We show, that the quotient of the premoduli space by the reduced gauge group is isomorphic as a U(1)-bundle to the quotient of the premoduli space by the based gauge group. The total space of this new representation of the Seiberg-Witten bundle carries a natural quotient L2-metric, and the bundle projection is a Riemannian submersion with respect to these metrics. We compute explicit formulae for the sectional curvature of the moduli space in terms of Green operators of the elliptic complex associated with a monopole. Further, we construct a Riemannian metric on the cobordism between moduli spaces for different perturbations. The second construction of a Riemannian metric on the moduli space uses a canonical global gauge fixing, which represents the total space of the Seiberg-Witten bundle as a finite dimensional submanifold of the configuration space. We consider the Seiberg-Witten moduli space on a simply connected Käuhler surface. We show that the moduli space (when nonempty) is a complex projective space, if the perturbation does not admit reducible monpoles, and that the moduli space consists of a single point otherwise. The Seiberg-Witten bundle can then be identified with the Hopf fibration. On the complex projective plane with a special Spin-C structure, our Riemannian metrics on the moduli space are Fubini-Study metrics. Correspondingly, the metrics on the total space of the Seiberg-Witten bundle are Berger metrics. We show that the diameter of the moduli space shrinks to 0 when the perturbation approaches the wall of reducible perturbations. Finally we show, that the quotient L2-metric on the Seiberg-Witten moduli space on a Kähler surface is a Kähler metric.
Systems of Systems (SoS) have received a lot of attention recently. In this thesis we will focus on SoS that are built atop the techniques of Service-Oriented Architectures and thus combine the benefits and challenges of both paradigms. For this thesis we will understand SoS as ensembles of single autonomous systems that are integrated to a larger system, the SoS. The interesting fact about these systems is that the previously isolated systems are still maintained, improved and developed on their own. Structural dynamics is an issue in SoS, as at every point in time systems can join and leave the ensemble. This and the fact that the cooperation among the constituent systems is not necessarily observable means that we will consider these systems as open systems. Of course, the system has a clear boundary at each point in time, but this can only be identified by halting the complete SoS. However, halting a system of that size is practically impossible. Often SoS are combinations of software systems and physical systems. Hence a failure in the software system can have a serious physical impact what makes an SoS of this kind easily a safety-critical system. The contribution of this thesis is a modelling approach that extends OMG's SoaML and basically relies on collaborations and roles as an abstraction layer above the components. This will allow us to describe SoS at an architectural level. We will also give a formal semantics for our modelling approach which employs hybrid graph-transformation systems. The modelling approach is accompanied by a modular verification scheme that will be able to cope with the complexity constraints implied by the SoS' structural dynamics and size. Building such autonomous systems as SoS without evolution at the architectural level --- i. e. adding and removing of components and services --- is inadequate. Therefore our approach directly supports the modelling and verification of evolution.
In einer verschränkten Lektüre von Curtius, Auerbach und Bachtin macht die Dissertation sichtbar, wie die Autoren mit ihren Arbeiten zur europäischen Literaturgeschichte nach einer ethischen Orientierung in der Krise der Moderne suchen. Ihr Konzept einer philologisch fundierten Geschichtsphilosophie in praktischer Absicht wird sowohl kultur- und theoriegeschichtlich aufbereitet, als auch anhand detaillierter Textanalysen nachvollzogen.
Der Blick auf den geschichtsphilosophischen Aspekt ihrer Forschungsarbeit erweist sich hierbei nicht nur insoweit als fruchtbar, als er sich als Schlüssel offenbart, philologische Mikrologie und breite Zusammenschau sowie ideengeschichtliche und gesellschaftliche Entwicklungen zu verknüpfen. Ihr Ansatz offenbart sich auch als wesentlich differenzierter, als es die gängigen Vorbehalte gegenüber der Geschichtsphilosophie vermuten lassen.
Die Untersuchung erweitert aus diesem Grund den methodischen Diskurshorizont, indem sie die Möglichkeiten einer kritischen Geschichtsphilosophie für gegenwärtige Fragen der Literaturgeschichte neu justiert. Dies geschieht über den Zugang so unterschiedlicher Rezeptionen wie der von Anselm Haverkamp, Edward Said, Terry Eagleton und Homi Bhabha, die einen Diskussionsraum eröffnen, welcher den eigenen historischen Standpunkt der Dissertation im Kontext von Postmoderne und Postkolonialismus reflektiert.
Obwohl in den unionalen Verträgen bis heute keine Vorschrift bezüglich einer Staatshaftung der Mitgliedstaaten für Entscheidungen ihrer Gerichte existiert, hat der Gerichtshof der Europäischen Union (EuGH) in einer Reihe von Entscheidungen eine solche Haftung entwickelt und präzisiert. Die vorliegende Arbeit analysiert eingehend diese Rechtsprechung mitsamt den sich daraus ergebenden facettenreichen Rechtsfragen. Im ersten Kapitel widmet sich die Arbeit der historischen Entwicklung der unionsrechtlichen Staatshaftung im Allgemeinen, ausgehend von dem bekannten Francovich-Urteil aus dem Jahr 1991. Sodann werden im zweiten Kapitel die zur Haftung für judikatives Unrecht grundlegenden Entscheidungen in den Rechtssachen Köbler und Traghetti vorgestellt. In dem sich anschließenden dritten Kapitel wird der Rechtscharakter der unionsrechtlichen Staatshaftung – einschließlich der Frage einer Subsidiarität des unionsrechtlichen Anspruchs gegenüber bestehenden nationalen Staatshaftungsansprüchen – untersucht. Das vierte Kapitel widmet sich der Frage, ob eine unionsrechtliche Staatshaftung für judikatives Unrecht prinzipiell anzuerkennen ist, wobei die wesentlichen für und gegen eine solche Haftung sprechenden Argumente ausführlich behandelt und bewertet werden. Im fünften Kapitel werden die im Zusammenhang mit den unionsrechtlichen Haftungsvoraussetzungen stehenden Probleme der Haftung für letztinstanzliche Gerichtsentscheidungen detailliert erörtert. Zugleich wird der Frage nachgegangen, ob eine Haftung für fehlerhafte unterinstanzliche Gerichtsentscheidungen zu befürworten ist. Das sechste Kapitel befasst sich mit der Ausgestaltung der unionsrechtlichen Staatshaftung für letztinstanzliche Gerichtsentscheidungen durch die Mitgliedstaaten, wobei u.a. zur Anwendbarkeit der deutschen Haftungsprivilegien bei judikativem Unrecht auf den unionsrechtlichen Staatshaftungsanspruch Stellung genommen wird. Im letzten Kapitel wird der Frage nachgegangen, ob der EuGH überhaupt über eine Kompetenz zur Schaffung der Staatshaftung für letztinstanzliche Gerichtsentscheidungen verfügte. Abschließend werden die wichtigsten Ergebnisse der Arbeit präsentiert und ein Ausblick auf weitere mögliche Auswirkungen und Entwicklungen der unionsrechtlichen Staatshaftung für judikatives Unrecht gegeben.
Hyperspectral remote sensing of the spatial and temporal heterogeneity of low Arctic vegetation
(2019)
Arctic tundra ecosystems are experiencing warming twice the global average and Arctic vegetation is responding in complex and heterogeneous ways. Shifting productivity, growth, species composition, and phenology at local and regional scales have implications for ecosystem functioning as well as the global carbon and energy balance. Optical remote sensing is an effective tool for monitoring ecosystem functioning in this remote biome. However, limited field-based spectral characterization of the spatial and temporal heterogeneity limits the accuracy of quantitative optical remote sensing at landscape scales. To address this research gap and support current and future satellite missions, three central research questions were posed:
• Does canopy-level spectral variability differ between dominant low Arctic vegetation communities and does this variability change between major phenological phases?
• How does canopy-level vegetation colour images recorded with high and low spectral resolution devices relate to phenological changes in leaf-level photosynthetic pigment concentrations?
• How does spatial aggregation of high spectral resolution data from the ground to satellite scale influence low Arctic tundra vegetation signatures and thereby what is the potential of upcoming hyperspectral spaceborne systems for low Arctic vegetation characterization?
To answer these questions a unique and detailed database was assembled. Field-based canopy-level spectral reflectance measurements, nadir digital photographs, and photosynthetic pigment concentrations of dominant low Arctic vegetation communities were acquired at three major phenological phases representing early, peak and late season. Data were collected in 2015 and 2016 in the Toolik Lake Research Natural Area located in north central Alaska on the North Slope of the Brooks Range. In addition to field data an aerial AISA hyperspectral image was acquired in the late season of 2016. Simulations of broadband Sentinel-2 and hyperspectral Environmental and Mapping Analysis Program (EnMAP) satellite reflectance spectra from ground-based reflectance spectra as well as simulations of EnMAP imagery from aerial hyperspectral imagery were also obtained.
Results showed that canopy-level spectral variability within and between vegetation communities differed by phenological phase. The late season was identified as the most discriminative for identifying many dominant vegetation communities using both ground-based and simulated hyperspectral reflectance spectra. This was due to an overall reduction in spectral variability and comparable or greater differences in spectral reflectance between vegetation communities in the visible near infrared spectrum.
Red, green, and blue (RGB) indices extracted from nadir digital photographs and pigment-driven vegetation indices extracted from ground-based spectral measurements showed strong significant relationships. RGB indices also showed moderate relationships with chlorophyll and carotenoid pigment concentrations. The observed relationships with the broadband RGB channels of the digital camera indicate that vegetation colour strongly influences the response of pigment-driven spectral indices and digital cameras can track the seasonal development and degradation of photosynthetic pigments.
Spatial aggregation of hyperspectral data from the ground to airborne, to simulated satel-lite scale was influenced by non-photosynthetic components as demonstrated by the distinct shift of the red edge to shorter wavelengths. Correspondence between spectral reflectance at the three scales was highest in the red spectrum and lowest in the near infra-red. By artificially mixing litter spectra at different proportions to ground-based spectra, correspondence with aerial and satellite spectra increased. Greater proportions of litter were required to achieve correspondence at the satellite scale.
Overall this thesis found that integrating multiple temporal, spectral, and spatial data is necessary to monitor the complexity and heterogeneity of Arctic tundra ecosystems. The identification of spectrally similar vegetation communities can be optimized using non-peak season hyperspectral data leading to more detailed identification of vegetation communities. The results also highlight the power of vegetation colour to link ground-based and satellite data. Finally, a detailed characterization non-photosynthetic ecosystem components is crucial for accurate interpretation of vegetation signals at landscape scales.
Business process management is an acknowledged asset for running an organization in a productive and sustainable way. One of the most important aspects of business process management, occurring on a daily basis at all levels, is decision making. In recent years, a number of decision management frameworks have appeared in addition to existing business process management systems. More recently, Decision Model and Notation (DMN) was developed by the OMG consortium with the aim of complementing the widely used Business Process Model and Notation (BPMN). One of the reasons for the emergence of DMN is the increasing interest in the evolving paradigm known as the separation of concerns. This paradigm states that modeling decisions complementary to processes reduces process complexity by externalizing decision logic from process models and importing it into a dedicated decision model. Such an approach increases the agility of model design and execution. This provides organizations with the flexibility to adapt to the ever increasing rapid and dynamic changes in the business ecosystem. The research gap, identified by us, is that the separation of concerns, recommended by DMN, prescribes the externalization of the decision logic of process models in one or more separate decision models, but it does not specify this can be achieved.
The goal of this thesis is to overcome the presented gap by developing a framework for discovering decision models in a semi-automated way from information about existing process decision making. Thus, in this thesis we develop methodologies to extract decision models from: (1) control flow and data of process models that exist in enterprises; and (2) from event logs recorded by enterprise information systems, encapsulating day-to-day operations. Furthermore, we provide an extension of the methodologies to discover decision models from event logs enriched with fuzziness, a tool dealing with partial knowledge of the process execution information. All the proposed techniques are implemented and evaluated in case studies using real-life and synthetic process models and event logs. The evaluation of these case studies shows that the proposed methodologies provide valid and accurate output decision models that can serve as blueprints for executing decisions complementary to process models. Thus, these methodologies have applicability in the real world and they can be used, for example, for compliance checks, among other uses, which could improve the organization's decision making and hence it's overall performance.
One third of the world's population lives in areas where earthquakes causing at least slight damage are frequently expected. Thus, the development and testing of global seismicity models is essential to improving seismic hazard estimates and earthquake-preparedness protocols for effective disaster-risk mitigation. Currently, the availability and quality of geodetic data along plate-boundary regions provides the opportunity to construct global models of plate motion and strain rate, which can be translated into global maps of forecasted seismicity. Moreover, the broad coverage of existing earthquake catalogs facilitates in present-day the calibration and testing of global seismicity models. As a result, modern global seismicity models can integrate two independent factors necessary for physics-based, long-term earthquake forecasting, namely interseismic crustal strain accumulation and sudden lithospheric stress release.
In this dissertation, I present the construction of and testing results for two global ensemble seismicity models, aimed at providing mean rates of shallow (0-70 km) earthquake activity for seismic hazard assessment. These models depend on the Subduction Megathrust Earthquake Rate Forecast (SMERF2), a stationary seismicity approach for subduction zones, based on the conservation of moment principle and the use of regional "geodesy-to-seismicity" parameters, such as corner magnitudes, seismogenic thicknesses and subduction dip angles. Specifically, this interface-earthquake model combines geodetic strain rates with instrumentally-recorded seismicity to compute long-term rates of seismic and geodetic moment. Based on this, I derive analytical solutions for seismic coupling and earthquake activity, which provide this earthquake model with the initial abilities to properly forecast interface seismicity. Then, I integrate SMERF2 interface-seismicity estimates with earthquake computations in non-subduction zones provided by the Seismic Hazard Inferred From Tectonics based on the second iteration of the Global Strain Rate Map seismicity approach to construct the global Tectonic Earthquake Activity Model (TEAM). Thus, TEAM is designed to reduce number, and potentially spatial, earthquake inconsistencies of its predecessor tectonic earthquake model during the 2015-2017 period. Also, I combine this new geodetic-based earthquake approach with a global smoothed-seismicity model to create the World Hybrid Earthquake Estimates based on Likelihood scores (WHEEL) model. This updated hybrid model serves as an alternative earthquake-rate approach to the Global Earthquake Activity Rate model for forecasting long-term rates of shallow seismicity everywhere on Earth.
Global seismicity models provide scientific hypotheses about when and where earthquakes may occur, and how big they might be. Nonetheless, the veracity of these hypotheses can only be either confirmed or rejected after prospective forecast evaluation. Therefore, I finally test the consistency and relative performance of these global seismicity models with independent observations recorded during the 2014-2019 pseudo-prospective evaluation period. As a result, hybrid earthquake models based on both geodesy and seismicity are the most informative seismicity models during the testing time frame, as they obtain higher information scores than their constituent model components. These results support the combination of interseismic strain measurements with earthquake-catalog data for improved seismicity modeling. However, further prospective evaluations are required to more accurately describe the capacities of these global ensemble seismicity models to forecast longer-term earthquake activity.
Climatic variations and human activity now and increasingly in the future cause land cover changes and introduce perturbations in the terrestrial carbon reservoirs in vegetation, soil and detritus. Optical remote sensing and in particular Imaging Spectroscopy has shown the potential to quantify land surface parameters over large areas, which is accomplished by taking advantage of the characteristic interactions of incident radiation and the physico-chemical properties of a material. The objective of this thesis is to quantify key soil parameters, including soil organic carbon, using field and Imaging Spectroscopy. Organic carbon, iron oxides and clay content are selected to be analyzed to provide indicators for ecosystem function in relation to land degradation, and additionally to facilitate a quantification of carbon inventories in semiarid soils. The semiarid Albany Thicket Biome in the Eastern Cape Province of South Africa is chosen as study site. It provides a regional example for a semiarid ecosystem that currently undergoes land changes due to unadapted management practices and furthermore has to face climate change induced land changes in the future. The thesis is divided in three methodical steps. Based on reflectance spectra measured in the field and chemically determined constituents of the upper topsoil, physically based models are developed to quantify soil organic carbon, iron oxides and clay content. Taking account of the benefits limitations of existing methods, the approach is based on the direct application of known diagnostic spectral features and their combination with multivariate statistical approaches. It benefits from the collinearity of several diagnostic features and a number of their properties to reduce signal disturbances by influences of other spectral features. In a following step, the acquired hyperspectral image data are prepared for an analysis of soil constituents. The data show a large spatial heterogeneity that is caused by the patchiness of the natural vegetation in the study area that is inherent to most semiarid landscapes. Spectral mixture analysis is performed and used to deconvolve non-homogenous pixels into their constituent components. For soil dominated pixels, the subpixel information is used to remove the spectral influence of vegetation and to approximate the pure spectral signature coming from the soil. This step is an integral part when working in natural non-agricultural areas where pure bare soil pixels are rare. It is identified as the largest benefit within the multi-stage methodology, providing the basis for a successful and unbiased prediction of soil constituents from hyperspectral imagery. With the proposed approach it is possible (1) to significantly increase the spatial extent of derived information of soil constituents to areas with about 40 % vegetation coverage and (2) to reduce the influence of materials such as vegetation on the quantification of soil constituents to a minimum. Subsequently, soil parameter quantities are predicted by the application of the feature-based soil prediction models to the maps of locally approximated soil signatures. Thematic maps showing the spatial distribution of the three considered soil parameters in October 2009 are produced for the Albany Thicket Biome of South Africa. The maps are evaluated for their potential to detect erosion affected areas as effects of land changes and to identify degradation hot spots in regard to support local restoration efforts. A regional validation, carried out using available ground truth sites, suggests remaining factors disturbing the correlation of spectral characteristics and chemical soil constituents. The approach is developed for semiarid areas in general and not adapted to specific conditions in the study area. All processing steps of the developed methodology are implemented in software modules, where crucial steps of the workflow are fully automated. The transferability of the methodology is shown for simulated data of the future EnMAP hyperspectral satellite. Soil parameters are successfully predicted from these data despite intense spectral mixing within the lower spatial resolution EnMAP pixels. This study shows an innovative approach to use Imaging Spectroscopy for mapping of key soil constituents, including soil organic carbon, for large areas in a non-agricultural ecosystem and under consideration of a partially vegetation coverage. It can contribute to a better assessment of soil constituents that describe ecosystem processes relevant to detect and monitor land changes. The maps further provide an assessment of the current carbon inventory in soils, valuable for carbon balances and carbon mitigation products.
