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‘Smart’ Janus emulsions
(2021)
Emulsions constitute one of the most prominent and continuously evolving research areas in Colloid Chemistry, which involves the preparation of mixtures or dispersions of immiscible components in a continuous medium. Besides conventional oil-in-water or water-in-oil emulsions, other emulsions of complex droplet morphologies have recently attracted significant research interests. Especially Janus emulsions, in which each droplet is comprised of two distinct sub-regions, have shown versatile potential applications. One of their advantages is the possibility of compartmentalization, which enables to play with two different chemistries in a single droplet. Though microfluidic methods are conventionally used to prepare Janus emulsions, their industrial applications are largely hindered by low throughput and extensive instrumentations. Recently, it has been discovered that simply one-pot moderate/high energy emulsification is also capable of developing Janus morphology, although their preparation and stabilization remain rather substantially challenging. This cumulative doctoral thesis focuses on the preparation and characterization of ‘smart’ Janus emulsions, i.e. Janus emulsions with special stimuli-responsive features. One-step moderate/high energy emulsification of olive and silicone oil in an aqueous medium was carried out. Special consideration was devoted to the interfacial tensions among the components to maintain the criteria of forming characteristic droplet architectures, in addition to avoiding multiple emulsion destabilization phenomena like imminent phase separation or even separated droplet formation. A series of investigations were conducted related to the formation of complexes of charged macromolecules and role of them as stabilizers to achieve stable Janus emulsions for a realistic timeframe (more than 3 months). The correlation between the size of the stabilizer particles and the droplet size of emulsion was established. Furthermore, it was observed that Janus emulsion gels with interesting rheological properties can be fabricated in the presence of suitable polyelectrolyte complexes. Janus emulsions that could be influenced by pH, temperature or magnetic field were successfully produced in presence of characteristic stimuli-responsive stabilizers. Afterwards, the effect of these changes was studied by different characterization techniques. The size and morphology could be tuned easily by changing the pH. The incorporation of iron oxide magnetic nanoparticles (synthesized separately by a co-precipitation method) to one component of the Janus emulsion was carried out so that the movement and orientation of the complex droplets in aqueous media could be controlled by an external magnetic field. Additionally, temperature-triggered instantaneous reversible breakdown of Janus droplets was also accomplished. The responses of the Janus droplets by the stimuli were well-documented and explained. Another goal of the present contribution was to exploit this special morphological feature of emulsions as a template for producing porous materials. This was demonstrated by the preparation of ultralight magnetic responsive aerogels, utilizing Janus emulsion gels. The produced aerogels also showed the capacity to separate toxic dye from water. To the best of our knowledge, this is the first example of investigation towards batch scale production of Janus emulsion with such special stimuli-responsive properties by a simple bulk emulsification method.
The present work deals with the variation in the linearisation of German infinitival complements from a diachronic perspective. Based on the observation that in present-day German the position of infinitival complements is restricted by properties of the matrix verb (Haider, 2010, Wurmbrand, 2001), whereas this appears much more liberal in older stages of German (Demske, 2008, Maché and Abraham, 2011, Demske, 2015), this dissertation investigates the emergence of those restrictions and the factors that have led to a reduced, yet still existing variability. The study contrasts infinitival complements of two types of matrix verbs, namely raising and control verbs. In present-day German, these show different syntactic behaviour and opposite preferences as far as the position of the infinitive is concerned: while infinitival complements of raising verbs build a single clausal domain with the with the matrix verb and occur obligatorily intraposed, infinitive complements of control verbs can form clausal constituents and occur predominantly extraposed. This correlation is not attested in older stages of German, at least not until Early New High German.
Drawing on diachronic corpus data, the present work provides a description of the changes in the linearisation of infinitival complements from Early New High German to present-day German which aims at finding out when the correlation between infinitive type and word order emerged and further examines their possible causes. The study shows that word order change in German infinitival complements is not a case of syntactic change in the narrow sense, but that the diachronic variation results from the interaction of different language-internal and language-external factors and that it reflects, on the one hand, the influence of language modality on the emerging standard language and, on the other hand, a process of specialisation.
In modern times of evolving globalization and continuous technological developments, organizations are required to respond to ever-changing demands. Therefore, to be successful in today’s highly uncertain environments, organizations need employees to actively search for opportunities, anticipate challenges, and act ahead. In other words, employee proactivity in the workplace represents a highly valuable resource in nowadays organizations. Empirical studies conducted as part of this thesis advance the research on the outcomes of proactivity from the individual perspective. The main contribution of this thesis pertains to revealing several important individual and contextual conditions under which engaging in proactivity will have negative and positive effects on employees’ well-being and their consequent behaviours, as well as shedding light on the unique psychological mechanisms through which these effects unfold. From a practical standpoint, this research underscores the importance of creating work environments that support employees’ autonomous motivation for proactivity and urge organizations and managers to be mindful about the pressures they place on employees to be proactive at work. Besides, this thesis stimulates research efforts aimed at further extending our knowledge of when and how individual proactive behaviours at work will do more good than harm for those who enact them.
Virtualizing physical space
(2021)
The true cost for virtual reality is not the hardware, but the physical space it requires, as a one-to-one mapping of physical space to virtual space allows for the most immersive way of navigating in virtual reality. Such “real-walking” requires physical space to be of the same size and the same shape of the virtual world represented. This generally prevents real-walking applications from running on any space that they were not designed for.
To reduce virtual reality’s demand for physical space, creators of such applications let users navigate virtual space by means of a treadmill, altered mappings of physical to virtual space, hand-held controllers, or gesture-based techniques. While all of these solutions succeed at reducing virtual reality’s demand for physical space, none of them reach the same level of immersion that real-walking provides.
Our approach is to virtualize physical space: instead of accessing physical space directly, we allow applications to express their need for space in an abstract way, which our software systems then map to the physical space available. We allow real-walking applications to run in spaces of different size, different shape, and in spaces containing different physical objects. We also allow users immersed in different virtual environments to share the same space.
Our systems achieve this by using a tracking volume-independent representation of real-walking experiences — a graph structure that expresses the spatial and logical relationships between virtual locations, virtual elements contained within those locations, and user interactions with those elements. When run in a specific physical space, this graph representation is used to define a custom mapping of the elements of the virtual reality application and the physical space by parsing the graph using a constraint solver. To re-use space, our system splits virtual scenes and overlap virtual geometry. The system derives this split by means of hierarchically clustering of our virtual objects as nodes of our bi-partite directed graph that represents the logical ordering of events of the experience. We let applications express their demands for physical space and use pre-emptive scheduling between applications to have them share space. We present several application examples enabled by our system. They all enable real-walking, despite being mapped to physical spaces of different size and shape, containing different physical objects or other users.
We see substantial real-world impact in our systems. Today’s commercial virtual reality applications are generally designing to be navigated using less immersive solutions, as this allows them to be operated on any tracking volume. While this is a commercial necessity for the developers, it misses out on the higher immersion offered by real-walking. We let developers overcome this hurdle by allowing experiences to bring real-walking to any tracking volume, thus potentially bringing real-walking to consumers.
Die eigentlichen Kosten für Virtual Reality Anwendungen entstehen nicht primär durch die erforderliche Hardware, sondern durch die Nutzung von physischem Raum, da die eins-zu-eins Abbildung von physischem auf virtuellem Raum die immersivste Art von Navigation ermöglicht. Dieses als „Real-Walking“ bezeichnete Erlebnis erfordert hinsichtlich Größe und Form eine Entsprechung von physischem Raum und virtueller Welt. Resultierend daraus können Real-Walking-Anwendungen nicht an Orten angewandt werden, für die sie nicht entwickelt wurden.
Um den Bedarf an physischem Raum zu reduzieren, lassen Entwickler von Virtual Reality-Anwendungen ihre Nutzer auf verschiedene Arten navigieren, etwa mit Hilfe eines Laufbandes, verfälschten Abbildungen von physischem zu virtuellem Raum, Handheld-Controllern oder gestenbasierten Techniken. All diese Lösungen reduzieren zwar den Bedarf an physischem Raum, erreichen jedoch nicht denselben Grad an Immersion, den Real-Walking bietet.
Unser Ansatz zielt darauf, physischen Raum zu virtualisieren: Anstatt auf den physischen Raum direkt zuzugreifen, lassen wir Anwendungen ihren Raumbedarf auf abstrakte Weise formulieren, den unsere Softwaresysteme anschließend auf den verfügbaren physischen Raum abbilden. Dadurch ermöglichen wir Real-Walking-Anwendungen Räume mit unterschiedlichen Größen und Formen und Räume, die unterschiedliche physische Objekte enthalten, zu nutzen. Wir ermöglichen auch die zeitgleiche Nutzung desselben Raums durch mehrere Nutzer verschiedener Real-Walking-Anwendungen.
Unsere Systeme erreichen dieses Resultat durch eine Repräsentation von Real-Walking-Erfahrungen, die unabhängig sind vom gegebenen Trackingvolumen – eine Graphenstruktur, die die räumlichen und logischen Beziehungen zwischen virtuellen Orten, den virtuellen Elementen innerhalb dieser Orte, und Benutzerinteraktionen mit diesen Elementen, ausdrückt. Bei der Instanziierung der Anwendung in einem bestimmten physischen Raum wird diese Graphenstruktur und ein Constraint Solver verwendet, um eine individuelle Abbildung der virtuellen Elemente auf den physischen Raum zu erreichen. Zur mehrmaligen Verwendung des Raumes teilt unser System virtuelle Szenen und überlagert virtuelle Geometrie. Das System leitet diese Aufteilung anhand eines hierarchischen Clusterings unserer virtuellen Objekte ab, die als Knoten unseres bi-partiten, gerichteten Graphen die logische Reihenfolge aller Ereignisse repräsentieren. Wir verwenden präemptives Scheduling zwischen den Anwendungen für die zeitgleiche Nutzung von physischem Raum. Wir stellen mehrere Anwendungsbeispiele vor, die Real-Walking ermöglichen – in physischen Räumen mit unterschiedlicher Größe und Form, die verschiedene physische Objekte oder weitere Nutzer enthalten.
Wir sehen in unseren Systemen substantielles Potential. Heutige Virtual Reality-Anwendungen sind bisher zwar so konzipiert, dass sie auf einem beliebigen Trackingvolumen betrieben werden können, aber aus kommerzieller Notwendigkeit kein Real-Walking beinhalten. Damit entgeht Entwicklern die Gelegenheit eine höhere Immersion herzustellen. Indem wir es ermöglichen, Real-Walking auf jedes Trackingvolumen zu bringen, geben wir Entwicklern die Möglichkeit Real-Walking zu ihren Nutzern zu bringen.
Rheology describes the flow of matter under the influence of stress, and - related to solids- it investigates how solids subjected to stresses deform. As the deformation of the Earth’s outer layers, the lithosphere and the crust, is a major focus of rheological studies, rheology in the geosciences describes how strain evolves in rocks of variable composition and temperature under tectonic stresses. It is here where deformation processes shape the form of ocean basins and mountain belts that ultimately result from the complex interplay between lithospheric plate motion and the susceptibility of rocks to the influence of plate-tectonic forces. A rigorous study of the strength of the lithosphere and deformation phenomena thus requires in-depth studies of the rheological characteristics of the involved materials and the temporal framework of deformation processes.
This dissertation aims at analyzing the influence of the physical configuration of the lithosphere on the present-day thermal field and the overall rheological characteristics of the lithosphere to better understand variable expressions in the formation of passive continental margins and the behavior of strike-slip fault zones. The main methodological approach chosen is to estimate the present-day thermal field and the strength of the lithosphere by 3-D numerical modeling. The distribution of rock properties is provided by 3-D structural models, which are used as the basis for the thermal and rheological modeling. The structural models are based on geophysical and geological data integration, additionally constrained by 3-D density modeling. More specifically, to decipher the thermal and rheological characteristics of the lithosphere in both oceanic and continental domains, sedimentary basins in the Sea of Marmara (continental transform setting), the SW African passive margin (old oceanic crust), and the Norwegian passive margin (young oceanic crust) were selected for this study.
The Sea of Marmara, in northwestern Turkey, is located where the dextral North Anatolian Fault zone (NAFZ) accommodates the westward escape of the Anatolian Plate toward the Aegean. Geophysical observations indicate that the crust is heterogeneous beneath the Marmara basin, but a detailed characterization of the lateral crustal heterogeneities is presented for the first time in this study. Here, I use different gravity datasets and the general non-uniqueness in potential field modeling, to propose three possible end-member scenarios of crustal configuration. The models suggest that pronounced gravitational anomalies in the basin originate from significant density heterogeneities within the crust. The rheological modeling reveals that associated variations in lithospheric strength control the mechanical segmentation of the NAFZ. Importantly, a strong crust that is mechanically coupled to the upper mantle spatially correlates with aseismic patches where the fault bends and changes its strike in response to the presence of high-density lower crustal bodies. Between the bends, mechanically weaker crustal domains that are decoupled from the mantle are characterized by creep.
For the passive margins of SW Africa and Norway, two previously published 3-D conductive and lithospheric-scale thermal models were analyzed. These 3-D models differentiate various sedimentary, crustal, and mantle units and integrate different geophysical data, such as seismic observations and the gravity field. Here, the rheological modeling suggests that the present-day lithospheric strength across the oceanic domain is ultimately affected by the age and past thermal and tectonic processes as well as the depth of the thermal lithosphere-asthenosphere boundary, while the configuration of the crystalline crust dominantly controls the rheological behavior of the lithosphere beneath the continental domains of both passive margins.
The thermal and rheological models show that the variations of lithospheric strength are fundamentally influenced by the temperature distribution within the lithosphere. Moreover, as the composition of the lithosphere significantly influences the present-day thermal field, it therefore also affects the rheological characteristics of the lithosphere. Overall my studies add to our understanding of regional tectonic deformation processes and the long-term behavior of sedimentary basins; they confirm other analyses that have pointed out that crustal heterogeneities in the continents result in diverse lithospheric thermal characteristics, which in turn results in higher complexity and variations of rheological behavior compared to oceanic domains with a thinner, more homogeneous crust.
The Earth's electron radiation belts exhibit a two-zone structure, with the outer belt being highly dynamic due to the constant competition between a number of physical processes, including acceleration, loss, and transport. The flux of electrons in the outer belt can vary over several orders of magnitude, reaching levels that may disrupt satellite operations. Therefore, understanding the mechanisms that drive these variations is of high interest to the scientific community.
In particular, the important role played by loss mechanisms in controlling relativistic electron dynamics has become increasingly clear in recent years. It is now widely accepted that radiation belt electrons can be lost either by precipitation into the atmosphere or by transport across the magnetopause, called magnetopause shadowing. Precipitation of electrons occurs due to pitch-angle scattering by resonant interaction with various types of waves, including whistler mode chorus, plasmaspheric hiss, and electromagnetic ion cyclotron waves. In addition, the compression of the magnetopause due to increases in solar wind dynamic pressure can substantially deplete electrons at high L shells where they find themselves in open drift paths, whereas electrons at low L shells can be lost through outward radial diffusion. Nevertheless, the role played by each physical process during electron flux dropouts still remains a fundamental puzzle.
Differentiation between these processes and quantification of their relative contributions to the evolution of radiation belt electrons requires high-resolution profiles of phase space density (PSD). However, such profiles of PSD are difficult to obtain due to restrictions of spacecraft observations to a single measurement in space and time, which is also compounded by the inaccuracy of instruments. Data assimilation techniques aim to blend incomplete and inaccurate spaceborne data with physics-based models in an optimal way. In the Earth's radiation belts, it is used to reconstruct the entire radial profile of electron PSD, and it has become an increasingly important tool in validating our current understanding of radiation belt dynamics, identifying new physical processes, and predicting the near-Earth hazardous radiation environment.
In this study, sparse measurements from Van Allen Probes A and B and Geostationary Operational Environmental Satellites (GOES) 13 and 15 are assimilated into the three-dimensional Versatile Electron Radiation Belt (VERB-3D) diffusion model, by means of a split-operator Kalman filter over a four-year period from 01 October 2012 to 01 October 2016. In comparison to previous works, the 3D model accounts for more physical processes, namely mixed pitch angle-energy diffusion, scattering by EMIC waves, and magnetopause shadowing. It is shown how data assimilation, by means of the innovation vector (the residual between observations and model forecast), can be used to account for missing physics in the model. This method is used to identify the radial distances from the Earth and the geomagnetic conditions where the model is inconsistent with the measured PSD for different values of the adiabatic invariants mu and K. As a result, the Kalman filter adjusts the predictions in order to match the observations, and this is interpreted as evidence of where and when additional source or loss processes are active.
Furthermore, two distinct loss mechanisms responsible for the rapid dropouts of radiation belt electrons are investigated: EMIC wave-induced scattering and magnetopause shadowing. The innovation vector is inspected for values of the invariant mu ranging from 300 to 3000 MeV/G, and a statistical analysis is performed to quantitatively assess the effect of both processes as a function of various geomagnetic indices, solar wind parameters, and radial distance from the Earth. The results of this work are in agreement with previous studies that demonstrated the energy dependence of these two mechanisms. EMIC wave scattering dominates loss at lower L shells and it may amount to between 10%/hr to 30%/hr of the maximum value of PSD over all L shells for fixed first and second adiabatic invariants. On the other hand, magnetopause shadowing is found to deplete electrons across all energies, mostly at higher L shells, resulting in loss from 50%/hr to 70%/hr of the maximum PSD. Nevertheless, during times of enhanced geomagnetic activity, both processes can operate beyond such location and encompass the entire outer radiation belt.
The results of this study are two-fold. Firstly, it demonstrates that the 3D data assimilative code provides a comprehensive picture of the radiation belts and is an important step toward performing reanalysis using observations from current and future missions. Secondly, it achieves a better understanding and provides critical clues of the dominant loss mechanisms responsible for the rapid dropouts of electrons at different locations over the outer radiation belt.
In the frame of a world fighting a dramatic global warming caused by human-related activities, research towards the development of renewable energies plays a crucial role. Solar energy is one of the most important clean energy sources and its role in the satisfaction of the global energy demand is set to increase. In this context, a particular class of materials captured the attention of the scientific community for its attractive properties: halide perovskites. Devices with perovskite as light-absorber saw an impressive development within the last decade, reaching nowadays efficiencies comparable to mature photovoltaic technologies like silicon solar cells. Yet, there are still several roadblocks to overcome before a wide-spread commercialization of this kind of devices is enabled. One of the critical points lies at the interfaces: perovskite solar cells (PSCs) are made of several layers with different chemical and physical features. In order for the device to function properly, these properties have to be well-matched.
This dissertation deals with some of the challenges related to interfaces in PSCs, with a focus on the interface between the perovskite material itself and the subsequent charge transport layer. In particular, molecular assemblies with specific properties are deposited on the perovskite surface to functionalize it. The functionalization results in energy level alignment adjustment, interfacial losses reduction, and stability improvement.
First, a strategy to tune the perovskite’s energy levels is introduced: self-assembled monolayers of dipolar molecules are used to functionalize the surface, obtaining simultaneously a shift in the vacuum level position and a saturation of the dangling bonds at the surface. A shift in the vacuum level corresponds to an equal change in work function, ionization energy, and electron affinity. The direction of the shift depends on the direction of the collective interfacial dipole. The magnitude of the shift can be tailored by controlling the deposition parameters, such as the concentration of the solution used for the deposition. The shift for different molecules is characterized by several non-invasive techniques, including in particular Kelvin probe. Overall, it is shown that it is possible to shift the perovskite energy levels in both directions by several hundreds of meV. Moreover, interesting insights on the molecules deposition dynamics are revealed.
Secondly, the application of this strategy in perovskite solar cells is explored. Devices with different perovskite compositions (“triple cation perovskite” and MAPbBr3) are prepared. The two resulting model systems present different energetic offsets at the perovskite/hole-transport layer interface. Upon tailored perovskite surface functionalization, the devices show a stabilized open circuit voltage (Voc) enhancement of approximately 60 meV on average for devices with MAPbBr3, while the impact is limited on triple-cation solar cells. This suggests that the proposed energy level tuning method is valid, but its effectiveness depends on factors such as the significance of the energetic offset compared to the other losses in the devices.
Finally, the above presented method is further developed by incorporating the ability to interact with the perovskite surface directly into a novel hole-transport material (HTM), named PFI. The HTM can anchor to the perovskite halide ions via halogen bonding (XB). Its behaviour is compared to that of another HTM (PF) with same chemical structure and properties, except for the ability of forming XB. The interaction of perovskite with PFI and PF is characterized through UV-Vis, atomic force microscopy and Kelvin probe measurements combined with simulations. Compared to PF, PFI exhibits enhanced resilience against solvent exposure and improved energy level alignment with the perovskite layer. As a consequence, devices comprising PFI show enhanced Voc and operational stability during maximum-power-point tracking, in addition to hysteresis reduction. XB promotes the formation of a high-quality interface by anchoring to the halide ions and forming a stable and ordered interfacial layer, showing to be a particularly interesting candidate for the development of tailored charge transport materials in PSCs.
Overall, the results exposed in this dissertation introduce and discuss a versatile tool to functionalize the perovskite surface and tune its energy levels. The application of this method in devices is explored and insights on its challenges and advantages are given. Within this frame, the results shed light on XB as ideal interaction for enhancing stability and efficiency in perovskite-based devices.
Transient permeability in porous and fractured sandstones mediated by fluid-rock interactions
(2021)
Understanding the fluid transport properties of subsurface rocks is essential for a large number of geotechnical applications, such as hydrocarbon (oil/gas) exploitation, geological storage (CO2/fluids), and geothermal reservoir utilization. To date, the hydromechanically-dependent fluid flow patterns in porous media and single macroscopic rock fractures have received numerous investigations and are relatively well understood. In contrast, fluid-rock interactions, which may permanently affect rock permeability by reshaping the structure and changing connectivity of pore throats or fracture apertures, need to be further elaborated. This is of significant importance for improving the knowledge of the long-term evolution of rock transport properties and evaluating a reservoir’ sustainability. The thesis focuses on geothermal energy utilization, e.g., seasonal heat storage in aquifers and enhanced geothermal systems, where single fluid flow in porous rocks and rock fracture networks under various pressure and temperature conditions dominates.
In this experimental study, outcrop samples (i.e., Flechtinger sandstone, an illite-bearing Lower Permian rock, and Fontainebleau sandstone, consisting of pure quartz) were used for flow-through experiments under simulated hydrothermal conditions. The themes of the thesis are (1) the investigation of clay particle migration in intact Flechtinger sandstone and the coincident permeability damage upon cyclic temperature and fluid salinity variations; (2) the determination of hydro-mechanical properties of self-propping fractures in Flechtinger and Fontainebleau sandstones with different fracture features and contrasting mechanical properties; and (3) the investigation of the time-dependent fracture aperture evolution of Fontainebleau sandstone induced by fluid-rock interactions (i.e., predominantly pressure solution). Overall, the thesis aims to unravel the mechanisms of the instantaneous reduction (i.e., direct responses to thermo-hydro-mechanical-chemical (THMC) conditions) and progressively-cumulative changes (i.e., time-dependence) of rock transport properties.
Permeability of intact Flechtinger sandstone samples was measured under each constant condition, where temperature (room temperature up to 145 °C) and fluid salinity (NaCl: 0 ~ 2 mol/l) were stepwise changed. Mercury intrusion porosimetry (MIP), electron microprobe analysis (EMPA), and scanning electron microscopy (SEM) were performed to investigate the changes of local porosity, microstructures, and clay element contents before and after the experiments. The results indicate that the permeability of illite-bearing Flechtinger sandstones will be impaired by heating and exposure to low salinity pore fluids. The chemically induced permeability variations prove to be path-dependent concerning the applied succession of fluid salinity changes. The permeability decay induced by a temperature increase and a fluid salinity reduction operates by relatively independent mechanisms, i.e., thermo-mechanical and thermo-chemical effects.
Further, the hydro-mechanical investigations of single macroscopic fractures (aligned, mismatched tensile fractures, and smooth saw-cut fractures) illustrate that a relative fracture wall offset could significantly increase fracture aperture and permeability, but the degree of increase depends on fracture surface roughness. X-ray computed tomography (CT) demonstrates that the contact area ratio after the pressure cycles is inversely correlated to the fracture offset. Moreover, rock mechanical properties, determining the strength of contact asperities, are crucial so that relatively harder rock (i.e., Fontainebleau sandstone) would have a higher self-propping potential for sustainable permeability during pressurization. This implies that self-propping rough fractures with a sufficient displacement are efficient pathways for fluid flow if the rock matrix is mechanically strong.
Finally, two long-term flow-through experiments with Fontainebleau sandstone samples containing single fractures were conducted with an intermittent flow (~140 days) and continuous flow (~120 days), respectively. Permeability and fluid element concentrations were measured throughout the experiments. Permeability reduction occurred at the beginning stage when the stress was applied, while it converged at later stages, even under stressed conditions. Fluid chemistry and microstructure observations demonstrate that pressure solution governs the long-term fracture aperture deformation, with remarkable effects of the pore fluid (Si) concentration and the structure of contact grain boundaries. The retardation and the cessation of rock fracture deformation are mainly induced by the contact stress decrease due to contact area enlargement and a dissolved mass accumulation within the contact boundaries. This work implies that fracture closure under constant (pressure/stress and temperature) conditions is likely a spontaneous process, especially at the beginning stage after pressurization when the contact area is relatively small. In contrast, a contact area growth yields changes of fracture closure behavior due to the evolution of contact boundaries and concurrent changes in their diffusive properties. Fracture aperture and thus permeability will likely be sustainable in the long term if no other processes (e.g., mineral precipitations in the open void space) occur.
River flooding poses a threat to numerous cities and communities all over the world. The detection, quantification and attribution of changes in flood characteristics is key to assess changes in flood hazard and help affected societies to timely mitigate and adapt to emerging risks. The Rhine River is one of the major European rivers and numerous large cities reside at its shores. Runoff from several large tributaries superimposes in the main channel shaping the complex from regime. Rainfall, snowmelt as well as ice-melt are important runoff components. The main objective of this thesis is the investigation of a possible transient merging of nival and pluvial Rhine flood regimes under global warming. Rising temperatures cause snowmelt to occur earlier in the year and rainfall to be more intense. The superposition of snowmelt-induced floods originating from the Alps with more intense rainfall-induced runoff from pluvial-type tributaries might create a new flood type with potentially disastrous consequences.
To introduce the topic of changing hydrological flow regimes, an interactive web application that enables the investigation of runoff timing and runoff season- ality observed at river gauges all over the world is presented. The exploration and comparison of a great diversity of river gauges in the Rhine River Basin and beyond indicates that river systems around the world undergo fundamental changes. In hazard and risk research, the provision of background as well as real-time information to residents and decision-makers in an easy accessible way is of great importance. Future studies need to further harness the potential of scientifically engineered online tools to improve the communication of information related to hazards and risks.
A next step is the development of a cascading sequence of analytical tools to investigate long-term changes in hydro-climatic time series. The combination of quantile sampling with moving average trend statistics and empirical mode decomposition allows for the extraction of high resolution signals and the identification of mechanisms driving changes in river runoff. Results point out that the construction and operation of large reservoirs in the Alps is an important factor redistributing runoff from summer to winter and hint at more (intense) rainfall in recent decades, particularly during winter, in turn increasing high runoff quantiles. The development and application of the analytical sequence represents a further step in the scientific quest to disentangling natural variability, climate change signals and direct human impacts.
The in-depth analysis of in situ snow measurements and the simulations of the Alpine snow cover using a physically-based snow model enable the quantification of changes in snowmelt in the sub-basin upstream gauge Basel. Results confirm previous investigations indicating that rising temperatures result in a decrease in maximum melt rates. Extending these findings to a catchment perspective, a threefold effect of rising temperatures can be identified: snowmelt becomes weaker, occurs earlier and forms at higher elevations. Furthermore, results indicate that due to the wide range of elevations in the basin, snowmelt does not occur simultaneously at all elevation, but elevation bands melt together in blocks. The beginning and end of the release of meltwater seem to be determined by the passage of warm air masses, and the respective elevation range affected by accompanying temperatures and snow availability. Following those findings, a hypothesis describing elevation-dependent compensation effects in snowmelt is introduced: In a warmer world with similar sequences of weather conditions, snowmelt is moved upward to higher elevations, i.e., the block of elevation bands providing most water to the snowmelt-induced runoff is located at higher elevations. The movement upward the elevation range makes snowmelt in individual elevation bands occur earlier. The timing of the snowmelt-induced runoff, however, stays the same. Meltwater from higher elevations, at least partly, replaces meltwater from elevations below.
The insights on past and present changes in river runoff, snow covers and underlying mechanisms form the basis of investigations of potential future changes in Rhine River runoff. The mesoscale Hydrological Model (mHM) forced with an ensemble of climate projection scenarios is used to analyse future changes in streamflow, snowmelt, precipitation and evapotranspiration at 1.5, 2.0 and
3.0 ◦ C global warming. Simulation results suggest that future changes in flood characteristics in the Rhine River Basin are controlled by increased precipitation amounts on the one hand, and reduced snowmelt on the other hand. Rising temperatures deplete seasonal snowpacks. At no time during the year, a warming climate results in an increase in the risk of snowmelt-driven flooding. Counterbalancing effects between snowmelt and precipitation often result in only little and transient changes in streamflow peaks. Although, investigations point at changes in both rainfall and snowmelt-driven runoff, there are no indications of a transient merging of nival and pluvial Rhine flood regimes due to climate warming. Flooding in the main tributaries of the Rhine, such as the Moselle River, as well as the High Rhine is controlled by both precipitation and snowmelt. Caution has to be exercised labelling sub-basins such as the Moselle catchment as purely pluvial-type or the Rhine River Basin at Basel as purely nival-type. Results indicate that this (over-) simplifications can entail misleading assumptions with regard to flood-generating mechanisms and changes in flood hazard. In the framework of this thesis, some progress has been made in detecting, quantifying and attributing past, present and future changes in Rhine flow/flood characteristics. However, further studies are necessary to pin down future changes in the flood genesis of Rhine floods, particularly very rare events.