Aufgrund verschiedener wissenschaftlicher Erkenntnisse wird jungen Sporttreibenden vom Gebrauch von Nahrungsergänzungsmitteln (NEM) abgeraten. Diese Dissertation verfolgt vor dem Hintergrund der Theorie der Zielsysteme (TDZ) das Ziel der Erstellung anwendungsorientieren Handlungswissens, anhand dessen Interventionsempfehlungen zur Reduzierung des prävalenten NEM-Konsums im Nachwuchssport ableitbar sind. Insgesamt wurden sechs Untersuchungen durchgeführt. Die Versuchsteilnehmenden absolvierten in sämtlichen Studien eine Variante der lexikalischen Entscheidungsaufgabe. Diese Aufgabe diente der Operationalisierung von automatisch aktivier- und abrufbaren nahrungsergänzungsmittelbezogenen Ziel-Mittel-Relationen.
In einer Stichprobe von Sportstudierenden zeigte sich, dass NEM mit dem Ziel Leistung assoziiert sind (Studie 1). Unter Berücksichtigung des NEM-Konsums wurde dieses Ergebnis für Nachwuchsathletinnen und -athleten aus dem Breitensport repliziert (Studie 2). Zusätzlich konnte in beiden Studien die Bedeutung dieser Ziel-Mittel-Relationen für das Verhalten nachgewiesen werden. In den nachfolgenden Untersuchungen wurden spezifische Veränderungsmechanismen der verhaltensleitenden Ziel-Mittel-Relation aus Leistung und NEM zunächst an Sportstudierenden experimentell evaluiert. Durch das Herausstellen der fehlenden leistungssteigernden Wirkung von NEM konnte diese Zielassoziation nicht modifiziert werden (Studie 3). Das Betonen gesundheitsschädigender Konsequenzen (Studie 4) und das Akzentuieren einer gesunden Ernährung (Studie 5) erwiesen sich demgegenüber als geeignet zur Veränderung der Ziel-Mittel-Relation. Das Herausstellen einer gesunden Ernährung führte deskriptiv bei Nachwuchsathletinnen und -athleten ebenfalls zur Modifikation der Zielassoziation (Studie 6). Die inferenzstatistische Bestätigung der Ergebnisse dieser Studie steht aufgrund der geringen Teststärke der Untersuchung noch aus.
Insgesamt verdeutlichen die Ergebnisse, dass die auf Ebene automatischer Kognitionen bestehende und verhaltensleitende Assoziation des Gebrauchs von NEM mit Leistung durch die Akzentuierung gesundheitlicher Perspektiven experimentell verändert werden kann. Abschließend wird die theoretische und praktische Bedeutung des erstellten Handlungswissen für künftige Interventionsempfehlungen zur Reduzierung des Gebrauchs von NEM diskutiert.
Internalin J (InlJ) gehört zu der Klasse der bakteriellen, cysteinhaltigen (leucine-rich repeat) LRR Proteine. Bei den Internalinen handelt es sich um meist invasions-assoziierte Proteine der Listerien. Die LRR-Domäne von InlJ ist aus 15 regelmäßig wiederkehrenden, stark konservierten Sequenzeinheiten (repeats, 21 Aminosäuren) aufgebaut. Ein interessantes Detail dieses Internalins ist das stark konservierte Cystein innerhalb der repeats. Daraus ergibt sich eine ungewöhnliche Anordnung von 12 Cysteinen in einem Stapel. Die Häufigkeit von Cysteinen in InlJ ist für ein extrazelluläres Protein von L. monocytogenes außergewöhnlich, und die Frage nach ihrer Funktion daher umso brennender. Im Vergleich zum ubiquitären Vorkommen der sogenannten repeat-Proteine in der Natur sind Studien zu ihrer Stabilität und Faltung nicht äquivalent vertreten. Die zentrale Eigenschaft der repeat-Proteine ist ihr modularer Aufbau, der durch einfache Topologie gekennzeichnet ist und auf kurzreichenden Wechselwirkungen basiert. Diese Topologie macht repeat-Proteine zu idealen Modellproteinen, um die stabilitätsrelevanten Wechselwirkungen zu separieren und zuzuordnen. In der vorliegenden Arbeit wurde die Faltung und Entfaltung von InlJ umfassend charakterisiert und die Relevanz der Cysteine näher beleuchtet. Die spektroskopische Charakterisierung von InlJ zeigte, dass dessen Faltungszustand durch zwei Tryptophane im N- und C-Terminus fluoreszenzspektroskopisch gut zugänglich ist. Die thermodynamische Stabilität wurde mittels fluoreszenz-detektierten, Guanidiniumchlorid-induzierten Gleichgewichtsexperimenten bestimmt. Um die kinetischen Eigenschaften von InlJ zu erfassen, wurden die Faltungs- sowie die Entfaltungsreaktion spektroskopisch untersucht. Die Identifizierung der produktiven Faltungsreaktion war lediglich durch die Anwendung des reversen Doppelsprungexperiments möglich. Die Auswertung erfolgte nach dem Zweizustandsmodell, wonach die Faltung dem „Alles-oder-Nichts“ Prinzip folgt. Die Gültigkeit dieser Annahme wurde durch die kinetische Charakterisierung bestätigt. Es wurde sowohl in den Gleichgewichtsexperimenten als auch in den kinetisch erhaltenen Daten eine hohe freie Stabilisierungsenthalpie festgestellt. Die hohe Stabilität von InlJ geht mit hoher Kooperativität einher. Die kinetischen Daten zeigen zudem, dass die hohe Kooperativität hauptsächlich der Faltungsreaktion entstammt. Der Tanford-Wert von 0.93 impliziert, dass die Oberflächenänderung während der Faltung bereits zum größten Teil erfolgt ist, bevor der Übergangszustand ausgebildet wurde. Direkte strukturelle Informationen über den Übergangszustand wurden mit Hilfe von Mutationsstudien erhalten. Zu diesem Zweck wurden 12 der 14 Cysteine gegen ein Alanin ausgetauscht. Die repeats 1 bis 11 von InlJ beinhalten jeweils ein Cystein, deren Anordnung eine Leiter ergibt. Deren Substitutionen haben einen vergleichbar destabilisierenden Effekt auf InlJ von durchschnittlich 4.8 kJ/mol. Die Verlangsamung der Faltung deutet daraufhin, dass die Interaktionen der repeats 5 bis 11 im Übergangszustand bereits voll ausgebildet sind. Demnach liegt bei InlJ ein zentraler Faltungsnukleus vor. Im Rahmen dieser Promotionsarbeit wurde eine hohe Stabilität und ein stark-kooperatives Verhalten für das extrazelluläre Protein InlJ beobachtet. Diese Erkenntnisse könnten wichtige Beiträge zur Entwicklung artifizieller repeat-Proteine leisten, deren Verwendung sich stetig ausweitet.
Ausgehend von der Beobachtung, dass die aktuelle Digitalisierungsforschung die Ambivalenz der Digitalisierung zwar erkennt, aber nicht zum Gegenstand ihrer Analysen macht, fokussiert die vorliegende kumulative Dissertation auf die ambivalente Dichotomie aus Potenzialen und Problemen, die mit digitalen Transformationen von Organisationen einhergeht. Entlang von sechs Publikationen wird mit einem systemtheoretischen Blick auf Organisationen die spannungsvolle Dichotomie hinsichtlich dreier ambivalenter Verhältnisse aufgezeigt: Erstens wird in Bezug auf das Verhältnis von Digitalisierung und Postbürokratie deutlich, dass digitale Transformationen das Potenzial aufweisen, postbürokratische Arbeitsweisen zu erleichtern. Parallel ergibt sich das Problem, dass auf Konsens basierende postbürokratische Strukturen Digitalisierungsinitiativen erschweren, da diese auf eine Vielzahl von Entscheidungen angewiesen sind. Zweitens zeigt sich mit Blick auf das ambivalente Verhältnis von Digitalisierung und Vernetzung, dass einerseits organisationsweite Kooperation ermöglicht wird, während sich andererseits die Gefahr digitaler Widerspruchskommunikation auftut. Beim dritten Verhältnis zwischen Digitalisierung und Gender deutet sich das mit neuen digitalen Technologien einhergehende Potenzial für Gender Inklusion an, während zugleich das Problem einprogrammierter Gender Biases auftritt, die Diskriminierungen oftmals verschärfen. Durch die Gegenüberstellung der Potenziale und Probleme wird nicht nur die Ambivalenz organisationaler Digitalisierung analysierbar und verständlich, es stellt sich auch heraus, dass mit digitalen Transformationen einen doppelte Formalisierung einhergeht: Organisationen werden nicht nur mit den für Reformen üblichen Anpassungen der formalen Strukturen konfrontiert, sondern müssen zusätzlich formale Entscheidungen zu Technikeinführung und -beibehaltung treffen sowie formale Lösungen etablieren, um auf unvorhergesehene Potenziale und Probleme reagieren. Das Ziel der Dissertation ist es, eine analytisch generalisierte Heuristik an die Hand zu geben, mit deren Hilfe die Errungenschaften und Chancen digitaler Transformationen identifiziert werden können, während sich parallel ihr Verhältnis zu den gleichzeitig entstehenden Herausforderungen und Folgeproblemen erklären lässt.
Black shales are sedimentary rocks with a high content of organic carbon, which leads to a dark grayish to black color. Due to their potential to contain oil or gas, black shales are of great interest for the support of the worldwide energy supply. An integrated seismic investigation of the Lower Palaeozoic black shales was carried out at the Danish island Bornholm to locate the shallow-lying Alum Shale layer and its surrounding formations and to characterize its potential as a source rock. Therefore, two seismic experiments at a total of three crossing profiles were carried out in October 2010 and in June 2012 in the southern part of the island. Two different active measurements were conducted with either a weight drop source or a minivibrator. Additionally, the ambient noise field was recorded at the study location over a time interval of about one day, and also a laboratory analysis of borehole samples was carried out. The seismic profiles were positioned as close as possible to two scientific boreholes which were used for comparative purposes. The seismic field data was analyzed with traveltime tomography, surface wave inversion and seismic interferometry to obtain the P-wave and S-wave velocity models of the subsurface. The P-wave velocity models which were determined for all three profiles clearly locate the Alum Shale layer between the Komstad Limestone layer on top and the Læså Sandstone Formation at the base of the models. The black shale layer has P-wave velocities around 3 km/s which are lower compared to the adjacent formations. Due to a very good agreement of the sonic log and the vertical velocity profiles of the two seismic lines, which are directly crossing the borehole where the sonic log was conducted, the reliability of the traveltime tomography is proven. A correlation of the seismic velocities with the content of organic carbon is an important task for the characterization of the reservoir properties of a black shale formation. It is not possible without calibration but in combination with a full 2D tomographic image of the subsurface it gives the subsurface distribution of the organic material. The S-wave model obtained with surface wave inversion of the vibroseis data of one of the profiles images the Alum Shale layer also very well with S-wave velocities around 2 km/s. Although individual 1D velocity models for each of the source positions were determined, the subsurface S-wave velocity distribution is very uniform with a good match between the single models. A really new approach described here is the application of seismic interferometry to a really small study area and a quite short time interval. Also new is the selective procedure of only using time windows with the best crosscorrelation signals to achieve the final interferograms. Due to the small scale of the interferometry even P-wave signals can be observed in the final crosscorrelations. In the laboratory measurements the seismic body waves were recorded for different pressure and temperature stages. Therefore, samples of different depths of the Alum Shale were available from one of the scientific boreholes at the study location. The measured velocities have a high variance with changing pressure or temperature. Recordings with wave propagation both parallel and perpendicular to the bedding of the samples reveal a great amount of anisotropy for the P-wave velocity, whereas the S-wave velocity is almost independent of the wave direction. The calculated velocity ratio is also highly anisotropic with very low values for the perpendicular samples and very high values for the parallel ones. Interestingly, the laboratory velocities of the perpendicular samples are comparable to the velocities of the field experiments indicating that the field measurements are sensitive to wave propagation in vertical direction. The velocity ratio is also calculated with the P-wave and S-wave velocity models of the field experiments. Again, the Alum Shale can be clearly separated from the adjacent formations because it shows overall very low vP/vS ratios around 1.4. The very low velocity ratio indicates the content of gas in the black shale formation. With the combination of all the different methods described here, a comprehensive interpretation of the seismic response of the black shale layer can be made and the hydrocarbon source rock potential can be estimated.
Durch die anthropogene Nutzung sind viele Auen in Mitteleuropa verändert worden, wobei insbesondere die Retentionsflächen stark verringert wurden. Während Auen seit längerem im Fokus der wissenschaftlichen Bearbeitung stehen, gibt es bisher große Wissensdefizite in der Frage der Auenreaktivierungen. Zum einen sind derartige Projekte bisher kaum verwirklicht und zum anderen ist ein langfristiges Monitoring notwendig, um die Anpassung von Biozönosen an die veränderten Standortbedingungen beobachten zu können. Um die Folgen derartiger Eingriffe zu analysieren, bieten sich computergestützte Modellierungen der Landschaftsentwicklung an, wie sie in der vorliegenden Arbeit verwirklicht wurden. Ziel der Arbeit war, mit Hilfe eines Geografischen Informationssystems (GIS) das Entwicklungspotenzial der Landschaft bei verschiedenen Rückdeichungsvarianten auf der Ebene der Biotoptypen darzustellen. Dabei ging es nicht um die Erstellung eines allgemein gültigen Auenmodells sondern um die Erarbeitung eines Modells für einen konkreten Anwendungsfall. Der erarbeitete Ansatz sollte zudem für die landschaftsplanerische Praxis geeignet sein. Als Beispielgebiete wurden Flächen an der Mittleren Elbe bei Rogätz und Sandau, beide im nördlichen Teil von Sachsen-Anhalt, ausgewählt. Die vorliegende Arbeit gliedert sich in zwei Teile. Im ersten Teil werden Erhebungen und Auswertungen als Grundlage der Modellentwicklung dargestellt. Dazu wurden die Biotoptypen der Beispielgebiete flächendeckend erhoben und mit punktuellen Vegetationserhebungen ergänzt. Aus dem Forschungsprojekt "Rückgewinnung von Retentionsflächen und Altauenreaktivierung an der Mittleren Elbe in Sachsen-Anhalt" des Bundesministeriums für Bildung und Forschung (BMBF) standen standortökologische Daten der Hydrologie und Bodenkunde zur Verfügung. Ziel der Auswertung war, Schlüsselfaktoren für Hydrologie und Bodenbedingungen innerhalb der rezenten Aue zu identifizieren, die zur Ausprägung bestimmter Biotoptypen führen. Im zweiten Teil der Arbeit wurde ein Modell für Biotoptypenpotenziale auf den geplanten Rück–deichungsflächen entwickelt. Das Modell bearbeitet die Datenbank der verwendeten GIS-Dateien, die auf Daten zum Bestand beruht und um solche der Prognose der Standortökologie (Hydrologie und Boden) im Rückdeichungsfalle aus dem BMBF-Projekt erweitert wurde. Weitere Voraussetzung für die Modellierung war die Erarbeitung von Leitbildern, in denen unterschiedliche Nutzungsszenarios für die Landschaft nach Deichrückverlegung hypothetisch festgelegt wurden. Insbesondere die Nutzungsintensität wurde variiert, von einer Variante intensiver land- und forstwirtschaftlicher Nutzung über sogenannte integrierte Entwicklungsziele aus dem BMBF-Projekt bis hin zu einer Variante der Naturschutznutzung. Zusätzlich wurde eine zukünftige Potentielle Natürliche Vegetation modelliert. Eine Überprüfung des Modell fand für den Raum der rezenten Aue in der intensiven Nutzungsvariante statt, die der gegenwärtigen Nutzung am nächsten kommt. Werden Informationen des Bestandsbiotoptyps als Korrekturgröße in das Modell einbezogen, konnte für viele Biotoptypen eine Trefferquote von über 90 % erreicht werden. Bei flächenmäßig weniger bedeutenden Bio–toptypen lag dieser Wert aufgrund der schmaleren Datenbasis zwischen 20 und 40 %. Als Ergebnis liegt für unterschiedliche Deichvarianten und Leitbilder in den Beispielgebieten die Landschaftsentwicklung als Biotoppotenzial vor. Als eine vereinfachte Regionalisierung der punktuellen Vegetationsdaten wurde im Modell geprüft, inwieweit die modellierten Biotopflächen der Charakteristik der pflanzensoziologischen Aufnahmen aus der rezenten Aue entsprechen. In dem Falle wurde die Pflanzengesellschaft der jeweiligen ökologisch im Rahmen der Untersuchung einheitlichen Flächeneinheit zugeordnet. Anteilig lässt sich damit die Biotopprognosefläche pflanzensoziologisch konkretisieren. Die vorliegende Arbeit gehört zu den bisher wenigen Arbeiten, die sich mit den Folgen von Auenreaktivierung auf die Entwicklung der Landschaft auseinandersetzen. Sie zeigt eine Möglichkeit auf, Prognosemodelle für Biotoptypen und Vegetation anhand begrenzter Felduntersuchungen zu entwerfen. Derartige Modelle können zum Verständnis von Eingriffen in den Naturhaushalt, wie sie die Deichrückverlegungen darstellen, beitragen und eine Folgenabschätzung unterstützen.
The thesis assesses the contribution of technology option of Carbon Capture and Sequestration (CCS) to climate change mitigation. CCS means that CO2 is captured at large industrial facilities and sequestered in goelogical structures. The technology uses the endogenous growth model MIND. Herein the various climate change mitigation options of reducing economic growth, increasing energy efficiency, changing the energy mix and CCS are assessed simultaneously. An important question is whether CCS is a temporary or long-term solution. The results show that in the middle of the 21st century CCS has its peak contribution, which allows prolonged use of relatively cheap fossil energy carriers. However, this leads to delayed introduction of renewable energy carriers. The technology path ways are accombined with different costs of climate change mitigation. The use of CCS delays and reduces the costs of climate change mitigation. However, the delayed introduction of renewable energy carriers leads to reduced technological learning, which induces higher costs in the longer term. All in all the temporary use of CCS reduces the costs of climate change mitigation costs. The result is robust, which is tested with various uncertainty analysis.
Data integration aims to combine data of different sources and to provide users with a unified view on these data. This task is as challenging as valuable. In this thesis we propose algorithms for dependency discovery to provide necessary information for data integration. We focus on inclusion dependencies (INDs) in general and a special form named conditional inclusion dependencies (CINDs): (i) INDs enable the discovery of structure in a given schema. (ii) INDs and CINDs support the discovery of cross-references or links between schemas. An IND “A in B” simply states that all values of attribute A are included in the set of values of attribute B. We propose an algorithm that discovers all inclusion dependencies in a relational data source. The challenge of this task is the complexity of testing all attribute pairs and further of comparing all of each attribute pair's values. The complexity of existing approaches depends on the number of attribute pairs, while ours depends only on the number of attributes. Thus, our algorithm enables to profile entirely unknown data sources with large schemas by discovering all INDs. Further, we provide an approach to extract foreign keys from the identified INDs. We extend our IND discovery algorithm to also find three special types of INDs: (i) Composite INDs, such as “AB in CD”, (ii) approximate INDs that allow a certain amount of values of A to be not included in B, and (iii) prefix and suffix INDs that represent special cross-references between schemas. Conditional inclusion dependencies are inclusion dependencies with a limited scope defined by conditions over several attributes. Only the matching part of the instance must adhere the dependency. We generalize the definition of CINDs distinguishing covering and completeness conditions and define quality measures for conditions. We propose efficient algorithms that identify covering and completeness conditions conforming to given quality thresholds. The challenge for this task is twofold: (i) Which (and how many) attributes should be used for the conditions? (ii) Which attribute values should be chosen for the conditions? Previous approaches rely on pre-selected condition attributes or can only discover conditions applying to quality thresholds of 100%. Our approaches were motivated by two application domains: data integration in the life sciences and link discovery for linked open data. We show the efficiency and the benefits of our approaches for use cases in these domains.
Untersuchungen an neuartigen sauerstoffsubstituierten Donoren und Akzeptoren für Singulettsauerstoff
(2019)
Im Verlauf dieser Arbeit wurden Aromaten wie Naphthaline und Anthracene mit Singulettsauerstoff, einer reaktiven Form des gewöhnlichen Sauerstoffs, zu sogenannten Endoperoxiden umgesetzt. Die hier eingesetzten Systeme wurden mit funktionellen Gruppen modifiziert, die über eine Sauerstoffbrücke mit dem Aromaten verknüpft sind. Die daraus entstandenen Endoperoxide sind meist besonders labil und konnten in dieser Arbeit isoliert und umfassend untersucht werden.
Hierbei wurde zum einen das Reaktionsverhalten untersucht. Es konnte gezeigt werden, dass die Aromaten in Abhängigkeit ihrer funktionellen Gruppen unterschiedlich schnell mit Singulettsauerstoff reagieren. Die so ermittelten Reaktivitäten wurden zusätzlich durch theoretische Berechnungen gestützt.
Die resultierenden Endoperoxide wurden unter verschiedenen Bedingungen wie erhöhter Temperatur oder einem sauren bzw. basischen Milieu auf ihre Stabilität hin untersucht. Dabei konnte gezeigt werden, dass die auf Naphthalinen basierenden Endoperoxiden den gebundenen Singulettsauerstoff in guten Ausbeuten oft schon bei sehr niedrigen Temperaturen (−40 bis 0 °C) freisetzen. Diese Verbindungen können daher als milde Quellen dieser reaktiven Sauerstoffspezies eingesetzt werden. Weiterhin konnten bei den Anthracenendoperoxiden Zerfallsmechanismen aufgeklärt und andere reaktive Sauerstoffspezies wie Wasserstoffperoxid oder Persäuren nachgewiesen werden.
Zu den Modifikationen der Aromaten gehören auch Glucosereste. Dadurch könnten sich die hier hergestellten Endoperoxide als vielversprechende Verbindungen in der Krebstherapie herausstellen, da Krebszellen deutlich stärker als gesunde Zellen kohlenhydratreiche Verbindungen für ihren Stoffwechsel benötigen. Bei der Spaltung von Endoperoxiden mit Glucosesubstituenten werden ebenfalls reaktive Sauerstoffspezies frei, die so zum Zelltod führen könnten.
Business process management is an established technique for business organizations to manage and support their processes. Those processes are typically represented by graphical models designed with modeling languages, such as the Business Process Model and Notation (BPMN).
Since process models do not only serve the purpose of documentation but are also a basis for implementation and automation of the processes, they have to satisfy certain correctness requirements. In this regard, the notion of soundness of workflow nets was developed, that can be applied to BPMN process models in order to verify their correctness. Because the original soundness criteria are very restrictive regarding the behavior of the model, different variants of the soundness notion have been developed for situations in which certain violations are not even harmful.
All of those notions do only consider the control-flow structure of a process model, however. This poses a problem, taking into account the fact that with the recent release and the ongoing development of the Decision Model and Notation (DMN) standard, an increasing number of process models are complemented by respective decision models. DMN is a dedicated modeling language for decision logic and separates the concerns of process and decision logic into two different models, process and decision models respectively.
Hence, this thesis is concerned with the development of decisionaware soundness notions, i.e., notions of soundness that build upon the original soundness ideas for process models, but additionally take into account complementary decision models. Similar to the various notions of workflow net soundness, this thesis investigates different notions of decision soundness that can be applied depending on the desired degree of restrictiveness. Since decision tables are a standardized means of DMN to represent decision logic, this thesis also puts special focus on decision tables, discussing how they can be translated into an unambiguous format and how their possible output values can be efficiently determined.
Moreover, a prototypical implementation is described that supports checking a basic version of decision soundness. The decision soundness notions were also empirically evaluated on models from participants of an online course on process and decision modeling as well as from a process management project of a large insurance company. The evaluation demonstrates that violations of decision soundness indeed occur and can be detected with our approach.
Die Toxizität und Kanzerogenität von rein aromatischen polyzyklischen aromatischen Kohlenwasserstoffen (PAK) ist seit Jahrzehnten bekannt und umfassend erforscht. Die alkylierten PAK (alkPAK) besitzen jedoch aufgrund ihrer Alkylgruppe eine weitere Möglichkeit zur Bioaktivierung und müssen daher gesondert betrachtet werden. Die Alkylgruppe wird zunächst hydroxyliert, anschließend zur Säure oxidiert oder direkt konjugiert. Entstehen hierbei instabile benzylische Sulfokonjugate, so können diese DNA-Addukte bilden und zu Mutationen führen. In Hinblick auf die Bioaktivierung von alkPAK galt es daher zu klären welchen Einfluss die Struktur auf die benzylische Hydroxylierung hat und welche humanen Formen der löslichen Sulfotransferasen besonders an der Umsetzung der alkPAK-Derivate beteiligt sind. Die Untersuchung der Albuminbindung von Schwefelsäureestern sowie ihre Aufnahme in Nierenzellen sollten Aufschluss hinsichtlich möglicher Transportvorgänge geben. Für die in-vivo-Situation wurde weiterhin die Modulation des Metabolismus ausgewählter benzylischer Alkohole durch verschiedene Nahrungsmittelbestandteile, Arzneimittel und Fremdstoffe an Ratten untersucht. Als Biomarker wurden benzylische Carbonsäuren im Urin und die entsprechenden Mercaptursäuren in Urin und Fäzes betrachtet. Zunächst wurde anhand von Inkubationen mit Rattenlebermikrosomen festgestellt, dass insbesondere größere Ringsystemen wie etwa alkylierte Benzo[a]pyrene im Gegensatz zu Methylpyrenen in wesentlich geringerem Umfang zum benzylischen Alkohol umgesetzt werden. Dies wurde auch in Untersuchungen mit humanen Lebermikrosomen bestätigt. Untersuchungen an einzelnen humanen Cytochromen P450 zeigten, dass insbesondere die durch PAK induzierbaren Formen hCYP1A1 und 1B1 hohe Umsatzraten aufwiesen. Die hepatisch exprimierten Formen hCYP1A2 und 3A4 waren jedoch auch zur Bildung der benzylischen Alkohole in der Lage. Für die anschließende Sulfonierung der benzylischen Alkohole wurden besonders hohe Aktivitäten mit den humanen Sulfotransferasen hSULT1A1, 1A2, 1C2 und 1E1 festgestellt. Aufgrund der Enzymexpression und der guten Durchblutung, die eine gute Substratversorgung ermöglicht, ist die Leber als Hauptort der benzylischen Hydroxylierung und Sulfonierung anzusehen. Ergebnisse unserer Arbeitsgruppe zeigen jedoch, dass nach 1-Hydroxymethylpyren-Applikation bei Ratten die Niere die höchste Zahl an DNA-Addukten aufweist. Wegen der Fokussierung der Sulfonierung auf die Leber ist die systemische Verteilung der Schwefelsäureester die einzig plausible Erklärung. So wurde im Rahmen dieser Arbeit eine hochaffine Bindungsstelle für 2-Sulfoxymethylpyren an Albumin beschrieben und die Aufnahme von benzylischen Sulfaten durch die humanen organischen Anionentransporter hOAT1, 3 und 4 in Nierenzellen in vitro gezeigt. Für die in-vivo-Situation wurde der Einfluss von Ethanol, 4-Methylpyrazol, Pentachlorphenol, Quercetin und Disulfiram untersucht. Neben der durch die Detoxifizierung mittels Alkoholdehydrogenase und Aldehyddehydrogenase entstandenen benzylischen Carbonsäure kann als Biomarker die entsprechende Mercaptursäure herangezogen werden. Sie ist ein indirekter Nachweis für die reaktiven und toxischen benzylischen Sulfate der alkPAK. Für die beiden im Tierversuch eingesetzten benzylischen Alkohole (1-Hydroxymethylpyren und 1-Hydroxymethyl-8-methylpyren) konnte sie in Urin und Fäzes nachgewiesen werden. Es wurde jedoch ein deutlicher Unterschied in der gebildeten Menge sowie der Verteilung zwischen Urin und Fäzes für die beiden Mercaptursäuren festgestellt. Hierfür sind wahrscheinlich Unterschiede im Transport der benzylischen Schwefelsäureester sowie der Spezifität der an der Mercaptursäurebildung beteiligten Enzyme verantwortlich. In diesem Zusammenhang konnte gezeigt werden, dass der humane organische Anionentransporter hOAT1 1,8-Dimethylpyrenmercaptursäure nicht und der hOAT3 nur mit niedrigen Umsatzraten transportiert. Bei den Modulatoren zeigte die Gabe der kompetitiven Alkoholdehydrogenase-Hemmstoffe Ethanol und 4-Methylpyrazol die Bedeutung der Alkoholdehydrogenasen für die Entgiftung der benzylischen Alkohole: Die Oxidation zur entsprechenden Carbonsäure war reduziert und die Bildung der Mercaptursäure erhöht. Eine Hemmung der Toxifizierung vermittelt durch Sulfotransferase-Inhibitoren konnte nur für Pentachlorphenol beim Metabolismus des 1-Hydroxymethylpyrens beobachtet werden. Gleichzeitig erwies sich Pentachlorphenol als kompetitiver Alkoholdehydrogenase-Inhibitor, da eine signifikant geminderte Carbonsäureausscheidung zu beobachten war. Bei 1-Hydroxymethyl-8-methylpyren traten diese Effekte nicht auf. Die unterschiedlichen bzw. unterschiedlich starken Effekte der Modulatoren beim Metabolismus der verschiedenen benzylischen Alkohole bestätigen die Beobachtungen aus den in-vitro-Untersuchungen, dass unterschiedliche Enzym- und Transporteraffinitäten und –aktivitäten vorliegen.
Surface displacement at volcanic edifices is related to subsurface processes associated with magma movements, fluid transfers within the volcano edifice and gravity-driven deformation processes. Understanding of associated ground displacements is of importance for assessment of volcanic hazards. For example, volcanic unrest is often preceded by surface uplift, caused by magma intrusion and followed by subsidence, after the withdrawal of magma. Continuous monitoring of the surface displacement at volcanoes therefore might allow the forecasting of upcoming eruptions to some extent. In geophysics, the measured surface displacements allow the parameters of possible deformation sources to be estimated through analytical or numerical modeling. This is one way to improve the understanding of subsurface processes acting at volcanoes. Although the monitoring of volcanoes has significantly improved in the last decades (in terms of technical advancements and number of monitored volcanoes), the forecasting of volcanic eruptions remains puzzling. In this work I contribute towards the understanding of the subsurface processes at volcanoes and thus to the improvement of volcano eruption forecasting. I have investigated the displacement field of Llaima volcano in Chile and of Tendürek volcano in East Turkey by using synthetic aperture radar interferometry (InSAR). Through modeling of the deformation sources with the extracted displacement data, it was possible to gain insights into potential subsurface processes occurring at these two volcanoes that had been barely studied before. The two volcanoes, although of very different origin, composition and geometry, both show a complexity of interacting deformation sources. At Llaima volcano, the InSAR technique was difficult to apply, due to the large decorrelation of the radar signal between the acquisition of images. I developed a model-based unwrapping scheme, which allows the production of reliable displacement maps at the volcano that I used for deformation source modeling. The modeling results show significant differences in pre- and post-eruptive magmatic deformation source parameters. Therefore, I conjecture that two magma chambers exist below Llaima volcano: a post-eruptive deep one and a shallow one possibly due to the pre-eruptive ascent of magma. Similar reservoir depths at Llaima have been confirmed by independent petrologic studies. These reservoirs are interpreted to be temporally coupled. At Tendürek volcano I have found long-term subsidence of the volcanic edifice, which can be described by a large, magmatic, sill-like source that is subject to cooling contraction. The displacement data in conjunction with high-resolution optical images, however, reveal arcuate fractures at the eastern and western flank of the volcano. These are most likely the surface expressions of concentric ring-faults around the volcanic edifice that show low magnitudes of slip over a long time. This might be an alternative mechanism for the development of large caldera structures, which are so far assumed to be generated during large catastrophic collapse events. To investigate the potential subsurface geometry and relation of the two proposed interacting sources at Tendürek, a sill-like magmatic source and ring-faults, I have performed a more sophisticated numerical modeling approach. The optimum source geometries show, that the size of the sill-like source was overestimated in the simple models and that it is difficult to determine the dip angle of the ring-faults with surface displacement data only. However, considering physical and geological criteria a combination of outward-dipping reverse faults in the west and inward-dipping normal faults in the east seem to be the most likely. Consequently, the underground structure at the Tendürek volcano consists of a small, sill-like, contracting, magmatic source below the western summit crater that causes a trapdoor-like faulting along the ring-faults around the volcanic edifice. Therefore, the magmatic source and the ring-faults are also interpreted to be temporally coupled. In addition, a method for data reduction has been improved. The modeling of subsurface deformation sources requires only a relatively small number of well distributed InSAR observations at the earth’s surface. Satellite radar images, however, consist of several millions of these observations. Therefore, the large amount of data needs to be reduced by several orders of magnitude for source modeling, to save computation time and increase model flexibility. I have introduced a model-based subsampling approach in particular for heterogeneously-distributed observations. It allows a fast calculation of the data error variance-covariance matrix, also supports the modeling of time dependent displacement data and is, therefore, an alternative to existing methods.