The optical properties of chromophores, especially organic dyes and optically active inorganic molecules, are determined by their chemical structures, surrounding media, and excited state behaviors. The classical optical go-to techniques for spectroscopic investigations are absorption and luminescence spectroscopy. While both techniques are powerful and easy to apply spectroscopic methods, the limited time resolution of luminescence spectroscopy and its reliance on luminescent properties can make its application, in certain cases, complex, or even impossible. This can be the case when the investigated molecules do not luminesce anymore due to quenching effects, or when they were never luminescent in the first place. In those cases, transient absorption spectroscopy is an excellent and much more sophisticated technique to investigate such systems. This pump-probe laser-spectroscopic method is excellent for mechanistic investigations of luminescence quenching phenomena and photoreactions. This is due to its extremely high time resolution in the femto- and picosecond ranges, where many intermediate or transient species of a reaction can be identified and their kinetic evolution can be observed. Furthermore, it does not rely on the samples being luminescent, due to the active sample probing after excitation. In this work it is shown, that with transient absorption spectroscopy it was possible to identify the luminescence quenching mechanisms and thus luminescence quantum yield losses of the organic dye classes O4-DBD, S4-DBD, and pyridylanthracenes. Hence, the population of their triplet states could be identified as the competitive mechanism to their luminescence. While the good luminophores O4-DBD showed minor losses, the S4-DBD dye luminescence was almost entirely quenched by this process. However, for pyridylanthracenes, this phenomenon is present in both the protonated and unprotonated forms and moderately effects the luminescence quantum yield. Also, the majority of the quenching losses in the protonated forms are caused by additional non-radiative processes introduced by the protonation of the pyridyl rings. Furthermore, transient absorption spectroscopy can be applied to investigate the quenching mechanisms of uranyl(VI) luminescence by chloride and bromide. The reduction of the halides by excited uranyl(VI) leads to the formation of dihalide radicals X^(·−2). This excited state redox process is thus identified as the quenching mechanism for both halides, and this process, being diffusion-limited, can be suppressed by cryogenically freezing the samples or by observing these interactions in media with a lower dielectric constant, such as ACN and acetone.
The trace elements zinc and manganese are essential for human health, especially due to their enzymatic and protein stabilizing functions. If these elements are ingested in amounts exceeding the requirements, regulatory processes for maintaining their physiological concentrations (homeostasis) can be disturbed. Those homeostatic dysregulations can cause severe health effects including the emergence of neurodegenerative disorders such as Parkinson’s disease (PD). The concentrations of essential trace elements also change during the aging process. However, the relations of cause and consequence between increased manganese and zinc uptake and its influence on the aging process and the emergence of the aging-associated PD are still rarely understood. This doctoral thesis therefore aimed to investigate the influence of a nutritive zinc and/or manganese oversupply on the metal homeostasis during the aging process. For that, the model organism Caenorhabditis elegans (C. elegans) was applied. This nematode suits well as an aging and PD model due to properties such as its short life cycle and its completely sequenced, genetically amenable genome. Different protocols for the propagation of zinc- and/or manganese-supplemented young, middle-aged and aged C. elegans were established. Therefore, wildtypes, as well as genetically modified worm strains modeling inheritable forms of parkinsonism were applied. To identify homeostatic and neurological alterations, the nematodes were investigated with different methods including the analysis of total metal contents via inductively-coupled plasma tandem mass spectrometry, a specific probe-based method for quantifying labile zinc, survival assays, gene expression analysis as well as fluorescence microscopy for the identification and quantification of dopaminergic neurodegeneration.. During aging, the levels of iron, as well as zinc and manganese increased.. Furthermore, the simultaneous oversupply with zinc and manganese increased the total zinc and manganese contents to a higher extend than the single metal supplementation. In this relation the C. elegans metallothionein 1 (MTL-1) was identified as an important regulator of metal homeostasis. The total zinc content and the concentration of labile zinc were age-dependently, but differently regulated. This elucidates the importance of distinguishing these parameters as two independent biomarkers for the zinc status. Not the metal oversupply, but aging increased the levels of dopaminergic neurodegeneration. Additionally, nearly all these results yielded differences in the aging-dependent regulation of trace element homeostasis between wildtypes and PD models. This confirms that an increased zinc and manganese intake can influence the aging process as well as parkinsonism by altering homeostasis although the underlying mechanisms need to be clarified in further studies.
Water-deficits can cause lethal damage to organisms, which is rooted in cellular dehydration. Many plant species, but also other organisms have developed mechanisms to tolerate such stresses, such as the expression of LEA proteins. Many studies report on physiological protective functions of LEA proteins but lack information about their precise mechanisms on a molecular level. Most LEA proteins are intrinsically disordered in dilute solution but may adopt a distinct secondary structure upon changes in solvent conditions. Understanding the molecular mechanism of how LEA proteins contribute to the counteraction of cellular damage during water-deficits may in the long-term pave the way for breeding crops that are resistant to the effects of global warming. The objective of the work at hand is to improve the biophysical understanding of the sequencestructure-function relationship of LEA proteins as membrane stabilizers, based on the LEA_4 family of the model plant A. thaliana. This is pursued by using a combination of spectroscopic and scattering techniques, supported by bioinformatics and computational analyses. Eight out of the 18 LEA_4 proteins are experimentally assessed revealing that a coil-helix transition in response to water-deficit is a common feature, as predicted for the entire family. In addition, they all stabilize simple membrane models during a freeze/ thaw cycle. Three-dimensional structure prediction of representative members suggests that their completely folded states are represented by a sequential arrangement of alpha-helical segments connected by unstructured linkers, which is experimentally verified for the LEA_4 protein COR15A. The unstructured linker region of COR15A represents a conserved motif among its closest homologs and is, therefore, of particular interest. Facilitating a set of seven designed and investigated COR15A mutants uncovers a complex interplay of transient interactions between the amphipathic alpha-helical segments, mediated by the linker, which fine-tunes folding transitions and structural ensembles upon reduced water-availability. Finally, alpha-helicity is also induced in COR15A upon temperature decrease, which is enhanced in the presence of osmolytes. In addition, high solution osmolarity induced secondary structure is followed by oligomerization of COR15A. Interestingly, the functionality of COR15A, in terms of liposome stabilization, strongly correlates with its alpha-helix ratio in the folded state. The present work significantly improves the understanding of the sequence-structure-function relationship for LEA_4 proteins and offers novel findings on folding mechanisms and oligomerization of COR15A.
In our daily life, recurrence plays an important role on many spatial and temporal scales and in different contexts. It is the foundation of learning, be it in an evolutionary or in a neural context. It therefore seems natural that recurrence is also a fundamental concept in theoretical dynamical systems science. The way in which states of a system recur or develop in a similar way from similar initial states makes it possible to infer information about the underlying dynamics of the system. The mathematical space in which we define the state of a system (state space) is often high dimensional, especially in complex systems that can also exhibit chaotic dynamics. The recurrence plot (RP) enables us to visualize the recurrences of any high-dimensional systems in a two-dimensional, binary representation. Certain patterns in RPs can be related to physical properties of the underlying system, making the qualitative and quantitative analysis of RPs an integral part of nonlinear systems science. The presented work has a methodological focus and further develops recurrence analysis (RA) by addressing current research questions related to an increasing amount of available data and advances in machine learning techniques. By automatizing a central step in RA, namely the reconstruction of the state space from measured experimental time series, and by investigating the impact of important free parameters this thesis aims to make RA more accessible to researchers outside of physics.
The first part of this dissertation is concerned with the reconstruction of the state space from time series. To this end, a novel idea is proposed which automates the reconstruction problem in the sense that there is no need to preprocesse the data or estimate parameters a priori. The key idea is that the goodness of a reconstruction can be evaluated by a suitable objective function and that this function is minimized in the embedding process. In addition, the new method can process multivariate time series input data. This is particularly important because multi-channel sensor-based observations are ubiquitous in many research areas and continue to increase. Building on this, the described minimization problem of the objective function is then processed using a machine learning approach.
In the second part technical and methodological aspects of RA are discussed. First, we mathematically justify the idea of setting the most influential free parameter in RA, the recurrence threshold ε, in relation to the distribution of all pairwise distances in the data. This is especially important when comparing different RPs and their quantification statistics and is fundamental to any comparative study. Second, some aspects of recurrence quantification analysis (RQA) are examined. As correction schemes for biased RQA statistics, which are based on diagonal lines, we propose a simple method for dealing with border effects of an RP in RQA and a skeletonization algorithm for RPs. This results in less biased (diagonal line based) RQA statistics for flow-like data. Third, a novel type of RQA characteristic is developed, which can be viewed as a generalized non-linear powerspectrum of high dimensional systems. The spike powerspectrum transforms a spike-train like signal into its frequency domain. When transforming the diagonal line-dependent recurrence rate (τ-RR) of a RP in this way, characteristic periods, which can be seen in the state space representation of the system can be unraveled. This is not the case, when Fourier transforming τ-RR.
Finally, RA and RQA are applied to climate science in the third part and neuroscience in the fourth part. To the best of our knowledge, this is the first time RPs and RQA have been used to analyze lake sediment data in a paleoclimate context. Therefore, we first elaborate on the basic formalism and the interpretation of visually visible patterns in RPs in relation to the underlying proxy data. We show that these patterns can be used to classify certain types of variability and transitions in the Potassium record from six short (< 17m) sediment cores collected during the Chew Bahir Drilling Project. Building on this, the long core (∼ m composite) from the same site is analyzed and two types of variability and transitions are
identified and compared with ODP Site wetness index from the eastern Mediterranean. Type variability likely reflects the influence of precessional forcing in the lower latitudes at times of maximum values of the long eccentricity cycle ( kyr) of the earth’s orbit around the sun, with a tendency towards extreme events. Type variability appears to be related to the minimum values of this cycle and corresponds to fairly rapid transitions between relatively dry and relatively wet conditions.
In contrast, RQA has been applied in the neuroscientific context for almost two decades. In the final part, RQA statistics are used to quantify the complexity in a specific frequency band of multivariate EEG (electroencephalography) data. By analyzing experimental data, it can be shown that the complexity of the signal measured in this way across the sensorimotor cortex decreases as motor tasks are performed. The results are consistent with and comple- ment the well known concepts of motor-related brain processes. We assume that the thus discovered features of neuronal dynamics in the sensorimotor cortex together with the robust RQA methods for identifying and classifying these contribute to the non-invasive EEG-based development of brain-computer interfaces (BCI) for motor control and rehabilitation.
The present work is an important step towards a robust analysis of complex systems based on recurrence.
The Central Andes region in South America is characterized by a complex and heterogeneous deformation system. Recorded seismic activity and mapped neotectonic structures indicate that most of the intraplate deformation is located along the margins of the orogen, in the transitions to the foreland and the forearc. Furthermore, the actively deforming provinces of the foreland exhibit distinct deformation styles that vary along strike, as well as characteristic distributions of seismicity with depth. The style of deformation transitions from thin-skinned in the north to thick-skinned in the south, and the thickness of the seismogenic layer increases to the south. Based on geological/geophysical observations and numerical modelling, the most commonly invoked causes for the observed heterogeneity are the variations in sediment thickness and composition, the presence of inherited structures, and changes in the dip of the subducting Nazca plate. However, there are still no comprehensive investigations on the relationship between the lithospheric composition of the Central Andes, its rheological state and the observed deformation processes. The central aim of this dissertation is therefore to explore the link between the nature of the lithosphere in the region and the location of active deformation. The study of the lithospheric composition by means of independent-data integration establishes a strong base to assess the thermal and rheological state of the Central Andes and its adjacent lowlands, which alternatively provide new foundations to understand the complex deformation of the region. In this line, the general workflow of the dissertation consists in the construction of a 3D data-derived and gravity-constrained density model of the Central Andean lithosphere, followed by the simulation of the steady-state conductive thermal field and the calculation of strength distribution. Additionally, the dynamic response of the orogen-foreland system to intraplate compression is evaluated by means of 3D geodynamic modelling.
The results of the modelling approach suggest that the inherited heterogeneous composition of the lithosphere controls the present-day thermal and rheological state of the Central Andes, which in turn influence the location and depth of active deformation processes. Most of the seismic activity and neo--tectonic structures are spatially correlated to regions of modelled high strength gradients, in the transition from the felsic, hot and weak orogenic lithosphere to the more mafic, cooler and stronger lithosphere beneath the forearc and the foreland. Moreover, the results of the dynamic simulation show a strong localization of deviatoric strain rate second invariants in the same region suggesting that shortening is accommodated at the transition zones between weak and strong domains. The vertical distribution of seismic activity appears to be influenced by the rheological state of the lithosphere as well. The depth at which the frequency distribution of hypocenters starts to decrease in the different morphotectonic units correlates with the position of the modelled brittle-ductile transitions; accordingly, a fraction of the seismic activity is located within the ductile part of the crust. An exhaustive analysis shows that practically all the seismicity in the region is restricted above the 600°C isotherm, in coincidence with the upper temperature limit for brittle behavior of olivine. Therefore, the occurrence of earthquakes below the modelled brittle-ductile could be explained by the presence of strong residual mafic rocks from past tectonic events. Another potential cause of deep earthquakes is the existence of inherited shear zones in which brittle behavior is favored through a decrease in the friction coefficient. This hypothesis is particularly suitable for the broken foreland provinces of the Santa Barbara System and the Pampean Ranges, where geological studies indicate successive reactivation of structures through time. Particularly in the Santa Barbara System, the results indicate that both mafic rocks and a reduction in friction are required to account for the observed deep seismic events.
The survey of the prevalence of chronic ankle instability in elite Taiwanese basketball athletes
(2021)
BACKGROUND: Ankle sprains are common in basketball. It could develop into Chronic Ankle Instability (CAI) causing decreased quality of life, functional performance, early osteoarthritis, and increased risk of other injuries. To develop a strategy of CAI prevention, localized epidemiology data and a valid/reliable tool are essential. However, the epidemiological data of CAI is not conclusive from previous studies and the prevalence of CAI in Taiwanese basketball athletes are not clear. In addition, a valid and reliable tool among the Taiwan-Chinese version to evaluate ankle instability is missing.
PURPOSE: The aims were to have an overview of the prevalence of CAI in sports population using a systematic review, to develop a valid and reliable cross-cultural adapted Cumberland Ankle Instability Tool Questionnaire (CAIT) in Taiwan-Chinese (CAIT-TW), and to survey the prevalence of CAI in elite basketball athletes in Taiwan using CAIT-TW.
METHODS: Firstly, a systematic search was conducted. Research articles applying CAI related questionnaires in order to survey the prevalence of CAI were included in the review. Second, the English version of CAIT was translated and cross-culturally adapted into the CAIT-TW. The construct validity, test-retest reliability, internal consistency, and cutoff score of CAIT-TW were evaluated in an athletic population (N=135). Finally, the cross-sectional data of CAI prevalence in 388 elite Taiwanese basketball athletes were presented. Demographics, presence of CAI, and difference of prevalence between gender, different competitive levels and play positions were evaluated.
RESULTS: The prevalence of CAI was 25%, ranging between 7% and 53%. The prevalence of CAI among participants with a history of ankle sprains was 46%, ranging between 9% and 76%. In addition, the cross-cultural adapted CAIT-TW showed a moderate to strong construct validity, an excellent test-retest reliability, a good internal consistency, and a cutoff score of 21.5 for the Taiwanese athletic population. Finally, 26% of Taiwanese basketball athletes had unilateral CAI while 50% of them had bilateral CAI. In addition, women athletes in the investigated cohort had a higher prevalence of CAI than men. There was no difference in prevalence between competitive levels and among play positions.
CONCLUSION: The systematic review shows that the prevalence of CAI has a wide range among included studies. This could be due to the different exclusion criteria, age, sports discipline, or other factors among the included studies. For future studies, standardized criteria to investigate the epidemiology of CAI are required. The CAI epidemiological study should be prospective. Factors affecting the prevalence of CAI ability should be investigated and described. The translated CAIT-TW is a valid and reliable tool to differentiate between stable and unstable ankles in athletes and may further apply for research or daily practice in Taiwan. In the Taiwanese basketball population, CAI is highly prevalent. This might relate to the research method, preexisting ankle instability, and training-related issues. Women showed a higher prevalence of CAI than men. When applying the preventive measure, gender should be taken into consideration.
Flooding is a vast problem in many parts of the world, including Europe. It occurs mainly due to extreme weather conditions (e.g. heavy rainfall and snowmelt) and the consequences of flood events can be devastating. Flood risk is mainly defined as a combination of the probability of an event and its potential adverse impacts. Therefore, it covers three major dynamic components: hazard (physical characteristics of a flood event), exposure (people and their physical environment that being exposed to flood), and vulnerability (the elements at risk). Floods are natural phenomena and cannot be fully prevented. However, their risk can be managed and mitigated. For a sound flood risk management and mitigation, a proper risk assessment is needed. First of all, this is attained by a clear understanding of the flood risk dynamics. For instance, human activity may contribute to an increase in flood risk. Anthropogenic climate change causes higher intensity of rainfall and sea level rise and therefore an increase in scale and frequency of the flood events. On the other hand, inappropriate management of risk and structural protection measures may not be very effective for risk reduction. Additionally, due to the growth of number of assets and people within the flood-prone areas, risk increases. To address these issues, the first objective of this thesis is to perform a sensitivity analysis to understand the impacts of changes in each flood risk component on overall risk and further their mutual interactions. A multitude of changes along the risk chain are simulated by regional flood model (RFM) where all processes from atmosphere through catchment and river system to damage mechanisms are taken into consideration. The impacts of changes in risk components are explored by plausible change scenarios for the mesoscale Mulde catchment (sub-basin of the Elbe) in Germany.
A proper risk assessment is ensured by the reasonable representation of the real-world flood event. Traditionally, flood risk is assessed by assuming homogeneous return periods of flood peaks throughout the considered catchment. However, in reality, flood events are spatially heterogeneous and therefore traditional assumption misestimates flood risk especially for large regions. In this thesis, two different studies investigate the importance of spatial dependence in large scale flood risk assessment for different spatial scales. In the first one, the “real” spatial dependence of return period of flood damages is represented by continuous risk modelling approach where spatially coherent patterns of hydrological and meteorological controls (i.e. soil moisture and weather patterns) are included. Further the risk estimations under this modelled dependence assumption are compared with two other assumptions on the spatial dependence of return periods of flood damages: complete dependence (homogeneous return periods) and independence (randomly generated heterogeneous return periods) for the Elbe catchment in Germany. The second study represents the “real” spatial dependence by multivariate dependence models. Similar to the first study, the three different assumptions on the spatial dependence of return periods of flood damages are compared, but at national (United Kingdom and Germany) and continental (Europe) scales. Furthermore, the impacts of the different models, tail dependence, and the structural flood protection level on the flood risk under different spatial dependence assumptions are investigated.
The outcomes of the sensitivity analysis framework suggest that flood risk can vary dramatically as a result of possible change scenarios. The risk components that have not received much attention (e.g. changes in dike systems and in vulnerability) may mask the influence of climate change that is often investigated component.
The results of the spatial dependence research in this thesis further show that the damage under the false assumption of complete dependence is 100 % larger than the damage under the modelled dependence assumption, for the events with return periods greater than approximately 200 years in the Elbe catchment. The complete dependence assumption overestimates the 200-year flood damage, a benchmark indicator for the insurance industry, by 139 %, 188 % and 246 % for the UK, Germany and Europe, respectively. The misestimation of risk under different assumptions can vary from upstream to downstream of the catchment. Besides, tail dependence in the model and flood protection level in the catchments can affect the risk estimation and the differences between different spatial dependence assumptions.
In conclusion, the broader consideration of the risk components, which possibly affect the flood risk in a comprehensive way, and the consideration of the spatial dependence of flood return periods are strongly recommended for a better understanding of flood risk and consequently for a sound flood risk management and mitigation.
Proteins of halophilic organisms that accumulate molar concentrations of KCl in their cytoplasm have much higher content in acidic amino acids than proteins of mesophilic organisms. It has been proposed that this excess is necessary to maintain proteins hydrated in an environment with low water activity: either via direct interactions between water and the carboxylate groups of acidic amino acids or via cooperative interactions between acidic amino acids and hydrated cations, which would stabilize the folded protein. In the course of this Ph.D. study, we investigated these possibilities using atomistic molecular dynamics simulations and classical force fields. High quality parameters describing the interaction between K+ and carboxylate groups present in acidic amino acids are indispensable for this study. We first evaluated the quality of the default parameters for these ions within the widely used AMBER ff14SB force field for proteins and found that they perform poorly. We propose new parameters, which reproduce solution activity derivatives of potassium acetate solutions up to 2 mol/kg and the distances between potassium ions and carboxylate groups observed in x-ray structures of proteins. To understand the role of acidic amino acids in protein hydration, we investigated this aspect for 5 halophilic proteins in comparison with 5 mesophilic ones. Our results do not support the necessity of acidic amino acids to keep folded proteins hydrated. Proteins with a larger fraction of acidic amino acids indeed have higher hydration levels. However, the hydration level of each protein is identical at low (b_KCl = 0.15 mol/kg) and high (b_KCl = 2 mol/kg) KCl concentration. It has also been proposed that cooperative interactions between acidic amino acids with nearby hydrated cations stabilize the folded protein and slow down its solvation shell; according to this theory, the cations would be preferentially excluded from the unfolded structure. We investigate this possibility through extensive free energy calculation simulations. We find that cooperative interactions between neighboring acidic amino acids exist and are mediated by the ions in solution but are present in both folded and unfolded structures of halophilic proteins. The translational dynamics of the solvation shell is barely distinguishable between halophilic and mesophilic proteins; therefore, such a cooperative effect does not result in unusually slow solvent dynamics as has been suggested.
The spread of antibiotic-resistant bacteria poses a globally increasing threat to public health care. The excessive use of antibiotics in animal husbandry can develop resistances in the stables. Transmission through direct contact with animals and contamination of food has already been proven. The excrements of the animals combined with a binding material enable a further potential path of spread into the environment, if they are used as organic manure in agricultural landscapes. As most of the airborne bacteria are attached to particulate matter, the focus of the work will be the atmospheric dispersal via the dust fraction.
Field measurements on arable lands in Brandenburg, Germany and wind erosion studies in a wind tunnel were conducted to investigate the risk of a potential atmospheric dust-associated spread of antibiotic-resistant bacteria from poultry manure fertilized agricultural soils. The focus was to (i) characterize the conditions for aerosolization and (ii) qualify and quantify dust emissions during agricultural operations and wind erosion.
PM10 (PM, particulate matter with an aerodynamic diameter smaller than 10 µm) emission factors and bacterial fluxes for poultry manure application and incorporation have not been previously reported before. The contribution to dust emissions depends on the water content of the manure, which is affected by the manure pretreatment (fresh, composted, stored, dried), as well as by the intensity of manure spreading from the manure spreader. During poultry manure application, PM10 emission ranged between 0.05 kg ha-1 and 8.37 kg ha-1. For comparison, the subsequent land preparation contributes to 0.35 – 1.15 kg ha-1 of PM10 emissions. Manure particles were still part of dust emissions but they were accounted to be less than 1% of total PM10 emissions due to the dilution of poultry manure in the soil after manure incorporation. Bacterial emissions of fecal origin were more relevant during manure application than during the subsequent manure incorporation, although PM10 emissions of manure incorporation were larger than PM10 emissions of manure application for the non-dried manure variants.
Wind erosion leads to preferred detachment of manure particles from sandy soils, when poultry manure has been recently incorporated. Sorting effects were determined between the low-density organic particles of manure origin and the soil particles of mineral origin close above the threshold of 7 m s-1. In dependence to the wind speed, potential erosion rates between 101 and 854 kg ha-1 were identified, if 6 t ha-1 of poultry manure were applied. Microbial investigation showed that manure bacteria got detached more easily from the soil surface during wind erosion, due to their attachment on manure particles.
Although antibiotic-resistant bacteria (ESBL-producing E. coli) were still found in the poultry barns, no further contamination could be detected with them in the manure, fertilized soils or in the dust generated by manure application, land preparation or wind erosion. Parallel studies of this project showed that storage of poultry manure for a few days (36 – 72 h) is sufficient to inactivate ESBL-producing E. coli. Further antibiotic-resistant bacteria, i.e. MRSA and VRE, were only found sporadically in the stables and not at all in the dust. Therefore, based on the results of this work, the risk of a potential infection by dust-associated antibiotic-resistant bacteria can be considered as low.
Conceptual knowledge about objects, people and events in the world is central to human cognition, underlying core cognitive abilities such as object recognition and use, and word comprehension. Previous research indicates that concepts consist of perceptual and motor features represented in modality-specific perceptual-motor brain regions. In addition, cross-modal convergence zones integrate modality-specific features into more abstract conceptual representations.
However, several questions remain open: First, to what extent does the retrieval of perceptual-motor features depend on the concurrent task? Second, how do modality-specific and cross-modal regions interact during conceptual knowledge retrieval? Third, which brain regions are causally relevant for conceptually-guided behavior? This thesis addresses these three key issues using functional magnetic resonance imaging (fMRI) and transcranial magnetic stimulation (TMS) in the healthy human brain.
Study 1 - an fMRI activation study - tested to what extent the retrieval of sound and action features of concepts, and the resulting engagement of auditory and somatomotor brain regions depend on the concurrent task. 40 healthy human participants performed three different tasks - lexical decision, sound judgment, and action judgment - on words with a high or low association to sounds and actions. We found that modality-specific regions selectively respond to task-relevant features: Auditory regions selectively responded to sound features during sound judgments, and somatomotor regions selectively responded to action features during action judgments. Unexpectedly, several regions (e.g. the left posterior parietal cortex; PPC) exhibited a task-dependent response to both sound and action features. We propose these regions to be "multimodal", and not "amodal", convergence zones which retain modality-specific information.
Study 2 - an fMRI connectivity study - investigated the functional interaction between modality-specific and multimodal areas during conceptual knowledge retrieval. Using the above fMRI data, we asked (1) whether modality-specific and multimodal regions are functionally coupled during sound and action feature retrieval, (2) whether their coupling depends on the task, (3) whether information flows bottom-up, top-down, or bidirectionally, and (4) whether their coupling is behaviorally relevant. We found that functional coupling between multimodal and modality-specific areas is task-dependent, bidirectional, and relevant for conceptually-guided behavior. Left PPC acted as a connectivity "switchboard" that flexibly adapted its coupling to task-relevant modality-specific nodes.
Hence, neuroimaging studies 1 and 2 suggested a key role of left PPC as a multimodal convergence zone for conceptual knowledge. However, as neuroimaging is correlational, it remained unknown whether left PPC plays a causal role as a multimodal conceptual hub. Therefore, study 3 - a TMS study - tested the causal relevance of left PPC for sound and action feature retrieval. We found that TMS over left PPC selectively impaired action judgments on low sound-low action words, as compared to sham stimulation. Computational simulations of the TMS-induced electrical field revealed that stronger stimulation of left PPC was associated with worse performance on action, but not sound, judgments. These results indicate that left PPC causally supports conceptual processing when action knowledge is task-relevant and cannot be compensated by sound knowledge. Our findings suggest that left PPC is specialized for action knowledge, challenging the view of left PPC as a multimodal conceptual hub.
Overall, our studies support "hybrid theories" which posit that conceptual processing involves both modality-specific perceptual-motor regions and cross-modal convergence zones. In our new model of the conceptual system, we propose conceptual processing to rely on a representational hierarchy from modality-specific to multimodal up to amodal brain regions. Crucially, this hierarchical system is flexible, with different regions and connections being engaged in a task-dependent fashion. Our model not only reconciles the seemingly opposing grounded cognition and amodal theories, it also incorporates task dependency of conceptually-related brain activity and connectivity, thereby resolving several current issues on the neural basis of conceptual knowledge retrieval.
Patterning along the apical-basal (A-B) axis is a crucial step during the early stages of plant embryogenesis and leads to the establishment of two poles of which each will develop their own stem cell niches. The activity of these meristems is responsible for post-embryonic growth, with the shoot apical meristem (SAM) generating the above-ground organs and the root apical meristem (RAM) producing the subterranean structures of the plant. While several transcriptional regulators governing A-B patterning have been identified, precisely how their regulatory function is orchestrated remains elusive. This study focuses on transcriptional co-regulators LEUNIG (LUG) and closely related LEUNIG_HOMOLOG (LUH) and their role in the formation of A-B patterning during embryogenesis as well as their post-embryonic maintenance. A link between the LUG regulatory complex and SAM formation and maintenance comes from the observation that lug mutants heterozygous for the luh allele (lug luh+/-) often have enlarged SAMs resulting from misregulated cell divisions. A more severe phenotype is observed in lug luh double mutants which are embryonically lethal. In this study, a detailed characterisation of lug luh embryo phenotype reveals that these mutants display aberrant cell divisions along the A-B axis, which correlates with defects in auxin distribution, complete loss of apical identity, and altered expression of transcription factors determining basal fate. Like other co-regulators, LUG and LUH lack intrinsic DNA-binding domains and instead must interact with DNA-binding cofactors to ensure recruitment to regulatory elements of target genes. This either involves direct contact between the co-regulators and transcription factors (TFs) or the formation of higher-order complexes with adaptor proteins such as SEUSS (SEU) or related SEUSS-LIKEs (SLKs), which facilitate binding to specific TFs. Results presented in this study provide insight into the molecular framework for the LUG regulatory complex activity during embryogenesis. Both yeast and in planta assays showed that LUG/LUH and SEU/SLKs physically associate with a variety of WUSCHEL-RELATED HOMEOBOX (WOX) TFs including members of the WOX2-module. Furthermore, genetic interactions between members of the WOX2-module and the LUG regulatory complex, support their mutual action during embryogenesis. Based on the reduced activity of HOMEODOMAIN LEUCINE-ZIPPER CLASS III (HD-ZIPIII) promoters in lug luh embryos, a model is proposed in which the LUG regulatory complex functions together with WOX2-module to promote apical identity and subsequent SAM initiation through regulation of the HD-ZIPIIIs. The activity of the LUG complex in promoting basal embryo identity through positive regulation of microRNA165/166 suggests that this complex also has functions that are independent of the WOX2-module. Preliminary work reported in this study further uncovered the role of the LUG regulatory complex in post-embryonic development. While the fasciated inflorescence meristems of lug luh+/- plants displayed defects in auxin transport and altered activity of stem cell markers, embryonically rescued lug luh mutants formed flat and differentiated SAMs. In addition, rescued lug luh mutants exhibited severely disorganised RAM and defects in quiescent center (QC) specification, supporting the involvement of the LUG complex in post-embryonic RAM maintenance.
The development of type 2 diabetes (T2D) is driven by genetic as well as life style factors. However, even genetically identical female NZO mice on a high-fat diet show a broad variation in T2D onset. The main objective of this study was to elucidate and investigate early epigenetic determinants of type 2 diabetes. Prior to other experiments, early fat content of the liver (<55.2 HU) in combination with blood glucose concentrations (>8.8 mM) were evaluated as best predictors of diabetes in NZO females. Then, DNA methylome and transcriptome were profiled to identify molecular pathophysiological changes in the liver before diabetes onset. The major finding of this thesis is that alterations in the hepatic DNA methylome precede diabetes onset. Of particular interest were 702 differentially methylated regions (DMRs), of which 506 DMRs had genic localization. These inter-individual DMRs were enriched by fivefold in the KEGG pathway type 2 diabetes mellitus, independent of the level of gene expression, demonstrating an epigenetic predisposition toward diabetes. Interestingly, among the list of hepatic DMRs, eleven DMRs were associated with known imprinted genes in the mouse genome. Thereby, six DMRs (Nap1l5, Mest, Plagl1, Gnas, Grb10 and Slc38a4) localized to imprinting control regions, including five iDMRs that exhibited hypermethylation in livers of diabetes-prone mice. This suggests that gain of DNA methylation in multiple loci of the paternal alleles has unfavourable metabolic consequences for the offspring. Further, the comparative liver transcriptome analysis demonstrated differences in expression levels of 1492 genes related to metabolically relevant pathways, such as citrate cycle and fatty acid metabolism. The integration of hepatic transcriptome and DNA methylome indicated that 449 differentially expressed genes were potentially regulated by DNA methylation, including genes implicated in insulin signaling. In addition, liver transcriptomic profiling of diabetes-resistant and diabetes-prone mice revealed a potential transcriptional dysregulation of 17 hepatokines, in particular Hamp. The hepatic expression of Hamp was decreased by 52% in diabetes-prone mice, on account of an increase in DNA methylation of promoter CpG-118. Hence, HAMP protein levels were lower in mice prone to develop diabetes, which correlated to higher liver triglyceride levels.. In sum, the identified DNA methylation changes appear to collectively favor the initiation and progression of diabetes in female NZO mice. In near future, epigenetic biomarkers are likely to contribute to improved diagnosis for T2D.
The High Energy Stereoscopic System (H.E.S.S.) is an array of five imaging atmospheric Cherenkov telescopes located in the Khomas Highland of Namibia. H.E.S.S. operates in a wide energy range from several tens of GeV to several tens of TeV, reaching the best sensitivity around 1 TeV or at lower energies. However, there are many important topics – such as the search for Galactic PeVatrons, the study of gamma-ray production scenarios for sources (hadronic vs. leptonic), EBL absorption studies – which require good sensitivity at energies above 10 TeV. This work aims at improving the sensitivity of H.E.S.S. and increasing the gamma-ray statistics at high energies. The study investigates an enlargement of the H.E.S.S. effective field of view using events with larger offset angles in the analysis. The greatest challenges in the analysis of large-offset events are a degradation of the reconstruction accuracy and a rise of the background rate as the offset angle increases. The more sophisticated direction reconstruction method (DISP) and improvements to the standard background rejection technique, which by themselves are effective ways to increase the gamma-ray statistics and improve the sensitivity of the analysis, are implemented to overcome the above-mentioned issues. As a result, the angular resolution at the preselection level is improved by 5 - 10% for events at 0.5◦ offset angle and by 20 - 30% for events at 2◦ offset angle. The background rate at large offset angles is decreased nearly to a level typical for offset angles below 2.5◦. Thereby, sensitivity improvements of 10 - 20% are achieved for the proposed analysis compared to the standard analysis at small offset angles. Developed analysis also allows for the usage of events at large offset angles up to approximately 4◦, which was not possible before. This analysis method is applied to the analysis of the Galactic plane data above 10 TeV. As a result, 40 sources out of the 78 presented in the H.E.S.S. Galactic plane survey (HGPS) are detected above 10 TeV. Among them are representatives of all source classes that are present in the HGPS catalogue; namely, binary systems, supernova remnants, pulsar wind nebulae and composite objects. The potential of the improved analysis method is demonstrated by investigating the more than 10 TeV emission for two objects: the region associated with the shell-type SNR HESS J1731−347 and the PWN candidate associated with PSR J0855−4644 that is coincident with Vela Junior (HESS J0852−463).
The aim of the doctoral project was to answer the question of whether the structural word-initial noun capitalization, as it can otherwise only be found in Luxembourgish alongside German, has a function that is advantageous for the reader. The overriding hypothesis was that an advantage is achieved by activating a syntactic category, namely the core of a noun phrase, through the parafoveal perception of the capital letters. This perception from the corner of the eye should make it possible to preprocess the following noun. As a result, sentence processing should be facilitated, which should ultimately be reflected in overall faster reading times and fixation durations.
The structure of the project includes three studies, some of which included different participant groups:
Study 1:
Study design: Semantic priming using garden-path sentences should bring out the functionality of noun capitalization for the reader
Participant groups: German natives reading German
Study 2:
Study design: same design as study 1, but in English
Participant groups:
English natives without any knowledge of German reading English
English natives who regularly read German reading English
German with high proficiency in English reading English
Study 3:
Study design:
Influence of the noun frequency on a potential preprocessing using the boundary paradigm; Study languages: German and English
Participant groups:
German natives reading German
English natives without any knowledge of German reading English
German with high proficiency in English reading English
Brief summary: The noun capitalization clearly has an impact on sentence processing in both German and English. It cannot be confirmed that this has a substantial, decisive advantage.
Membrane contact sites are of particular interest in the field of synthetic biology and biophysics. They are involved in a great variety of cellular functions. They form in between two cellular organelles or an organelle and the plasma membrane in order to establish a communication path for molecule transport or signal transmission.
The development of an artificial membrane system which can mimic membrane contact sites using bottom up synthetic biology was the goal of this research study. For this, a multi - compartmentalised giant unilamellar vesicle (GUV) system was created with the membrane of the outer vesicle mimicking the plasma membrane and the inner GUVs posing as cellular organelles.
In the following steps, three different strategies were used to achieve an internal membrane - membrane adhesion.
The majority of baryons in the Universe is believed to reside in the intergalactic medium (IGM). This makes the IGM an important component in understanding cosmological structure formation. It is expected to trace the same dark matter distribution as galaxies, forming structures like filaments and clusters. However, whereas galaxies can be observed to be arranged along these large-scale structures, the spatial distribution of the diffuse IGM is not as easily unveiled. Absorption line studies of quasar (QSO) spectra can help with mapping the IGM, as well as the boundary layer between IGM and galaxies: the circumgalactic medium (CGM). By studying gas in the Local Group, as well as in the IGM, this study aims to get a better understanding of how the gas is linked to the large-scale structure of the local Universe and the galaxies residing in that structure.
Chapter 1 gives an introduction to the CGM and IGM, while the methods used in this study are explained in Chapter 2. Chapter 3 starts on a relatively small cosmological scale, namely that of our Local Group, which includes i.a. the Milky Way (MW) and the M31. Within the CGM of the MW, there exist denser clouds, some of which are infalling while others are moving away from the Galactic disc. To study these clouds, 29 QSO spectra obtained with the Cosmic Origins Spectrograph (COS) aboard the Hubble Space Telescope (HST) were analysed. Abundances of Si II, Si III, Si IV, C II, and C IV were measured for 69 HVCs belonging to two samples: one in the direction of the LG’s barycentre and the other in the anti-barycentre direction. Their velocities range from -100 ≥ vLSR ≥ -400 km/s for the barycentre sample and between +100 ≤ vLSR ≤ +300 km/s for the anti-barycentre sample. By using Cloudy models, these data could then be used to derive gas volume densities for the HVCs. Because of the relationship between density and pressure of the ambient medium, which is in turn determined by the Galactic radiation field, the distances of the HVCs could be estimated. From this, a subsample of absorbers located in the direction of M31 was found to exist outside of the MW’s virial radius, their low densities (log nH ≤ -3.54) making it likely for them to be part of the gas in between the MW and M31. No such low-density absorbers were found in the anti-barycentre sample. Our results thus hint at gas following the dark matter potential, which would be deeper between the MW and M31 as they are by far the most massive members of the LG.
From this bridge of gas in the LG, this study zooms out to the large-scale structure of the local Universe (z ~ 0) in Chapter 4. Galaxy data from the V8k catalogue and QSO spectra from COS were used to study the relation between the galaxies tracing large-scale filaments and the gas existing outside of those galaxies. This study used the filaments defined in Courtois et al. (2013). A total of 587 Lyman α (Lyα) absorbers were found in the 302 QSO spectra in the velocity range 1070 - 6700 km/s. After selecting sightlines passing through or close to these filaments, model spectra were made for 91 sightlines and 215 (227) Lyα absorbers (components) were measured in this sample. The velocity gradient along each filament was calculated and 74 absorbers were found within 1000 km/s of the nearest filament segment.
In order to find whether the absorbers are more tied to galaxies or to the large-scale structure, equivalent widths of the Lyα absorbers were plotted against both galaxy and filament impact parameters. While stronger absorbers do tend to be closer to either galaxies or filaments, there is a large scatter in this relation. Despite this large scatter, this study found that the absorbers do not follow a random distribution either. They cluster less strongly around filaments than galaxies, but stronger than random distributions, as confirmed by a Kolmogorov-Smirnov test.
Furthermore, the column density distribution function found in this study has a slope of -β = 1.63±0.12 for the total sample and -β =1.47±0.24 for the absorbers within 1000 km/s of a filament. The shallower slope for the latter subsample could indicate an excess of denser absorbers within the filament, but they are consistent within errors. These values are in agreement with values found in e.g. Lehner et al. (2007); Danforth et al. (2016).
The picture that emerges from this study regarding the relation between the IGM and the large-scale structure in the local Universe fits with what is found in other studies: while at least part of the gas traces the same filamentary structure as galaxies, the relation is complex. This study has shown that by taking a large sample of sightlines and comparing the data gathered from those with galaxy data, it is possible to study the gaseous large-scale structure. This approach can be used in the future together with simulations to get a better understanding of structure formation and evolution in the Universe.
Mental health problems are highly prevalent worldwide. Fortunately, psychotherapy has proven highly effective in the treatment of a number of mental health issues, such as depression and anxiety disorders. In contrast, psychotherapy training as is practised currently cannot be considered evidence-based. Thus, there is much room for improvement. The integration of simulated patients (SPs) into psychotherapy training and research is on the rise. SPs originate from the medical education and have, in a number of studies, been demonstrated to contribute to effective learning environments. Nevertheless, there has been voiced criticism regarding the authenticity of SP portrayals, but few studies have examined this to date.
Based on these considerations, this dissertation explores SPs’ authenticity while portraying a mental disorder, depression. Altogether, the present cumulative dissertation consists of three empirical papers. At the time of printing, Paper I and Paper III have been accepted for publication, and Paper II is under review after a minor revision.
First, Paper I develops and validates an observer-based rating-scale to assess SP authenticity in psychotherapeutic contexts. Based on the preliminary findings, it can be concluded that the Authenticity of Patient Demonstrations scale is a reliable and valid tool that can be used for recruiting, training, and evaluating the authenticity of SPs.
Second, Paper II tests whether student SPs are perceived as more authentic after they receive an in-depth role-script compared to those SPs who only receive basic information on the patient case. To test this assumption, a randomised controlled study design was implemented and the hypothesis could be confirmed. As a consequence, when engaging SPs, an in-depth role-script with details, e.g. on nonverbal behaviour and feelings of the patient, should be provided.
Third, Paper III demonstrates that psychotherapy trainees cannot distinguish between trained SPs and real patients and therefore suggests that, with proper training, SPs are a promising training method for psychotherapy.
Altogether, the dissertation shows that SPs can be trained to portray a depressive patient authentically and thus delivers promising evidence for the further dissemination of SPs.
This thesis focuses on the synthesis of novel functional materials based on plasmonic nanoparticles. Three systems with targeted surface modification and functionalization have been designed and synthesized, involving modified perylenediimide doped silica-coated silver nanowires, polydopamine or TiO2 coated gold-palladium nanorods and thiolated poly(ethylene glycol) (PEG-SH)/dodecanethiol (DDT) modified silver nanospheres. Their possible applications as plasmonic resonators, chiral sensors as well as photo-catalysts have been studied. In addition, the interaction between silver nanospheres and 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) molecules has also been investigated in detail.
In the first part of the thesis, surface modification on Ag nanowires (NWs) with optimized silica coating through a modified Stöber method has been firstly conducted, employing sodium hydroxide (NaOH) to replace ammonia solution (NH4OH). The coated silver nanowires with a smooth silica shell have been investigated by single-particle dark-field scattering spectroscopy, transmission electron microscopy and electron-energy loss spectroscopy to characterize the morphologies and structural components. The silica-coated silver nanowires can be further functionalized with fluorescent molecules in the silica shell via a facile one-step coating method. The as-synthesized nanowire is further coupled with a gold nanosphere by spin-coating for the application of the sub-diffractional chiral sensor for the first time. The exciton-plasmon-photon interconversion in the system eases the signal detection in the perfectly matched 1D nanostructure and contributes to the high contrast of the subwavelength chiral sensing for the polarized light.
In the second part of the thesis, dumbbell-shaped Au-Pd nanorods coated with a layer of polydopamine (PDA) or titanium dioxide (TiO2) have been constructed. The PDA- and TiO2- coated Au-Pd nanorods show a strong photothermal conversion performance under NIR illumination. Moreover, the catalytic performance of the particles has been investigated using the reduction of 4-nitrophenol (4-NP) as the model reaction. Under light irradiation, the PDA-coated Au-Pd nanorods exhibit a superior catalytic activity by increasing the reaction rate constant of 3 times. The Arrhenius-like behavior of the reaction with similar activation energies in the presence and absence of light irradiation indicates the photoheating effect to be the dominant mechanism of the reaction acceleration. Thus, we attribute the enhanced performance of the catalysis to the strong photothermal effect that is driven by the optical excitation of the gold surface plasmon as well as the synergy with the PDA layer.
In the third part, the kinetic study on the adsorption of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquino-dimethane (F4TCNQ) on the surface of Ag nanoparticles (Ag NPs) in chloroform has been reported in detail. Based on the results obtained from the UV-vis-NIR absorption spectroscopy, cryogenic transmission electron microscopy (cryo-TEM), scanning nano-beam electron diffraction (NBED) and electron energy loss spectroscopy (EELS), a two-step interaction kinetics has been proposed for the Ag NPs and F4TCNQ molecules. It includes the first step of electron transfer from Ag NPs to F4TCNQ indicated by the ionization of F4TCNQ, and the second step of the formation of Ag-F4TCNQ complex. The whole process has been followed via UV-vis-NIR absorption spectroscopy, which reveals distinct kinetics at two stages: the instantaneous ionization and the long-term complex formation. The kinetics and the influence of the molar ratio of Ag NPs/F4TCNQ molecules on the interaction between Ag NPs and F4TCNQ molecules in the organic solution are reported herein for the first time. Furthermore, the control experiment with silica-coated Ag NPs indicates that the charge transfer at the surface between Ag NPs and F4TCNQ molecules has been prohibited by a silica layer of 18 nm.
Synthesis and Characterization of Upconversion Nanaparticles for Applications in Life Sciences
(2021)
Supernova remnants (SNRs) are discussed as the most promising sources of galactic cosmic rays (CR). The diffusive shock acceleration (DSA) theory predicts particle spectra in a rough agreement with observations. Upon closer inspection, however, the photon spectra of observed SNRs indicate that the particle spectra produced at SNRs shocks deviate from the standard expectation. This work suggests a viable explanation for a softening of the particle spectra in SNRs. The basic idea is the re-acceleration of particles in the turbulent region immediately downstream of the shock. This thesis shows that at the re-acceleration of particles by the fast-mode waves in the downstream region can be efficient enough to impact particle spectra over several decades in energy. To demonstrate this, a generic SNR model is presented, where the evolution of particles is described by the reduced transport equation for CR. It is shown that the resulting particle and the corresponding synchrotron spectra are significantly softer compared to the standard case. Next, this work outlines RATPaC, a code developed to model particle acceleration and corresponding photon emissions in SNRs. RATPaC solves the particle transport equation in test-particle mode using hydrodynamic simulations of the SNR plasma flow. The background magnetic field can be either computed from the induction equation or follows analytic profiles. This work presents an extended version of RATPaC that accounts for stochastic re-acceleration by fast-mode waves that provide diffusion of particles in momentum space. This version is then applied to model the young historical SNR Tycho. According to radio observations, Tycho’s SNR features the radio spectral index of approximately −0.65. In previous modeling approaches, this fact has been attributed to the strongly distinctive Alfvénic drift, which is assumed to operate in the shock vicinity. In this work, the problems and inconsistencies of this scenario are discussed. Instead, stochastic re-acceleration of electrons in the immediate downstream region of Tycho’s SNR is suggested as a cause for the soft radio spectrum. Furthermore, this work investigates two different scenarios for magnetic-field distributions inside Tycho’s SNR. It is concluded that magnetic-field damping is needed to account for the observed filaments in the radio range. Two models are presented for Tycho’s SNR, both of them feature strong hadronic contribution. Thus, a purely leptonic model is considered as very unlikely. Additionally, to the detailed modeling of Tycho’s SNR, this dissertation presents a relatively simple one-zone model for the young SNR Cassiopeia A and an interpretation for the recently analyzed VERITAS and Fermi-LAT data. It shows that the γ-ray emission of Cassiopeia A cannot be explained without a hadronic contribution and that the remnant accelerates protons up to TeV energies. Thus, Cassiopeia A is found to be unlikely a PeVatron.
Natural products have proved to be a major resource in the discovery and development of many pharmaceuticals that are in use today. There is a wide variety of biologically active natural products that contain conjugated polyenes or benzofuran structures. Therefore, new synthetic methods for the construction of such building blocks are of great interest to synthetic chemists. The recently developed one-pot tethered ring-closing metathesis approach allows for the formation of Z,E-dienoates in high stereoselectivity. The extension of this method with a Julia-Kocienski olefination protocol would allow for the formation of conjugated trienes in a stereoselective manner. This strategy was applied in the total synthesis of conjugated triene containing (+)-bretonin B. Additionally, investigations of cross metathesis using methyl substituted olefins were pursued. This methodology was applied, as a one-pot cross metathesis/ring-closing metathesis sequence, in the total synthesis of benzofuran containing 7-methoxywutaifuranal. Finally, the design and synthesis of a catalyst for stereoretentive metathesis in aqueous media was investigated.
An ever-increasing number of prediction models is published every year in different medical specialties. Prognostic or diagnostic in nature, these models support medical decision making by utilizing one or more items of patient data to predict outcomes of interest, such as mortality or disease progression. While different computer tools exist that support clinical predictive modeling, I observed that the state of the art is lacking in the extent to which the needs of research clinicians are addressed. When it comes to model development, current support tools either 1) target specialist data engineers, requiring advanced coding skills, or 2) cater to a general-purpose audience, therefore not addressing the specific needs of clinical researchers. Furthermore, barriers to data access across institutional silos, cumbersome model reproducibility and extended experiment-to-result times significantly hampers validation of existing models. Similarly, without access to interpretable explanations, which allow a given model to be fully scrutinized, acceptance of machine learning approaches will remain limited. Adequate tool support, i.e., a software artifact more targeted at the needs of clinical modeling, can help mitigate the challenges identified with respect to model development, validation and interpretation. To this end, I conducted interviews with modeling practitioners in health care to better understand the modeling process itself and ascertain in what aspects adequate tool support could advance the state of the art. The functional and non-functional requirements identified served as the foundation for a software artifact that can be used for modeling outcome and risk prediction in health research. To establish the appropriateness of this approach, I implemented a use case study in the Nephrology domain for acute kidney injury, which was validated in two different hospitals. Furthermore, I conducted user evaluation to ascertain whether such an approach provides benefits compared to the state of the art and the extent to which clinical practitioners could benefit from it. Finally, when updating models for external validation, practitioners need to apply feature selection approaches to pinpoint the most relevant features, since electronic health records tend to contain several candidate predictors. Building upon interpretability methods, I developed an explanation-driven recursive feature elimination approach. This method was comprehensively evaluated against state-of-the art feature selection methods. Therefore, this thesis' main contributions are three-fold, namely, 1) designing and developing a software artifact tailored to the specific needs of the clinical modeling domain, 2) demonstrating its application in a concrete case in the Nephrology context and 3) development and evaluation of a new feature selection approach applicable in a validation context that builds upon interpretability methods. In conclusion, I argue that appropriate tooling, which relies on standardization and parametrization, can support rapid model prototyping and collaboration between clinicians and data scientists in clinical predictive modeling.
In the light of climate change, rising demands for agricultural products and the intensification and specialization of agricultural systems, ensuring an adequate and reliable supply of food is fundamental for food security. Maintaining diversity and redundancy has been postulated as one generic principle to increase the resilience of agricultural production and other ecosystem services. For example, if one crop fails due to climate instability and extreme events, others can compensate the losses. Crop diversity might be particularly important if different crops show asynchronous production trends. Furthermore, spatial heterogeneity has been suggested to increase stability at larger scales as production losses in some areas can be buffered by surpluses in undisturbed ones. Besides systematically investigating the mechanisms underlying stability, identifying transformative pathways that foster them is important.
In my thesis, I aim at answering the following questions: (i) How does yield stability differ between nations, regions and farms, and what is the effect of crop diversity on yield stability in relation to agricultural inputs, climate heterogeneity, climate instability and time at the national, regional or farm level? (ii) Is asynchrony between crops a better predictor of production stability than crop diversity? (iii) What is the effect of asynchrony between and within crops on stability and how is it related to crop diversity and space, respectively? (iv) What is the state of the art and what are knowledge gaps in exploring resilience and its multidimensionality in ecological and social-ecological systems with agent-based models and what are potential ways forward?
In the first chapter, I provide the theoretical background for the subsequent analyses. I stress the need to better understand the resilience of social-ecological systems and particularly the stability of agricultural production. Moreover, I introduce diversity and spatial heterogeneity as two prominently discussed resilience mechanisms and describe approaches to assess resilience.
In the second chapter, I combined agriculture and climate data at three levels of organization and spatial extents to investigate yield stability patterns and their relation to crop diversity, fertilizer, irrigation, climate heterogeneity and instability and time of nations globally, regions in Europe and farms in Germany using statistical analyses. Yield stability decreased from the national to the farm level. Several nations and regions substantially contributed to larger-scale stability. Crop diversity was positively associated with yield stability across all three levels of organization. This effect was typically more profound at smaller scales and in variable climates. In addition to crop diversity, climate heterogeneity was an important stabilizing mechanism especially at larger scales. These results confirm the stabilizing effect of crop diversity and spatial heterogeneity, yet their importance depends on the scale and agricultural management.
Building on the findings of the second chapter, I deepened in the third chapter my research on the effect of crop diversity at the national level. In particular, I tested if asynchrony between crops, i.e. between the temporal production patterns of different crops, better predicts agricultural production stability than crop diversity. The stabilizing effect of asynchrony was multiple times higher than the effect of crop diversity, i.e. asynchrony is one important property that can explain why a higher diversity supports the stability of national food production. Therefore, strategies to stabilize agricultural production through crop diversification also need to account for the asynchrony of the crops considered.
The previous chapters suggest that both asynchrony between crops and spatial heterogeneity are important stabilizing mechanisms. In the fourth chapter, I therefore aimed at better understanding the relative importance of asynchrony between and within crops, i.e. between the temporal production patterns of different crops and between the temporal production patterns of different cultivation areas of the same crop. Better understanding their relative importance is important to inform agricultural management decisions, but so far this has been hardly assessed. To address this, I used crop production data to study the effect of asynchrony between and within crops on the stability of agricultural production in regions in Germany and nations in Europe. Both asynchrony between and within crops consistently stabilized agricultural production. Adding crops increased asynchrony between crops, yet this effect levelled off after eight crops in regions in Germany and after four crops in nations in Europe. Combining already ten farms within a region led to high asynchrony within crops, indicating distinct production patters, while this effect was weaker when combining multiple regions within a nation. The results suggest, that both mechanisms need to be considered in agricultural management strategies that strive for more resilient farming systems.
The analyses in the foregoing chapters focused at different levels of organization, scales and factors potentially influencing agricultural stability. However, these statistical analyses are restricted by data availability and investigate correlative relationships, thus they cannot provide a mechanistic understanding of the actual processes underlying resilience. In this regard, agent-based models (ABM) are a promising tool. Besides their ability to measure different properties and to integrate multiple situations through extensive manipulation in a fully controlled system, they can capture the emergence of system resilience from individual interactions and feedbacks across different levels of organization. In the fifth chapter, I therefore reviewed the state of the art and potential knowledge gaps in exploring resilience and its multidimensionality in ecological and social-ecological systems with ABMs. Next, I derived recommendations for a more effective use of ABMs in resilience research. The review suggests that the potential of ABMs is not utilized in most models as they typically focus on a single dimension of resilience and are mostly limited to one reference state, disturbance type and scale. Moreover, only few studies explicitly test the ability of different mechanisms to support resilience. To solve real-world problems related to the resilience of complex systems, ABMs need to assess multiple stability properties for different situations and under consideration of the mechanisms that are hypothesized to render a system resilient.
In the sixth chapter, I discuss the major conclusions that can be drawn from the previous chapters. Moreover, I showcase the use of simulation models to identify management strategies to enhance asynchrony and thus stability, and the potential of ABMs to identify pathways to implement such strategies.
The results of my thesis confirm the stabilizing effect of crop diversity, yet its importance depends on the scale, agricultural management and climate. Moreover, strategies to stabilize agricultural production through crop diversification also need to account for the asynchrony of the crops considered. As spatial heterogeneity and particularly asynchrony within crops strongly enhances stability, integrated management approaches are needed that simultaneously address multiple resilience mechanisms at different levels of organization, scales and time horizons. For example, the simulation suggests that only increasing the number of crops at both the pixel and landscape level avoids trade-offs between asynchrony between and within crops. If their potential is better exploited, agent-based models have the capacity to systematically assess resilience and to identify comprehensive pathways towards resilient farming systems.
The propagation of test fields, such as electromagnetic, Dirac or linearized gravity, on a fixed spacetime manifold is often studied by using the geometrical optics approximation. In the limit of infinitely high frequencies, the geometrical optics approximation provides a conceptual transition between the test field and an effective point-particle description. The corresponding point-particles, or wave rays, coincide with the geodesics of the underlying spacetime. For most astrophysical applications of interest, such as the observation of celestial bodies, gravitational lensing, or the observation of cosmic rays, the geometrical optics approximation and the effective point-particle description represent a satisfactory theoretical model. However, the geometrical optics approximation gradually breaks down as test fields of finite frequency are considered.
In this thesis, we consider the propagation of test fields on spacetime, beyond the leading-order geometrical optics approximation. By performing a covariant Wentzel-Kramers-Brillouin analysis for test fields, we show how higher-order corrections to the geometrical optics approximation can be considered. The higher-order corrections are related to the dynamics of the spin internal degree of freedom of the considered test field. We obtain an effective point-particle description, which contains spin-dependent corrections to the geodesic motion obtained using geometrical optics. This represents a covariant generalization of the well-known spin Hall effect, usually encountered in condensed matter physics and in optics. Our analysis is applied to electromagnetic and massive Dirac test fields, but it can easily be extended to other fields, such as linearized gravity. In the electromagnetic case, we present several examples where the gravitational spin Hall effect of light plays an important role. These include the propagation of polarized light rays on black hole spacetimes and cosmological spacetimes, as well as polarization-dependent effects on the shape of black hole shadows. Furthermore, we show that our effective point-particle equations for polarized light rays reproduce well-known results, such as the spin Hall effect of light in an inhomogeneous medium, and the relativistic Hall effect of polarized electromagnetic wave packets encountered in Minkowski spacetime.
Spatiotemporal variations of key air pollutants and greenhouse gases in the Himalayan foothills
(2021)
South Asia is a rapidly developing, densely populated and highly polluted region that is facing the impacts of increasing air pollution and climate change, and yet it remains one of the least studied regions of the world scientifically. In recognition of this situation, this thesis focuses on studying (i) the spatial and temporal variation of key greenhouse gases (CO2 and CH4) and air pollutants (CO and O3) and (ii) the vertical distribution of air pollutants (PM, BC) in the foothills of the Himalaya. Five sites were selected in the Kathmandu Valley, the capital region of Nepal, along with two sites outside of the valley in the Makawanpur and Kaski districts, and conducted measurements during the period of 2013-2014 and 2016. These measurements are analyzed in this thesis.
The CO measurements at multiple sites in the Kathmandu Valley showed a clear diurnal cycle: morning and evening levels were high, with an afternoon dip. There are slight differences in the diurnal cycles of CO2 and CH4, with the CO2 and CH4 mixing ratios increasing after the afternoon dip, until the morning peak the next day. The mixing layer height (MLH) of the nocturnal stable layer is relatively constant (~ 200 m) during the night, after which it transitions to a convective mixing layer during the day and the MLH increases up to 1200 m in the afternoon. Pollutants are thus largely trapped in the valley from the evening until sunrise the following day, and the concentration of pollutants increases due to emissions during the night. During afternoon, the pollutants are diluted due to the circulation by the valley winds after the break-up of the mixing layer. The major emission sources of GHGs and air pollutants in the valley are transport sector, residential cooking, brick kilns, trash burning, and agro-residue burning. Brick industries are influential in the winter and pre-monsoon season. The contribution of regional forest fires and agro-residue burning are seen during the pre-monsoon season. In addition, relatively higher CO values were also observed at the valley outskirts (Bhimdhunga and Naikhandi), which indicates the contribution of regional emission sources. This was also supported by the presence of higher concentrations of O3 during the pre-monsoon season.