Core-shell upconversion nanoparticles - investigation of dopant intermixing and surface modification
(2022)
Frequency upconversion nanoparticles (UCNPs) are inorganic nanocrystals capable to up-convert incident photons of the near-infrared electromagnetic spectrum (NIR) into higher energy photons. These photons are re-emitted in the range of the visible (Vis) and even ultraviolet (UV) light. The frequency upconversion process (UC) is realized with nanocrystals doped with trivalent lanthanoid ions (Ln(III)). The Ln(III) ions provide the electronic (excited) states forming a ladder-like electronic structure for the Ln(III) electrons in the nanocrystals. The absorption of at least two low energy photons by the nanoparticle and the subsequent energy transfer to one Ln(III) ion leads to the promotion of one Ln(III) electron into higher excited electronic states. One high energy photon will be emitted during the radiative relaxation of the electron in the excited state back into the electronic ground state of the Ln(III) ion. The excited state electron is the result of the previous absorption of at least two low energy photons.
The UC process is very interesting in the biological/medical context. Biological samples (like organic tissue, blood, urine, and stool) absorb high-energy photons (UV and blue light) more strongly than low-energy photons (red and NIR light). Thanks to a naturally occurring optical window, NIR light can penetrate deeper than UV light into biological samples. Hence, UCNPs in bio-samples can be excited by NIR light. This possibility opens a pathway for in vitro as well as in vivo applications, like optical imaging by cell labeling or staining of specific organic tissue. Furthermore, early detection and diagnosis of diseases by predictive and diagnostic biomarkers can be realized with bio-recognition elements being labeled to the UCNPs. Additionally, "theranostic" becomes possible, in which the identification and the treatment of a disease are tackled simultaneously.
For this to succeed, certain parameters for the UCNPs must be met: high upconversion efficiency, high photoluminescence quantum yield, dispersibility, and dispersion stability in aqueous media, as well as availability of functional groups to introduce fast and easy bio-recognition elements. The UCNPs used in this work were prepared with a solvothermal decomposition synthesis yielding in particles with NaYF4 or NaGdF4 as host lattice. They have been doped with the Ln(III) ions Yb3+ and Er3+, which is only one possible upconversion pair. Their upconversion efficiency and photoluminescence quantum yield were improved by adding a passivating shell to reduce surface quenching.
However, the brightness of core-shell UCNPs stays behind the expectations compared to their bulk material (being at least μm-sized particles). The core-shell structures are not clearly separated from each other, which is a topic in literature. Instead, there is a transition layer between the core and the shell structure, which relates to the migration of the dopants within the host lattice during the synthesis. The ion migration has been examined by time-resolved laser spectroscopy and the interlanthanoid resonance energy transfer (LRET) in the two different host lattices from above. The results are
presented in two publications, which dealt with core-shell-shell structured nanoparticles. The core is doped with the LRET-acceptor (either Nd3+ or Pr3+). The intermediate shell serves as an insulation shell of pure host lattice material, whose shell thickness has been varied within one set of samples having the same composition, so that the spatial separation of LRET-acceptor and -donor changes. The outer shell with the same host lattice is doped with the LRET-donor (Eu3+). The effect of the increasing insulation shell thickness is significant, although the LRET cannot be suppressed completely.
Next to the Ln(III) migration within a host lattice, various phase transfer reactions were investigated in order to subsequently perform surface modifications for bioapplications. One result out of this research has been published using a promising ligand, that equips the UCNP with bio-modifiable groups and has good potential for bio-medical applications. This particular ligand mimics natural occurring mechanisms of mussel protein adhesion and of blood coagulation, which is why the UCNPs are encapsulated very effectively. At the same time, bio-functional groups are introduced. In a proof-of-concept, the encapsulated UCNP has been coupled successfully with a dye (which is representative for a biomarker) and the system’s photoluminescence properties have been investigated.
Complex networks have been successfully employed to represent different levels of biological systems, ranging from gene regulation to protein-protein interactions and metabolism. Network-based research has mainly focused on identifying unifying structural properties, including small average path length, large clustering coefficient, heavy-tail degree distribution, and hierarchical organization, viewed as requirements for efficient and robust system architectures. Existing studies estimate the significance of network properties using a generic randomization scheme - a Markov-chain switching algorithm - which generates unrealistic reactions in metabolic networks, as it does not account for the physical principles underlying metabolism. Therefore, it is unclear whether the properties identified with this generic approach are related to the functions of metabolic networks. Within this doctoral thesis, I have developed an algorithm for mass-balanced randomization of metabolic networks, which runs in polynomial time and samples networks almost uniformly at random. The properties of biological systems result from two fundamental origins: ubiquitous physical principles and a complex history of evolutionary pressure. The latter determines the cellular functions and abilities required for an organism’s survival. Consequently, the functionally important properties of biological systems result from evolutionary pressure. By employing randomization under physical constraints, the salient structural properties, i.e., the smallworld property, degree distributions, and biosynthetic capabilities of six metabolic networks from all kingdoms of life are shown to be independent of physical constraints, and thus likely to be related to evolution and functional organization of metabolism. This stands in stark contrast to the results obtained from the commonly applied switching algorithm. In addition, a novel network property is devised to quantify the importance of reactions by simulating the impact of their knockout. The relevance of the identified reactions is verified by the findings of existing experimental studies demonstrating the severity of the respective knockouts. The results suggest that the novel property may be used to determine the reactions important for viability of organisms. Next, the algorithm is employed to analyze the dependence between mass balance and thermodynamic properties of Escherichia coli metabolism. The thermodynamic landscape in the vicinity of the metabolic network reveals two regimes of randomized networks: those with thermodynamically favorable reactions, similar to the original network, and those with less favorable reactions. The results suggest that there is an intrinsic dependency between thermodynamic favorability and evolutionary optimization. The method is further extended to optimizing metabolic pathways by introducing novel chemically feasibly reactions. The results suggest that, in three organisms of biotechnological importance, introduction of the identified reactions may allow for optimizing their growth. The approach is general and allows identifying chemical reactions which modulate the performance with respect to any given objective function, such as the production of valuable compounds or the targeted suppression of pathway activity. These theoretical developments can find applications in metabolic engineering or disease treatment. The developed randomization method proposes a novel approach to measuring the significance of biological network properties, and establishes a connection between large-scale approaches and biological function. The results may provide important insights into the functional principles of metabolic networks, and open up new possibilities for their engineering.
Text is a ubiquitous entity in our world and daily life. We encounter it nearly everywhere in shops, on the street, or in our flats. Nowadays, more and more text is contained in digital images. These images are either taken using cameras, e.g., smartphone cameras, or taken using scanning devices such as document scanners. The sheer amount of available data, e.g., millions of images taken by Google Streetview, prohibits manual analysis and metadata extraction. Although much progress was made in the area of optical character recognition (OCR) for printed text in documents, broad areas of OCR are still not fully explored and hold many research challenges. With the mainstream usage of machine learning and especially deep learning, one of the most pressing problems is the availability and acquisition of annotated ground truth for the training of machine learning models because obtaining annotated training data using manual annotation mechanisms is time-consuming and costly. In this thesis, we address of how we can reduce the costs of acquiring ground truth annotations for the application of state-of-the-art machine learning methods to optical character recognition pipelines. To this end, we investigate how we can reduce the annotation cost by using only a fraction of the typically required ground truth annotations, e.g., for scene text recognition systems. We also investigate how we can use synthetic data to reduce the need of manual annotation work, e.g., in the area of document analysis for archival material. In the area of scene text recognition, we have developed a novel end-to-end scene text recognition system that can be trained using inexact supervision and shows competitive/state-of-the-art performance on standard benchmark datasets for scene text recognition. Our method consists of two independent neural networks, combined using spatial transformer networks. Both networks learn together to perform text localization and text recognition at the same time while only using annotations for the recognition task. We apply our model to end-to-end scene text recognition (meaning localization and recognition of words) and pure scene text recognition without any changes in the network architecture.
In the second part of this thesis, we introduce novel approaches for using and generating synthetic data to analyze handwriting in archival data. First, we propose a novel preprocessing method to determine whether a given document page contains any handwriting. We propose a novel data synthesis strategy to train a classification model and show that our data synthesis strategy is viable by evaluating the trained model on real images from an archive. Second, we introduce the new analysis task of handwriting classification. Handwriting classification entails classifying a given handwritten word image into classes such as date, word, or number. Such an analysis step allows us to select the best fitting recognition model for subsequent text recognition; it also allows us to reason about the semantic content of a given document page without the need for fine-grained text recognition and further analysis steps, such as Named Entity Recognition. We show that our proposed approaches work well when trained on synthetic data. Further, we propose a flexible metric learning approach to allow zero-shot classification of classes unseen during the network’s training. Last, we propose a novel data synthesis algorithm to train off-the-shelf pixel-wise semantic segmentation networks for documents. Our data synthesis pipeline is based on the famous Style-GAN architecture and can synthesize realistic document images with their corresponding segmentation annotation without the need for any annotated data!
Die Autoren untersuchten mit Hilfe einer Fragebogenstudie das Sexualverhalten von StudentenInnen und KrankenpflegeschülernInnen unter der Bedrohung durch AIDS(n = 593). Als Ergebnis lässt sich festhalten, dass unterschiedliche Personengruppen mit unterschiedlichen Einstellungen, mit unterschiedlichem Wissen über HIV und AIDS, mit unterschiedlichem Sexualverhalten sowie einem unterschiedlichen Grad von persönlicher Betroffenheit auf differenzierte Weise angesprochen und zur Prävention angeleitet werden müssen. Die berufliche Nähe zu HIV und AIDS hat keinen Einfluss auf die sexuellen Einstellungen und Verhaltensweisen. Nur durch eine Selbststeuerung kann einer Gefahrensituation, wie sie eine mögliche HIV-Infektion darstellt, begegnet werden. Von daher muss neben der persönlichen Betroffenheit auch die Einsicht gegeben sein, dass ich mich als Individuum eigenständig vor dieser Gefahr schützen kann. Ferner muss dieses Verhalten in die eigene Lebenswelt eingepasst und von der eigenen sozialen Umgebung getragen werden. Präventionsbemühungen müssen auf kompetenzsteigernde, ressourcenorientierte und differenzierte Maßnahmen setzen. Ansätze von Furchtappellen und Lustfeindlichkeit wirken kontraproduktiv. Eine Beschränkung der Prävention auf individuumzentrierte Maßnahmen ist wenig effektiv, sofern gesellschaftliche und strukturelle Bedingungen ausgeblendet werden. Ziel von Sexualpädagogik und AIDS-Präventionsarbeit muss es daher sein, eine von allen geteilte Kommunikationsstruktur für Intimität zu entwickeln.
The life cycle of higher plants is based on recurring phases of growth and development based on repetitive sequences of cell division, cell expansion and cell differentiation. This dissertation deals with two projects, each of them investigating two different topics that are related to cell expansion. The first project is examining an Arabidopsis thaliana mutant exhibiting overall cell enlargement and the second project is analysing two naturally occurring floral morphs of Amsinckia spectabilis (Boraginaceae) differing (amongst others) in style length and anther heights due to differences in longitudinal cell elongation. The EMS-mutant eop1 was shown to exhibit a petal size increase of 26% caused by cell enlargement. Further phenotypes were detected, such as cotyledon size increase (based on larger cells) as well as increased carpel, sepal, leaf and pollen sizes. Plant height was shown to be increased and more highly branched trichomes explained the hairy eop1 phenotype. Fine mapping revealed the causal SNP to be a C to T transition at the last nucleotide of intron 7 of the INCURVATA11 (ICU11) gene, a 2-oxoglutarate /Fe(II)-dependant dioxygenase, and thus causing missplicing of the mRNA. Two T-DNA insertion lines (icu11-2 & icu11-4) confirmed ICU11 as causal gene by exhibiting increased petal size. A comparison of three icu11 alleles, which possessed different mutation-related changes, either overexpressing ICU11 or modified mRNAs, was the base for investigating the molecular mechanism that underlies the observed phenotype. Different approaches revealed contradictory results regarding ICU11 protein functionality in the icu11 mutants. A complementation assay proved the three mutants to be exchangeable and ICU11 overexpression in the wild-type led to an icu11-like phenotype, arguing for all three icu11 mutants to be GOF mutants. Contradicting this conclusion, the icu11-4 line could be rescued by a genomic ICU11 transgene. A model, based on the assumption that an overexpression of ICU11 is inhibiting the function of the protein, and thus causing the same effect as a LOF protein was proposed. Further, icu11-3 (eop1) mutants were shown to have an increased resistance towards paclobutrazol, a gibberellin (GA) inhibitor and an upregulation of AtGA20ox2, a main GA biosynthesis gene. Additionally, ICU11 subcellular localization was discovered to be cytoplasmic, supporting the assumption, that ICU11 affects GA biosynthesis and overall GA level, possibly explaining the observed (GA-overdose) phenotype.
The second project aimed to identify the genetic base of the S-locus in Amsinckia spectabilis, as the Amsinckia genus represents untypical characteristics for a heterostylous species, such as no obvious self-incompatibility (SI) and the repeated transition towards homostylous and fully selfing variants. The work was based on three Amsinckia spectabilis forms: a heterostylous form, consisting of two floral morphs with reciprocal positioning of sexual organs (S-morph: high anthers and a short style and L-morph: low anthers and a long style), and two homostylous forms, one large-flowered and partially selfing and the other small-flowered and fully selfing. The maintenance of the two floral morphs is genetically based on the S-locus region, containing genes that encode for the morph-specific traits, which are marked by a tight linkage due to suppressed recombination. Natural populations are found to possess a 1:1 S:L morph ratio, that can be explained by predominant disassortative mating of the two morphs, causing the occurrence of the dominant S-allele only in the heterozygous state (heterozygous (Ss) for the S-morph and homozygous recessive (ss) for the L-morph). Investigation of morph-specific phenotypes detected 56% elongated L-morph styles and 58% higher positioned S-morph anthers. Approximately 50% of the observed size differences were explained by an increase in cell elongation. Moreover, additional phenotypes were found, such as 21% enlarged S-morph pollen and no obvious SI, confirmed by hand pollinated seed counts, in vivo pollen tube growth and the development of homozygous dominant SS individuals via selfing. The Amsinckia spec. S-locus was assumed to at least consist of the G- (style length), the A- (anther height) and the P- (pollen size) locus. Comparative Transcriptomics of the two morphs revealed 22 differentially expressed markers that were found to be located within two contigs of a SS individual PacBio genome assembly, allowing the localization of the S-locus to be delimited to a region of approximately 23 Mb. Contradictory to revealed S-loci within the plant kingdom, no strong argument for a present hemizygous region was found to be causal for the suppressed recombination of the S-locus, so that an inversion was assumed to be the causal mechanism.
Als Grundlage vieler statistischer Verfahren wird der Prozess der Entstehung von Daten modelliert, um dann weitere Schätz- und Testverfahren anzuwenden. Diese Arbeit befasst sich mit der Frage, wie diese Spezifikation für parametrische Modelle selbst getestet werden kann. In Erweiterung bestehender Verfahren werden Tests mit festem Kern eingeführt und ihre asymptotischen Eigenschaften werden analysiert. Es wird gezeigt, dass die Bestimmung der kritischen Werte mit mehreren Stichprobenwiederholungsverfahren möglich ist. Von diesen ist eine neue Monte-Carlo-Approximation besonders wichtig, da sie die Komplexität der Berechnung deutlich verringern kann. Ein bedingter Kleinste-Quadrate-Schätzer für nichtlineare parametrische Modelle wird definiert und seine wesentlichen asymptotischen Eigenschaften werden hergeleitet. Sämtliche Versionen der Tests und alle neuen Konzepte wurden in Simulationsstudien untersucht, deren wichtigste Resultate präsentiert werden. Die praktische Anwendbarkeit der Testverfahren wird an einem Datensatz zur Produktwahl dargelegt, der mit multinomialen Logit-Modellen analysiert werden soll.
Carbonfasern haben sich in der Luft- und Raumfahrt etabliert und gewinnen in Alltagsanwendungen wie dem Automobilbereich, Windkraft- und Sportbereich durch ihre hohen Zugfestigkeiten, insbesondere ihrer hohen E-Moduli, und ihrer geringen Dichte immer mehr an Bedeutung. Auf Grund ihrer hohen Kosten, welche sich zur Hälfte aus der Precursorherstellung, inklusive seiner Synthese und seinem Verspinnprozess, dem Lösungsspinnverfahren, ergeben, erhalten zunehmend alternative und schmelzspinnbare Precursoren Interesse. Für die Carbonfaserherstellung wird fast ausschließlich Polyacrylnitril (PAN) verwendet, das vor dem Schmelzen irreversible exotherme Zyklisierungsreaktionen aufweist, welchen sich seine Zersetzung anschließt. Eine Möglichkeit der Reduzierung der Schmelztemperatur von Polymeren ist die Einbringung von Comonomeren zur Erhöhung des freien Volumens und die Reduzierung der intermolekularen Wechselwirkungen als interne Weichmacher. Wie am Fraunhofer IAP gezeigt wurde, kann mittels 2-Methoxyethylacrylat (MEA) die Schmelztemperatur zu neuartigen PAN-basierten Precursoren verringert werden. Um den PAN-co-MEA-Precursor für die nachfolgenden Prozessschritte der Carbonfaserherstellung zu verwenden, müssen die thermoplastischen Fasern in thermisch stabile Fasern ohne thermoplastisches Verhalten überführt werden. Es wurde ein neuer Prozessschritt (Prästabilisierung) eingeführt, welcher unter alkalischen Bedingungen zur Abspaltung der Comonomerseitenkette führt. Neben der Esterhydrolyse finden Reaktionen statt, welche an diesem Material noch nicht hinreichend untersucht wurden. Weiterhin stellt sich die Frage nach der Kinetik der Prästabilisierung und der Ermittlung einer geeigneten Prozessführung.
Hierzu wurde die Prästabilisierung in den Labormaßstab überführt und die möglichen Zusammensetzungen des aus DMSO und einer KOH-Lösung bestehenden Reaktionsmediums evaluiert. Weiterhin wurde die Behandlung bei verschiedenen Prästabilisierungszeiten von maximal 30 min und Temperaturen von 40, 50 und 60 °C durchgeführt, um primär mittels NMR-Spektroskopie die chemischen Strukturänderungen aufzuklären. Die Esterhydrolyse des Comonomers, welche zur Abspaltung des 2-Methoxyethanols führt, wurde mittels 1H-NMR-spektroskopischer Untersuchungen detektiert.
Es wurde ein Modell aufgestellt, das die chemisch-physikalischen Strukturänderungen während der Prästabilisierung aufzeigt. Die zuerst ablaufende Reaktion ist die Esterhydrolyse am Comonomer, welche vom Faserrand nach innen verläuft und durch die Präsenz des DMSO in Kombination mit der KOH-Lösung (Superbase) initiiert wird. Der zeitliche Reaktionsverlauf der Esterhydrolyse kann in drei Bereiche eingeteilt werden. Der erste Bereich ab dem Prästabilisierungsbeginn wird durch die Diffusion der basischen Anionen in die Faser, der zweite Bereich durch die Reaktion an der Estergruppe des Comonomers und der dritte Bereich durch letzte Reaktionen im Faserinneren und diffusiven Prozessen der Produkte und Edukte charakterisiert. Der zweite Bereich kann mit einer Reaktion pseudo 1. Ordnung abgebildet werden, da in diesem Bereich bereits eine ausreichende Diffusion der Edukte in die Faser stattgefunden hat. Bei 50 °C spielt die Diffusion im ersten Bereich im Vergleich zur Reaktion eine untergeordnete Rolle. Mit Erhöhung der Temperatur auf 60 °C kann eine im Verhältnis geringere Diffusions- als Reaktionsgeschwindigkeit beobachtet werden. Die Nebenreaktionen wurden mittels 13C-CP/MAS-NMR-spektroskopischen, elementaranlaytischen Untersuchungen sowie Doppelbrechungsmessungen charakterisiert. Während der alkalischen Esterhydrolyse beginnt die Reduzierung der Nitrilgruppen unter der Bildung von primären Carbonsäureamiden und Carbonsäuren. Zur Beschreibung dieser Umsetzung wurde eine Methode entwickelt, welche die Addition von 13C-CP/MAS-NMR-Spektren der Modellsubstanzen PAN, PAM und PAA beinhaltet. Weitere stattfindende Reaktionen sind die Bildung von konjugierten Doppelbindungen, welche insbesondere auf eine Zyklisierung der Nitrile hinweisen. Die nasschemisch initiierte Zyklisierung der Nitrilgruppen kann zu kürzeren Stabilisierungszeiten und einem besser kontrollierbaren Stabilisierungsprozess durch geringere Wärmefreisetzung und schlussendlich zu einer Kostenersparnis des gesamten Verfahrens führen. Die Umsetzung der Nitrilgruppen konnte mit einer Reaktion pseudo 1. Ordnung gut abgebildet werden. DMSO initiiert die Esterhydrolyse, wobei die KOH-Konzentration einen höheren Einfluss auf die Reaktionsgeschwindigkeit der Ester- und Nitrilhydrolyse als die DMSO-Konzentration besitzt. Beide Reaktionen zeigen eine vergleichbare Abhängigkeit von der Temperatur. Die Erhöhung der Prästabilisierungszeit und der KOH- bzw. DMSO-Konzentration führt zur Migration niedermolekularer Bestandteile des Fasermaterials an die Oberfläche und der Bildung punktueller Ablagerungen bis hin zu miteinander verbundenen Einzelfasern. Eine weitere Erhöhung der Prästabilisierungszeit bzw. der Konzentration führt zu einem steigenden Carbonsäureanteil und zur Quellung des Fasermaterials, wodurch die Ablagerungen in das Reaktionsmedium diffundieren. Die Ablagerungen enthalten Chlor, welches durch den Waschvorgang mit HCl in das Materialsystem gelangt ist und durch Parameteranpassungen reduziert wurde. Die schmelzbaren Fasern konnten durch die Prästabilisierung erfolgreich über eine Kern-Mantel-Struktur in nicht-thermoplastische Fasern überführt werden.
Zur Ermittlung eines geeigneten Prozessfensters für nachfolgende thermische Beanspruchungen der prästabilisierten Fasern wurden drei Kriterien identifiziert, anhand welcher die Evaluation erfolgte. Das erste Kriterium beinhaltet die Notwendigkeit der vollständigen Aufhebung der thermoplastischen Eigenschaft der Fasern. Als zweites Kriterium diente die Fasermorphologie. Anhand von REM-Aufnahmen wurden Faserbündel mit separierten Einzelfasern ohne Ablagerungen für die nachfolgende Stabilisierung ausgewählt. Das dritte Kriterium bezieht sich auf eine möglichst geringe Umsetzung der Nitrilgruppen, um Prästabilisierungsbedingungen mit Nebenreaktionen zu vermeiden.
Aus den Untersuchungen konnte eine Prästabilisierungstemperatur von 60 °C als geeignet identifiziert werden. Weiterhin führen hoch alkalische Zusammensetzungen des Reaktionsmediums mit KOH-Konzentrationen von 1, 1,5 und 2 M, vorzugsweise 1,5 M und 50 vol% DMSO mit Reaktionszeiten von unter 10 min zu geeigneten Fasern. Ein MEA-Anteil unterhalb von 2 mol% bewirkt eine Überführung in die Unschmelzbarkeit. Thermisch stabile und für die nachfolgende Stabilisierung geeignete Fasern besitzen weiterhin 68 – 80 mol% Nitrilgruppen, 20 – 25 mol% Carbonsäuren, bis zu 15 mol% primäre Carbonsäureamide und zyklisierte Strukturen.
Im Landschaftszustand und in der Landschaftsentwicklung kommen funktionale Beziehungen zwischen dem naturbedingten Energie-, Wasser- und Stoffhaushalt einerseits und den Auswirkungen der Landnutzung andererseits zum Ausdruck. Gegenwärtig verändert der globale Anstieg der bodennahen Temperaturen vielerorts den landschaftlichen Energie-, Wasser- und Stoffhaushalt, wobei besonders in Trockengebieten zu erwarten ist, dass dieser Trend in Verbindung mit einer unangepassten Landnutzung das Regenerationsvermögen der Vegetation einschränkt und zur Zerstörung der Bodendecke führt. Für die Mongolei und für benachbarte Gebiete Asiens sind in Szenarien zur globalen Erwärmung hohe Werte des Temperaturanstiegs prognostiziert worden. Eine globale Einschätzung der anthropogen induzierten Bodendegradation hat diese Region als stark oder extrem stark betroffen eingestuft. Vor diesem Hintergrund wurde im Uvs-Nuur-Becken, das im Nordwesten der Mongolei und damit in einer der trockensten Regionen des Landes gelegen ist, untersucht, wie sich der globale Temperaturanstieg auf der lokalen und regionalen Ebene widerspiegelt und wie der Landschaftshaushalt dabei verändert wird. Die Auswirkungen des sommerlichen Witterungsverlaufes auf den Landschaftszustand sind 1997 bis 1999 an einem Transsekt erfasst worden, das sich zwischen dem Kharkhiraa-Gebirge am Westrand des Beckens und dem See Uvs Nuur im Beckeninneren von den Polsterfluren und Matten der alpinen Stufe über die Gebirgswaldsteppe, die Trockensteppe bis zur Halbwüste erstreckt. An neun Messpunkten wurden witterungsklimatische Daten in Verbindung mit Merkmalen der Vegetation, des Bodens und der Bodenfeuchte aufgenommen. Die im Sommer 1998 gewonnenen Messwerte wurden mit Hilfe einer Clusteranalyse gebündelt und verdichtet. Auf dieser Grundlage konnten landschaftliche Zustandsformen inhaltlich gekennzeichnet, zeitlich eingeordnet und durch Zeit-Verhaltens-Modelle (Stacks) abgebildet werden. Aus den Zeit-Verhaltens-Modellen wird ersichtlich, dass man Zustandsformen, in denen die Hitze und die Trockenheit des Sommers 1998 besonders stark zum Ausdruck kommen, an allen Messpunkten beobachten kann, nimmt man die Station auf dem fast 3.000 m hohen Gipfel des Khukh Uul sowie die grundwasserbeeinflusste Station in unmittelbarer Seenähe aus. In ihrer extremen Form sind Trockenperioden jedoch nur im Beckeninneren und am Fuß der Randgebirge, also in der Halbwüste, in der Trockensteppe und in der Wiesensteppe aufgetreten. Im Bergwald sowie im Bereich der alpinen Matten und Polsterfluren fehlen sie. Am stärksten sind die grundwasserfreien Bereiche der Halbwüste von der Hitze und Niederschlagsarmut des Sommers 1998 betroffen. An vier Fünfteln der Tage des Beobachtungszeitraumes herrscht an diesem Messpunkt extreme Trockenheit. Es fällt entweder gar kein Niederschlag oder nur so wenig, dass der seit dem Frühjahr erschöpfte Bodenwasservorrat nicht aufgefüllt wird. Das Verhältnis zwischen Niederschlag und potenzieller Verdunstung liegt hier bei 1:12. In der Halbwüste zeichnet sich eine fortschreitende Desertifikation ab, zumal hier eine nichtangepasste Weidenutzung dominiert, in der Ziegen eine immer größere Rolle spielen. Dies gilt insbesondere für Bereiche in Siedlungsnähe. Örtlich ist auch der Bestand der Trockensteppe gefährdet, die sich an die Halbwüste zum Beckenrand hin anschließt. Hier ist nicht nur die Viehdichte am höchsten, sondern hier werden auch die meisten unbefestigten Fahrwege wild angelegt und die Bodendecke damit zerstört. Dies kann im Endeffekt zu einem Übergreifen von Prozessen der Desertifikation führen. Aus methodischer Sicht zeigt sich, dass die Kennzeichnung landschaftlicher Zustandsformen durch Zeit-Verhaltens-Modelle die Ermittlung der Auswirkungen von Witterung und Klima auf den Landschaftszustand erleichtert, da sie deren Aussage konzentriert. Zur Interpretation der Ergebnisse ist jedoch ein Rückgriff auf die beschreibende Darstellung der Messwerte notwendig. Die im westlichen Uvs-Nuur-Becken und seinen Randgebirgen angewandte Verfahrensweise ermöglicht es, globale Aussagen zur globalen Erwärmung der Kontinente regional oder lokal zu überprüfen und zu untersetzen."
The Southern Central Andes (33°-36°S) are an excellent natural laboratory to study orogenic deformation processes, where boundary conditions, such as the geometry of the subducted plate, impose an important control on the evolution of the orogen. On the other hand, the South American plate presents a series of heterogeneities that additionally impart control on the mode of deformation. This thesis aims to test the control of this last factor over the construction of the Cenozoic Andean orogenic system.
From the integration of surface and subsurface information in the southern area (34-36°S), the evolution of Andean deformation over the steeply dipping subduction segment was studied. A structural model was developed evaluating the stress state from the Miocene to the present-day and its influence in the migration of magmatic fluids and hydrocarbons. Based on these data, together with the data generated by other researchers in the northern zone of the study area (33-34°S), geodynamic numerical modeling was performed to test the hypothesis of the decisive role of upper-plate heterogeneities in the Andean evolution. Geodynamic codes (LAPEX-2D and ASPECT) which simulate the behavior of materials with elasto-visco-plastic rheologies under deformation, were used. The model results suggest that upper-plate contractional deformation is significantly controlled by the strength of the lithosphere, which is defined by the composition of the upper and lower crust, and by the proportion of lithospheric mantle, which in turn is determined by previous tectonic events. In addition, the previous regional tectono-magmatic events also defined the composition of the crust and its geometry, which is another factor that controls the localization of deformation. Accordingly, with more felsic lower crustal composition, the deformation follows a pure-shear mode, while more mafic compositions induce a simple-shear deformation mode. On the other hand, it was observed that initial lithospheric thickness may fundamentally control the location of deformation, with zones characterized by thin lithosphere are prone to concentrate it. Finally, it was found that an asymmetric lithosphere-astenosphere boundary resulting from corner flow in the mantle wedge of the eastward-directed subduction zone tends to generate east-vergent detachments.
Sin pragmática no sería posible la comunicación, puesto que no podríamos interpretar enunciados lingüísticos. A cualquier aprendiente de una lengua que no domina, no le basta con ser competente lingüísticamente, puesto que su fin es comunicarse con otras personas y en contextos determinados. Solo una enseñanza que facilite la habilidad de producir y comprender enunciados para realizar actos de lengua, seleccionando los más apropiados para un contexto determinado, podrá preciarse de ser eficiente.
El trabajo que aquí se presenta pretende dar a conocer a la comunidad científica y, en especial, a los y las involucradas directa e indirectamente en el proceso de enseñanza, el concepto de pragmática verbal y contrastarlo con otros como gramática, cultura o interculturalidad, así como concienciarlos de la importancia y de la necesidad imperiosa del establecimiento de la pragmática como disciplina relevante en el proceso comunicativo y, en especial, de su inclusión sistemática y manifiesta en los libros de texto de español como lengua extranjera elaborados para el contexto escolar. Para ello se investiga la presencia de elementos pragmáticos y el fomento de la competencia pragmática en libros de texto para principiantes, por ser estos el material utilizado por excelencia en las escuelas y por su relevancia a la hora de especificar contenidos, tipo de progresión y metodología.
Cyanobacteria are an abundant bacterial group and are found in a variety of ecological niches all around the globe. They can serve as a real threat for fish or mammals and can restrict the use of lakes or rivers for recreational purposes or as a source of drinking water, when they form blooms. One of the most abundant bloom-forming cyanobacteria is Microcystis aeruginosa.
In the first part of the study, the role and possible dynamics of RubisCO in M. aeruginosa during high-light irradiation were examined. Its response was analyzed on the protein and peptide level via immunoblotting, immunofluorescence microscopy and with high performance liquid chromatography (HPLC). It was revealed that large amounts of RubisCO were located outside of carboxysomes under the applied high light stress. RubisCO aggregated mainly underneath the cytoplasmic membrane. There it forms a putative Calvin-Benson-Bassham (CBB) super complex together with other enzymes of photosynthesis. This complex could be part of an alternative carbon-concentrating mechanism (CCM) in M. aeruginosa, which enables a faster, and energy saving adaptation to high light stress of the whole bloom.
Furthermore, the re-localization of RubisCO was delayed in the microcystin-deficient mutant ΔmcyB and RubisCO was more evenly distributed over the cell in comparison to the wild type. Since ΔmcyB is not harmed in its growth, possibly other produced cyanopeptides as aeruginosin or cyanopeptolin also play a role in the stabilization of RubisCO and the putative CBB complex, especially in the microcystin-free mutant.
In the second part of this work, the possible role of microcystin as an extracellular signaling peptide during the diurnal cycle was studied. HPLC analysis showed a strong increase of extracellular microcystin in the wild type when the population entered nighttime and it resumed into the next day as well. Together with the increase of extracellular microcystin, a strong decrease of protein-bound intracellular microcystin was observed via immunoblot analysis. Interestingly, the signal of the large subunit of RubisCO (RbcL) also diminished when high amounts of microcystin were present in the surrounding medium. Microcystin addition experiments to M. aeruginosa WT and ΔmcyB cultures support this observation, since the immunoblot signal of both subunits of RubisCO and CcmK, a shell protein of carboxysomes, diminished after the addition of microcystin. In addition, the fluctuation of cyanopeptolin during the diurnal cycle indicates a more prominent role of other cyanopeptides besides microcystin as a signaling peptide, intracellularly as well as extracellularly.