The mixing ratios of CO2 (419.3 ±6.0 ppm) and CH4 (2.192 ±0.066 ppm) in the valley were much higher than at background sites, including the Mauna Loa observatory (CO2: 396.8 ± 2.0 ppm, CH4:1.831 ± 0.110 ppm) and Waligaun (CO2: 397.7 ± 3.6 ppm, CH4: 1.879 ± 0.009 ppm), China, as well as at an urban site Shadnagar (CH4: 1.92 ± 0.07 ppm) in India.
The daily 8 hour maximum O3 average in the Kathmandu Valley exceeds the WHO recommended value during more than 80% of the days during the pre-monsoon period, which represents a significant risk for human health and ecosystems in the region. Moreover, in the measurements of the vertical distribution of particulate matter, which were made using an ultralight aircraft, and are the first of their kind in the region, an elevated polluted layer at around ca. 3000 m asl. was detected over the Pokhara Valley. The layer could be associated with the large-scale regional transport of pollution. These contributions towards understanding the distributions of key air pollutants and their main sources will provide helpful information for developing management plans and policies to help reduce the risks for the millions of people living in the region.
Centroid moment tensor inversion can provide insight into ongoing tectonic processes and active faults. In the Alpine mountains (central Europe), challenges result from low signal-to-noise ratios of earthquakes with small to moderate magnitudes and complex wave propagation effects through the heterogeneous crustal structure of the mountain belt. In this thesis, I make use of the temporary installation of the dense AlpArray seismic network (AASN) to establish a work flow to study seismic source processes and enhance the knowledge of the Alpine seismicity. The cumulative thesis comprises four publications on the topics of large seismic networks, seismic source processes in the Alps, their link to tectonics and stress field, and the inclusion of small magnitude earthquakes into studies of active faults.
Dealing with hundreds of stations of the dense AASN requires the automated assessment of data and metadata quality. I developed the open source toolbox AutoStatsQ to perform an automated data quality control. Its first application to the AlpArray seismic network has revealed significant errors of amplitude gains and sensor orientations. A second application of the orientation test to the Turkish KOERI network, based on Rayleigh wave polarization, further illustrated the potential in comparison to a P wave polarization method. Taking advantage of the gain and orientation results of the AASN, I tested different inversion settings and input data types to approach the specific challenges of centroid moment tensor (CMT) inversions in the Alps. A comparative study was carried out to define the best fitting procedures.
The application to 4 years of seismicity in the Alps (2016-2019) substantially enhanced the amount of moment tensor solutions in the region. We provide a list of moment tensors solutions down to magnitude Mw 3.1. Spatial patterns of typical focal mechanisms were analyzed in the seismotectonic context, by comparing them to long-term seismicity, historical earthquakes and observations of strain rates. Additionally, we use our MT solutions to investigate stress regimes and orientations along the Alpine chain. Finally, I addressed the challenge of including smaller magnitude events into the study of active faults and source processes. The open-source toolbox Clusty was developed for the clustering of earthquakes based on waveforms recorded across a network of seismic stations. The similarity of waveforms reflects both, the location and the similarity of source mechanisms. Therefore the clustering bears the opportunity to identify earthquakes of similar faulting styles, even when centroid moment tensor inversion is not possible due to low signal-to-noise ratios of surface waves or oversimplified velocity models. The toolbox is described through an application to the Zakynthos 2018 aftershock sequence and I subsequently discuss its potential application to weak earthquakes (Mw<3.1) in the Alps.
Lie group method in combination with Magnus expansion is utilized to develop a universal method applicable to solving a Sturm–Liouville Problem (SLP) of any order with arbitrary boundary conditions. It is shown that the method has ability to solve direct regular and some singular SLPs of even orders (tested up to order eight), with a mix of boundary conditions (including non-separable and finite singular endpoints), accurately and efficiently.
The present technique is successfully applied to overcome the difficulties in finding suitable sets of eigenvalues so that the inverse SLP problem can be effectively solved.
Next, a concrete implementation to the inverse Sturm–Liouville problem
algorithm proposed by Barcilon (1974) is provided. Furthermore, computational feasibility and applicability of this algorithm to solve inverse Sturm–Liouville problems of order n=2,4 is verified successfully. It is observed that the method is successful even in the presence of significant noise, provided that the assumptions of the algorithm are satisfied.
In conclusion, this work provides methods that can be adapted successfully for solving a direct (regular/singular) or inverse SLP of an arbitrary order with arbitrary boundary conditions.
Major challenges during geothermal exploration and exploitation include the structural-geological characterization of the geothermal system and the application of sustainable monitoring concepts to explain changes in a geothermal reservoir during production and/or reinjection of fluids. In the absence of sufficiently permeable reservoir rocks, faults and fracture networks are preferred drilling targets because they can facilitate the migration of hot and/or cold fluids. In volcanic-geothermal systems considerable amounts of gas emissions can be released at the earth surface, often related to these fluid-releasing structures.
In this thesis, I developed and evaluated different methodological approaches and measurement concepts to determine the spatial and temporal variation of several soil gas parameters to understand the structural control on fluid flow. In order to validate their potential as innovative geothermal exploration and monitoring tools, these methodological approaches were applied to three different volcanic-geothermal systems. At each site an individual survey design was developed regarding the site-specific questions.
The first study presents results of the combined measurement of CO2 flux, ground temperatures, and the analysis of isotope ratios (δ13CCO2, 3He/4He) across the main production area of the Los Humeros geothermal field, to identify locations with a connection to its supercritical (T > 374◦C and P > 221 bar) geothermal reservoir. The results of the systematic and large-scale (25 x 200 m) CO2 flux scouting survey proved to be a fast and flexible way to identify areas of anomalous degassing. Subsequent sampling with high resolution surveys revealed the actual extent and heterogenous pattern of anomalous degassing areas. They have been related to the internal fault hydraulic architecture and allowed to assess favourable structural settings for fluid flow such as fault intersections. Finally, areas of unknown structurally controlled permeability with a connection to the superhot geothermal reservoir have been determined, which represent promising targets for future geothermal exploration and development.
In the second study, I introduce a novel monitoring approach by examining the variation of CO2 flux to monitor changes in the reservoir induced by fluid reinjection. For that reason, an automated, multi-chamber CO2 flux system was deployed across the damage zone of a major normal fault crossing the Los Humeros geothermal field. Based on the results of the CO2 flux scouting survey, a suitable site was selected that had a connection to the geothermal reservoir, as identified by hydrothermal CO2 degassing and hot ground temperatures (> 50 °C). The results revealed a response of gas emissions to changes in reinjection rates within 24 h, proving an active hydraulic communication between the geothermal reservoir and the earth surface. This is a promising monitoring strategy that provides nearly real-time and in-situ data about changes in the reservoir and allows to timely react to unwanted changes (e.g., pressure decline, seismicity).
The third study presents results from the Aluto geothermal field in Ethiopia where an area-wide and multi-parameter analysis, consisting of measurements of CO2 flux, 222Rn, and 220Rn activity concentrations and ground temperatures was conducted to detect hidden permeable structures. 222Rn and 220Rn activity concentrations are evaluated as a complementary soil gas parameter to CO2 flux, to investigate their potential to understand tectono-volcanic degassing. The combined measurement of all parameters enabled to develop soil gas fingerprints, a novel visualization approach. Depending on the magnitude of gas emissions and their migration velocities the study area was divided in volcanic (heat), tectonic (structures), and volcano-tectonic dominated areas. Based on these concepts, volcano-tectonic dominated areas, where hot hydrothermal fluids migrate along permeable faults, present the most promising targets for future geothermal exploration and development in this geothermal field. Two of these areas have been identified in the south and south-east which have not yet been targeted for geothermal exploitation. Furthermore, two unknown areas of structural related permeability could be identified by 222Rn and 220Rn activity concentrations.
Eventually, the fourth study presents a novel measurement approach to detect structural controlled CO2 degassing, in Ngapouri geothermal area, New Zealand. For the first time, the tunable diode laser (TDL) method was applied in a low-degassing geothermal area, to evaluate its potential as a geothermal exploration method. Although the sampling approach is based on profile measurements, which leads to low spatial resolution, the results showed a link between known/inferred faults and increased CO2 concentrations. Thus, the TDL method proved to be a successful in the determination of structural related permeability, also in areas where no obvious geothermal activity is present. Once an area of anomalous CO2 concentrations has been identified, it can be easily complemented by CO2 flux grid measurements to determine the extent and orientation of the degassing segment.
With the results of this work, I was able to demonstrate the applicability of systematic and area-wide soil gas measurements for geothermal exploration and monitoring purposes. In particular, the combination of different soil gases using different measurement networks enables the identification and characterization of fluid-bearing structures and has not yet been used and/or tested as standard practice. The different studies present efficient and cost-effective workflows and demonstrate a hands-on approach to a successful and sustainable exploration and monitoring of geothermal resources. This minimizes the resource risk during geothermal project development. Finally, to advance the understanding of the complex structure and dynamics of geothermal systems, a combination of comprehensive and cutting-edge geological, geochemical, and geophysical exploration methods is essential.
Massive Open Online Courses (MOOCs) open up new opportunities to learn a wide variety of skills online and are thus well suited for individual education, especially where proffcient teachers are not available locally. At the same time, modern society is undergoing a digital transformation, requiring the training of large numbers of current and future employees. Abstract thinking, logical reasoning, and the need to formulate instructions for computers are becoming increasingly relevant. A holistic way to train these skills is to learn how to program. Programming, in addition to being a mental discipline, is also considered a craft, and practical training is required to achieve mastery. In order to effectively convey programming skills in MOOCs, practical exercises are incorporated into the course curriculum to offer students the necessary hands-on experience to reach an in-depth understanding of the programming concepts presented. Our preliminary analysis showed that while being an integral and rewarding part of courses, practical exercises bear the risk of overburdening students who are struggling with conceptual misunderstandings and unknown syntax. In this thesis, we develop, implement, and evaluate different interventions with the aim to improve the learning experience, sustainability, and success of online programming courses. Data from four programming MOOCs, with a total of over 60,000 participants, are employed to determine criteria for practical programming exercises best suited for a given audience.
Based on over five million executions and scoring runs from students' task submissions, we deduce exercise difficulties, students' patterns in approaching the exercises, and potential flaws in exercise descriptions as well as preparatory videos. The primary issue in online learning is that students face a social gap caused by their isolated physical situation. Each individual student usually learns alone in front of a computer and suffers from the absence of a pre-determined time structure as provided in traditional school classes. Furthermore, online learning usually presses students into a one-size-fits-all curriculum, which presents the same content to all students, regardless of their individual needs and learning styles. Any means of a personalization of content or individual feedback regarding problems they encounter are mostly ruled out by the discrepancy between the number of learners and the number of instructors. This results in a high demand for self-motivation and determination of MOOC participants. Social distance exists between individual students as well as between students and course instructors. It decreases engagement and poses a threat to learning success. Within this research, we approach the identified issues within MOOCs and suggest scalable technical solutions, improving social interaction and balancing content difficulty.
Our contributions include situational interventions, approaches for personalizing educational content as well as concepts for fostering collaborative problem-solving. With these approaches, we reduce counterproductive struggles and create a universal improvement for future programming MOOCs. We evaluate our approaches and methods in detail to improve programming courses for students as well as instructors and to advance the state of knowledge in online education.
Data gathered from our experiments show that receiving peer feedback on one's programming problems improves overall course scores by up to 17%. Merely the act of phrasing a question about one's problem improved overall scores by about 14%. The rate of students reaching out for help was significantly improved by situational just-in-time interventions. Request for Comment interventions increased the share of students asking for help by up to 158%. Data from our four MOOCs further provide detailed insight into the learning behavior of students. We outline additional significant findings with regard to student behavior and demographic factors. Our approaches, the technical infrastructure, the numerous educational resources developed, and the data collected provide a solid foundation for future research.
The goal of this dissertation is to empirically evaluate the predictions of two classes of models applied to language processing: the similarity-based interference models (Lewis & Vasishth, 2005; McElree, 2000) and the group of smaller-scale accounts that we will refer to as faulty encoding accounts (Eberhard, Cutting, & Bock, 2005; Bock & Eberhard, 1993). Both types of accounts make predictions with regard to processing the same class of structures: sentences containing a non-subject (interfering) noun in addition to a subject noun and a verb. Both accounts make the same predictions for processing ungrammatical sentences with a number-mismatching interfering noun, and this prediction finds consistent support in the data. However, the similarity-based interference accounts predict similar effects not only for morphosyntactic, but also for the semantic level of language organization. We verified this prediction in three single-trial online experiments, where we found consistent support for the predictions of the similarity-based interference account. In addition, we report computational simulations further supporting the similarity-based interference accounts. The combined evidence suggests that the faulty encoding accounts are not required to explain comprehension of ill-formed sentences.
For the processing of grammatical sentences, the accounts make conflicting predictions, and neither the slowdown predicted by the similarity-based interference account, nor the complementary slowdown predicted by the faulty encoding accounts were systematically observed. The majority of studies found no difference between the compared configurations. We tested one possible explanation for the lack of predicted difference, namely, that both slowdowns are present simultaneously and thus conceal each other. We decreased the amount of similarity-based interference: if the effects were concealing each other, decreasing one of them should allow the other to surface. Surprisingly, throughout three larger-sample single-trial online experiments, we consistently found the slowdown predicted by the faulty encoding accounts, but no effects consistent with the presence of inhibitory interference.
The overall pattern of the results observed across all the experiments reported in this dissertation is consistent with previous findings: predictions of the interference accounts for the processing of ungrammatical sentences receive consistent support, but the predictions for the processing of grammatical sentences are not always met. Recent proposals by Nicenboim et al. (2016) and Mertzen et al. (2020) suggest that interference might arise only in people with high working memory capacity or under deep processing mode. Following these proposals, we tested whether interference effects might depend on the depth of processing: we manipulated the complexity of the training materials preceding the grammatical experimental sentences while making no changes to the experimental materials themselves. We found that the slowdown predicted by the faulty encoding accounts disappears in the deep processing mode, but the effects consistent with the predictions of the similarity-based interference account do not arise.
Independently of whether similarity-based interference arises under deep processing mode or not, our results suggest that the faulty encoding accounts cannot be dismissed since they make unique predictions with regard to processing grammatical sentences, which are supported by data. At the same time, the support is not unequivocal: the slowdowns are present only in the superficial processing mode, which is not predicted by the faulty encoding accounts. Our results might therefore favor a much simpler system that superficially tracks number features and is distracted by every plural feature.
Shape-Memory effects of thermoplatic multiblock copolymers with overlapping thermal transitions
(2021)
While the last few decades have seen impressive improvements in several areas in Natural Language Processing, asking a computer to make sense of the discourse of utterances in a text remains challenging. There are several different theories that aim to describe and analyse the coherent structure that a well-written text inhibits. These theories have varying degrees of applicability and feasibility for practical use. Presumably the most data-driven of these theories is the paradigm that comes with the Penn Discourse TreeBank, a corpus annotated for discourse relations containing over 1 million words. Any language other than English however, can be considered a low-resource language when it comes to discourse processing.
This dissertation is about shallow discourse parsing (discourse parsing following the paradigm of the Penn Discourse TreeBank) for German. The limited availability of annotated data for German means the potential of modern, deep-learning based methods relying on such data is also limited. This dissertation explores to what extent machine-learning and more recent deep-learning based methods can be combined with traditional, linguistic feature engineering to improve performance for the discourse parsing task. A pivotal role is played by connective lexicons that exhaustively list the discourse connectives of a particular language along with some of their core properties.
To facilitate training and evaluation of the methods proposed in this dissertation, an existing corpus (the Potsdam Commentary Corpus) has been extended and additional data has been annotated from scratch. The approach to end-to-end shallow discourse parsing for German adopts a pipeline architecture and either presents the first results or improves over state-of-the-art for German for the individual sub-tasks of the discourse parsing task, which are, in processing order, connective identification, argument extraction and sense classification. The end-to-end shallow discourse parser for German that has been developed for the purpose of this dissertation is open-source and available online.
In the course of writing this dissertation, work has been carried out on several connective lexicons in different languages. Due to their central role and demonstrated usefulness for the methods proposed in this dissertation, strategies are discussed for creating or further developing such lexicons for a particular language, as well as suggestions on how to further increase their usefulness for shallow discourse parsing.
Background: A growing body of research has documented negative effects of sexualization in the media on individuals’ self-objectification. This research is predominantly built on studies examining traditional media, such as magazines and television, and young female samples. Furthermore, longitudinal studies are scarce, and research is missing studying mediators of the relationship. The first aim of the present PhD thesis was to investigate the relations between the use of sexualized interactive media and social media and self-objectification. The second aim of this work was to examine the presumed processes within understudied samples, such as males and females beyond college age, thus investigating the moderating roles of age and gender. The third aim was to shed light on possible mediators of the relation between sexualized media and self-objectification.
Method: The research aims were addressed within the scope of four studies. In an experiment, women’s self-objectification and body satisfaction was measured after playing a video game with a sexualized vs. a nonsexualized character that was either personalized or generic. The second study investigated the cross-sectional link between sexualized television use and self-objectification and consideration of cosmetic surgery in a sample of women across a broad age spectrum, examining the role of age in the relations. The third study looked at the cross-sectional link between male and female sexualized images on Instagram and their associations with self-objectification among a sample of male and female adolescents. Using a two-wave longitudinal design, the fourth study examined sexualized video game and Instagram use as predictors of adolescents’ self-objectification. Path models were conceptualized for the second, third and fourth study, in which media use predicted body surveillance via appearance comparisons (Study 4), thin-ideal internalization (Study 2, 3, 4), muscular-ideal internalization (Study 3, 4), and valuing appearance (all studies).
Results: The results of the experimental study revealed no effect of sexualized video game characters on women’s self-objectification and body satisfaction. No moderating effect of personalization emerged. Sexualized television use was associated to consideration of cosmetic surgery via body surveillance and valuing appearance for women of all ages in Study 2, while no moderating effect of age was found. Study 3 revealed that seeing sexualized male images on Instagram was indirectly associated with higher body surveillance via muscular-ideal internalization for boys and girls. Sexualized female images were indirectly linked to higher body surveillance via thin-ideal internalization and valuing appearance over competence only for girls. The longitudinal analysis of Study 4 showed no moderating effect of gender: For boys and girls, sexualized video game use at T1 predicted body surveillance at T2 via appearance comparisons, thin-ideal internalization and valuing appearance over competence. Furthermore, the use of sexualized Instagram images at T1 predicted body surveillance at T2 via valuing appearance.
Conclusion: The findings show that sexualization in the media is linked to self-objectification among a variety of media formats and within diverse groups of people. While the longitudinal study indicates that sexualized media predict self-objectification over time, the experimental null findings warrant caution regarding this temporal order. The results demonstrate that several mediating variables might be involved in this link. Possible implications for research and practice, such as intervention programs and policy-making, are discussed.
Role of dietary sulfonates in the stimulation of gut bacteria promoting intestinal inflammation
(2021)
The interplay between intestinal microbiota and host has increasingly been recognized as a major factor impacting health. Studies indicate that diet is the most influential determinant affecting the gut microbiota. A diet rich in saturated fat was shown to stimulate the growth of the colitogenic bacterium Bilophila wadsworthia by enhancing the secretion of the bile acid taurocholate (TC). The sulfonated taurine moiety of TC is utilized as a substrate by B. wadsworthia. The resulting overgrowth of B. wadsworthia was accompanied by an increased incidence and severity of colitis in interleukin (IL)-10-deficient mice, which are genetically prone to develop inflammation.
Based on these findings, the question arose whether the intake of dietary sulfonates also stimulates the growth of B. wadsworthia and thereby promotes intestinal inflammation in genetically susceptible mice. Dietary sources of sulfonates include green vegetables and cyanobacteria, which contain the sulfolipids sulfoquinovosyl diacylglycerols (SQDG) in considerable amounts. Based on literature reports, the gut commensal Escherichia coli is able to release sulfoquinovose (SQ) from SQDG and in further steps, convert SQ to 2,3-dihydroxypropane-1-sulfonate (DHPS) and dihydroxyacetone phosphate. DHPS may then be utilized as a growth substrate by B. wadsworthia, which results in the formation of sulfide. Both, sulfide formation and a high abundance of B. wadsworthia have been associated with intestinal inflammation.
In the present study, conventional IL-10-deficient mice were fed either a diet supplemented with the SQDG-rich cyanobacterium Spirulina (20%, SD) or a control diet. In addition SQ, TC, or water were orally applied to conventional or gnotobiotic IL-10-deficient mice. The gnotobiotic mice harbored a simplified human intestinal microbiota (SIHUMI) either with or without B. wadsworthia. During the intervention period, the body weight of the mice was monitored, the colon permeability was assessed and fecal samples were collected. After the three-week intervention, the animals were examined with regard to inflammatory parameters, microbiota composition and sulfonate concentrations in different intestinal sites.
None of the mice treated with the above-mentioned sulfonates showed weight loss or intestinal inflammation. Solely mice fed SD or gavaged with TC displayed a slight immune response. These mice also displayed an altered microbiota composition, which was not observed in mice gavaged with SQ. The abundance of B. wadsworthia was strongly reduced in mice fed SD, while that of mice treated with SQ or TC was in part slightly increased. The intestinal SQ-concentration was elevated in mice orally treated with SD or SQ, whereas neither TC nor taurine concentrations were consistently elevated in mice gavaged with TC. Additional colonization of SIHUMI mice with B. wadsworthia resulted in a mild inflammatory response, but only in mice treated with TC. In general, TC-mediated effects on the immune system and abundance of B. wadsworthia were not as strong as described in the literature.
In summary, neither the tested dietary sulfonates nor TC led to bacteria-induced intestinal inflammation in the IL-10-deficient mouse model, which was consistently observed in both conventional and gnotobiotic mice. For humans, this means that foods containing SQDG, such as spinach or Spirulina, do not increase the risk of intestinal inflammation.
As part of our everyday life we consume breaking news and interpret it based on our own viewpoints and beliefs. We have easy access to online social networking platforms and news media websites, where we inform ourselves about current affairs and often post about our own views, such as in news comments or social media posts. The media ecosystem enables opinions and facts to travel from news sources to news readers, from news article commenters to other readers, from social network users to their followers, etc. The views of the world many of us have depend on the information we receive via online news and social media. Hence, it is essential to maintain accurate, reliable and objective online content to ensure democracy and verity on the Web. To this end, we contribute to a trustworthy media ecosystem by analyzing news and social media in the context of politics to ensure that media serves the public interest. In this thesis, we use text mining, natural language processing and machine learning techniques to reveal underlying patterns in political news articles and political discourse in social networks.
Mainstream news sources typically cover a great amount of the same news stories every day, but they often place them in a different context or report them from different perspectives. In this thesis, we are interested in how distinct and predictable newspaper journalists are, in the way they report the news, as a means to understand and identify their different political beliefs. To this end, we propose two models that classify text from news articles to their respective original news source, i.e., reported speech and also news comments. Our goal is to capture systematic quoting and commenting patterns by journalists and news commenters respectively, which can lead us to the newspaper where the quotes and comments are originally published. Predicting news sources can help us understand the potential subjective nature behind news storytelling and the magnitude of this phenomenon. Revealing this hidden knowledge can restore our trust in media by advancing transparency and diversity in the news.
Media bias can be expressed in various subtle ways in the text and it is often challenging to identify these bias manifestations correctly, even for humans. However, media experts, e.g., journalists, are a powerful resource that can help us overcome the vague definition of political media bias and they can also assist automatic learners to find the hidden bias in the text. Due to the enormous technological advances in artificial intelligence, we hypothesize that identifying political bias in the news could be achieved through the combination of sophisticated deep learning modelsxi and domain expertise. Therefore, our second contribution is a high-quality and reliable news dataset annotated by journalists for political bias and a state-of-the-art solution for this task based on curriculum learning. Our aim is to discover whether domain expertise is necessary for this task and to provide an automatic solution for this traditionally manually-solved problem. User generated content is fundamentally different from news articles, e.g., messages are shorter, they are often personal and opinionated, they refer to specific topics and persons, etc. Regarding political and socio-economic news, individuals in online communities make use of social networks to keep their peers up-to-date and to share their own views on ongoing affairs. We believe that social media is also an as powerful instrument for information flow as the news sources are, and we use its unique characteristic of rapid news coverage for two applications. We analyze Twitter messages and debate transcripts during live political presidential debates to automatically predict the topics that Twitter users discuss. Our goal is to discover the favoured topics in online communities on the dates of political events as a way to understand the political subjects of public interest. With the up-to-dateness of microblogs, an additional opportunity emerges, namely to use social media posts and leverage the real-time verity about discussed individuals to find their locations.
That is, given a person of interest that is mentioned in online discussions, we use the wisdom of the crowd to automatically track her physical locations over time. We evaluate our approach in the context of politics, i.e., we predict the locations of US politicians as a proof of concept for important use cases, such as to track people that
are national risks, e.g., warlords and wanted criminals.
Soft actuators have drawn significant attention due to their relevance for applications, such as artificial muscles in devices developed for medicine and robotics. Tuning their performance and expanding their functionality are frequently done by means of chemical modification. The introduction of structural elements rendering non-synthetic modification of the performance possible, as well as control over physical appearance and facilitating their recycling is a subject of a great interest in the field of smart materials. The primary aim of this thesis was to create a shape-memory polymeric actuator, where the capability for non-synthetic tuning of the actuation performance is combined with reprocessability. Physically cross-linked polymeric matrices provide a solid material platform, where the in situ processing methods can be employed for modification of the composition and morphology, resulting in the fine tuning of the related mechanical properties and shape-memory actuation capability.
The morphological features, required for shape-memory polymeric actuators, namely two crystallisable domains and anchoring points for physical cross-links, were embedded into a multiblock copolymer with poly(ε-caprolactone) and poly(L-lactide) segments (PLLA-PCL). Here, the melting transition of PCL was bisected into the actuating and skeleton-forming units, while the cross-linking was introduced via PLA stereocomplexation in blends with oligomeric poly(D-lactide) (ODLA). PLLA segment number average length of 12-15 repeating units was experimentally defined to be capable of the PLA stereocomplexes formation, but not sufficient for the isotactic crystallisation. Multiblock structure and phase dilution broaden the PCL melting transition, facilitating its separation into two conditionally independent crystalline domains. Low molar mass of the PLA stereocomplex components and a multiblock structure enables processing and reprocessing of the PLLA-PCL / ODLA blends with common non-destructive techniques. The modularity of the PLLA-PCL structure and synthetic approach allows for independent tuning of the properties of its components. The designed material establishes a solid platform for non-synthetic tuning of thermomechanical and structural properties of thermoplastic elastomers.
To evaluate the thermomechanical stability of the formed physical network, three criteria were appraised. As physical cross-links, PLA stereocomplexes have to be evenly distributed within the material matrix, their melting temperature shall not overlap with the thermal transitions of the PCL domains and they have to maintain the structural integrity within the strain ε ranges further applied in the shape-memory actuation experiments. Assigning PCL the function of the skeleton-forming and actuating units, and PLA stereocomplexes the role of physical netpoints, shape-memory actuation was realised in the PLLA-PCL / ODLA blends. Reversible strain of shape-memory actuation was found to be a function of PLA stereocomplex crystallinity, i.e. physical cross-linking density, with a maximum of 13.4 ± 1.5% at PLA stereocomplex content of 3.1 ± 0.3 wt%. In this way, shape-memory actuation can be tuned via adjusting the composition of the PLLA-PCL / ODLA blend. This makes the developed material a valuable asset in the production of cost-effective tunable soft polymeric actuators for the applications in medicine and soft robotics.
Polymeric semiconductors are strong contenders for replacing traditional inorganic semiconductors in electronic applications requiring low power, low cost and flexibility, such as biosensors, flexible solar cells and electronic displays. Molecular doping has the potential to enable this revolution by improving the conductivity and charge transport properties of this class of materials. Despite decades of research in this field, gaps in our understanding of the nature of dopant–polymer interactions has resulted in limited commercialization of this technology. This work aims at providing a deeper insight into the underlying mechanisms of molecular p-doping of semiconducting polymers in the solution and solid-state, and thereby bring the scientific community closer to realizing the dream of making organic semiconductors commonplace in the electronics industry. The role of 1) dopant size/shape, 2) polymer chain aggregation and 3) charge delocalization on the doping mechanism and efficiency is addressed using optical (UV-Vis-NIR) and electron paramagnetic resonance (EPR) spectroscopies. By conducting a comprehensive study of the nature and concentration of the doping-induced species in solutions of the polymer poly(3-hexylthiophene) (P3HT) with 3 different dopants, we identify the unique optical signatures of the delocalized polaron, localized polaron and charge-transfer complex, and report their extinction coefficient values. Furthermore, with X-ray diffraction, atomic force microscopy and electrical conductivity measurements, we study the impact of processing technique and doping mechanism on the morphology and thereby, charge transport through the doped films.
This work demonstrates that the doping mechanism and type of doping-induced species formed are strongly influenced by the polymer backbone arrangement rather than dopant shape/size. The ability of the polymer chain to aggregate is found to be crucial for efficient charge transfer (ionization) and polaron delocalization. At the same time, our results suggest that the high ionization efficiency of a dopant–polymer system in solution may subsequently hinder efficient charge transport in the solid-state due to the reduction in the fraction of tie chains, which enable charges to move efficiently between aggregated domains in the films. This study demonstrates the complex multifaceted nature of polymer doping while providing important hints for the future design of dopant-host systems and film fabrication techniques.
Bottom-up synthetic biology is used for the understanding of how a cell works. It is achieved through developing techniques to produce lipid-based vesicular structures as cellular mimics. The most common techniques used to produce cellular mimics or synthetic cells is through electroformation and swelling method. However, the abovementioned techniques cannot efficiently encapsulate macromolecules such as proteins, enzymes, DNA and even liposomes as synthetic organelles. This urges the need to develop new techniques that can circumvent this issue and make the artificial cell a reality where it is possible to imitate a eukaryotic cell through encapsulating macromolecules. In this thesis, the aim to construct a cell system using giant unilamellar vesicles (GUVs) to reconstitute the mitochondrial molybdenum cofactor biosynthetic pathway. This pathway is highly conserved among all life forms, and therefore is known for its biological significance in disorders induced through its malfunctioning. Furthermore, the pathway itself is a multi-step enzymatic reaction that takes place in different compartments. Initially, GTP in the mitochondrial matrix is converted to cPMP in the presence of cPMP synthase. Further, produced cPMP is transported across the membrane to the cytosol, to be converted by MPT synthase into MPT. This pathway provides a possibility to address the general challenges faced in the development of a synthetic cell, to encapsulate large biomolecules with good efficiency and greater control and to evaluate the enzymatic reactions involved in the process.
For this purpose, the emulsion-based technique was developed and optimised to allow rapid production of GUVs (~18 min) with high encapsulation efficiency (80%). This was made possible by optimizing various parameters such as density, type of oil, the impact of centrifugation speed/time, lipid concentration, pH, temperature, and emulsion droplet volume. Furthermore, the method was optimised in microtiter plates for direct experimentation and visualization after the GUV formation. Using this technique, the two steps - formation of cPMP from GTP and the formation of MPT from cPMP were encapsulated in different sets of GUVs to mimic the two compartments. Two independent fluorescence-based detection systems were established to confirm the successful encapsulation and conversion of the reactants. Alternatively, the enzymes produced using bacterial expression and measured. Following the successful encapsulation and evaluation of enzymatic reactions, cPMP transport across mitochondrial membrane has been mimicked using GUVs using a complex mitochondrial lipid composition. It was found that the cPMP interaction with the lipid bilayer results in transient pore-formation and leakage of internal contents.
Overall, it can be concluded that in this thesis a novel technique has been optimised for fast production of functional synthetic cells. The individual enzymatic steps of the Moco biosynthetic pathway have successfully implemented and quantified within these cellular mimics.
Ionizing radiation is used in cancer radiation therapy to effectively damage the DNA of tumors leading to cell death and reduction of the tumor tissue. The main damage is due to generation of highly reactive secondary species such as low-energy electrons (LEE) with the most probable energy around 10 eV through ionization of water molecules in the cells. A simulation of the dose distribution in the patient is required to optimize the irradiation modality in cancer radiation therapy, which must be based on the fundamental physical processes of high-energy radiation with the tissue. In the present work the accurate quantification of DNA radiation damage in the form of absolute cross sections for LEE-induced DNA strand breaks (SBs) between 5 and 20 eV is done by using the DNA origami technique. This method is based on the analysis of well-defined DNA target sequences attached to DNA origami triangles with atomic force microscopy (AFM) on the single molecule level. The present work focuses on poly-adenine sequences (5'-d(A4), 5'-d(A8), 5'-d(A12), 5'-d(A16), and 5'- d(A20)) irradiated with 5.0, 7.0, 8.4, and 10 eV electrons. Independent of the DNA length, the strand break cross section shows a maximum around 7.0 eV electron energy for all investigated oligonucleotides confirming that strand breakage occurs through the initial formation of negative ion resonances. Additionally, DNA double strand breaks from a DNA hairpin 5'-d(CAC)4T(Bt-dT)T2(GTG)4 are examined for the first time and are compared with those of DNA single strands 5'-d(CAC)4 and 5'- d(GTG)4. The irradiation is made in the most likely energy range of 5 to 20 eV with an anionic resonance maximum around 10 eV independently of the DNA sequence. There is a clear difference between σSSB and σDSB of DNA single and double strands, where the strand break for ssDNA are always higher in all electron energies compared to dsDNA by the factor 3. A further part of this work deals with the characterization and analysis of new types of radiosensitizers used in chemoradiotherapy, which selectively increases the DNA damage upon radiation. Fluorinated DNA sequences with 2'-fluoro-2'-deoxycytidine (dFC) show an increased sensitivity at 7 and 10 eV compared to the unmodified DNA sequences by an enhancement factor between 2.1 and 2.5. In addition, light-induced oxidative damage of 5'-d(GTG)4 and 5'-d((CAC)4T(Bt-dT)T2(GTG)4) modified DNA origami triangles by singlet oxygen 1O2 generated from three photoexcited DNA groove binders [ANT994], [ANT1083] and [Cr(ddpd)2][BF4]3 illuminated in different experiments with UV-Vis light at 430, 435 and 530 nm wavelength is demonstrated. The singlet oxygen induced generation of DNA damage could be detected in both aqueous and dry environments for [ANT1083] and [Cr(ddpd)2][BF4]3.
The ubiquitin-proteasome-system (UPS) is a cellular cascade involving three enzymatic steps for protein ubiquitination to target them to the 26S proteasome for proteolytic degradation. Several components of the UPS have been shown to be central for regulation of defense responses during infections with phytopathogenic bacteria. Upon recognition of the pathogen, local defense is induced which also primes the plant to acquire systemic resistance (SAR) for enhanced immune responses upon challenging infections. Here, ubiquitinated proteins were shown to accumulate locally and systemically during infections with Psm and after treatment with the SAR-inducing metabolites salicylic acid (SA) and pipecolic acid (Pip). The role of the 26S proteasome in local defense has been described in several studies, but the potential role during SAR remains elusive and was therefore investigated in this project by characterizing the Arabidopsis proteasome mutants rpt2a-2 and rpn12a-1 during priming and infections with Pseudomonas. Bacterial replication assays reveal decreased basal and systemic immunity in both mutants which was verified on molecular level showing impaired activation of defense- and SAR-genes. rpt2a-2 and rpn12a-1 accumulate wild type like levels of camalexin but less SA. Endogenous SA treatment restores local PR gene expression but does not rescue the SAR-phenotype. An RNAseq experiment of Col-0 and rpt2a-2 reveal weak or absent induction of defense genes in the proteasome mutant during priming. Thus, a functional 26S proteasome was found to be required for induction of SAR while compensatory mechanisms can still be initiated.
E3-ubiquitin ligases conduct the last step of substrate ubiquitination and thereby convey specificity to proteasomal protein turnover. Using RNAseq, 11 E3-ligases were found to be differentially expressed during priming in Col-0 of which plant U-box 54 (PUB54) and ariadne 12 (ARI12) were further investigated to gain deeper understanding of their potential role during priming.
PUB54 was shown to be expressed during priming and /or triggering with virulent Pseudomonas. pub54 I and pub54-II mutants display local and systemic defense comparable to Col-0. The heavy-metal associated protein 35 (HMP35) was identified as potential substrate of PUB54 in yeast which was verified in vitro and in vivo. PUB54 was shown to be an active E3-ligase exhibiting auto-ubiquitination activity and performing ubiquitination of HMP35. Proteasomal turnover of HMP35 was observed indicating that PUB54 targets HMP35 for ubiquitination and subsequent proteasomal degradation. Furthermore, hmp35-I benefits from increased resistance in bacterial replication assays. Thus, HMP35 is potentially a negative regulator of defense which is targeted and ubiquitinated by PUB54 to regulate downstream defense signaling. ARI12 is transcriptionally activated during priming or triggering and hyperinduced during priming and triggering. Gene expression is not inducible by the defense related hormone salicylic acid (SA) and is dampened in npr1 and fmo1 mutants consequently depending on functional SA- and Pip-pathways, respectively. ARI12 accumulates systemically after priming with SA, Pip or Pseudomonas. ari12 mutants are not altered in resistance but stable overexpression leads to increased resistance in local and systemic tissue. During priming and triggering, unbalanced ARI12 levels (i.e. knock out or overexpression) leads to enhanced FMO1 activation indicating a role of ARI12 in Pip-mediated SAR. ARI12 was shown to be an active E3-ligase with auto-ubiquitination activity likely required for activation with an identified ubiquitination site at K474. Mass spectrometrically identified potential substrates were not verified by additional experiments yet but suggest involvement of ARI12 in regulation of ROS in turn regulating Pip-dependent SAR pathways.
Thus, data from this project provide strong indications about the involvement of the 26S proteasome in SAR and identified a central role of the two so far barely described E3-ubiquitin ligases PUB54 and ARI12 as novel components of plant defense.
Over the last decades, the rate of near-surface warming in the Arctic is at least double than elsewhere on our planet (Arctic amplification). However, the relative contribution of different feedback processes to Arctic amplification is a topic of ongoing research, including the role of aerosol and clouds. Lidar systems are well-suited for the investigation of aerosol and optically-thin clouds as they provide vertically-resolved information on fine temporal scales. Global aerosol models fail to converge on the sign of the Arctic aerosol radiative effect (ARE). In the first part of this work, the optical and microphysical properties of Arctic aerosol were characterized at case study level in order to assess the short-wave (SW) ARE. A long-range transport episode was first investigated. Geometrically similar aerosol layers were captured over three locations. Although the aerosol size distribution was different between Fram Strait(bi-modal) and Ny-Ålesund (fine mono-modal), the atmospheric column ARE was similar. The latter was related to the domination of accumulation mode aerosol. Over both locations top of the atmosphere (TOA) warming was accompanied by surface cooling.
Subsequently, the sensitivity of ARE was investigated with respect to different aerosol and spring-time ambient conditions. A 10% change in the single-scattering albedo (SSA) induced higher ARE perturbations compared to a 30% change in the aerosol extinction coefficient. With respect to ambient conditions, the ARETOA was more sensitive to solar elevation changes compared to AREsur f ace. Over dark surfaces the ARE profile was exclusively negative, while over bright surfaces a negative to positive shift occurred above the aerosol layers. Consequently, the sign of ARE can be highly sensitive in spring since this season is characterized by transitional surface albedo conditions.
As the inversion of the aerosol microphysics is an ill-posed problem, the inferred aerosol size distribution of a low-tropospheric event was compared to the in-situ measured distribution. Both techniques revealed a bi-modal distribution, with good agreement in the total volume concentration. However, in terms of SSA a disagreement was found, with the lidar inversion indicating highly scattering particles and the in-situ measurements pointing to absorbing particles. The discrepancies could stem from assumptions in the inversion (e.g. wavelength-independent refractive index) and errors in the conversion of the in-situ measured light attenuation into absorption. Another source of discrepancy might be related to an incomplete capture of fine particles in the in-situ sensors. The disagreement in the most critical parameter for the Arctic ARE necessitates further exploration in the frame of aerosol closure experiments. Care must be taken in ARE modelling studies, which may use either the in-situ or lidar-derived SSA as input.
Reliable characterization of cirrus geometrical and optical properties is necessary for improving their radiative estimates. In this respect, the detection of sub-visible cirrus is of special importance. The total cloud radiative effect (CRE) can be negatively biased, should only the optically-thin and opaque cirrus contributions are considered. To this end, a cirrus retrieval scheme was developed aiming at increased sensitivity to thin clouds. The cirrus detection was based on the wavelet covariance transform (WCT) method, extended by dynamic thresholds. The dynamic WCT exhibited high sensitivity to faint and thin cirrus layers (less than 200 m) that were partly or completely undetected by the existing static method. The optical characterization scheme extended the Klett–Fernald retrieval by an iterative lidar ratio (LR) determination (constrained Klett). The iterative process was constrained by a reference value, which indicated the aerosol concentration beneath the cirrus cloud. Contrary to existing approaches, the aerosol-free assumption was not adopted, but the aerosol conditions were approximated by an initial guess. The inherent uncertainties of the constrained Klett were higher for optically-thinner cirrus, but an overall good agreement was found with two established retrievals. Additionally, existing approaches, which rely on aerosol-free assumptions, presented increased accuracy when the proposed reference value was adopted. The constrained Klett retrieved reliably the optical properties in all cirrus regimes, including upper sub-visible cirrus with COD down to 0.02.
Cirrus is the only cloud type capable of inducing TOA cooling or heating at daytime. Over the Arctic, however, the properties and CRE of cirrus are under-explored. In the final part of this work, long-term cirrus geometrical and optical properties were investigated for the first time over an Arctic site (Ny-Ålesund). To this end, the newly developed retrieval scheme was employed. Cirrus layers over Ny-Ålesund seemed to be more absorbing in the visible spectral region compared to lower latitudes and comprise relatively more spherical ice particles. Such meridional differences could be related to discrepancies in absolute humidity and ice nucleation mechanisms. The COD tended to decline for less spherical and smaller ice particles probably due to reduced water vapor deposition on the particle surface. The cirrus optical properties presented weak dependence on ambient temperature and wind conditions.
Over the 10 years of the analysis, no clear temporal trend was found and the seasonal cycle was not pronounced. However, winter cirrus appeared under colder conditions and stronger winds. Moreover, they were optically-thicker, less absorbing and consisted of relatively more spherical ice particles. A positive CREnet was primarily revealed for a broad range of representative cloud properties and ambient conditions. Only for high COD (above 10) and over tundra a negative CREnet was estimated, which did not hold true over snow/ice surfaces. Consequently, the COD in combination with the surface albedo seem to play the most critical role in determining the CRE sign over the high European Arctic.
Negotiations between buyers and suppliers directly influence a company’s costs, revenue, and consequently its profits. The outcome of these negotiations relies heavily on the companies’ as well as the negotiators’ power position. Across three empirical articles the author demonstrates how the own power position can first be identified as well as improved and subsequently used to maximize profits in negotiations between sellers and buyers. In the first paper the sources underlying buyer and supplier power are identified and weighted. The results of the first paper show the impact of each single sources on the buyer and supplier power. The number of suppliers available for one product is by far the most important source of power for both sides. The results indicate that a higher number of suppliers leads to a better power position of the buyer and simultaneously to an inferior power position of a single supplier. The second paper aims to examine the impact of the number of suppliers on the outcome of buyer-seller-negotiations thereby considering the innovation level of the products purchased. The results of the second study which are based on real negotiation data from a German car manufacturer indicate that the number of available suppliers has a stronger impact on the negotiation outcome for innovative than for functional, less innovative products. The third paper analyzes how the ability to take the counterpart’s perspective (perspective taking ability) influences the negotiation outcome. This relationship is examined for different power positions. The results indicate that a negotiator’s high perspective taking ability leads to a more unfavorable negotiation outcome compared to low perspective taking ability. Simultaneously, high perspective taking ability causes a more positive perception of the conducted negotiation than low perspective taking ability. This contradictory effect of perspective taking ability bears the risk for buyers and suppliers to assess an unfavorable outcome as positive. Finally, the results of the papers are summarized and discussed. The dissertation concludes with implications for practice, limitations of the work, and approaches for future research.
Background and objectives: The intricate interdependencies between the musculoskeletal and neural systems build the foundation for postural control in humans, which is a prerequisite for successful performance of daily and sports-specific activities. Balance training (BT) is a well-established training method to improve postural control and its components (i.e., static/dynamic steady-state, reactive, proactive balance). The effects of BT have been studied in adult and youth populations, but were systematically and comprehensively assessed only in young and old adults. Additionally, when taking a closer look at established recommendations for BT modalities (e.g., training period, frequency, volume), standardized means to assess and control the progressive increase in exercise intensity are missing. Considering that postural control is primarily neuronally driven, intensity is not easy to quantify. In this context, a measure of balance task difficulty (BTD) appears to be an auspicious alternative as a training modality to monitor BT and control training progression. However, it remains unclear how a systematic increase in BTD affects balance performance and neurophysiological outcomes. Therefore, the primary objectives of the present thesis were to systematically and comprehensively assess the effects of BT on balance performance in healthy youth and establish dose-response relationships for an adolescent population. Additionally, this thesis aimed to investigate the effects of a graded increase in BTD on balance performance (i.e., postural sway) and neurophysiological outcomes (i.e, leg muscle activity, leg muscle coactivation, cortical activity) in adolescents.
Methods: Initially, a systematic review and meta-analysis on the effects of BT on balance performance in youth was conducted per the Preferred Reporting Items for Systematic Reviews and Meta-Analysis statement guidelines. Following this complementary analysis, thirteen healthy adolescents (3 female/ 10 male) aged 16-17 years were enrolled for two cross-sectional studies. The participants executed bipedal balance tasks on a multidirectional balance board that allowed six gradually increasing levels of BTD by narrowing the balance boards’ base of support. During task performance, two pressure sensitive mats fixed on the balance board recorded postural sway. Leg muscle activity and leg muscle coactivation were assessed via electromyography while electroencephalography was used to monitor cortical activity.
Results: Findings from the systematic review and meta-analysis indicated moderate-to-large effects of BT on static and dynamic balance performance in youth (static: weighted mean standardized mean differences [SMDwm] = 0.71; dynamic: SMDwm = 1.03). In adolescents, training-induced effects were moderate and large for static (SMDwm = 0.61) and dynamic (SMDwm = 0.86) balance performance, respectively. Independently (i.e. modality-specific) calculated dose-response relationships identified a training period of 12 weeks, a frequency of two training sessions per week, a total of 24-36 sessions, a duration of 4-15 minutes, and a total duration of 31-60 minutes as the training modalities with the largest effect on overall balance performance in adolescents. However, the implemented meta-regression indicated that none of these training modalities (R² = 0%) could predict the observed performance-increasing effects of BT.
Results from the first cross-sectional study revealed that a gradually increasing level of BTD caused increases in postural sway (p < 0.001; d = 6.36), higher leg muscle activity (p < 0.001; 2.19 < d < 4.88), and higher leg muscle coactivation (p < 0.001; 1.32 < d < 1.41). Increases in postural sway and leg muscle activity were mainly observed during low and high levels of task difficulty during continuous performance of the respective balance task. Results from the second cross-sectional study indicated frequency-specific increases/decreases in cortical activity of different brain areas (p < 0.005; 0.92 < d < 1.80) as a function of BTD. Higher cortical activity within the theta frequency band in the frontal and central right brain areas was observed with increasing postural demands. Concomitantly, activity in the alpha-2 frequency band was attenuated in parietal brain areas.
Conclusion: BT is an effective method to increase static and dynamic balance performance and, thus, improve postural control in healthy youth populations. However, none of the reported training modalities (i.e., training period, frequency, volume) could explain the effects on balance performance. Furthermore, a gradually increasing level of task difficulty resulted in increases in postural sway, leg muscle activity, and coactivation. Frequency and brain area-specific increases/decreases in cortical activity emphasize the involvement of frontoparietal brain areas in regulatory processes of postural control dependent on BTD. Overall, it appears that increasing BTD can be easily accomplished by narrowing the base of support. Since valid methods to assess and quantify BT intensity do not exist, increasing BTD appears to be a very useful candidate to implement and monitor progression in BT programs in healthy adolescents.
Geochemical processes such as mineral dissolution and precipitation alter the microstructure of rocks, and thereby affect their hydraulic and mechanical behaviour. Quantifying these property changes and considering them in reservoir simulations is essential for a sustainable utilisation of the geological subsurface. Due to the lack of alternatives, analytical methods and empirical relations are currently applied to estimate evolving hydraulic and mechanical rock properties associated with chemical reactions. However, the predictive capabilities of analytical approaches remain limited, since they assume idealised microstructures, and thus are not able to reflect property evolution for dynamic processes. Hence, aim of the present thesis is to improve the prediction of permeability and stiffness changes resulting from pore space alterations of reservoir sandstones.
A detailed representation of rock microstructure, including the morphology and connectivity of pores, is essential to accurately determine physical rock properties. For that purpose, three-dimensional pore-scale models of typical reservoir sandstones, obtained from highly resolved micro-computed tomography (micro-CT), are used to numerically calculate permeability and stiffness. In order to adequately depict characteristic distributions of secondary minerals, the virtual samples are systematically altered and resulting trends among the geometric, hydraulic, and mechanical rock properties are quantified. It is demonstrated that the geochemical reaction regime controls the location of mineral precipitation within the pore space, and thereby crucially affects the permeability evolution. This emphasises the requirement of determining distinctive porosity-permeability relationships
by means of digital pore-scale models. By contrast, a substantial impact of spatial alterations patterns on the stiffness evolution of reservoir sandstones are only observed in case of certain microstructures, such as highly porous granular rocks or sandstones comprising framework-supporting cementations. In order to construct synthetic granular samples a process-based approach is proposed including grain deposition and diagenetic cementation. It is demonstrated that the generated samples reliably represent the microstructural complexity of natural sandstones. Thereby, general limitations of imaging techniques can be overcome and various realisations of granular rocks can be flexibly produced. These can be further altered by virtual experiments, offering a fast and cost-effective way to examine the impact of precipitation, dissolution or fracturing on various petrophysical correlations.
The presented research work provides methodological principles to quantify trends in permeability and stiffness resulting from geochemical processes. The calculated physical property relations are directly linked to pore-scale alterations, and thus have a higher accuracy than commonly applied analytical approaches. This will considerably improve the predictive capabilities of reservoir models, and is further relevant to assess and reduce potential risks, such as productivity or injectivity losses as well as reservoir compaction or fault reactivation. Hence, the proposed method is of paramount importance for a wide range of natural and engineered subsurface applications, including geothermal energy systems, hydrocarbon reservoirs, CO2 and energy storage as well as hydrothermal deposit exploration.
As the ongoing trend of developing smart materials that can reversibly switch geometry stimulated by environmental control addressed increasing attention in many research fields, especially for biomedical or soft robotic applications. Shape-memory polymers (SMPs), which can change shape, stiffness, size, and structure when exposed to an external stimulus, are intensively explored as encouraging material candidates for achieving multifunctionality, and for miniaturizing into micro-components to expand the applications. Besides, the geometrical design has gained growing attention for creating engineering applications, such as bi-stable mechanisms, and has the potential to be explored by implementing SMP for new functions. In this context, this thesis aimed to develop smart micro-/nano-objects based on SMP and explore new functions by geometrical design using SMP. Here, two types of stimuli-responsive objects capable of one-way temperature-memory effect (TME) or free-standing reversible actuation e.g., micro/nanofibers (i) and microcuboids (ii) at different aspects were explored. At first, it was hypothesized that the advanced atomic force microscopy (AFM) platform can be established to study individual polymeric micro-/nanofibers (i) in terms of incorporation and characterization of a reversible shape-memory actuation capability. Crystallizable material was chosen for preparing the fibers and the molecular alignment within the fibers among different diameters will influence the crystallization-induced elongation during cooling that determined the reversible effect. For the second type, microcuboids (ii), it was hypothesized that a programming and quantification approach can be developed to enable the realization and characterization of a one-way micro-TME and micro-shape-memory polymer actuation (SMPA) in microcuboids. The responsive temperature of one-way shape transformation can be tuned by programming temperature (Tp) and the separation temperature (Tsep) for post-programming can influence the actuation. Finally, a geometrical design with bi-stability was combined with SME to create new functions of shape actuation. It was hypothesized that the predicted bi-stable or mono-stable structures can be achieved with the aid of digital fabrication methods. Using shape-memory effect (SME), the alteration of bi-stable and mono-stable can initiate shape transformation with a larger magnitude and higher energy output.
In the first part, the method to quantify the reversible SMPA of a single micro/nano crystallizable fiber with geometry change during the actuation was explored. Electrospinning was used to prepare poly (ε-caprolactone) (PCL) micro/nanofiber with different diameters, which were fixed by UV glue and crosslinked on the structured silicon wafer. Using AFM, the programming, as well as the observation of recovery and reversible displacement of the fiber, were performed by vertical three-point bending at the free suspended part. A plateau tip was chosen to achieve stable contact and longer working distance for performing larger deformation, enabling intensified reversible SMPA of single fibers. In this way, programming strains of 39 ± 1% or 46 ± 1% were realized for fiber with a diameter of 1 ± 0.2 µm and 300 ± 50 nm, which were bent at 80 °C and fixed at 10 °C. Values for the reversible elongation of εrev = 3.4 ± 0.1% and 10.5 ± 0.1% were obtained for a single micro and nanofiber respectively between 10 and 60 °C. The higher actuation effect observed for nanofiber demonstrated that the highly compact and oriented crystallites in nanofibers, which determined the pronounced εrev compared to the thick microfibers. Besides, a stable reversible actuation of a nanofiber can be tracked by AFM tip up to 10 cycles, indicating a sustainable application can be achieved on the fiber actuators. The findings obtained for cPCL micro-/nano-fibers will help design and evaluate the next generation polymeric microactuators or micromanipulators.
The second part of the thesis studies the shape-memory effect (SME) of a single individual SMP micro-object by controlling deformation temperatures during programming and actuation temperatures during reversible change. In this work, microcuboids of crosslinked poly[ethylene-co-(vinyl acetate)] (cPEVA) elastomers with 18 wt% vinyl acetate (VA) contents were successfully prepared by template-based replication from polydimethylsiloxane (PDMS) mold. The micro-TME and micro-SMPA were observed and studied based on micro-geometry change using optical microscopy (OM) and AFM. Different switching temperatures of shape recovery were achieved from 55 °C to 86 °C by tuning Tp from 55 °C to 100 °C, indicating a successful implementation of micro-TME on individual microcuboid. For micro-SMPA functionalization, microcuboids were deformed by compression at 100 °C and the change in single particle height was monitored during cyclic heating and cooling between various Tseps from 60 °C to 85 °C and 20 °C. The micro-SMPA on a single microcuboid was achieved with a reversible strain in the range of 2 to 7%, whereby higher compression ratio CR and Tsep induced prominent reversible strain. The results achieved in this work demonstrated the successful functionalization of microcuboids with different SMEs by controlling temperatures during programming and actuation processes. Based on these achievements, such micro-objects can be further designed as on demand switchable microactuators or release systems with adjustable working temperatures.
In the last part of the work, a new function of shape-memory polymeric bi-stable 3D structured film was designed and fabricated. The SME and geometrical design of compliant mechanics were merged to enable switching between bi-stable and mono-stable states, which generate snap movement that mimics the Venus flytrap. A truncated tetrahedron structure with a slope angle as a tunable parameter to alter the bi-stability was chosen for the study to combine with
SME. It was anticipated that the structured film designed with a slope angle of 30° exhibited mono-stable behavior, and such a structure with a slope angle of 45° exhibited bi-stable behavior. Then the structured SMP film of designed mono-stable shape was successfully fabricated using soft lithography based on 3D printed master molds supported from digital manufacturing. The structured mold was also used in programming the SMP film into the structure with a higher slope angle to attain bi-stability. Finally, the switching between bi-stable and mono-stable states was successfully realized using SME, which introduces snapping movement triggered by heat. The implementation of compliant mechanisms by the SME increased the magnitude of thermally induced reconfiguration without additional external force.
To sum up, the results of the thesis support the development of smart objects capable of one-way micro-TME, free-standing reversible actuation, or bi-stability mediated shape-memory reconfiguration. Electrospinning and template-based method were used for fabrication with good control of geometry and low size dispersity. Microscopy methods especially the AFM platform with decent sensitivity was developed for implementation as well as characterization of SME on individual micro-/nanoobjects. Implementation of bi-stability improves the shape transformation amplitude of thermally triggered SMP. These findings can give novel insights for designing polymer-based actuators or soft robotics.
Digital software platforms such as iOS or Android evolve quickly. Through regular updates, their set of built-in (core) features increases. While innovation allows strengthening platforms amidst competition, it can hurt contributors when introducing core features that are already provided by third-party developers (Platform Coring).
This book addresses the underexplored phenomenon of Platform Coring and provides strategical guidance for platform owners and third-party contributors. Platform owners are well-advised to carefully consider the benefits and risks for their platform ecosystem.
The book contributes by highlighting avenues to employ Platform Coring for the competitive advantage of the platform and ecosystem simultaneously.
Filaments are omnipresent features in the solar chromosphere, one of the atmospheric layers of the Sun, which is located above the photosphere, the visible surface of the Sun. They are clouds of plasma reaching from the photosphere to the chromosphere, and even to the outer-most atmospheric layer, the corona. They are stabalized by the magnetic field. If the magnetic field is disturbed, filaments can erupt as coronal mass ejections (CME), releasing plasma into space, which can also hit the Earth. A special type of filaments are polar crown filaments, which form at the interface of the unipolar field of the poles and flux of opposite magnetic polarity, which was transported towards the poles. This flux transport is related to the global dynamo of the Sun and can therefore be analyzed indirectly with polar crown filaments. The main objective of this thesis is to better understand the physical properties and environment of high-latitude and polar crown filaments, which can be approached from two perspectives: (1) analyzing the large-scale properties of high-latitude and polar crown filaments with full-disk Hα observations from the Chromospheric Telescope (ChroTel) and (2) determining the relation of polar crown and high-latitude filaments from the chromosphere to the lower-lying photosphere with high-spatial resolution observations of the Vacuum Tower Telescope (VTT), which reveal the smallest details.
The Chromospheric Telescope (ChroTel) is a small 10-cm robotic telescope at Observatorio del Teide on Tenerife (Spain), which observes the entire Sun in Hα, Ca IIK, and He I 10830 Å. We present a new calibration method that includes limb-darkening correction, removal of non-uniform filter transmission, and determination of He I Doppler velocities. Chromospheric full-disk filtergrams are often obtained with Lyot filters, which may display non-uniform transmission causing large-scale intensity variations across the solar disk. Removal of a 2D symmetric limb-darkening function from full-disk images results in a flat background. However, transmission artifacts remain and are even more distinct in these contrast-enhanced images. Zernike polynomials are uniquely appropriate to fit these large-scale intensity variations of the background. The Zernike coefficients show a distinct temporal evolution for ChroTel data, which is likely related to the telescope’s alt-azimuth mount that introduces image rotation. In addition, applying this calibration to sets of seven filtergrams that cover the He I triplet facilitates determining chromospheric Doppler velocities. To validate the method, we use three datasets with varying levels of solar activity. The Doppler velocities are benchmarked with respect to co-temporal high-resolution spectroscopic data of the GREGOR Infrared Spectrograph (GRIS). Furthermore, this technique can be applied to ChroTel Hα and Ca IIK data. The calibration method for ChroTel filtergrams can be easily adapted to other full-disk data exhibiting unwanted large-scale variations. The spectral region of the He I triplet is a primary choice for high-resolution near-infrared spectropolarimetry. Here, the improved calibration of ChroTel data will provide valuable context data.
Polar crown filaments form above the polarity inversion line between the old magnetic flux of the previous cycle and the new magnetic flux of the current cycle. Studying their appearance and their properties can lead to a better understanding of the solar cycle. We use full-disk data of the ChroTel at Observatorio del Teide, Tenerife, Spain, which were taken in three different chromospheric absorption lines (Hα 6563 Å, Ca IIK 3933 Å, and He I 10830 Å), and we create synoptic maps. In addition, the spectroscopic He I data allow us to compute Doppler velocities and to create synoptic Doppler maps. ChroTel data cover the rising and decaying phase of Solar Cycle 24 on about 1000 days between 2012 and 2018. Based on these data, we automatically extract polar crown filaments with image-processing tools and study their properties. We compare contrast maps of polar crown filaments with those of quiet-Sun filaments. Furthermore, we present a super-synoptic map summarizing the entire ChroTel database. In summary, we provide statistical properties, i.e. number and location of filaments, area, and tilt angle for both the maximum and declining phase of Solar Cycle 24. This demonstrates that ChroTel provides a
promising dataset to study the solar cycle.