Actin-based directional motility is important for embryonic development, wound healing, immune responses, and development of tissues. Actin and myosin are essential players in this process that can be subdivided into protrusion, adhesion, and traction. Protrusion is the forward movement of the membrane at the leading edge of the cell. Adhesion is required to enable movement along a substrate, and traction finally leads to the forward movement of the entire cell body, including its organelles. While actin polymerization is the main driving force in cell protrusions, myosin motors lead to the contraction of the cell body. The goal of this work was to study the regulatory mechanisms of the motile machinery by selecting a representative key player for each stage of the signaling process: the regulation of Arp2/3 activity by WASP (actin system), the role of cGMP in myosin II assembly (myosin system), and the influence of phosphoinositide signaling (upstream receptor pathway). The model organism chosen for this work was the social ameba Dictyostelium discoideum, due to the well-established knowledge of its cytoskeletal machinery, the easy handling, and the high motility of its vegetative and starvation developed cells. First, I focused on the dynamics of the actin cytoskeleton by modulating the activity of one of its key players, the Arp2/3 complex. This was achieved using the carbazole derivative Wiskostatin, an inhibitor of the Arp2/3 activator WASP. Cells treated with Wiskostatin adopted a round shape, with no of few pseudopodia. With the help of a microfluidic cell squeezer device, I could show that Wiskostatin treated cells display a reduced mechanical stability, comparable to cells treated with the actin disrupting agent Latrunculin A. Furthermore, the WASP inhibited cells adhere stronger to a surface and show a reduced motility and chemotactic performance. However, the overall F-actin content in the cells was not changed. Confocal microscopy and TIRF microscopy imaging showed that the cells maintained an intact actin cortex. Localized dynamic patches of increased actin polymerization were observed that, however, did not lead to membrane deformation. This indicated that the mechanisms of actin-driven force generation were impaired in Wiskostatin treated cells. It is concluded that in these cells, an altered architecture of the cortical network leads to a reduced overall stiffness of the cell, which is insufficient to support the force generation required for membrane deformation and pseudopod formation. Second, the role of cGMP in myosin II dynamics was investigated. Cyclic GMP is known to regulate the association of myosin II with the cytoskeleton. In Dictyostelium, intracellular cGMP levels increase when cells are exposed to chemoattractants, but also in response to osmotic stress. To study the influence of cyclic GMP on actin and myosin II dynamics, I used the laser-induced photoactivation of a DMACM-caged-Br-cGMP to locally release cGMP inside the cell. My results show that cGMP directly activates the myosin II machinery, but is also able to induce an actin response independently of cAMP receptor activation and signaling. The actin response was observed in both vegetative and developed cells. Possible explanations include cGMP-induced actin polymerization through VASP (vasodilator-stimulated phosphoprotein) or through binding of cGMP to cyclic nucleotide-dependent kinases. Finally, I investigated the role of phosphoinositide signaling using the Polyphosphoinositide-Binding Peptide (PBP10) that binds preferentially to PIP2. Phosphoinositides can recruit actin-binding proteins to defined subcellular sites and alter their activity. Neutrophils, as well as developed Dictyostelium cells produce PIP3 in the plasma membrane at their leading edge in response to an external chemotactic gradient. Although not essential for chemotaxis, phosphoinositides are proposed to act as an internal compass in the cell. When treated with the peptide PBP10, cells became round, with fewer or no pseudopods. PH-CRAC translocation to the membrane still occurs, even at low cAMP stimuli, but cell motility (random and directional) was reduced. My data revealed that the decrease in the pool of available PIP2 in the cell is sufficient to impair cell motility, but enough PIP2 remains so that PIP3 is formed in response to chemoattractant stimuli. My data thus highlights how sensitive cell motility and morphology are to changes in the phosphoinositide signaling. In summary, I have analyzed representative regulatory mechanisms that govern key parts of the motile machinery and characterized their impact on cellular properties including mechanical stability, adhesion and chemotaxis.
Studies on the unsustainable use of groundwater resources are still considered incipient since it is frequently a poorly understood and managed, devalued and inadequately protected natural resource. Groundwater Recharge (GWR) is one of the most challenging elements to estimate since it can rarely be measured directly and cannot easily be derived from existing data. To overcome these limitations, many hydro(geo)logists have combined different approaches to estimate large-scale GWR, namely: remote sensing products, such as IMERG product; Water Budget Equation, also in combination with hydrological models, and; Geographic Information System (GIS), using estimation formulas. For intermediary-scale GWR estimation, there exist: Non-invasive Cosmic-Ray Neutron Sensing (CRNS); wireless networks from local soil probes; and soil hydrological models, such as HYDRUS. Accordingly, this PhD thesis aims, on the one hand, to demonstrate a GIS-based model coupling for estimating the GWR distribution on a large scale in tropical wet basins. On the other hand, it aims to use the time series from CRNS and invasive soil moisture probes to inversely calibrate the soil hydraulic properties, and based on this, estimating the intermediary-scale GWR using a soil hydrological model. For such purpose, two tropical wet basins located in a complex sedimentary aquifer in the coastal Northeast region of Brazil were selected. These are the João Pessoa Case Study Area and the Guaraíra Experimental Basin. Several satellite products in the first area were used as input to the GIS-based water budget equation model for estimating the water balance components and GWR in 2016 and 2017. In addition, the point-scale measurement and CRNS data were used in the second area to determine the soil hydraulic properties, and to estimate the GWR in the 2017-2018 and 2018-2019 hydrological years. The resulting values of GWR on large- and intermediary-scale were then compared and validated by the estimates obtained by groundwater table fluctuations. The GWR rates for IMERG- and rain-gauge-based scenarios showed similar coefficients between 68% and 89%, similar mean errors between 30% and 34%, and slightly-different bias between -13% and 11%. The results of GWR rates for soil probes and CRNS soil moisture scenarios ranged from -5.87 to -61.81 cm yr-1, which corresponds to 5% and 38% of the precipitation. The calculations of the mean GWR rates on large-scale, based on remote sensing data, and on intermediary-scale, based on CRNS data, held similar results for the Podzol soil type, namely 17.87% and 17% of the precipitation. It is then concluded that the proposed methodologies allowed for estimating realistically the GWR over the study areas, which can be a ground-breaking step towards improving the water management and decision-making in the Northeast of Brazil.
Die Tailspike Proteine (TSP) der Bakteriophagen P22, Sf6 und HK620 dienen der Erkennung von Kohlenhydratstrukturen auf ihren gram-negativen Wirtsbakterien und zeigen, von den ersten 110 Aminosäuren des N-Terminus abgesehen, keine Sequenzübereinstimmung. Mit Röntgenkristallstrukturanalyse konnte gezeigt werden, dass HK620TSP und Sf6TSP ebenfalls zu einer parallelen, rechtsgängigen beta-Helix falten, wie dies schon für P22TSP bekannt war. Die Kohlenhydratbindestelle ist bei Sf6TSP im Vergleich zu P22TSP zwischen die Untereinheiten verschoben.
In the last two decades, process mining has developed from a niche
discipline to a significant research area with considerable impact on academia and industry. Process mining enables organisations to identify the running business processes from historical execution data. The first requirement of any process mining technique is an event log, an artifact that represents concrete business process executions in the form of sequence of events. These logs can be extracted from the organization's information systems and are used by process experts to retrieve deep insights from the organization's running processes. Considering the events pertaining to such logs, the process models can be automatically discovered and enhanced or annotated with performance-related information. Besides behavioral information, event logs contain domain specific data, albeit implicitly. However, such data are usually overlooked and, thus, not utilized to their full potential.
Within the process mining area, we address in this thesis the research gap of discovering, from event logs, the contextual information that cannot be captured by applying existing process mining techniques. Within this research gap, we identify four key problems and tackle them by looking at an event log from different angles. First, we address the problem of deriving an event log in the absence of a proper database access and domain knowledge. The second problem is related to the under-utilization of the implicit domain knowledge present in an event log that can increase the understandability of the discovered process model. Next, there is a lack of a holistic representation of the historical data manipulation at the process model level of abstraction. Last but not least, each process model presumes to be independent of other process models when discovered from an event log, thus, ignoring possible data dependencies between processes within an organization.
For each of the problems mentioned above, this thesis proposes a dedicated method. The first method provides a solution to extract an event log only from the transactions performed on the database that are stored in the form of redo logs. The second method deals with discovering the underlying data model that is implicitly embedded in the event log, thus, complementing the discovered process model with important domain knowledge information. The third method captures, on the process model level, how the data affects the running process instances. Lastly, the fourth method is about the discovery of the relations between business processes (i.e., how they exchange data) from a set of event logs and explicitly representing such complex interdependencies in a business process architecture.
All the methods introduced in this thesis are implemented as a prototype and their feasibility is proven by being applied on real-life event logs.
Das 1817 erstmals schriftlich erwähnte Selen galt lange Zeit nur als toxisch und sogar als procancerogen, bis es 1957 von Schwarz und Foltz als essentielles Spurenelement erkannt wurde, dessen biologische Funktionen in Säugern durch Selenoproteine vermittelt werden. Die Familie der Glutathionperoxidasen nimmt hierbei eine wichtige Stellung ein. Für diese sind konkrete Funktionen und die dazugehörigen molekularen Mechanismen, welche über die von ihnen katalysierte Hydroperoxidreduktion und damit verbundene antioxidative Kapazität hinausgehen, bislang nur unzureichend beschrieben worden. Die Funktion der gastrointestinalen Glutathionperoxidase (GI-GPx) wird als Barriere gegen eine Hydroperoxidabsorption im Gastrointestinaltrakt definiert. Neuen Erkenntnissen zufolge wird die GI-GPx aber auch in verschiedenen Tumoren verstärkt exprimiert, was weitere, bis dato unbekannte, Funktionen dieses Enzymes wahrscheinlich macht. Um mögliche neue Funktionen der GI-GPx, vor allem während der Cancerogenese, abzuleiten, wurde hier die transkriptionale Regulation der GI-GPx detaillierter untersucht. Die Sequenzanalyse des humanen GI-GPx-Promotors ergab das Vorhandensein von zwei möglichen "antioxidant response elements" (ARE), bei welchen es sich um Erkennungssequenzen des Transkriptionsfaktors Nrf2 handelt. Die meisten der bekannten Nrf2-Zielgene gehören in die Gruppe der Phase-II-Enzyme und verfügen über antioxidative und/oder detoxifizierende Eigenschaften. Sowohl auf Promotorebene als auch auf mRNA- und Proteinebene konnte die Expression der GI-GPx durch typische, in der Nahrung enthaltene, Nrf2-Aktivatoren wie z.B. Sulforaphan oder Curcumin induziert werden. Eine direkte Beteiligung von Nrf2 wurde durch Cotransfektion von Nrf2 selbst bzw. von Keap1, das Nrf2 im Cytoplasma festhält, demonstriert. Somit konnte die GI-GPx eindeutig als Nrf2-Zielgen identifiziert werden. Ob sich die GI-GPx in die Gruppe der antiinflammatorischen und anticancerogenen Phase-II-Enzyme einordnen lässt, bleibt noch zu untersuchen. Die Phospholipidhydroperoxid Glutathionperoxidase (PHGPx) nimmt aufgrund ihres breiten Substratspektrums, ihrer hohen Lipophilie und ihrer Fähigkeit, Thiole zu modifizieren, eine Sonderstellung innerhalb der Familie der Glutathionperoxidasen ein. Mit Hilfe eines PHGPx-überexprimierenden Zellmodells wurden deshalb Beeinflussungen des zellulären Redoxstatus und daraus resultierende Veränderungen in der Aktivität redoxsensitiver Transkriptionsfaktorsysteme und in der Expression atheroskleroserelevanter Adhäsionsmoleküle untersucht. Als Transkriptionsfaktoren wurden NF-kB und Nrf2 ausgewählt. Die Bindung von NF-kB an sein entsprechendes responsives Element in der DNA erfordert das Vorhandensein freier Thiole, wohingegen Nrf2 durch Thiolmodifikation von Keap1 freigesetzt wird und in den Kern transloziert. Eine erhöhte Aktivität der PHGPx resultierte in einer Erhöhung des Verhältnisses von GSH zu GSSG, andererseits aber in einer verminderten Markierbarkeit freier Proteinthiole. PHGPx-Überexpression reduzierte die IL-1-induzierte NF-kB-Aktivität, die sich in einer verminderten NF-kB-DNA-Bindefähigkeit und Transaktivierungsaktivität ausdrückte. Auch war die Proliferationsrate der Zellen vermindert. Die Expression des NF-kB-regulierten vaskulären Zelladhäsionsmoleküls, VCAM-1, war ebenfalls deutlich verringert. Umgekehrt war in PHGPx-überexprimierenden Zellen eine erhöhte Nrf2-Aktivität und Expression der Nrf2-abhängigen Hämoxygenase-1 zu verzeichnen. Letzte kann für die meisten der beobachteten Effekte verantwortlich gemacht werden. Die hier dargestellten Ergebnisse verdeutlichen, dass eine Modifizierung von Proteinthiolen als wichtige Determinante für die Regulation der Expression und Funktion von Glutathionperoxidasen angesehen werden kann. Entgegen früheren Vermutungen, welche oxidative Vorgänge generell mit pathologischen Veränderungen assoziierten, scheint ein moderater oxidativer Stress, bedingt durch eine transiente Thiolmodifikation, durchaus günstige Auswirkungen zu haben, da, wie hier dargelegt, verschiedene, miteinander interagierende, cytoprotektive Mechanismen ausgelöst werden. Hieran wird deutlich, dass sich "antioxidative Wirkung" oder "oxidativer Stress" keineswegs nur auf "gute" oder "schlechte" Vorgänge beschränken lassen, sondern im Zusammenhang mit den beeinflussten (patho)physiologischen Prozessen und dem Ausmaß der "Störung" des physiologischen Redoxgleichgewichtes betrachtet werden müssen.
Classical semiconductor physics has been continuously improving electronic components such as diodes, light-emitting diodes, solar cells and transistors based on highly purified inorganic crystals over the past decades. Organic semiconductors, notably polymeric, are a comparatively young field of research, the first light-emitting diode based on conjugated polymers having been demonstrated in 1990. Polymeric semiconductors are of tremendous interest for high-volume, low-cost manufacturing ("printed electronics"). Due to their rather simple device structure mostly comprising only one or two functional layers, polymeric diodes are much more difficult to optimize compared to small-molecular organic devices. Usually, functions such as charge injection and transport are handled by the same material which thus needs to be highly optimized. The present work contributes to expanding the knowledge on the physical mechanisms determining device performance by analyzing the role of charge injection and transport on device efficiency for blue and white-emitting devices, based on commercially relevant spiro-linked polyfluorene derivatives. It is shown that such polymers can act as very efficient electron conductors and that interface effects such as charge trapping play the key role in determining the overall device efficiency. This work contributes to the knowledge of how charges drift through the polymer layer to finally find neutral emissive trap states and thus allows a quantitative prediction of the emission color of multichromophoric systems, compatible with the observed color shifts upon driving voltage and temperature variation as well as with electrical conditioning effects. In a more methodically oriented part, it is demonstrated that the transient device emission observed upon terminating the driving voltage can be used to monitor the decay of geminately-bound species as well as to determine trapped charge densities. This enables direct comparisons with numerical simulations based on the known properties of charge injection, transport and recombination. The method of charge extraction under linear increasing voltages (CELIV) is investigated in some detail, correcting for errors in the published approach and highlighting the role of non-idealized conditions typically present in experiments. An improved method is suggested to determine the field dependence of charge mobility in a more accurate way. Finally, it is shown that the neglect of charge recombination has led to a misunderstanding of experimental results in terms of a time-dependent mobility relaxation.
Glycosylphosphatidylinositols (GPIs) are highly complex glycolipids that serve as membrane anchors to a large variety of eukaryotic proteins. These are covalently attached to a group of peripheral proteins called GPI-anchored proteins (GPI-APs) through a post-translational modification in the endoplasmic reticulum. The GPI anchor is a unique structure composed of a glycan, with phospholipid tail at one end and a phosphoethanolamine linker at the other where the protein attaches. The glycan part of the GPI comprises a conserved pseudopentasaccharide core that could branch out to carry additional glycosyl or phosphoethanolamine units. GPI-APs are involved in a diverse range of cellular processes, few of which are signal transduction, protein trafficking, pathogenesis by protozoan parasites like the malaria- causing parasite Plasmodium falciparum. GPIs can also exist freely on the membrane surface without an attached protein such as those found in parasites like Toxoplasma gondii, the causative agent of Toxoplasmosis. These molecules are both structurally and functionally diverse, however, their structure-function relationship is still poorly understood. This is mainly because no clear picture exists regarding how the protein and the glycan arrange with respect to the lipid layer. Direct experimental evidence is rather scarce, due to which inconclusive pictures have emerged, especially regarding the orientation of GPIs and GPI-APs on membrane surfaces and the role of GPIs in membrane organization. It appears that computational modelling through molecular dynamics simulations would be a useful method to make progress. In this thesis, we attempt to explore characteristics of GPI anchors and GPI-APs embedded in lipid bilayers by constructing molecular models at two different resolutions – all-atom and coarse-grained.