The cyclic behavior of polar crown filaments can be monitored by regular full-disk Hα observations. ChroTel provides such regular observations of the Sun in three chromospheric wavelengths. To analyze the cyclic behavior and the statistical properties of polar crown filaments, we have to extract the filaments from the images. Manual extraction is tedious, and extraction with morphological image processing tools produces a large number of false positive detections and the manual extraction of these takes too much time. Automatic object detection and extraction in a reliable manner allows us to process more data in a shorter time. We will present an overview of the ChroTel database and a proof of concept of a machine learning application, which allows us a unified extraction of, for example, filaments from ChroTel data.
The chromospheric Hα spectral line dominates the spectrum of the Sun and other stars. In the stellar regime, this spectral line is already used as a powerful tracer of magnetic activity. For the Sun, other tracers are typically used to monitor solar activity. Nonetheless, the Sun is observed constantly in Hα with globally distributed ground-based full-disk imagers. The aim of this study is to introduce Hα as a tracer of solar activity and compare it to other established indicators. We discuss the newly created imaging Hα excess in the perspective of possible application for modelling of stellar atmospheres. In particular, we try to determine how constant is the mean intensity of the Hα excess and number density of low-activity regions between solar maximum and minimum. Furthermore, we investigate whether the active region coverage fraction or the changing emission strength in the active regions dominates time variability in solar Hα observations. We use ChroTel observations of full-disk Hα filtergrams and morphological image processing techniques to extract the positive and negative imaging Hα excess, for bright features (plage regions) and dark absorption features (filaments and sunspots), respectively. We describe the evolution of the Hα excess during Solar Cycle 24 and compare it to other well established tracers: the relative sunspot number, the F10.7 cm radio flux, and the Mg II index. Moreover, we discuss possible applications of the Hα excess for stellar activity diagnostics and the contamination of exoplanet transmission spectra. The positive and negative Hα excess follow the behavior of the solar activity over the course of the cycle. Thereby, positive Hα excess is closely correlated to the chromospheric Mg II index. On the other hand, the negative Hα excess, created from dark features like filaments and sunspots, is introduced as a tracer of solar activity for the first time. We investigated the mean intensity distribution for active regions for solar minimum and maximum and found that the shape of both distributions is very similar but with different amplitudes. This might be related with the relatively stable coronal temperature component during the solar cycle. Furthermore, we found that the coverage fraction of Hα excess and the Hα excess of bright features are strongly correlated, which will influence modelling of stellar and exoplanet atmospheres.
High-resolution observations of polar crown and high-latitude filaments are scarce. We present a unique sample of such filaments observed in high-resolution Hα narrow-band filtergrams and broad-band images, which were obtained with a new fast camera system at the VTT. ChroTel provided full-disk context observations in Hα, Ca IIK, and He I 10830 Å. The Helioseismic and Magnetic Imager (HMI) and the Atmospheric Imaging Assembly (AIA) on board the Solar Dynamics Observatory (SDO) provided line-of-sight magnetograms and ultraviolet (UV) 1700 Å filtergrams, respectively. We study filigree in the vicinity of polar crown and high-latitude filaments and relate their locations to magnetic concentrations at the filaments’ footpoints. Bright points are a well studied phenomenon in the photosphere at low latitudes, but they were not yet studied in the quiet network close to the poles. We examine size, area, and eccentricity of bright points and find that their morphology is very similar to their counterparts at lower latitudes, but their sizes and areas are larger. Bright points at the footpoints of polar crown filaments are preferentially located at stronger magnetic flux concentrations, which are related to bright regions at the border of supergranules as observed in UV filtergrams. Examining the evolution of bright points on three consecutive days reveals that their amount increases while the filament decays, which indicates they impact the equilibrium of the cool plasma contained in filaments.
Previous behavioral studies showed that perceptual changes in infancy can be observed in multiple patterns, namely decline (e.g., Mattock et al., 2008; Yeung et al., 2013), maintenance (e.g., Chen & Kager, 2016) and U-shaped development (Liu & Kager, 2014).
This dissertation contributes further to the understanding of the developmental trajectory of phonological acquisition in infancy. The dissertation addresses the questions of how the perceptual sensitivity of lexical tones and vowels changes in infancy and how different experimental procedures contribute to our understanding. We used three experimental procedures to investigate German-learning infants’ discrimination abilities. In Studies 1 and 3 (Chapters 5 and 7) we used behavioral methods (habituation and familiarization procedures) and in Study 2 (Chapter 6) we measured neural correlates.
Study 1 showed a U-shaped developmental pattern: 6- and 18-month-olds discriminated a lexical tone contrast, but not the 9-month-olds. In addition, we found an effect of experimental procedure: infants discriminated the tone contrast at 6 months in a habituation but not in a familiarization procedure. In Study 2, we observed mismatch responses (MMR) to a non-native tone contrast and a native-like vowel in 6- and 9-month-olds. In 6-month-olds, both contrasts elicited positive MMRs. At 9 months, the vowel contrast elicited an adult-like negative MMR, while the tone contrast elicited a positive MMR. Study 3 demonstrated a change in perceptual sensitivity to a vowel contrast between 6 and 9 months. In contrast to the 6-month-old infants, the 9-month-old infants discriminated the tested vowel contrast asymmetrically.
We suggest that the shifts in perceptual sensitivity between 6 and 9 months are functional rather than perceptual. In the case of lexical tone discrimination, infants may have already learned by 9 months of age that pitch is not relevant at the lexical level in German, since the infants in Study 1 showed no perceptual sensitivity to the contrast tested. Nevertheless, the brain responded to the contrast, especially since pitch differences are also part of the German intonation system (Gussenhoven, 2004). The role of the intonation system in pitch discrimination could be supported by the recovery of behavioral discrimination at 18 months of age, as well as behavioral and neural discrimination in German-speaking adults.
Past and present biodiversity in northeastern Siberia inferred from sedimentary DNA metabarcoding
(2021)
The arctic-boreal treeline is a transition zone from taiga to tundra covering a vast area in Siberia. It often features large environmental gradients and reacts sensitively to changes in the environment. For example, the expansion of shrubs and a northward movement of the treeline are observable in Siberia as a response to the warming climate. The changes in vegetation across the treeline are known to influence the water chemistry in the lakes. This causes further alteration to the composition and diversity of sensitive aquatic organisms such as diatoms and macrophytes. Despite the rising awareness of the complex climate-feedback mechanisms of terrestrial plants, the understanding of their assembly rules and about responses of aquatic biomes in the surrounding treeline lakes is still limited. The goal of this thesis is to examine the previous and present biodiversity of terrestrial and freshwater biomes from the Siberian treeline ecotone, as well as their reactions to environmental changes. In particular, this thesis attempts to examine the performance of applying sedimentary DNA metabarcoding in terrestrial plants, aquatic macrophytes and diatoms, their spatial patterns along the environmental gradients and their temporal patterns throughout the climate transition from the late Pleistocene to Holocene. Sedimentary DNA metabarcoding combined with next-generation sequencing is applied as a primary tool to explore the composition and diversity of terrestrial plants, diatoms and aquatic macrophytes. The main study area is located in Chukotka of northeastern Siberia in the Arctic, a biodiversity hotspot due to its continental location and the diverse habitats of the glacial refugium. The modern diatom diversity was assessed with a specific diatom metabarcoding marker and morphological identification. Both approaches agree to a dominance of Fragilariaceae and Aulacoseiraceae, as well as on the environmental influential indicators of the diatom community. The high diversity of Fragilariaceae identified in the thermokarst lakes is found to follow the vegetation gradient along the treeline, suggesting that diatom metabarcoding can decipher relationships between diatom assemblage shifts and the relevant environmental changes. In particular, the metabarcoding approach detects diversification of fragilarioids in glacial lakes which is not visible using morphology. Sedimentary ancient DNA records indicate a vegetation mosaic of forb-dominated steppe-tundra during 28-19 ka, followed by a shift to dwarf-shrub tundra during 19-14 ka. During the most recent 14 thousand years, the vegetation consists of deciduous shrublands, then a change to boreal forest is observed. Investigations on the alpha diversity of the vegetation show that species richness is unexpectedly highest during pre-LGM, which is likely related to the extensive area that allows for more taxa. The optimum Holocene warming during 9-6 ka is not accompanied by a high richness as widely believed, but with an evenly distributed community by the fulfilment of erect shrubs. Furthermore, changes in taxonomic and phylogenetic diversity show complementary results in understanding community diversity. The composition and richness in the modern macrophytes community from Siberian Arctic and Chinese alpine are best co-influenced by July temperature and electrical conductivity.. Past macrophyte turnover during the late Pleistocene-Holocene is less noticeable in Siberia, whereas a pronounced community change from emergent to submerged plants is detected from Chinese alpine regions at about 14 ka due to increasing temperature and varying water conductivity. Finally, sedimentary DNA metabarcoding is a cost-effective and powerful proxy for ecological application, whereas completeness of the reference library, coverage and resolution of the metabarcoding marker are the major limitations of sedimentary DNA based diversity monitoring. The composition and richness in modern vegetation and macrophytes across broad spatial gradients is constrained by environmental variables, suggesting a potential usage for environmental monitoring. Diatom distributions are driven by different water variables along the treeline. Past records indicate that the shrub coverage has a noticeable influence on the assemblies of both terrestrial plants and aquatic macrophytes, though the shift in macrophyte community is relatively minor in the past 28 thousand years. In the long-term, the shrub expansion may eventually result in a genetically more diverse vegetation community but reduced species richness. When exceeding the optimal temperatures, further warming may lead to a decrease and putative loss of macrophytes and diatoms.
Partial synchronous states exist in systems of coupled oscillators between full synchrony and asynchrony. They are an important research topic because of their variety of different dynamical states. Frequently, they are studied using phase dynamics. This is a caveat, as phase dynamics are generally obtained in the weak coupling limit of a first-order approximation in the coupling strength. The generalization to higher orders in the coupling strength is an open problem. Of particular interest in the research of partial synchrony are systems containing both attractive and repulsive coupling between the units. Such a mix of coupling yields very specific dynamical states that may help understand the transition between full synchrony and asynchrony. This thesis investigates partial synchronous states in mixed-coupling systems. First, a method for higher-order phase reduction is introduced to observe interactions beyond the pairwise one in the first-order phase description, hoping that these may apply to mixed-coupling systems. This new method for coupled systems with known phase dynamics of the units gives correct results but, like most comparable methods, is computationally expensive. It is applied to three Stuart-Landau oscillators coupled in a line with a uniform coupling strength. A numerical method is derived to verify the analytical results. These results are interesting but give importance to simpler phase models that still exhibit exotic states. Such simple models that are rarely considered are Kuramoto oscillators with attractive and repulsive interactions. Depending on how the units are coupled and the frequency difference between the units, it is possible to achieve many different states. Rich synchronization dynamics, such as a Bellerophon state, are observed when considering a Kuramoto model with attractive interaction in two subpopulations (groups) and repulsive interactions between groups. In two groups, one attractive and one repulsive, of identical oscillators with a frequency difference, an interesting solitary state appears directly between full and partial synchrony. This system can be described very well analytically.
During sentence reading the eyes quickly jump from word to word to sample visual information with the high acuity of the fovea. Lexical properties of the currently fixated word are known to affect the duration of the fixation, reflecting an interaction of word processing with oculomotor planning. While low level properties of words in the parafovea can likewise affect the current fixation duration, results concerning the influence of lexical properties have been ambiguous (Drieghe, Rayner, & Pollatsek, 2008; Kliegl, Nuthmann, & Engbert, 2006). Experimental investigations of such lexical parafoveal-on-foveal effects using the boundary paradigm have instead shown, that lexical properties of parafoveal previews affect fixation durations on the upcoming target words (Risse & Kliegl, 2014). However, the results were potentially confounded with effects of preview validity.
The notion of parafoveal processing of lexical information challenges extant models of eye movements during reading. Models containing serial word processing assumptions have trouble explaining such effects, as they usually couple successful word processing to saccade planning, resulting in skipping of the parafoveal word. Although models with parallel word processing are less restricted, in the SWIFT model (Engbert, Longtin, & Kliegl, 2002) only processing of the foveal word can directly influence the saccade latency.
Here we combine the results of a boundary experiment (Chapter 2) with a predictive modeling approach using the SWIFT model, where we explore mechanisms of parafoveal inhibition in a simulation study (Chapter 4). We construct a likelihood function for the SWIFT model (Chapter 3) and utilize the experimental data in a Bayesian approach to parameter estimation (Chapter 3 & 4).
The experimental results show a substantial effect of parafoveal preview frequency on fixation durations on the target word, which can be clearly distinguished from the effect of preview validity. Using the eye movement data from the participants, we demonstrate the feasibility of the Bayesian approach even for a small set of estimated parameters, by comparing summary statistics of experimental and simulated data. Finally, we can show that the SWIFT model can account for the lexical preview effects, when a mechanism for parafoveal inhibition is added. The effects of preview validity were modeled best, when processing dependent saccade cancellation was added for invalid trials. In the simulation study only the control condition of the experiment was used for parameter estimation, allowing for cross validation. Simultaneously the number of free parameters was increased. High correlations of summary statistics demonstrate the capabilities of the parameter estimation approach. Taken together, the results advocate for a better integration of experimental data into computational modeling via parameter estimation.
This dissertation was carried out as part of the international and interdisciplinary graduate school StRATEGy. This group has set itself the goal of investigating geological processes that take place on different temporal and spatial scales and have shaped the southern central Andes. This study focuses on claystones and carbonates of the Yacoraite Fm. that were deposited between Maastricht and Dan in the Cretaceous Salta Rift Basin. The former rift basin is located in northwest Argentina and is divided into the sub-basins Tres Cruces, Metán-Alemanía and Lomas de Olmedo. The overall motivation for this study was to gain new knowledge about the evolution of marine and lacustrine conditions during the Yacoraite Fm. Deposit in the Tres Cruces and Metán-Alemanía sub-basins. Other important aspects that were examined within the scope of this dissertation are the conversion of organic matter from Yacoraite Fm. into oil and its genetic relationship to selected oils produced and natural oil spills. The results of my study show that the Yacoraite Fm. began to be deposited under marine conditions and that a lacustrine environment developed by the end of the deposition in the Tres Cruces and Metán-Alemanía Basins. In general, the kerogen of Yacoraite Fm. consists mainly of the kerogen types II, III and II / III mixtures. Kerogen type III is mainly found in samples from the Yacoraite Fm., whose TOC values are low. Due to the adsorption of hydrocarbons on the mineral surfaces (mineral matrix effect), the content of type III kerogen with Rock-Eval pyrolysis in these samples could be overestimated. Investigations using organic petrography show that the organic particles of Yacoraite Fm. mainly consist of alginites and some vitrinite-like particles. The pyrolysis GC of the rock samples showed that the Yacoraite Fm. generates low-sulfur oils with a predominantly low-wax, paraffinic-naphthenic-aromatic composition and paraffinic wax-rich oils. Small proportions of paraffinic, low-wax oils and a gas condensate-generating facies are also predicted. Here, too, mineral matrix effects were taken into account, which can lead to a quantitative overestimation of the gas-forming character.
The results of an additional 1D tank modeling carried out show that the beginning (10% TR) of the oil genesis took place between ≈10 Ma and ≈4 Ma. Most of the oil (from ≈50% to 65%) was generated prior to the development of structural traps formed during the Plio-Pleistocene Diaguita deformation phase. Only ≈10% of the total oil generated was formed and potentially trapped after the formation of structural traps. Important factors in the risk assessment of this petroleum system, which can determine the small amounts of generated and migrated oil, are the generally low TOC contents and the variable thickness of the Yacoraite Fm. Additional risks are associated with a low density of information about potentially existing reservoir structures and the quality of the overburden.
This paper-based dissertation aims to contribute to the open innovation (OI) and technology management (TM) research fields by investigating their mechanisms, and potentials at the operational level. The dissertation connects the well-known concept of technology management with OI formats and applies these on specific manufacturing technologies within a clearly defined setting.
Technological breakthroughs force firms to continuously adapt and reinvent themselves. The pace of technological innovation and their impact on firms is constantly increasing due to more connected infrastructure and accessible resources (i.e. data, knowledge). Especially in the manufacturing sector it is one key element to leverage new technologies to stay competitive. These technological shifts call for new management practices.
TM supports firms with various tools to manage these shifts at different levels in the firm. It is a multifunctional and multidisciplinary field as it deals with all aspects of integrating technological issues into business decision-making and is directly relevant to a number of core business processes. Thus, it makes sense to utilize this theory and their practices as a foundation of this dissertation. However, considering the increasing complexity and number of technologies it is not sufficient anymore for firms to only rely on previous internal R&D and managerial practices. OI can expanse these practices by involving distributed innovation processes and accessing further external knowledge sources. This expansion can lead to an increasing innovation performance and thereby accelerate the time-to-market of technologies.
Research in this dissertation was based on the expectations that OI formats will support the R&D activities of manufacturing technologies on the operational level by providing access to resources, knowledge, and leading-edge technology. The dissertation represents uniqueness regarding the rich practical data sets (observations, internal documents, project reviews) drawn from a very large German high-tech firm. The researcher was embedded in an R&D unit within the operational TM department for manufacturing technologies. The analyses include 1.) an exploratory in-depth analysis of a crowdsourcing initiative to elaborate the impact on specific manufacturing technologies, 2.) a deductive approach for developing a technology evaluation score model to create a common understanding of the value of selected manufacturing technologies at the operational level, and 3.) an abductive reasoning approach in form of a longitudinal case study to derive important indicator for the in-process activities of science-based partnership university-industry collaboration format. Thereby, the dissertation contributed to research and practice 1.) linkages of TM and OI practices to assimilate technologies at the operational level, 2.) insights about the impact of CS on manufacturing technologies and a related guideline to execute CS initiatives in this specific environment 3.) introduction of manufacturing readiness levels and further criteria into the TM and OI research field to support decision-makers in the firm in gaining a common understanding of the maturity of manufacturing technologies and, 4.) context-specific important indicators for science based university-industry collaboration projects and a holistic framework to connect TM with the university-industry collaboration approach
The findings of this dissertation illustrate that OI formats can support the acceleration of time-to-market of manufacturing technologies and further improve the technical requirements of the product by leveraging external capabilities. The conclusions and implications made are intended to foster further research and improve managerial practices to evolve TM into an open collaborative context with interconnectivities between all internal and external involved technologies, individuals and organizational levels.
With ongoing anthropogenic global warming, some of the most vulnerable components of the Earth system might become unstable and undergo a critical transition. These subsystems are the so-called tipping elements. They are believed to exhibit threshold behaviour and would, if triggered, result in severe consequences for the biosphere and human societies. Furthermore, it has been shown that climate tipping elements are not isolated entities, but interact across the entire Earth system. Therefore, this thesis aims at mapping out the potential for tipping events and feedbacks in the Earth system mainly by the use of complex dynamical systems and network science approaches, but partially also by more detailed process-based models of the Earth system.
In the first part of this thesis, the theoretical foundations are laid by the investigation of networks of interacting tipping elements. For this purpose, the conditions for the emergence of global cascades are analysed against the structure of paradigmatic network types such as Erdös-Rényi, Barabási-Albert, Watts-Strogatz and explicitly spatially embedded networks. Furthermore, micro-scale structures are detected that are decisive for the transition of local to global cascades. These so-called motifs link the micro- to the macro-scale in the network of tipping elements. Alongside a model description paper, all these results are entered into the Python software package PyCascades, which is publicly available on github.
In the second part of this dissertation, the tipping element framework is first applied to components of the Earth system such as the cryosphere and to parts of the biosphere. Afterwards it is applied to a set of interacting climate tipping elements on a global scale. Using the Earth system Model of Intermediate Complexity (EMIC) CLIMBER-2, the temperature feedbacks are quantified, which would arise if some of the large cryosphere elements disintegrate over a long span of time. The cryosphere components that are investigated are the Arctic summer sea ice, the mountain glaciers, the Greenland and the West Antarctic Ice Sheets. The committed temperature increase, in case the ice masses disintegrate, is on the order of an additional half a degree on a global average (0.39-0.46 °C), while local to regional additional temperature increases can exceed 5 °C. This means that, once tipping has begun, additional reinforcing feedbacks are able to increase global warming and with that the risk of further tipping events.
This is also the case in the Amazon rainforest, whose parts are dependent on each other via the so-called moisture-recycling feedback. In this thesis, the importance of drought-induced tipping events in the Amazon rainforest is investigated in detail. Despite the Amazon rainforest is assumed to be adapted to past environmental conditions, it is found that tipping events sharply increase if the drought conditions become too intense in a too short amount of time, outpacing the adaptive capacity of the Amazon rainforest. In these cases, the frequency of tipping cascades also increases to 50% (or above) of all tipping events. In the model that was developed in this study, the southeastern region of the Amazon basin is hit hardest by the simulated drought patterns. This is also the region that already nowadays suffers a lot from extensive human-induced changes due to large-scale deforestation, cattle ranching or infrastructure projects.
Moreover, on the larger Earth system wide scale, a network of conceptualised climate tipping elements is constructed in this dissertation making use of a large literature review, expert knowledge and topological properties of the tipping elements. In global warming scenarios, tipping cascades are detected even under modest scenarios of climate change, limiting global warming to 2 °C above pre-industrial levels. In addition, the structural roles of the climate tipping elements in the network are revealed. While the large ice sheets on Greenland and Antarctica are the initiators of tipping cascades, the Atlantic Meridional Overturning Circulation (AMOC) acts as the transmitter of cascades. Furthermore, in our conceptual climate tipping element model, it is found that the ice sheets are of particular importance for the stability of the entire system of investigated climate tipping elements.
In the last part of this thesis, the results from the temperature feedback study with the EMIC CLIMBER-2 are combined with the conceptual model of climate tipping elements. There, it is observed that the likelihood of further tipping events slightly increases due to the temperature feedbacks even if no further CO$_2$ would be added to the atmosphere.
Although the developed network model is of conceptual nature, it is possible with this work for the first time to quantify the risk of tipping events between interacting components of the Earth system under global warming scenarios, by allowing for dynamic temperature feedbacks at the same time.
The self-assembly of amphiphilic polymers in aqueous systems is important for a plethora of applications, in particular in the field of cosmetics and detergents. When introducing thermoresponsive blocks, the aggregation behavior of these polymers can be controlled by changing the temperature. While confined to simple diblock copolymer systems for long, the complexity - and thus the versatility - of such smart systems can be strongly enlarged, once designed monomers, specific block sizes, different architectures, or additional functional groups such as hydrophobic stickers are implemented. In this work, the structure-property relationship of such thermoresponsive amphiphilic block copolymers was investigated by varying their structure systematically. The block copolymers were generally composed of a permanently hydrophobic sticker group, a permanently hydrophilic block, and a thermoresponsive block exhibiting a Lower Critical Solution Temperature (LCST) behavior. While the hydrophilic block consisted of N,N dimethylacrylamide (DMAm), different monomers were used for the thermoresponsive block, such as N n propylacrylamide (NPAm), N iso propylacrylamide (NiPAm), N,N diethylacrylamide (DEAm), N,N bis(2 methoxyethyl)acrylamide (bMOEAm), or N acryloylpyrrolidine (NAP) with different reported LCSTs of 25, 32, 33, 42 and 56 °C, respectively. The block copolymers were synthesized by successive reversible addition fragmentation chain transfer (RAFT) polymerization. For the polymers with the basic linear, the twinned hydrophobic and the symmetrical quasi miktoarm architectures, the results were well defined block sizes and end groups as well as narrow molar mass distributions (Ɖ ≤ 1.3). More complex architectures, such as the twinned thermoresponsive and the non-symmetrical quasi miktoarm one, were achieved by combining RAFT polymerization with a second technique, namely atom transfer radical polymerization (ATRP) or single unit monomer insertion (SUMI), respectively. The obtained block copolymers showed well defined block sizes, but due to the complexity of these reaction paths, the dispersities were generally higher (Ɖ ≤ 1.8) and some end groups were lost.
The thermoresponsive behavior of the block copolymers was investigated by turbidimetry and dynamic light scattering (DLS). Below the phase transition temperature, the polymers were soluble in water and small micellar structures were visible. However, above the phase transition temperature, the aggregation behavior was strongly dependent on the architecture and the chemical structure of the thermoresponsive block. Thermoresponsive blocks comprising PNAP and PbMOEAm with DPn = 40 showed no cloud point (CP), since their already high LCSTs were further increased by the attached hydrophilic block. Depending on the architecture as well as on the block size, block copolymers with PNiPAm, PDEAm and PNPAm showed different CP’s. Large aggregates were visible for block copolymers with PNiPAm and PDEAm above their CP. For PNPAm containing block copolymers, the phase transition was very sensitive towards the architecture resulting in either small or large aggregates.
In addition, fluorescence studies were performed using PDMAm and PNiPAm homo and block copolymers with linear architecture, functionalized with complementary fluorescence dyes introduced at the opposite chain ends. The thermoresponsive behavior was studied in pure aqueous solution as well as in an oil in water (o/w) microemulsion. The findings indicate that the block copolymer behaves as polymeric surfactant at low temperatures, with one relatively small hydrophobic end group and an extended hydrophilic chain forming ‘hairy micelles’ similar as the other synthesized architectures. Above the phase transition temperature of the PNiPAm block, however, the copolymer behaves as associative telechelic polymer with two non-symmetrical hydrophobic end groups, which do not mix. Thus, instead of a network of bridged ‘flower micelles’, large dynamic aggregates are formed. These are connected alternatingly by the original micellar cores as well as by clusters of the collapsed PNiPAm blocks. This type of bridged micelles is even more favored in the o/w microemulsion than in pure aqueous solution.
The Internet of Things (IoT) is a system of physical objects that can be discovered, monitored, controlled, or interacted with by electronic devices that communicate over various networking interfaces and eventually can be connected to the wider Internet. [Guinard and Trifa, 2016]. IoT devices are equipped with sensors and/or actuators and may be constrained in terms of memory, computational power, network bandwidth, and energy. Interoperability can help to manage such heterogeneous devices. Interoperability is the ability of different types of systems to work together smoothly. There are four levels of interoperability: physical, network and transport, integration, and data. The data interoperability is subdivided into syntactic and semantic data. Semantic data describes the meaning of data and the common understanding of vocabulary e.g. with the help of dictionaries, taxonomies, ontologies. To achieve interoperability, semantic interoperability is necessary.
Many organizations and companies are working on standards and solutions for interoperability in the IoT. However, the commercial solutions produce a vendor lock-in. They focus on centralized approaches such as cloud-based solutions. This thesis proposes a decentralized approach namely Edge Computing. Edge Computing is based on the concepts of mesh networking and distributed processing. This approach has an advantage that information collection and processing are placed closer to the sources of this information. The goals are to reduce traffic, latency, and to be robust against a lossy or failed Internet connection.
We see management of IoT devices from the network configuration management perspective. This thesis proposes a framework for network configuration management of heterogeneous, constrained IoT devices by using semantic descriptions for interoperability. The MYNO framework is an acronym for MQTT, YANG, NETCONF and Ontology. The NETCONF protocol is the IETF standard for network configuration management. The MQTT protocol is the de-facto standard in the IoT. We picked up the idea of the NETCONF-MQTT bridge, originally proposed by Scheffler and Bonneß[2017], and extended it with semantic device descriptions. These device descriptions provide a description of the device capabilities. They are based on the oneM2M Base ontology and formalized by the Semantic Web Standards.
The novel approach is using a ontology-based device description directly on a constrained device in combination with the MQTT protocol. The bridge was extended in order to query such descriptions. Using a semantic annotation, we achieved that the device capabilities are self-descriptive, machine readable and re-usable.
The concept of a Virtual Device was introduced and implemented, based on semantic device descriptions. A Virtual Device aggregates the capabilities of all devices at the edge network and contributes therefore to the scalability. Thus, it is possible to control all devices via a single RPC call.
The model-driven NETCONF Web-Client is generated automatically from this YANG model which is generated by the bridge based on the semantic device description. The Web-Client provides a user-friendly interface, offers RPC calls and displays sensor values. We demonstrate the feasibility of this approach in different use cases: sensor and actuator scenarios, as well as event configuration and triggering.
The semantic approach results in increased memory overhead. Therefore, we evaluated CBOR and RDF HDT for optimization of ontology-based device descriptions for use on constrained devices. The evaluation shows that CBOR is not suitable for long strings and RDF HDT is a promising candidate but is still a W3C Member Submission. Finally, we used an optimized JSON-LD format for the syntax of the device descriptions.
One of the security tasks of network management is the distribution of firmware updates. The MYNO Update Protocol (MUP) was developed and evaluated on constrained devices CC2538dk and 6LoWPAN. The MYNO update process is focused on freshness and authenticity of the firmware. The evaluation shows that it is challenging but feasible to bring the firmware updates to constrained devices using MQTT. As a new requirement for the next MQTT version, we propose to add a slicing feature for the better support of constrained devices. The MQTT broker should slice data to the maximum packet size specified by the device and transfer it slice-by-slice.
For the performance and scalability evaluation of MYNO framework, we setup the High Precision Agriculture demonstrator with 10 ESP-32 NodeMCU boards at the edge of the network. The ESP-32 NodeMCU boards, connected by WLAN, were equipped with six sensors and two actuators. The performance evaluation shows that the processing of ontology-based descriptions on a Raspberry Pi 3B with the RDFLib is a challenging task regarding computational power. Nevertheless, it is feasible because it must be done only once per device during the discovery process.
The MYNO framework was tested with heterogeneous devices such as CC2538dk from Texas Instruments, Arduino Yún Rev 3, and ESP-32 NodeMCU, and IP-based networks such as 6LoWPAN and WLAN.
Summarizing, with the MYNO framework we could show that the semantic approach on constrained devices is feasible in the IoT.