First, we show how to construct a modular molecular model of GPIs and GPI-anchored proteins that can be readily extended to a broad variety of systems, addressing the micro-heterogeneity of GPIs. We do so by creating a hybrid link to which GPIs of diverse branching and lipid tails of varying saturation with their optimized force fields, GLYCAM06 and Lipid14 respectively, can be attached. Using microsecond simulations, we demonstrate that GPI prefers to “flop-down” on the membrane, thereby, strongly interacting with the lipid heads, over standing upright like a “lollipop”. Secondly, we extend the model of the GPI core to carry out a systematic study of the structural aspects of GPIs carrying different side chains (parasitic and human GPI variants) inserted in lipid bilayers. Our results demonstrate the importance of the side branch residues as these are the most accessible, and thereby, recognizable epitopes. This finding qualitatively agrees with experimental observations that highlight the role of the side branches in immunogenicity of GPIs and the specificity thereof. The overall flop-down orientation of the GPIs with respect to the bilayer surface presents the side chain residues to face the solvent. Upon attaching the green fluorescent protein (GFP) to the GPI, it is seen to lie in close proximity to the bilayer, interacting both with the lipid heads and glycan part of the GPI. However the orientation of GFP is sensitive to the type of GPI it is attached to. Finally, we construct a coarse-grained model of the GPI and GPI-anchored GFP using a modified version of the MARTINI force-field, using which the timescale is enhanced by at least an order of magnitude compared to the atomistic system.
This study provides a theoretical perspective on the conformational behavior of the GPI core and some of its branched variations in presence of lipid bilayers, as well as draws comparisons with experimental observations. Our modular atomistic model of GPI can be further employed to study GPIs of variable branching, and thereby, aid in designing future experiments especially in the area of vaccines and drug therapies. Our coarse-grained model can be used to study dynamic aspects of GPIs and GPI-APs w.r.t plasma membrane organization. Furthermore, the backmapping technique of converting coarse-grained trajectory back to the atomistic model would enable in-depth structural analysis with ample conformational sampling.
Over the past decades, there has been a growing interest in ‘extreme events’ owing to the increasing threats that climate-related extremes such as floods, heatwaves, droughts, etc., pose to society. While extreme events have diverse definitions across various disciplines, ranging from earth science to neuroscience, they are characterized mainly as dynamic occurrences within a limited time frame that impedes the normal functioning of a system. Although extreme events are rare in occurrence, it has been found in various hydro-meteorological and physiological time series (e.g., river flows, temperatures, heartbeat intervals) that they may exhibit recurrent behavior, i.e., do not end the lifetime of the system. The aim of this thesis to develop some
sophisticated methods to study various properties of extreme events.
One of the main challenges in analyzing such extreme event-like time series is that they have large temporal gaps due to the paucity of the number of observations of extreme events. As a result, existing time series analysis tools are usually not helpful to decode the underlying
information. I use the edit distance (ED) method to analyze extreme event-like time series in their unaltered form. ED is a specific distance metric, mainly designed to measure the similarity/dissimilarity between point process-like data. I combine ED with recurrence plot techniques to identify the recurrence property of flood events in the Mississippi River in the United States. I also use recurrence quantification analysis to show the deterministic properties
and serial dependency in flood events.
After that, I use this non-linear similarity measure (ED) to compute the pairwise dependency in extreme precipitation event series. I incorporate the similarity measure within the framework of complex network theory to study the collective behavior of climate extremes. Under this architecture, the nodes are defined by the spatial grid points of the given spatio-temporal climate dataset. Each node is associated with a time series corresponding to the temporal evolution
of the climate observation at that grid point. Finally, the network links are functions of the pairwise statistical interdependence between the nodes. Various network measures, such as degree, betweenness centrality, clustering coefficient, etc., can be used to quantify the network’s topology. We apply the methodology mentioned above to study the spatio-temporal coherence pattern of extreme rainfall events in the United States and the Ganga River basin, which reveals its relation to various climate processes and the orography of the region.
The identification of precursors associated with the occurrence of extreme events in the near future is extremely important to prepare the masses for an upcoming disaster and mitigate the potential risks associated with such events. Under this motivation, I propose an in-data prediction recipe for predicting the data structures that typically occur prior to extreme events using the Echo state network, a type of Recurrent Neural Network which is a part of the reservoir
computing framework. However, unlike previous works that identify precursory structures in the same variable in which extreme events are manifested (active variable), I try to predict these structures by using data from another dynamic variable (passive variable) which does not show large excursions from the nominal condition but carries imprints of these extreme events. Furthermore, my results demonstrate that the quality of prediction depends on the magnitude
of events, i.e., the higher the magnitude of the extreme, the better is its predictability skill. I show quantitatively that this is because the input signals collectively form a more coherent pattern for an extreme event of higher magnitude, which enhances the efficiency of the machine to predict the forthcoming extreme events.
Intracontinental deformation usually is a result of tectonic forces associated with distant plate collisions. In general, the evolution of mountain ranges and basins in this environment is strongly controlled by the distribution and geometries of preexisting structures. Thus, predictive models usually fail in forecasting the deformation evolution in these kinds of settings. Detailed information on each range and basin-fill is vital to comprehend the evolution of intracontinental mountain belts and basins. In this dissertation, I have investigated the complex Cenozoic tectonic evolution of the western Tien Shan in Central Asia, which is one of the most active intracontinental ranges in the world. The work presented here combines a broad array of datasets, including thermo- and geochronology, paleoenvironmental interpretations, sediment provenance and subsurface interpretations in order to track changes in tectonic deformation. Most of the identified changes are connected and can be related to regional-scale processes that governed the evolution of the western Tien Shan.
The NW-SE trending Talas-Fergana fault (TFF) separates the western from the central Tien Shan and constitutes a world-class example of the influence of preexisting anisotropies on the subsequent structural development of a contractile orogen. While to the east most of ranges and basins have a sub-parallel E-W trend, the triangular-shaped Fergana basin forms a substantial feature in the western Tien Shan morphology with ranges on all three sides. In this thesis, I present 55 new thermochronologic ages (apatite fission track and zircon (U-Th)/He)) used to constrain exhumation histories of several mountain ranges in the western Tien Shan. At the same time, I analyzed the Fergana basin-fill looking for progressive changes in sedimentary paleoenvironments, source areas and stratal geometrical configurations in the subsurface and outcrops.
The data presented in this thesis suggests that low cooling rates (<1°C Myr-1), calm depositional environments, and low depositional rates (<10 m Myr-1) were widely distributed across the western Tien Shan, describing a quiescent tectonic period throughout the Paleogene. Increased cooling rates in the late Cenozoic occurred diachronously and with variable magnitudes in different ranges. This rapid cooling stage is interpreted to represent increased erosion caused by active deformation and constrains the onset of Cenozoic deformation in the western Tien Shan. Time-temperature histories derived from the northwestern Tien Shan samples show an increase in cooling rates by ~25 Ma. This event is correlated with a synchronous pulse
iv
in the South Tien Shan. I suggest that strike-slip motion along the TFF commenced at the Oligo-Miocene boundary, facilitating CCW rotation of the Fergana basin and enabling exhumation of the linked horsetail splays. Higher depositional rates (~150 m Myr-1) in the Oligo-Miocene section (Massaget Fm.) of the Fergana basin suggest synchronous deformation in the surrounding ranges. The central Alai Range also experienced rapid cooling around this time, suggesting that the onset of intramontane basin fragmentation and isolation is coeval. These results point to deformation starting simultaneously in the late Oligocene – early Miocene in geographically distant mountain ranges. I suggest that these early uplifts are controlled by reactivated structures (like the TFF), which are probably the frictionally weakest and most-suitably oriented for accommodating and transferring N-S horizontal shortening along the western Tien Shan.
Afterwards, in the late Miocene (~10 Ma), a period of renewed rapid cooling affected the Tien Shan and most mountain ranges and inherited structures started to actively deform. This episode is widely distributed and an increase in exhumation is interpreted in most of the sampled ranges. Moreover, the Pliocene section in the basin subsurface shows the higher depositional rates (>180 m Myr-1) and higher energy facies. The deformation and exhumation increase further contributed to intramontane basin partitioning. Overall, the interpretation is that the Tien Shan and much of Central Asia suffered a global increase in the rate of horizontal crustal shortening. Previously, stress transfer along the rigid Tarim block or Pamir indentation has been proposed to account for Himalayan hinterland deformation. However, the extent of the episode requires a different and broader geodynamic driver.
Planetary research is often user-based and requires considerable skill, time, and effort. Unfortunately, self-defined boundary conditions, definitions, and rules are often not documented or not easy to comprehend due to the complexity of research. This makes a comparison to other studies, or an extension of the already existing research, complicated. Comparisons are often distorted, because results rely on different, not well defined, or even unknown boundary conditions. The purpose of this research is to develop a standardized analysis method for planetary surfaces, which is adaptable to several research topics. The method provides a consistent quality of results. This also includes achieving reliable and comparable results and reducing the time and effort of conducting such studies. A standardized analysis method is provided by automated analysis tools that focus on statistical parameters. Specific key parameters and boundary conditions are defined for the tool application. The analysis relies on a database in which all key parameters are stored. These databases can be easily updated and adapted to various research questions. This increases the flexibility, reproducibility, and comparability of the research. However, the quality of the database and reliability of definitions directly influence the results. To ensure a high quality of results, the rules and definitions need to be well defined and based on previously conducted case studies. The tools then produce parameters, which are obtained by defined geostatistical techniques (measurements, calculations, classifications). The idea of an automated statistical analysis is tested to proof benefits but also potential problems of this method. In this study, I adapt automated tools for floor-fractured craters (FFCs) on Mars. These impact craters show a variety of surface features, occurring in different Martian environments, and having different fracturing origins. They provide a complex morphological and geological field of application. 433 FFCs are classified by the analysis tools due to their fracturing process. Spatial data, environmental context, and crater interior data are analyzed to distinguish between the processes involved in floor fracturing. Related geologic processes, such as glacial and fluvial activity, are too similar to be separately classified by the automated tools. Glacial and fluvial fracturing processes are merged together for the classification. The automated tools provide probability values for each origin model. To guarantee the quality and reliability of the results, classification tools need to achieve an origin probability above 50 %. This analysis method shows that 15 % of the FFCs are fractured by intrusive volcanism, 20 % by tectonic activity, and 43 % by water & ice related processes. In total, 75 % of the FFCs are classified to an origin type. This can be explained by a combination of origin models, superposition or erosion of key parameters, or an unknown fracturing model. Those features have to be manually analyzed in detail. Another possibility would be the improvement of key parameters and rules for the classification. This research shows that it is possible to conduct an automated statistical analysis of morphologic and geologic features based on analysis tools. Analysis tools provide additional information to the user and are therefore considered assistance systems.
The H.E.S.S. array is a third generation Imaging Atmospheric Cherenkov Telescope (IACT) array. It is located in the Khomas Highland in Namibia, and measures very high energy (VHE) gamma-rays. In Phase I, the array started data taking in 2004 with its four identical 13 m telescopes. Since then, H.E.S.S. has emerged as the most successful IACT experiment to date. Among the almost 150 sources of VHE gamma-ray radiation found so far, even the oldest detection, the Crab Nebula, keeps surprising the scientific community with unexplained phenomena such as the recently discovered very energetic flares of high energy gamma-ray radiation. During its most recent flare, which was detected by the Fermi satellite in March 2013, the Crab Nebula was simultaneously observed with the H.E.S.S. array for six nights. The results of the observations will be discussed in detail during the course of this work. During the nights of the flare, the new 24 m × 32 m H.E.S.S. II telescope was still being commissioned, but participated in the data taking for one night. To be able to reconstruct and analyze the data of the H.E.S.S. Phase II array, the algorithms and software used by the H.E.S.S. Phase I array had to be adapted. The most prominent advanced shower reconstruction technique developed by de Naurois and Rolland, the template-based model analysis, compares real shower images taken by the Cherenkov telescope cameras with shower templates obtained using a semi-analytical model. To find the best fitting image, and, therefore, the relevant parameters that describe the air shower best, a pixel-wise log-likelihood fit is done. The adaptation of this advanced shower reconstruction technique to the heterogeneous H.E.S.S. Phase II array for stereo events (i.e. air showers seen by at least two telescopes of any kind), its performance using MonteCarlo simulations as well as its application to real data will be described.
Meiner nichtreduktionistischen Lesart Gadamers, derzufolge eine wechselseitige konstitutive Relation zwischen „Sprache“ und „Erfahrung“ besteht, ist es gestattet, den Vorwurf, die Sprachphilosophie Gadamers führe in den Relativismus, den man häufig gegenüber sprachphilosophischen Positionen erhebt, abzuweisen. Manchen Denkern zufolge haben die Philosophen der Postmoderne, zu denen auch Gadamer gezählt wurde, eine einfache Umkehrung der beiden Pole des modernen Verhältnisses „Sprache“ – „Erfahrung“ vollzogen: Während die Sprache in der Moderne in ihrer Bedingtheit zur Erfahrung und als bloßes Ausdrucksmittel verstanden wurde, wurde dieses Verhältnis in der neueren Philosophie nur umgekehrt, insofern die Philosophie in der Sprache das Fundament für die Erfahrung sehe, wonach die Erfahrung als ein Ausdruck der Sprache erscheine. Die vorliegende Arbeit setzt sich mit diesem Relativismusvorwurf auseinander und beabsichtigt, eine wechselseitige Abhängigkeit zwischen Sprache und Erfahrung ausgehend von Hans-Georg Gadamers Werk zu entwickeln. Um das zu erreichen, wurden zunächst eine doppelte negative-positive Erfahrungsstruktur und dann einige phänomenologische und transzendentale Merkmale der Erfahrung auf dem historischen Hintergrund für Gadamers Erfahrungsbegriff herausgearbeitet. Somit machte sich die konstitutive Sprachlichkeit der Erfahrung erkennbar. In einer Auseinandersetzung mit dem Sprachbegriff auf der anderen Seite wurde sein dialogischer und welterschließender Charakter veranschaulicht, so dass auch seine Angewiesenheit auf die Welterfahrung offenkundig wurde.
Foreland-basin systems are excellent archives to decipher the feedbacks between surface and tectonic processes in orogens. The sedimentary architecture of a foreland-basin system reflects the balance between tectonic subsidence causing long-term accommodation space and sediment influx corresponding to efficiency of erosion and mass-redistribution processes. In order to explore the effects of climatic and tectonic forcing in such a system, I investigated the Oligo-Miocene foreland-basin sediments of the southern Alborz mountains, an intracontinental orogen in northern Iran, related to the Arabia-Eurasia continental collision. This work includes absolute dating methods such as 40Ar/39Ar and zircon (U-Th)/He thermochronology, magnetostratigraphy, sedimentological analysis, sandstone and conglomerate provenance study, carbon and oxygen isotope analysis, and clay mineralogy study. Results show a systematic correlation between coarsening-upward cycles and sediment accumulation rates in the basin on 105 to 106yr time scales. During thrust loading phases, the coarse-grained fraction supplied by the uplifting range is stored in the proximal part of the basin (sedimentary facies retrogradation), while fine-grained sediments are deposited in distal sectors. Variations in sediment provenance during these phases of enhanced tectonic activity give evidence for erosional unroofing phases and/or drainage-reorganization events. In addition, enhanced tectonic activity promoted the growth of topography and associated orographic barrier effects, as demonstrated by sedimentologic indicators and the analysis of stable C and O isotopes from calcareous paleosols and lacustrine/palustrine samples. Extensive progradation of coarse-grained deposits occurs during phases of decreased subsidence, when the coarse-grained fraction supplied by the uplifting range cannot be completely stored in the proximal part of the basin. In this environment, a reduction in basin subsidence is associated with laterally stacked fluvial channel deposits, and is related to intra-foreland uplift, as documented by growth strata, tectonic tilting, and sediment reworking. Increase in sediment accumulation rate associated with progradation of vertically-stacked coarse-grained fluvial channels also occurs. Paleosol O-isotope data shows that this increase is related to wetter climatic phases, suggesting that surface processes are more efficient and exhumation rates increase, giving rise to a positive feedback. Furthermore, isotopic and sedimentologic data show that starting from 10-9 Ma, climate became less arid with an increase in seasonality of precipitation. Because important changes were also recorded in the Mediterranean Sea and Asia at that time, the evidence for climatic variability observed in the Alborz mountains most likely reflects changes in Northern Hemisphere atmospheric circulation patterns. This study has additional implications for the evolution of the Alborz mountains and the Arabia-Eurasia continental collision zone. At the orogenic scale, the locus of deformation did not move steadily southward, but stepped forward and backward since Oligocene time. In particular, from ~ 17.5 to 6.2 Ma the orogen grew by a combination of frontal accretion and wedge-internal deformation on time scales of ca. 0.7 to 2 m.y. Moreover, the provenance data suggest that prior to 10-9 Ma the shortening direction changed from NW-SE to NNE-SSW, in agreement with structural data. On the scale of the entire collision zone, the evolution of the studied basins and adjacent mountain ranges suggests a new geodynamic model for the evolution of the Arabia-Eurasia continental collision zone. Numerous sedimentary basins in the Alborz mountains and in other locations of the Arabia-Eurasia collision zone record a change from a tensional (transtensional) to a compressional (transpressional) tectonic setting by ~ 36 Ma. I interpret this to reflect the onset of subduction of the stretched Arabian continental lithosphere beneath central Iran, leading to moderate plate coupling and lower- and upper-plate deformation (soft continental collision). The increase in deformation rates in the southern Alborz mountains from ~ 17.5 Ma suggests that significant upper-plate deformation must have started by the early Miocene most likely in response to an increase in degree of plate coupling. I suggest that this was related to the subduction of thicker Arabian continental lithosphere and the consequent onset of hard continental collision. This model reconciles the apparent lag time of 15-20 m.y between the late Eocene to early Oligocene age for the initial Arabia-Eurasia continental collision and the onset of widespread deformation across the collision zone to the north in early to late Miocene time.
Seit vier Jahrzehnten werden verschiedene Neurofeedbackmethoden bei der Behandlung unterschiedlicher Störungen, unter anderem bei AD/HS-Kindern, eingesetzt. Die Grundlage der Anwendung von Neurofeedback bei dieser Störung besteht darin, dass die Kinder Auffälligkeiten in ihrem EEG zeigen. Dort treten im Vergleich zu unauffälligen Kindern vermehrt Theta-Gehirnwellen und weniger Beta-Gehirnwellen auf. Mittels Neurofeedback wird versucht, die Gehirnfunktionen zu korrigieren. Zahlreiche Einzellfallstudien bestätigen die Wirksamkeit dieser Therapiemethode bei der AD/HS-Behandlung. Bisher wurde jedoch keine Studie veröffentlicht, in der die Wirksamkeit von Neurofeedback mit einer Placebogruppe verglichen wurde. Ziel der vorliegenden Studie war es, die Wirksamkeit eines Theta/Beta-Neurofeedbacks (NF) bei der Behandlung von AD/HS-Kindern zu überprüfen und mit einem EMG-Biofeedback (BF) als Placebobedingung zu vergleichen. Es wurden 35 ADHS-Kinder (6 -14 Jahre; 26 Jungen und 9 Mädchen) untersucht. Nach Standarddiagnostik und Vergabe der AD/HS-Diagnose durch einen unabhängigen Psychotherapeuten wurden die Kinder per Zufall zwei Gruppen (NF: n = 18 bzw. BF: n = 17) zugeteilt. Alle Kinder beider Gruppen erhielten ein 30 Sitzungen umfassendes Training mittels Theta/Beta-Neurofeedback bzw. EMG-Biofeedback. Unmittelbar vor und nach dem Training wurden Intelligenz- bzw. Aufmerksamkeitsleistungen untersucht und Einschätzungen des Verhaltens von Eltern und Lehrern erhoben. Im Anschluss an das Training erfolgte eine erneute diagnostische Einschätzung durch einen unabhängigen Psychotherapeuten. Die EEG-Daten in der NF-Gruppe zeigen eine Reduktion der Theta/Beta-Quotienten im Laufe der NF-Sitzungen. Die EMG-Daten zeigen für die EMG-Biofeedback-Bedingung gleichfalls eine Reduktion der EMG-Amplitude. Die Ergebnisse der zweifaktoriellen Varianzanalysen mit Messwiederholung auf einem Faktor zeigen für die angewendeten diagnostischen Verfahren die erwarteten signifikanten Interaktionen zwischen Messzeitpunkt und Gruppe. Die Ergebnisse des t-Tests zeigen signifikante Verbesserungen in der Aufmerksamkeitsleistung, dem Intelligenzniveau und im Verhalten der Kinder aus der NF-Gruppe im Vergleich zu den Resultaten des Prä-Tests. Die EMG-Biofeedbackgruppe zeigt mit Ausnahme einer Erhöhung des Arbeitstempos in den Paper-Pencil-Aufmerksamkeitstests (die im CPT nicht repliziert werden konnte) keine signifikanten Verbesserungen relativ zum Prä-Test. Nach dem Training erhielten 55,6 % (n = 10) der AD/HS-Kinder aus der Neurofeedbackgruppe und 23,5 % (n = 4) der Kinder aus der EMG-Biofeedbackgruppe keine AD/HS-Diagnose nach den Kriterien der ICD-10. Der Chi-Quadrat-Test zeigt jedoch lediglich einen tendenziell bedeutsamen Unterschied (p = .086). Insgesamt bestätigen die Ergebnisse die Wirksamkeit des Neurofeedbacks bei der Behandlung von ADHS-Kindern im Vergleich mit einer Placebogruppe. Weitere Studien in diesem Bereich sind notwendig, um die Wirksamkeit des Neurofeedbacktrainings im Vergleich zu einer Placebomethode bei der ADHS-Behandlung zu untersuchen.
Antarctic glacier forfields are extreme environments and pioneer sites for ecological succession. The Antarctic continent shows microbial community development as a natural laboratory because of its special environment, geographic isolation and little anthropogenic influence. Increasing temperatures due to global warming lead to enhanced deglaciation processes in cold-affected habitats and new terrain is becoming exposed to soil formation and accessible for microbial colonisation. This study aims to understand the structure and development of glacier forefield bacterial communities, especially how soil parameters impact the microorganisms and how those are adapted to the extreme conditions of the habitat. To this effect, a combination of cultivation experiments, molecular, geophysical and geochemical analysis was applied to examine two glacier forfields of the Larsemann Hills, East Antarctica. Culture-independent molecular tools such as terminal restriction length polymorphism (T-RFLP), clone libraries and quantitative real-time PCR (qPCR) were used to determine bacterial diversity and distribution. Cultivation of yet unknown species was carried out to get insights in the physiology and adaptation of the microorganisms. Adaptation strategies of the microorganisms were studied by determining changes of the cell membrane phospholipid fatty acid (PLFA) inventory of an isolated bacterium in response to temperature and pH fluctuations and by measuring enzyme activity at low temperature in environmental soil samples. The two studied glacier forefields are extreme habitats characterised by low temperatures, low water availability and small oligotrophic nutrient pools and represent sites of different bacterial succession in relation to soil parameters. The investigated sites showed microbial succession at an early step of soil formation near the ice tongue in comparison to closely located but rather older and more developed soil from the forefield. At the early step the succession is influenced by a deglaciation-dependent areal shift of soil parameters followed by a variable and prevalently depth-related distribution of the soil parameters that is driven by the extreme Antarctic conditions. The dominant taxa in the glacier forefields are Actinobacteria, Acidobacteria, Proteobacteria, Bacteroidetes, Cyanobacteria and Chloroflexi. The connection of soil characteristics with bacterial community structure showed that soil parameter and soil formation along the glacier forefield influence the distribution of certain phyla. In the early step of succession the relative undifferentiated bacterial diversity reflects the undifferentiated soil development and has a high potential to shift according to past and present environmental conditions. With progressing development environmental constraints such as water or carbon limitation have a greater influence. Adapting the culturing conditions to the cold and oligotrophic environment, the number of culturable heterotrophic bacteria reached up to 108 colony forming units per gram soil and 148 isolates were obtained. Two new psychrotolerant bacteria, Herbaspirillum psychrotolerans PB1T and Chryseobacterium frigidisoli PB4T, were characterised in detail and described as novel species in the family of Oxalobacteraceae and Flavobacteriaceae, respectively. The isolates are able to grow at low temperatures tolerating temperature fluctuations and they are not specialised to a certain substrate, therefore they are well-adapted to the cold and oligotrophic environment. The adaptation strategies of the microorganisms were analysed in environmental samples and cultures focussing on extracellular enzyme activity at low temperature and PLFA analyses. Extracellular phosphatases (pH 11 and pH 6.5), β-glucosidase, invertase and urease activity were detected in the glacier forefield soils at low temperature (14°C) catalysing the conversion of various compounds providing necessary substrates and may further play a role in the soil formation and total carbon turnover of the habitat. The PLFA analysis of the newly isolated species C. frigidisoli showed that the cold-adapted strain develops different strategies to maintain the cell membrane function under changing environmental conditions by altering the PLFA inventory at different temperatures and pH values. A newly discovered fatty acid, which was not found in any other microorganism so far, significantly increased at decreasing temperature and low pH and thus plays an important role in the adaption of C. frigidisoli. This work gives insights into the diversity, distribution and adaptation mechanisms of microbial communities in oligotrophic cold-affected soils and shows that Antarctic glacier forefields are suitable model systems to study bacterial colonisation in connection to soil formation.
Nowadays, business processes are increasingly supported by IT services that produce massive amounts of event data during process execution. Aiming at a better process understanding and improvement, this event data can be used to analyze processes using process mining techniques. Process models can be automatically discovered and the execution can be checked for conformance to specified behavior. Moreover, existing process models can be enhanced and annotated with valuable information, for example for performance analysis. While the maturity of process mining algorithms is increasing and more tools are entering the market, process mining projects still face the problem of different levels of abstraction when comparing events with modeled business activities. Mapping the recorded events to activities of a given process model is essential for conformance checking, annotation and understanding of process discovery results. Current approaches try to abstract from events in an automated way that does not capture the required domain knowledge to fit business activities. Such techniques can be a good way to quickly reduce complexity in process discovery. Yet, they fail to enable techniques like conformance checking or model annotation, and potentially create misleading process discovery results by not using the known business terminology.
In this thesis, we develop approaches that abstract an event log to the same level that is needed by the business. Typically, this abstraction level is defined by a given process model. Thus, the goal of this thesis is to match events from an event log to activities in a given process model. To accomplish this goal, behavioral and linguistic aspects of process models and event logs as well as domain knowledge captured in existing process documentation are taken into account to build semiautomatic matching approaches. The approaches establish a pre--processing for every available process mining technique that produces or annotates a process model, thereby reducing the manual effort for process analysts. While each of the presented approaches can be used in isolation, we also introduce a general framework for the integration of different matching approaches.
The approaches have been evaluated in case studies with industry and using a large industry process model collection and simulated event logs. The evaluation demonstrates the effectiveness and efficiency of the approaches and their robustness towards nonconforming execution logs.
Chitooligosaccharides are composed of glycosamin and N-acetylglycisamin residues. Gel permeations chromatography is employed for the separation of oligomers, cation exchange chromatography is used for the separation of homologes and isomers. Trideuterioacetylation of the chitooligosaccharides followed by MALDI-TOF mass spectrometry allowes for the quantitation of mixtures of homologes. vMALDI LTQ multiple-stage MS is employed for quantitative sequencing of complex mixtures of heterochitooligosaccharides. Pure homologes and isomers are applied to biological assays. Chitooligosaccahrides form high-affinity non-covalent complexes with HC gp-39 (human cartilage glycoprotein of 39 kDa). The affinity of the chitooligosaccharides depends on DP, FA and the sequence of glycosamin and N-acetylglycosamin moieties. (+)nanoESI Q TOF MS/MS is used for identification of a high-affinity binding chitooligosaccharide of a non-covalent chitinase B - chitooligosaccharide complex. DADAA is identified as the heterochitoisomer binding with highest affinity and biostability to HC gp-39. Fluorescence based enzyme assays confirm the results.
Zentrales Element dieser Arbeit ist die Synthese und Charakterisierung praktisch nutzbarer Ionogele. Die Basis der Polymerionogele bildet das Modellpolymer Polymethylmethacrylat. Als Additive kommen ionische Flüssigkeiten zum Einsatz, deren Grundlage Derivate des vielfach verwendeten Imidazoliumkations sind. Die Eigenschaften der eingebetteten ionischen Flüssigkeiten sind für die Ionogele funktionsgebend. Die Funktionalität der jeweiligen Gele und damit der Transfer der Eigenschaften von ionischen Flüssigkeiten auf die Ionogele wurde in der vorliegenden Arbeit mittels zahlreicher Charakterisierungstechniken überprüft und bestätigt. In dieser Arbeit wurden durch Ionogelbildung makroskopische Ionogelobjekte in Form von Folien und Vliesen erzeugt. Dabei kamen das Filmgießen und das Elektrospinnen als Methoden zur Erzeugung dieser Folien und Vliese zum Einsatz, woraus jeweils ein Modellsystem resultiert. Dadurch wird die vorliegende Arbeit in die Themenkomplexe „elektrisch halbleitende Ionogelfolien“ und „antimikrobiell aktive Ionogelvliese“ gegliedert. Der Einsatz von triiodidhaltigen ionischen Flüssigkeiten und einer Polymermatrix in einem diskontinuierlichen Gießprozess resultiert in elektrisch halbleitenden Ionogelfolien. Die flexiblen und transparenten Folien können Mittelpunkt zahlreicher neuer Anwendungsfelder im Bereich flexibler Elektronik sein. Das Elektrospinnen von Polymethylmethacrylat mit einer ionischen Flüssigkeit führte zu einem homogen Ionogelvlies, welches ein Modell für die Übertragung antimikrobiell aktiver Eigenschaften ionischer Flüssigkeiten auf poröse Strukturen zur Filtration darstellt. Gleichzeitig ist es das erste Beispiel für ein kupferchloridhaltiges Ionogel. Ionogele sind attraktive Materialien mit zahlreichen Anwendungsmöglichkeiten. Mit der vorliegenden Arbeit wird das Spektrum der Ionogele um ein elektrisch halbleitendes und ein antimikrobiell aktives Ionogel erweitert. Gleichzeitig wurden durch diese Arbeit der Gruppe der ionischen Flüssigkeiten drei Beispiele für elektrisch halbleitende ionische Flüssigkeiten sowie zahlreiche kupfer(II)chloridbasierte ionische Flüssigkeiten hinzugefügt.
Im Rahmen dieser Dissertation wurden die erstmaligen Totalsynthesen der Arylnaphthalen-Lignane Alashinol D, Vitexdoin C, Vitrofolal E, Noralashinol C1 und Ternifoliuslignan E vorgestellt. Der Schlüsselschritt der entwickelten Methode, basiert auf einer regioselektiven intramolekularen Photo-Dehydro-Diels-Alder (PDDA)-Reaktion, die mittels UV-Strahlung im Durchflussreaktor durchgeführt wurde. Bei der Synthese der PDDA-Vorläufer (Diarylsuberate) wurde eine Synthesestrategie nach dem Baukastenprinzip verfolgt. Diese ermöglicht die Darstellung asymmetrischer komplexer Systeme aus nur wenigen Grundbausteinen und die Totalsynthese einer Vielzahl an Lignanen. In systematischen Voruntersuchungen konnte zudem die klare Überlegenheit der intra- gegenüber der intermolekularen PDDA-Reaktion aufgezeigt werden. Dabei stellte sich eine Verknüpfung der beiden Arylpropiolester über einen Korksäurebügel, in para-Position, als besonders effizient heraus. Werden asymmetrisch substituierte Diarylsuberate, bei denen einer der endständigen Estersubstituenten durch eine Trimethylsilyl-Gruppe oder ein Wasserstoffatom ersetzt wurde, verwendet, durchlaufen diese Systeme eine regioselektive Cyclisierung und als Hauptprodukt werden Naphthalenophane mit einem Methylester in 3-Position erhalten. Mit Hilfe von umfangreichen Experimenten zur Funktionalisierung der 4-Position, konnte zudem gezeigt werden, dass die Substitution der nucleophilen Cycloallen-Intermediate, während der PDDA-Reaktion, generell durch die Zugabe von N-Halogen-Succinimiden möglich ist. In Anbetracht der geringen Ausbeuten haben diese intermolekularen Abfangreaktionen, jedoch keinen präparativen Nutzen für die Totalsynthesen von Lignanen. Mit dem Ziel die allgemeinen photochemischen Reaktionsbedingungen zu optimieren, wurde erstmalig die triplettsensibilisierte PDDA-Reaktion vorgestellt. Durch die Verwendung von Xanthon als Sensibilisator wurde der Einsatz von effizienteren UVA-Lichtquellen ermöglicht, wodurch die Gefahr einer Photozersetzung durch Überbestrahlung minimiert wurde. Im Vergleich zur direkten Anregung mit UVB-Strahlung, konnten die Ausbeuten mit indirekter Anregung durch einen Photokatalysator signifikant gesteigert werden. Die grundlegenden Erkenntnisse und die entwickelten Synthesestrategien dieser Arbeit, können dazu beitragen zukünftig die Erschließung neuer pharmakologisch interessanter Lignane voranzutreiben.
1 Bisher ist nur die semisynthetische Darstellung von Noralashinol C ausgehend von Hydroxymatairesinol literaturbekannt.