Permafrost is warming globally, which leads to widespread permafrost thaw and impacts the surrounding landscapes, ecosystems and infrastructure. Especially ice-rich permafrost is vulnerable to rapid and abrupt thaw, resulting from the melting of excess ground ice. Local remote sensing studies have detected increasing rates of abrupt permafrost disturbances, such as thermokarst lake change and drainage, coastal erosion and RTS in the last two decades. All of which indicate an acceleration of permafrost degradation.
In particular retrogressive thaw slumps (RTS) are abrupt disturbances that expand by up to several meters each year and impact local and regional topographic gradients, hydrological pathways, sediment and nutrient mobilisation into aquatic systems, and increased permafrost carbon mobilisation. The feedback between abrupt permafrost thaw and the carbon cycle is a crucial component of the Earth system and a relevant driver in global climate models. However, an assessment of RTS at high temporal resolution to determine the dynamic thaw processes and identify the main thaw drivers as well as a continental-scale assessment across diverse permafrost regions are still lacking.
In northern high latitudes optical remote sensing is restricted by environmental factors and frequent cloud coverage. This decreases image availability and thus constrains the application of automated algorithms for time series disturbance detection for large-scale abrupt permafrost disturbances at high temporal resolution. Since models and observations suggest that abrupt permafrost disturbances will intensify, we require disturbance products at continental-scale, which allow for meaningful integration into Earth system models.
The main aim of this dissertation therefore, is to enhance our knowledge on the spatial extent and temporal dynamics of abrupt permafrost disturbances in a large-scale assessment. To address this, three research objectives were posed:
1. Assess the comparability and compatibility of Landsat-8 and Sentinel-2 data for a combined use in multi-spectral analysis in northern high latitudes.
2. Adapt an image mosaicking method for Landsat and Sentinel-2 data to create combined mosaics of high quality as input for high temporal disturbance assessments in northern high latitudes.
3. Automatically map retrogressive thaw slumps on the landscape-scale and assess their high temporal thaw dynamics.
We assessed the comparability of Landsat-8 and Sentinel-2 imagery by spectral comparison of corresponding bands. Based on overlapping same-day acquisitions of Landsat-8 and Sentinel-2 we derived spectral bandpass adjustment coefficients for North Siberia to adjust Sentinel-2 reflectance values to resemble Landsat-8 and harmonise the two data sets. Furthermore, we adapted a workflow to combine Landsat and Sentinel-2 images to create homogeneous and gap-free annual mosaics. We determined the number of images and cloud-free pixels, the spatial coverage and the quality of the mosaic with spectral comparisons to demonstrate the relevance of the Landsat+Sentinel-2 mosaics. Lastly, we adapted the automatic disturbance detection algorithm LandTrendr for large-scale RTS identification and mapping at high temporal resolution. For this, we modified the temporal segmentation algorithm for annual gradual and abrupt disturbance detection to incorporate the annual Landsat+Sentinel-2 mosaics. We further parametrised the temporal segmentation and spectral filtering for optimised RTS detection, conducted further spatial masking and filtering, and implemented a binary object classification algorithm with machine-learning to derive RTS from the LandTrendr disturbance output. We applied the algorithm to North Siberia, covering an area of 8.1 x 106 km2.
The spectral band comparison between same-day Landsat-8 and Sentinel-2 acquisitions already showed an overall good fit between both satellite products. However, applying the acquired spectral bandpass coefficients for adjustment of Sentinel-2 reflectance values, resulted in a near-perfect alignment between the same-day images. It can therefore be concluded that the spectral band adjustment succeeds in adjusting Sentinel-2 spectral values to those of Landsat-8 in North Siberia.
The number of available cloud-free images increased steadily between 1999 and 2019, especially intensified after 2016 with the addition of Sentinel-2 images. This signifies a highly improved input database for the mosaicking workflow. In a comparison of annual mosaics, the Landsat+Sentinel-2 mosaics always fully covered the study areas, while Landsat-only mosaics contained data-gaps for the same years. The spectral comparison of input images and Landsat+Sentinel-2 mosaic showed a high correlation between the input images and the mosaic bands, testifying mosaicking results of high quality. Our results show that especially the mosaic coverage for northern, coastal areas was substantially improved with the Landsat+Sentinel-2 mosaics. By combining data from both Landsat and Sentinel-2 sensors we reliably created input mosaics at high spatial resolution for comprehensive time series analyses.
This research presents the first automatically derived assessment of RTS distribution and temporal dynamics at continental-scale. In total, we identified 50,895 RTS, primarily located in ice-rich permafrost regions, as well as a steady increase in RTS-affected areas between 2001 and 2019 across North Siberia. From 2016 onward the RTS area increased more abruptly, indicating heightened thaw slump dynamics in this period. Overall, the RTS-affected area increased by 331 % within the observation period. Contrary to this, five focus sites show spatiotemporal variability in their annual RTS dynamics, alternating between periods of increased and decreased RTS development. This suggests a close relationship to varying thaw drivers. The majority of identified RTS was active from 2000 onward and only a small proportion initiated during the assessment period. This highlights that the increase in RTS-affected area was mainly caused by enlarging existing RTS and not by newly initiated RTS.
Overall, this research showed the advantages of combining Landsat and Sentinel-2 data in northern high latitudes and the improvements in spatial and temporal coverage of combined annual mosaics. The mosaics build the database for automated disturbance detection to reliably map RTS and other abrupt permafrost disturbances at continental-scale. The assessment at high temporal resolution further testifies the increasing impact of abrupt permafrost disturbances and likewise emphasises the spatio-temporal variability of thaw dynamics across landscapes. Obtaining such consistent disturbance products is necessary to parametrise regional and global climate change models, for enabling an improved representation of the permafrost thaw feedback.
In the last five years, gravitational-wave astronomy has gone from a purerly theoretical field into a thriving experimental science. Several gravitational- wave signals, emitted by stellar-mass binary black holes and binary neutron stars, have been detected, and many more are expected in the future as consequence of the planned upgrades in the gravitational-wave detectors. The observation of the gravitational-wave signals from these systems, and the characterization of their sources, heavily relies on the precise models for the emitted gravitational waveforms. To take full advantage of the increased detector sensitivity, it is then necessary to also improve the accuracy of the gravitational-waveform models.
In this work, I present an updated version of the waveform models for spinning binary black holes within the effective-one-body formalism. This formalism is based on the notion that the solution to the relativistic two- body problem varies smoothly with the mass ratio of the binary system, from the equal-mass regime to the test-particle limit. For this reason, it provides an elegant method to combine, under a unique framework, the solution to the relativistic two-body problem in different regimes. The main two regimes that are combined under the effective-one-body formalism are the slow-motion, weak field limit (accessible through the post-Newtonian theory), and the extreme mass-ratio regime (described using the black-hole- perturbation theory). This formalism is nevertheless flexible enough to integrate information about the solution to the relativistic two-body problem obtained using other techniques, such as numerical relativity.
The novelty of the waveform models presented in this work is the inclusion of beyond-quadupolar terms in the waveforms emitted by spinning binary black holes. In fact, while the time variation of the source quadupole moment is the leading contribution to the waveforms emitted by binary black holes observable by LIGO and Virgo detectors, beyond-quadupolar terms can be important for binary systems with asymmetric masses, large total mass, or observed with large inclination angle with respect to the orbital angular momentum of the binary. For this purpose, I combine the approximate analytic expressions of these beyond-quadupolar terms, with their calculations from numerical relativity, to develop an accurate waveform model including inspiral, merger and ringdown for spinning binary black holes. I first construct this model in the simplified case of black holes with spins aligned with the orbital angular momentum of the binary, then I extend it to the case of generic spin orientations. Finally, I test the accuracy of both these models against a large number of waveforms obtained from numerical relativity. The waveform models I present in this work are the state of the art for spinning binary black holes, without restrictions in the allowed values for the masses and the spins of the system.
The measurement of the source properties of a binary system emitting gravitational waves requires to compute O(107 − 109) different waveforms. Since the waveform models mentioned before can require O(1 − 10)s to generate a single waveform, they can be difficult to use in data-analysis studies given the increasing number of sources observed by the LIGO and Virgo detectors. To overcome this obstacle, I use the reduced-order-modeling technique to develop a faster version of the waveform model for black holes with spins aligned to the orbital angular momentum of the binary. This version of the model is as accurate as the original and reduces the time for evaluating a waveform by two orders of magnitude.
The waveform models developed in this thesis have been used by the LIGO and Virgo collaborations in the inference of the source parameters of the gravitational-wave signals detected during the second observing run (O2), and first half of the third observing run (O3a) of LIGO and Virgo detectors. Here, I present a study on the source properties of the signals GW170729 and GW190412, for which I have been directly involved in the analysis. In addition, these models have been used by the LIGO and Virgo collaborations to perform tests on General Relativity employing the gravitational-wave signals detected during O3a, and to analyze the population of the observed binary black holes.
Breslau has been almost entirely forgotten in the Anglophone sphere as a place of Enlightenment. Moreover, in the context of the Jewish Enlightenment, Breslau has never been discussed as a place of intercultural exchange between German-speaking Jewish, Protestant and Catholic intellectuals. The story of Moses Hirschel offers us an excellent case-study to investigate the complex reciprocal relationship between Jewish and non-Jewish enlighteners in a prosperous and influential Central European city on the cusp of the 18th century.
The present work focuses on minimising the usage of toxic chemicals by integration of the biobased monomers, derived from fatty acid esters, to photopolymerization processes, which are known to be nature friendly. Internal double bond present in the oleic acid was converted to more reactive (meth)acrylate or epoxy group. Biobased starting materials, functionalized by different pendant groups, were used for photopolymerizing formulations to design of new polymeric structures by using ultraviolet light emitting diode (UV-LED) (395 nm) via free radical polymerization or cationic polymerization.
New (meth)acrylates (2,3 and 4) consisting of two isomers, methyl 9-((meth)acryloyloxy)-10-hydroxyoctadecanoate / methyl 9-hydroxy-10-((meth)acryloyloxy)octadecanoate (2 and 3) and methyl 9-(1H-imidazol-1-yl)-10-(methacryloyloxy)octadecanoate / methyl 9-(methacryloyloxy)-10-(1H-imidazol-1-yl)octadecanoate (4), modified from oleic acid mix, and ionic liquid monomers (1a and 1b) bearing long alkyl chain were polymerized photochemically. New (meth)acrylates are based on vegetable oil, and ionic liquids (ILs) have nonvolatile behaviour. Therefore, both monomer types have green approach. Photoinitiated polymerization of new (meth)acrylates and ionic liquids was investigated in the presence of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate (Irgacure® TPO−L) or di(4-methoxybenzoyl)diethylgermane (Ivocerin®) as photoinitiator (PI). Additionally, the results were discussed in comparison with those obtained from commercial 1,6-hexanediol di(meth)acrylate (5 and 6) for deeper investigation of biobased monomer’s potential to substitute petroleum derived materials with renewable resources for possible coating applications. Kinetic study shows that methyl 9-(1H-imidazol-1-yl)-10-(methacryloyloxy)octadecanoate / methyl 9-(methacryloyloxy)-10-(1H-imidazol-1-yl)octadecanoate (4) and ionic liquids (1a and 1b) have quantitative conversion after irradiation process which is important for practical applications. On the other hand, heat generation occurs in a longer time during the polymerization of biobased systems or ILs.
The poly(meth)acrylates modified from (meth)acrylated fatty acid methyl ester monomers generally show a low glass transition temperature because of the presence of long aliphatic chain in the polymer structure. However, poly(meth)acrylates containing aromatic group have higher glass transition temperature. Therefore, new 4-(4-methacryloyloxyphenyl)-butan-2-one (7) was synthesized which can be a promising candidate for the green techniques, such as light induced polymerization. Photokinetic investigation of the new monomer, 4-(4-methacryloyloxyphenyl)-butan-2-one (7), was discussed using Irgacure® TPO−L or Ivocerin® as photoinitiator. The reactivity of that monomer was compared to commercial 2-phenoxyethyl methacrylate (8) and phenyl methacrylate (9) basis of the differences on monomer structures. The photopolymer of 4-(4-methacryloyloxyphenyl)-butan-2-one (7) might be an interesting candidate for the coating application with the properties of quantitative conversion and high molecular weight. It also shows higher glass transition temperature.
In addition to the linear systems based on renewable materials, new crosslinked polymers were also designed in this thesis. Therefore, isomer mixture consisting of ethane-1,2-diyl bis(9-methacryloyloxy-10-hydroxy octadecanoate), ethane-1,2-diyl 9-hydroxy-10-methacryloyloxy-9’-methacryloyloxy10’-hydroxy octadecanoate and ethane-1,2-diyl bis(9-hydroxy-10-methacryloyloxy octadecanoate) (10) was synthesized by derivation of the oleic acid which has not been previously described in the literature. Crosslinked material based on this biobased monomer was produced by photoinitiated free radical polymerization using Irgacure® TPO−L or Ivocerin® as photoinitiator. Furthermore, material properties were diversified by copolymerization of 10 with 4-(4-methacryloyloxyphenyl)-butan-2-one (7) or methyl 9-(1H-imidazol-1-yl)-10-(methacryloyloxy)octadecanoate / methyl 9-(methacryloyloxy)-10-(1H-imidazol-1-yl)octadecanoate (4). In addition to this, influence of comonomer with different chemical structure on the network system was investigated by analysis of thermo-mechanical properties, crosslink density and molecular weight between two crosslink junctions. An increase in the glass transition temperature caused by copolymerization of biobased monomer 10 with the excess amount of 4-(4-methacryloyloxyphenyl)-butan-2-one (7) was confirmed by both techniques, differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). On the other hand, crosslink density decreased as a result of copolymerization reactions due to the reduction in the mean functionality of the system. Furthermore, surface characterization has been tested by contact angle measurements using solvents with different polarity.
This work also contributes to the limited data reported about cationic photopolymerization of the epoxidized vegetable oils in the literature in contrast to the widely investigation of thermal curing of the biorenewable epoxy monomers. In addition to the 9,10-epoxystearic acid methyl ester (11), a new monomer of bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) has been synthesized from oleic acid. These two biobased epoxies have been polymerized via cationic photoinitiated polymerization in the presence of bis(t-butyl)-iodonium-tetrakis(perfluoro-t-butoxy)aluminate ([Al(O-t-C4F9)4]-) and isopropylthioxanthone (ITX) as photinitiating system. Polymerization kinetic of 9,10-epoxystearic acid methyl ester (11) and bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) was investigated and compared with the kinetic of commercial monomers being 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexane carboxylate (13), 1,4-butanediol diglycidyl ether (14), and diglycidylether of bisphenol-A (15). Both biobased epoxies (11 and 12) showed higher conversion than cycloaliphatic epoxy (13), and lower reactivity than 1,4-butanediol diglycidyl ether (14). Additional network systems were designed by copolymerization of bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) and diglycidylether of bisphenol-A (15) in different molar ratios (1:1; 1:5; 1:9). It addresses that, final conversion is dependent on polymerization rate as well as physical processes such as vitrification during polymerization. Moreover, low glass transition temperature of homopolymer derived from bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) was successfully increased by copolymerization with diglycidylether bisphenol-A (15). On the other hand, the surface produced from bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) shows hydrophobic character. Higher concentration of biobased diepoxy (12) in the copolymerizing mixture decreases surface free energy. Network systems were also investigated according to the rubber elasticity theory. Crosslinked polymer derived from the mixture of bis-(9,10-epoxystearic acid) 1,2-ethanediyl ester (12) and diglycidylether of bisphenol-A (15) (molar ratio=1:5) exhibits almost ideal polymer network.
Polymeric films and coatings derived from semi-crystalline oligomers are of relevance for medical and pharmaceutical applications. In this context, the material surface is of particular importance, as it mediates the interaction with the biological system. Two dimensional (2D) systems and ultrathin films are used to model this interface. However, conventional techniques for their preparation, such as spin coating or dip coating, have disadvantages, since the morphology and chain packing of the generated films can only be controlled to a limited extent and adsorption on the substrate used affects the behavior of the films. Detaching and transferring the films prepared by such techniques requires additional sacrificial or supporting layers, and free-standing or self supporting domains are usually of very limited lateral extension. The aim of this thesis is to study and modulate crystallization, melting, degradation and chemical reactions in ultrathin films of oligo(ε-caprolactone)s (OCL)s with different end-groups under ambient conditions. Here, oligomeric ultrathin films are assembled at the air-water interface using the Langmuir technique. The water surface allows lateral movement and aggregation of the oligomers, which, unlike solid substrates, enables dynamic physical and chemical interaction of the molecules. Parameters like surface pressure (π), temperature and mean molecular area (MMA) allow controlled assembly and manipulation of oligomer molecules when using the Langmuir technique. The π-MMA isotherms, Brewster angle microscopy (BAM), and interfacial infrared spectroscopy assist in detecting morphological and physicochemical changes in the film. Ultrathin films can be easily transferred to the solid silicon surface via Langmuir Schaefer (LS) method (horizontal substrate dipping). Here, the films transferred on silicon are investigated using atomic force microscopy (AFM) and optical microscopy and are compared to the films on the water surface.
The semi-crystalline morphology (lamellar thicknesses, crystal number densities, and lateral crystal dimensions) is tuned by the chemical structure of the OCL end-groups (hydroxy or methacrylate) and by the crystallization temperature (Tc; 12 or 21 °C) or MMAs. Compression to lower MMA of ~2 Å2, results in the formation of a highly crystalline film, which consists of tightly packed single crystals. Preparation of tightly packed single crystals on a cm2 scale is not possible by conventional techniques. Upon transfer to a solid surface, these films retain their crystalline morphology whereas amorphous films undergo dewetting.
The melting temperature (Tm) of OCL single crystals at the water and the solid surface is found proportional to the inverse crystal thickness and is generally lower than the Tm of bulk PCL. The impact of OCL end-groups on melting behavior is most noticeable at the air-solid interface, where the methacrylate end-capped OCL (OCDME) melted at lower temperatures than the hydroxy end-capped OCL (OCDOL). When comparing the underlying substrate, melting/recrystallization of OCL ultrathin films is possible at lower temperatures at the air water interface than at the air-solid interface, where recrystallization is not visible. Recrystallization at the air-water interface usually occurs at a higher temperature than the initial Tc.
Controlled degradation is crucial for the predictable performance of degradable polymeric biomaterials. Degradation of ultrathin films is carried out under acidic (pH ~ 1) or enzymatic catalysis (lipase from Pseudomonas cepcia) on the water surface or on a silicon surface as transferred films. A high crystallinity strongly reduces the hydrolytic but not the enzymatic degradation rate. As an influence of end-groups, the methacrylate end-capped linear oligomer, OCDME (~85 ± 2 % end-group functionalization) hydrolytically degrades faster than the hydroxy end capped linear oligomer, OCDOL (~95 ± 3 % end-group functionalization) at different temperatures. Differences in the acceleration of hydrolytic degradation of semi-crystalline films were observed upon complete melting, partial melting of the crystals, or by heating to temperatures close to Tm. Therefore, films of densely packed single crystals are suitable as barrier layers with thermally switchable degradation rates.
Chemical modification in ultrathin films is an intricate process applicable to connect functionalized molecules, impart stability or create stimuli-sensitive cross-links. The reaction of end-groups is explored for transferred single crystals on a solid surface or amorphous monolayer at the air-water interface. Bulky methacrylate end-groups are expelled to the crystal surface during chain-folded crystallization. The density of end-groups is inversely proportional to molecular weight and hence very pronounced for oligomers. The methacrylate end-groups at the crystal surface, which are present at high concentration, can be used for further chemical functionalization. This is demonstrated by fluorescence microscopy after reaction with fluorescein dimethacrylate. The thermoswitching behavior (melting and recrystallization) of fluorescein functionalized single crystals shows the temperature-dependent distribution of the chemically linked fluorescein moieties, which are accumulated on the surfaces of crystals, and homogeneously dispersed when the crystals are molten. In amorphous monolayers at the air-water interface, reversible cross-linking of hydroxy-terminated oligo(ε-caprolactone) monolayers using dialdehyde (glyoxal) lead to the formation of 2D networks. Pronounced contraction in the area occurred for 2D OCL films in dependence of surface pressure and time indicating the reaction progress. Cross linking inhibited crystallization and retarded enzymatic degradation of the OCL film. Altering the subphase pH to ~2 led to cleavage of the covalent acetal cross-links. Besides as model systems, these reversibly cross-linked films are applicable for drug delivery systems or cell substrates modulating adhesion at biointerfaces.
Deoxyribonucleic acid (DNA) nanostructures enable the attachment of functional molecules to nearly any unique location on their underlying structure. Due to their single-base-pair structural resolution, several ligands can be spatially arranged and closely controlled according to the geometry of their desired target, resulting in optimized binding and/or signaling interactions.
This dissertation covers three main projects. All of them use variations of functionalized DNA nanostructures that act as platform for oligovalent presentation of ligands. The purpose of this work was to evaluate the ability of DNA nanostructures to precisely display different types of functional molecules and to consequently enhance their efficacy according to the concept of multivalency. Moreover, functionalized DNA structures were examined for their suitability in functional screening assays. The developed DNA-based compound ligands were used to target structures in different biological systems.
One part of this dissertation attempted to bind pathogens with small modified DNA nanostructures. Pathogens like viruses and bacteria are known for their multivalent attachment to host cells membranes. By blocking their receptors for recognition and/or fusion with their targeted host in an oligovalent manner, the objective was to impede their ability to adhere to and invade cells. For influenza A, only enhanced binding of oligovalent peptide-DNA constructs compared to the monovalent peptide could be observed, whereas in the case of respiratory syncytial virus (RSV), binding as well as blocking of the target receptors led to an increased inhibition of infection in vitro.
In the final part, the ability of chimeric DNA-peptide constructs to bind to and activate signaling receptors on the surface of cells was investigated. Specific binding of DNA trimers, conjugated with up to three peptides, to EphA2 receptor expressing cells was evaluated in flow cytometry experiments. Subsequently, their ability to activate these receptors via phosphorylation was assessed. EphA2 phosphorylation was significantly increased by DNA trimers carrying three peptides compared to monovalent peptide. As a result of activation, cells underwent characteristic morphological changes, where they "round up" and retract their periphery.
The results obtained in this work comprehensively prove the capability of DNA nanostructures to serve as stable, biocompatible, controllable platforms for the oligovalent presentation of functional ligands. Functionalized DNA nanostructures were used to enhance biological effects and as tool for functional screening of bio-activity. This work demonstrates that modified DNA structures have the potential to improve drug development and to unravel the activation of signaling pathways.
We investigate models for incremental binary classification, an example for supervised online learning. Our starting point is a model for human and machine learning suggested by E.M.Gold.
In the first part, we consider incremental learning algorithms that use all of the available binary labeled training data in order to compute the current hypothesis. For this model, we observe that the algorithm can be assumed to always terminate and that the distribution of the training data does not influence learnability. This is still true if we pose additional delayable requirements that remain valid despite a hypothesis output delayed in time. Additionally, we consider the non-delayable requirement of consistent learning. Our corresponding results underpin the claim for delayability being a suitable structural property to describe and collectively investigate a major part of learning success criteria. Our first theorem states the pairwise implications or incomparabilities between an established collection of delayable learning success criteria, the so-called complete map. Especially, the learning algorithm can be assumed to only change its last hypothesis in case it is inconsistent with the current training data. Such a learning behaviour is called conservative.
By referring to learning functions, we obtain a hierarchy of approximative learning success criteria. Hereby we allow an increasing finite number of errors of the hypothesized concept by the learning algorithm compared with the concept to be learned. Moreover, we observe a duality depending on whether vacillations between infinitely many different correct hypotheses are still considered a successful learning behaviour. This contrasts the vacillatory hierarchy for learning from solely positive information.
We also consider a hypothesis space located between the two most common hypothesis space types in the nearby relevant literature and provide the complete map.
In the second part, we model more efficient learning algorithms. These update their hypothesis referring to the current datum and without direct regress to past training data. We focus on iterative (hypothesis based) and BMS (state based) learning algorithms. Iterative learning algorithms use the last hypothesis and the current datum in order to infer the new hypothesis.
Past research analyzed, for example, the above mentioned pairwise relations between delayable learning success criteria when learning from purely positive training data. We compare delayable learning success criteria with respect to iterative learning algorithms, as well as learning from either exclusively positive or binary labeled data. The existence of concept classes that can be learned by an iterative learning algorithm but not in a conservative way had already been observed, showing that conservativeness is restrictive. An additional requirement arising from cognitive science research %and also observed when training neural networks is U-shapedness, stating that the learning algorithm does diverge from a correct hypothesis. We show that forbidding U-shapes also restricts iterative learners from binary labeled data.
In order to compute the next hypothesis, BMS learning algorithms refer to the currently observed datum and the actual state of the learning algorithm. For learning algorithms equipped with an infinite amount of states, we provide the complete map. A learning success criterion is semantic if it still holds, when the learning algorithm outputs other parameters standing for the same classifier. Syntactic (non-semantic) learning success criteria, for example conservativeness and syntactic non-U-shapedness, restrict BMS learning algorithms. For proving the equivalence of the syntactic requirements, we refer to witness-based learning processes. In these, every change of the hypothesis is justified by a later on correctly classified witness from the training data. Moreover, for every semantic delayable learning requirement, iterative and BMS learning algorithms are equivalent. In case the considered learning success criterion incorporates syntactic non-U-shapedness, BMS learning algorithms can learn more concept classes than iterative learning algorithms.
The proofs are combinatorial, inspired by investigating formal languages or employ results from computability theory, such as infinite recursion theorems (fixed point theorems).
The evolution of life on Earth has been driven by disturbances of different types and magnitudes over the 4.6 million years of Earth’s history (Raup, 1994, Alroy, 2008). One example for such disturbances are mass extinctions which are characterized by an exceptional increase in the extinction rate affecting a great number of taxa in a short interval of geologic time (Sepkoski, 1986). During the 541 million years of the Phanerozoic, life on Earth suffered five exceptionally severe mass extinctions named the “Big Five Extinctions”. Many mass extinctions are linked to changes in climate
(Feulner, 2009). Hence, the study of past mass extinctions is not only intriguing, but can also provide insights into the complex nature of the Earth system. This thesis aims at deepening our understanding of the triggers of mass extinctions and how they affected life. To accomplish this, I investigate changes in climate during two of the Big Five extinctions using a coupled climate model.
During the Devonian (419.2–358.9 million years ago) the first vascular plants and vertebrates evolved on land while extinction events occurred in the ocean (Algeo et al., 1995). The causes of these formative changes, their interactions and their links to changes in climate are still poorly understood. Therefore, we explore the sensitivity of the Devonian climate to various boundary conditions using an intermediate-complexity climate model (Brugger et al., 2019). In contrast to Le Hir et al. (2011), we find only a minor biogeophysical effect of changes in vegetation cover due to unrealistically high soil albedo values used in the earlier study. In addition, our results cannot support the strong influence of orbital parameters on the Devonian climate, as simulated with a climate model with a strongly simplified ocean model (De Vleeschouwer et al., 2013, 2014, 2017). We can only reproduce the changes in Devonian climate suggested by proxy data by decreasing atmospheric CO2. Still, finding agreement between the evolution of sea surface temperatures reconstructed from proxy data (Joachimski et al., 2009) and our simulations remains challenging and suggests a lower δ18O ratio of Devonian seawater. Furthermore, our study of the sensitivity of the Devonian climate reveals a prevailing mode of climate variability on a timescale of decades to centuries. The quasi-periodic ocean temperature fluctuations are linked to a physical mechanism of changing sea-ice cover, ocean convection and overturning in high northern latitudes.
In the second study of this thesis (Dahl et al., under review) a new reconstruction of atmospheric CO2 for the Devonian, which is based on CO2-sensitive carbon isotope fractionation in the earliest vascular plant fossils, suggests a much earlier drop of atmo- spheric CO2 concentration than previously reconstructed, followed by nearly constant CO2 concentrations during the Middle and Late Devonian. Our simulations for the Early Devonian with identical boundary conditions as in our Devonian sensitivity study (Brugger et al., 2019), but with a low atmospheric CO2 concentration of 500 ppm, show no direct conflict with available proxy and paleobotanical data and confirm that under the simulated climatic conditions carbon isotope fractionation represents a robust proxy for atmospheric CO2. To explain the earlier CO2 drop we suggest that early forms of vascular land plants have already strongly influenced weathering. This new perspective on the Devonian questions previous ideas about the climatic conditions and earlier explanations for the Devonian mass extinctions.
The second mass extinction investigated in this thesis is the end-Cretaceous mass extinction (66 million years ago) which differs from the Devonian mass extinctions in terms of the processes involved and the timescale on which the extinctions occurred. In the two studies presented here (Brugger et al., 2017, 2021), we model the climatic effects of the Chicxulub impact, one of the proposed causes of the end-Cretaceous extinction, for the first millennium after the impact. The light-dimming effect of stratospheric sulfate aerosols causes severe cooling, with a decrease of global annual mean surface air temperature of at least 26◦C and a recovery to pre-impact temperatures after more than 30 years. The sudden surface cooling of the ocean induces deep convection which brings nutrients from the deep ocean via upwelling to the surface ocean. Using an ocean biogeochemistry model we explore the combined effect of ocean mixing and iron-rich dust originating from the impactor on the marine biosphere. As soon as light levels have recovered, we find a short, but prominent peak in marine net primary productivity. This newly discovered mechanism could result in toxic effects for marine near-surface ecosystems. Comparison of our model results to proxy data (Vellekoop et al., 2014, 2016, Hull et al., 2020) suggests that carbon release from the terrestrial biosphere is required in addition to the carbon dioxide which can be attributed to the target material. Surface ocean acidification caused by the addition of carbon dioxide and sulfur is only moderate. Taken together, the results indicate a significant contribution of the Chicxulub impact to the end-Cretaceous mass extinction by triggering multiple stressors for the Earth system.
Although the sixth extinction we face today is characterized by human intervention in nature, this thesis shows that we can gain many insights into future extinctions from studying past mass extinctions, such as the importance of the rate of change (Rothman, 2017), the interplay of multiple stressors (Gunderson et al., 2016), and changes in the carbon cycle (Rothman, 2017, Tierney et al., 2020).
Magnetic strain contributions in laser-excited metals studied by time-resolved X-ray diffraction
(2021)
In this work I explore the impact of magnetic order on the laser-induced ultrafast strain response of metals. Few experiments with femto- or picosecond time-resolution have so far investigated magnetic stresses. This is contrasted by the industrial usage of magnetic invar materials or magnetostrictive transducers for ultrasound generation, which already utilize magnetostrictive stresses in the low frequency regime.
In the reported experiments I investigate how the energy deposition by the absorption of femtosecond laser pulses in thin metal films leads to an ultrafast stress generation. I utilize that this stress drives an expansion that emits nanoscopic strain pulses, so called hypersound, into adjacent layers. Both the expansion and the strain pulses change the average inter-atomic distance in the sample, which can be tracked with sub-picosecond time resolution using an X-ray diffraction setup at a laser-driven Plasma X-ray source. Ultrafast X-ray diffraction can also be applied to buried layers within heterostructures that cannot be accessed by optical methods, which exhibit a limited penetration into metals. The reconstruction of the initial energy transfer processes from the shape of the strain pulse in buried detection layers represents a contribution of this work to the field of picosecond ultrasonics.
A central point for the analysis of the experiments is the direct link between the deposited energy density in the nano-structures and the resulting stress on the crystal lattice. The underlying thermodynamical concept of a Grüneisen parameter provides the theoretical framework for my work. I demonstrate how the Grüneisen principle can be used for the interpretation of the strain response on ultrafast timescales in various materials and that it can be extended to describe magnetic stresses. The class of heavy rare-earth elements exhibits especially large magnetostriction effects, which can even lead to an unconventional contraction of the laser-excited transducer material. Such a dominant contribution of the magnetic stress to the motion of atoms has not been demonstrated previously. The observed rise time of the magnetic stress contribution in Dysprosium is identical to the decrease in the helical spin-order, that has been found previously using time-resolved resonant X-ray diffraction. This indicates that the strength of the magnetic stress can be used as a proxy of the underlying magnetic order. Such magnetostriction measurements are applicable even in case of antiparallel or non-collinear alignment of the magnetic moments and a vanishing magnetization.
The strain response of metal films is usually determined by the pressure of electrons and lattice vibrations. I have developed a versatile two-pulse excitation routine that can be used to extract the magnetic contribution to the strain response even if systematic measurements above and below the magnetic ordering temperature are not feasible. A first laser pulse leads to a partial ultrafast demagnetization so that the amplitude and shape of the strain response triggered by the second pulse depends on the remaining magnetic order. With this method I could identify a strongly anisotropic magnetic stress contribution in the magnetic data storage material iron-platinum and identify the recovery of the magnetic order by the variation of the pulse-to-pulse delay. The stark contrast of the expansion of iron-platinum nanograins and thin films shows that the different constraints for the in-plane expansion have a strong influence on the out-of-plane expansion, due to the Poisson effect. I show how such transverse strain contributions need to be accounted for when interpreting the ultrafast out-of-plane strain response using thermal expansion coefficients obtained in near equilibrium conditions.
This work contributes an investigation of magnetostriction on ultrafast timescales to the literature of magnetic effects in materials. It develops a method to extract spatial and temporal varying stress contributions based on a model for the amplitude and shape of the emitted strain pulses. Energy transfer processes result in a change of the stress profile with respect to the initial absorption of the laser pulses. One interesting example occurs in nanoscopic gold-nickel heterostructures, where excited electrons rapidly transport energy into a distant nickel layer, that takes up much more energy and expands faster and stronger than the laser-excited gold capping layer. Magnetic excitations in rare earth materials represent a large energy reservoir that delays the energy transfer into adjacent layers. Such magneto-caloric effects are known in thermodynamics but not extensively covered on ultrafast timescales. The combination of ultrafast X-ray diffraction and time-resolved techniques with direct access to the magnetization has a large potential to uncover and quantify such energy transfer processes.
The galactic interstellar medium is magnetized and turbulent. The magnetic field and turbulence play important roles in many astrophysical mechanisms, including cosmic ray transport, star formation, etc. Therefore, measurements of magnetic field and turbulence information are crucial for the proper interpretation of astronomical observations. Nonetheless, the magnetic field observation is quite challenging, especially, there is not universal magnetic tracer for diffuse medium. Moreover, the modelling of turbulence can be oversimplified due to the lack of observational tools to diagnose the plasma properties of the turbulence in the galactic interstellar medium. The studies presented in this thesis have addressed these challenges by bridging the theoretical studies of magnetic field and turbulence with numerical simulations and observations.
The following research are presented in this thesis. The first observational evidence of the novel magnetic tracer, ground state alignment (GSA), is discovered, revealing the three-dimensional magnetic field as well as 2 orders of magnitude higher precision comparing to previous observational study in the stellar atmosphere of the post-AGB 89 Herculis. Moreover, the application of GSA in the sub-millimeter fine-structure lines is comprehensively studied for different elements and with magnetohydrodynamic simulations. Furthermore, the influence of GSA effect on the spectroscopy is analyzed and it is found that measurable variation will be produced on the spectral line intensity and the line ratio without accounting for the optical pumping process or magnetic field.
Additionally, a novel method to measure plasma modes in the interstellar medium, Signatures from Polarization Analysis (SPA), is proposed and applied to real observations. Magneto-sonic modes are discovered in different types of interstellar medium. An explanation is provided for the long-standing mystery, the origin of γ-ray enhanced emission “Cygnus Cocoon”, based on the comparison between the outcome of SPA and multi-waveband observational data. These novel methods have strong potentials for broader observational applications and will play crucial roles in future multi-wavelength astronomy.
Silicate melts are major components of the Earth’s interior and as such they make an essential contribution in igneous processes, in the dynamics of the solid Earth and the chemical development of the entire Earth. Macroscopic physical and chemical properties such as density, compressibility, viscosity, degree of polymerization etc. are determined by the atomic structure of the melt. Depending on the pressure, but also on the temperature and the chemical composition, silicate melts show different structural properties. These properties are best described by the local coordination environment, i.e. symmetry and number of neighbors (coordination number) of an atom, as well as the distance between the central atom and its neighbors (inter-atomic distance). With increasing pressure and temperature, i.e. with increasing depth in the Earth, the density of the melt increases, which can lead to changes in coordination number and distances. If the coordination number remains the same, the distance usually decreases. If the coordination number increases, the distance can increase. These general trends can, however, vary greatly, which can be attributed in particular to the chemical composition.
Due to the fact that natural melts of the deep earth are not accessible to direct investigations, in order to understand their properties under the relevant conditions, extensive experimental and theoretical investigations have been carried out so far. This has often been studied using the example of amorphous samples of the end-members SiO2 and GeO2 , with the latter serving as a structural and chemical analog model to SiO2. Commonly, the experiments were carried out at high pressure and at room temperature. Natural melts are chemically much more complex than the simple end-member SiO2 and GeO2, so that observations made on them may lead to incorrect compression models. Furthermore, the investigations on glasses at room temperature can show potentially strong deviations from the properties of melts under natural thermodynamic conditions.
The aim of this thesis was to explain the influence of the composition and the temperature on the structural properties of the melts at high pressures. To understand this, we studied complex alumino-germanate and alumino-silicate glasses. More precisely, we studied synthetic glasses that have a composition like the mineral albite and like a mixture of albite-diopside at the eutectic point. The albite glass is structurally similar to a simplified granitic melt, while the albite-diopside glass simulates a simplified basaltic melt. To study the local coordination environment of the elements, we used X-ray absorption spectroscopy in combination with a diamond anvil cell. Because the diamonds have a high absorbance for X-rays with energies below 10 keV, the direct investigation of the geologically relevant elements such as Si, Al, Ca, Mg etc. with this spectroscopic probe technique in combination with a diamond anvil cell is not possible. Therefore the glasses were doped with Ge and Sr. These elements serve partially or fully as substitutes for important major elements. In this sense, Ge serves as an a substitute for Si and other network formers, while Sr replaces network modifiers such as Ca, Na, Mg etc.,
as well as other cations with a large ionic radius.
In the first step we studied the Ge K-edge in Ge-Albit-glass, NaAlGe3O8, at room temperature up to 131 GPa. This glass has a higher chemical complexity than SiO2 and GeO2, but it is still fully polymerized. The differences in the compression mechanism between this glass and the simple oxides can clearly be attributed to higher chemical complexity. The albite and albite-diopside compositions partially doped with Ge and Sr were probed at room temperature for Ge up to 164 GPa and for Sr up to 42 GPa. While the albite glass is nominally fully polymerized like NaAlGe3O8, the albite-diopside glass is partially depolymerized. The results show that structural changes take place in all three glasses in the first 25 to a maximum of 30 GPa, with both Ge and Sr reaching the maximum coordination number 6 and ∼9, respectively. At higher pressures, only isostructural shrinkage of the coordination polyhedra takes place in the glasses. The most important finding of the high pressure studies on the alumino-silicate and alumino-germanate glasses is that in these complex glasses the polyhedra show a much higher compressibility than what can be observed in the end-members. This is shown in particular by the strong shortening of the Ge-O distances in the amorphous NaAlGe3O8 and albite-diopside glass at pressures above 30 GPa.
In addition to the effects of the composition on the compaction process, we investigated the influence of temperature on the structural changes. To do this, we probed the albite-diopside glass, as it is chemically most similar to the melts in the lower mantle. We studied the Ge K edge of the sample with a resistively heated and a laser-heated diamond anvil cell, for a pressure range of up to 48 GPa and a temperature range of up to 5000 K. High temperatures at which the sample is liquid and that are relevant for the Earth mantle, have a significant impact on the structural transformation, with a shift of approx. 30% to significantly lower pressures, compared to the glasses at room temperature and below 1000 K.
The results of this thesis represent an important contribution to the understanding of the properties of melts at conditions of the lower mantle. In the context of the discussion about the existence and origin of ultra-dense silicate melts at the core-mantle boundary, these investigations show that the higher density compared to the surrounding material cannot be explained by only structural features, but by a distinct chemical composition. The results also suggest that only very low solubilities of noble gases are to be expected for melts in the lower mantle, so that the structural properties clearly influence the overall budget and transport of noble gases in the Earth’s mantle.
Learning to read in German
(2021)
In the present dissertation, the development of eye movement behavior and the perceptual span of German beginning readers was investigated in Grades 1 to 3 (Study 1) and longitudinally within a one-year time interval (Study 2), as well as in relation to intrinsic and extrinsic reading motivation (Study 3). The presented results are intended to fill the gap of only sparse information on young readers’ eye movements and completely missing information on German young readers’ perceptual span and its development. On the other hand, reading motivation data have been scrutinized with respect to reciprocal effects on reading comprehension but not with respect to more immediate, basic cognitive processing (e.g., word decoding) that is indicated by different eye movement measures. Based on a longitudinal study design, children in Grades 1–3 participated in a moving window reading experiment with eye movement recordings in two successive years. All children were participants of a larger longitudinal study on intrapersonal developmental risk factors in childhood and adolescence (PIER study). Motivation data and other psychometric reading data were collected during individual inquiries and tests at school. Data analyses were realized in three separate studies that focused on different but related aspects of reading and perceptual span development. Study 1 presents the first cross-sectional report on the perceptual span of beginning German readers. The focus was on reading rate changes in Grades 1 to 3 and on the issue of the onset of the perceptual span development and its dependence on basic foveal reading processes. Study 2 presents a successor of Study 1 providing first longitudinal data of the perceptual span in elementary school children. It also includes information on the stability of observed and predicted reading rates and perceptual span sizes and introduces a new measure of the perceptual span based on nonlinear mixed-effects models. Another issue addressed in this study is the longitudinal between-group comparison of slower and faster readers which refers to the detection of developmental patterns. Study 3 includes longitudinal reading motivation data and investigates the relation between different eye movement measures including perceptual span and intrinsic as well as extrinsic reading motivation. In Study 1, a decelerated increase in reading rate was observed between Grades 1 to 3. Grade effects were also reported for saccade length, refixation probability, and different fixation duration measures. With higher grade, mean saccade length increased, whereas refixation probability, first-fixation duration, gaze duration, and total reading time decreased. Perceptual span development was indicated by an increase in window size effects with grade level. Grade level differences with respect to window size effects were stronger between Grades 2 and 3 than between Grades 1 and 2. These results were replicated longitudinally in Study 2. Again, perceptual span size significantly changed between Grades 2 and 3, but not between Grades 1 and 2 or Grades 3 and 4. Observed and predicted reading rates were found to be highly stable after first grade, whereas stability of perceptual span was only moderate for all grade levels. Group differences between slower and faster readers in Year 1 remained observable in Year 2 showing a pattern of stable achievement differences rather than a compensatory pattern. Between Grades 2 and 3, between-group differences in reading rate even increased resulting in a Matthew effect. A similar effect was observed for perceptual span development between Grades 3 and 4. Finally, in Study 3, significant relations between beginning readers’ eye movements and their reading motivation were observed. In both years of measurement, higher intrinsic reading motivation was related to more skilled eye movement patterns as indicated by short fixations, longer saccades, and higher reading rates. In Year 2, intrinsic reading motivation was also significantly and negatively correlated with refixation probability. These correlational patterns were confirmed in cross-sectional linear models controlling for grade level and reading amount and including both reading motivation measures, extrinsic and intrinsic motivation. While there were significant positive relations between intrinsic reading motivation and word decoding as indicated by the above stated eye movement measures, extrinsic reading motivation only predicted variance in eye movements in Year 2 (significant for fixation durations and reading rate), with a consistently opposite pattern of effects as compared to intrinsic reading motivation. Finally, longitudinal effects of Year 1 intrinsic reading motivation on Year 2 word decoding were observed for gaze duration, total reading time, refixation probability, and perceptual span within cross-lagged panel models. These effects were reciprocal because all eye movement measures significantly predicted variance in intrinsic reading motivation. Extrinsic reading motivation in Year 1 did not affect any eye movement measure in Year 2, and vice versa, except for a significant, negative relation with perceptual span. Concluding, the present dissertation demonstrates that largest gains in reading development in terms of eye movement changes are observable between Grades 1 and 2. Together with the observed pattern of stable differences between slower and faster readers and a widening achievement gap between Grades 2 and 3 for reading rate, these results underline the importance of the first year(s) of formal reading instruction. The development of the perceptual span lags behind as it is most apparent between Grades 2 and 3. This suggests that efficient parafoveal processing presupposes a certain degree of foveal reading proficiency (e.g., word decoding). Finally, this dissertation demonstrates that intrinsic reading motivation—but not extrinsic motivation—effectively supports the development of skilled reading.
Learning analytics at scale
(2021)
Digital technologies are paving the way for innovative educational approaches. The learning format of Massive Open Online Courses (MOOCs) provides a highly accessible path to lifelong learning while being more affordable and flexible than face-to-face courses. Thereby, thousands of learners can enroll in courses mostly without admission restrictions, but this also raises challenges. Individual supervision by teachers is barely feasible, and learning persistence and success depend on students' self-regulatory skills. Here, technology provides the means for support. The use of data for decision-making is already transforming many fields, whereas in education, it is still a young research discipline. Learning Analytics (LA) is defined as the measurement, collection, analysis, and reporting of data about learners and their learning contexts with the purpose of understanding and improving learning and learning environments. The vast amount of data that MOOCs produce on the learning behavior and success of thousands of students provides the opportunity to study human learning and develop approaches addressing the demands of learners and teachers.
The overall purpose of this dissertation is to investigate the implementation of LA at the scale of MOOCs and to explore how data-driven technology can support learning and teaching in this context. To this end, several research prototypes have been iteratively developed for the HPI MOOC Platform. Hence, they were tested and evaluated in an authentic real-world learning environment. Most of the results can be applied on a conceptual level to other MOOC platforms as well. The research contribution of this thesis thus provides practical insights beyond what is theoretically possible. In total, four system components were developed and extended:
(1) The Learning Analytics Architecture: A technical infrastructure to collect, process, and analyze event-driven learning data based on schema-agnostic pipelining in a service-oriented MOOC platform. (2) The Learning Analytics Dashboard for Learners: A tool for data-driven support of self-regulated learning, in particular to enable learners to evaluate and plan their learning activities, progress, and success by themselves. (3) Personalized Learning Objectives: A set of features to better connect learners' success to their personal intentions based on selected learning objectives to offer guidance and align the provided data-driven insights about their learning progress. (4) The Learning Analytics Dashboard for Teachers: A tool supporting teachers with data-driven insights to enable the monitoring of their courses with thousands of learners, identify potential issues, and take informed action.
For all aspects examined in this dissertation, related research is presented, development processes and implementation concepts are explained, and evaluations are conducted in case studies. Among other findings, the usage of the learner dashboard in combination with personalized learning objectives demonstrated improved certification rates of 11.62% to 12.63%. Furthermore, it was observed that the teacher dashboard is a key tool and an integral part for teaching in MOOCs. In addition to the results and contributions, general limitations of the work are discussed—which altogether provide a solid foundation for practical implications and future research.
Modern knowledge bases contain and organize knowledge from many different topic areas. Apart from specific entity information, they also store information about their relationships amongst each other. Combining this information results in a knowledge graph that can be particularly helpful in cases where relationships are of central importance. Among other applications, modern risk assessment in the financial sector can benefit from the inherent network structure of such knowledge graphs by assessing the consequences and risks of certain events, such as corporate insolvencies or fraudulent behavior, based on the underlying network structure. As public knowledge bases often do not contain the necessary information for the analysis of such scenarios, the need arises to create and maintain dedicated domain-specific knowledge bases.
This thesis investigates the process of creating domain-specific knowledge bases from structured and unstructured data sources. In particular, it addresses the topics of named entity recognition (NER), duplicate detection, and knowledge validation, which represent essential steps in the construction of knowledge bases.
As such, we present a novel method for duplicate detection based on a Siamese neural network that is able to learn a dataset-specific similarity measure which is used to identify duplicates. Using the specialized network architecture, we design and implement a knowledge transfer between two deduplication networks, which leads to significant performance improvements and a reduction of required training data.
Furthermore, we propose a named entity recognition approach that is able to identify company names by integrating external knowledge in the form of dictionaries into the training process of a conditional random field classifier. In this context, we study the effects of different dictionaries on the performance of the NER classifier. We show that both the inclusion of domain knowledge as well as the generation and use of alias names results in significant performance improvements.
For the validation of knowledge represented in a knowledge base, we introduce Colt, a framework for knowledge validation based on the interactive quality assessment of logical rules. In its most expressive implementation, we combine Gaussian processes with neural networks to create Colt-GP, an interactive algorithm for learning rule models. Unlike other approaches, Colt-GP uses knowledge graph embeddings and user feedback to cope with data quality issues of knowledge bases. The learned rule model can be used to conditionally apply a rule and assess its quality.
Finally, we present CurEx, a prototypical system for building domain-specific knowledge bases from structured and unstructured data sources. Its modular design is based on scalable technologies, which, in addition to processing large datasets, ensures that the modules can be easily exchanged or extended. CurEx offers multiple user interfaces, each tailored to the individual needs of a specific user group and is fully compatible with the Colt framework, which can be used as part of the system.
We conduct a wide range of experiments with different datasets to determine the strengths and weaknesses of the proposed methods. To ensure the validity of our results, we compare the proposed methods with competing approaches.
Carbonatite magmatism is a highly efficient transport mechanism from Earth’s mantle to the crust, thus providing insights into the chemistry and dynamics of the Earth’s mantle. One evolving and promising tool for tracing magma interaction are stable iron isotopes, particularly because iron isotope fractionation is controlled by oxidation state and bonding environment. Meanwhile, a large data set on iron isotope fractionation in igneous rocks exists comprising bulk rock compositions and fractionation between mineral groups. Iron isotope data from natural carbonatite rocks are extremely light and of remarkably high variability. This resembles iron isotope data from mantle xenoliths, which are characterized by a variability in δ56Fe spanning three times the range found in basalts, and by the extremely light values of some whole rock samples, reaching δ56Fe as low as -0.69 ‰ in a spinel lherzolite. Cause to this large range of variations may be metasomatic processes, involving metasomatic agents like volatile bearing high-alkaline silicate melts or carbonate melts. The expected effects of metasomatism on iron isotope fractionation vary with parameters like melt/rock-ratio, reaction time, and the nature of metasomatic agents and mineral reactions involved. An alternative or additional way to enrich light isotopes in the mantle could be multiple phases of melt extraction. To interpret the existing data sets more knowledge on iron isotope fractionation factors is needed.
To investigate the behavior of iron isotopes in the carbonatite systems, kinetic and equilibration experiments in natro-carbonatite systems between immiscible silicate and carbonate melts were performed in an internally heated gas pressure vessel at intrinsic redox conditions at temperatures between 900 and 1200 °C and pressures of 0.5 and 0.7 GPa. The iron isotope compositions of coexisting silicate melt and carbonate melt were analyzed by solution MC-ICP-MS. The kinetic experiments employing a Fe-58 spiked starting material show that isotopic equilibrium is obtained after 48 hours. The experimental studies of equilibrium iron isotope fractionation between immiscible silicate and carbonate melts have shown that light isotopes are enriched in the carbonatite melt. The highest Δ56Fesil.m.-carb.melt (mean) of 0.13 ‰ was determined in a system with a strongly peralkaline silicate melt composition (ASI ≥ 0.21, Na/Al ≤ 2.7). In three systems with extremely peralkaline silicate melt compositions (ASI between 0.11 and 0.14) iron isotope fractionation could analytically not be resolved. The lowest Δ56Fesil.m.-carb.melt (mean) of 0.02 ‰ was determined in a system with an extremely peralkaline silicate melt composition (ASI ≤ 0.11 , Na/Al ≥ 6.1). The observed iron isotope fractionation is most likely governed by the redox conditions of the system. Yet, in the systems, where no fractionation occurred, structural changes induced by compositional changes possibly overrule the influence of redox conditions. This interpretation implicates, that the iron isotope system holds the potential to be useful not only for exploring redox conditions in magmatic systems, but also for discovering structural changes in a melt.
In situ iron isotope analyses by femtosecond laser ablation coupled to MC-ICP-MS on magnetite and olivine grains were performed to reveal variations in iron isotope composition on the micro scale. The investigated sample is a melilitite bomb from the Salt Lake Crater group at Honolulu (Oahu, Hawaii), showing strong evidence for interaction with a carbonatite melt. While magnetite grains are rather homogeneous in their iron isotope compositions, olivine grains span a far larger range in iron isotope ratios. The variability of δ56Fe in magnetite is limited from - 0.17 ‰ (± 0.11 ‰, 2SE) to +0.08 ‰ (± 0.09 ‰, 2SE). δ56Fe in olivine range from -0.66‰ (± 0.11 ‰, 2SE) to +0.10 ‰ (± 0.13 ‰, 2SE). Olivine and magnetite grains hold different informations regarding kinetic and equilibrium fractionation due to their different Fe diffusion coefficients. The observations made in the experiments and in the in situ iron isotope analyses suggest that the extremely light iron isotope signatures found in carbonatites are generated by several steps of isotope fractionation during carbonatite genesis. These may involve equilibrium and kinetic fractionation. Since iron isotopic signatures in natural systems are generated by a combination of multiple factors (pressure, temperature, redox conditions, phase composition and structure, time scale), multi tracer approaches are needed to explain signatures found in natural rocks.
Diabetes is a major public health problem with increasing global prevalence. Type 2 diabetes (T2D), which accounts for 90% of all diagnosed cases, is a complex polygenic disease also modulated by epigenetics and lifestyle factors. For the identification of T2D-associated genes, linkage analyses combined with mouse breeding strategies and bioinformatic tools were useful in the past. In a previous study in which a backcross population of the lean and diabetes-prone dilute brown non-agouti (DBA) mouse and the obese and diabetes-susceptible New Zealand obese (NZO) mouse was characterized, a major diabetes quantitative trait locus (QTL) was identified on chromosome 4. The locus was designated non-insulin dependent diabetes from DBA (Nidd/DBA). The aim of this thesis was (i) to perform a detailed phenotypic characterization of the Nidd/DBA mice, (ii) to further narrow the critical region and (iii) to identify the responsible genetic variant(s) of the Nidd/DBA locus. The phenotypic characterization of recombinant congenic mice carrying a 13.6 Mbp Nidd/DBA fragment with 284 genes presented a gradually worsening metabolic phenotype. Nidd/DBA allele carriers exhibited severe hyperglycemia (~19.9 mM) and impaired glucose clearance at 12 weeks of age. Ex vivo perifusion experiments with islets of 13-week-old congenic mice revealed a tendency towards reduced insulin secretion in homozygous DBA mice. In addition, 16-week-old mice showed a severe loss of β-cells and reduced pancreatic insulin content. Pathway analysis of transcriptome data from islets of congenic mice pointed towards a downregulation of cell survival genes. Morphological analysis of pancreatic sections displayed a reduced number of bi-hormonal cells co-expressing glucagon and insulin in homozygous DBA mice, which could indicate a reduced plasticity of endocrine cells in response to hyperglycemic stress. Further generation and phenotyping of recombinant congenic mice enabled the isolation of a 3.3 Mbp fragment that was still able to induce hyperglycemia and contained 61 genes. Bioinformatic analyses including haplotype mapping, sequence and transcriptome analysis were integrated in order to further reduce the number of candidate genes and to identify the presumable causative gene variant. Four putative candidate genes (Ttc39a, Kti12, Osbpl9, Calr4) were defined, which were either differentially expressed or carried a sequence variant. In addition, in silico ChIP-Seq analyses of the 3.3 Mbp region indicated a high number of SNPs located in active regions of binding sites of β-cell transcription factors. This points towards potentially altered cis-regulatory elements that could be responsible for the phenotype conferred by the Nidd/DBA locus. In summary, the Nidd/DBA locus mediates impaired glucose homeostasis and reduced insulin secretion capacity which finally leads to β-cell death. The downregulation of cell survival genes and reduced plasticity of endocrine cells could further contribute to the β-cell loss. The critical region was narrowed down to a 3.3 Mbp fragment containing 61 genes, of which four might be involved in the development of the diabetogenic Nidd/DBA phenotype.
Investigation of Sirtuin 3 overexpression as a genetic model of fasting in hypothalamic neurons
(2021)
Halide perovskites are a class of novel photovoltaic materials that have recently attracted much attention in the photovoltaics research community due to their highly promising optoelectronic properties, including large absorption coefficients and long carrier lifetimes. The charge carrier mobility of halide perovskites is investigated in this thesis by THz spectroscopy, which is a contact-free technique that yields the intra-grain sum mobility of electrons and holes
in a thin film.
The polycrystalline halide perovskite thin films, provided from Potsdam University, show moderate mobilities in the range from 21.5 to 33.5 cm2V-1s-1. It is shown in this work that the room temperature mobility is limited by charge carrier scattering at polar optical phonons. The mobility at low temperature is likely to be limited by scattering at charged and neutral impurities at impurity concentration N=1017-1018 cm-3. Furthermore, it is shown that exciton formation
may decrease the mobility at low temperatures. Scattering at acoustic phonons can be neglected at both low and room temperatures. The analysis of mobility spectra over a broad range of temperatures for perovskites with various cation compounds shows that cations have a minor impact on charge carrier mobility.
The low-dimensional thin films of quasi-2D perovskite with different numbers of [PbI6]4−sheets (n=2-4) alternating with long organic spacer molecules were provided by S. Zhang from Potsdam University. They exhibit mobilities in the range from 3.7 to 8 cm2V-1s-1. A clear
decrease of mobility is observed with decrease in number of metal-halide sheets n, which likely arises from charge carrier confinement within metal-halide layers. Modelling the measured THz mobility with the modified Drude-Smith model yields localization length from 0.9 to 3.7 nm, which agrees well on the thicknesses of the metal-halide layers. Additionally, the mobilities are found to be dependent on the orientation of the layers. The charge carrier dynamics is also
dependent on the number of metal-halide sheets n. For the thin films with n =3-4 the dynamics is similar to the 3D MHPs. However, the thin film with n = 2 shows clearly different dynamics, where the signs of exciton formation are observed within 390 fs timeframe after
photoexcitation.
Also, the charge carrier dynamics of CsPbI3 perovskite nanocrystals was investigated, in particular the effect of post treatments on the charge carrier transport.
The mitochondrial chaperone complex HSP60/HSP10 facilitates mitochondrial protein homeostasis by folding more than 300 mitochondrial matrix proteins. It has been shown previously that HSP60 is downregulated in brains of type 2 diabetic (T2D) mice and patients,
causing mitochondrial dysfunction and insulin resistance. As HSP60 is also decreased in peripheral tissues in T2D animals, this thesis investigated the effect of overall reduced HSP60 in the development of obesity and associated co-morbidities.
To this end, both female and male C57Bl/6N control (i.e. without further alterations in their genome, Ctrl) and heterozygous whole-body Hsp60 knock-out (Hsp60+/-) mice, which exhibit a 50 % reduction of HSP60 in all tissues, were fed a normal chow diet (NCD) or a highfat diet (HFD, 60 % calories from fat) for 16 weeks and were subjected to extensive metabolic phenotyping including indirect calorimetry, NMR spectroscopy, insulin, glucose and pyruvate tolerance tests, vena cava insulin injections, as well as histological and molecular analysis.
Interestingly, NCD feeding did not result in any striking phenotype, only a mild increase in energy expenditure in Hsp60+/- mice. Exposing mice to a HFD however revealed an increased body weight due to higher muscle mass in female Hsp60+/- mice, with a simultaneous decrease in energy expenditure. Additionally, these mice displayed decreased fasting glycemia. Opposingly, male Hsp60+/- compared to control mice showed lower body weight gain due to decreased fat mass and an increased energy expenditure, strikingly independent of lean mass. Further, only male Hsp60+/- mice display improved HOMA-IR and Matsuda
insulin sensitivity indices.
Despite the opposite phenotype in regards to body weight development, Hsp60+/- mice of both sexes show a significantly higher cell number, as well as a reduction in adipocyte size in the subcutaneous and gonadal white adipose tissue (sc/gWAT). Curiously, this adipocyte hyperplasia – usually associated with positive aspects of WAT function – is disconnected from metabolic improvements, as the gWAT of male Hsp60+/- mice shows mitochondrial dysfunction, oxidative stress, and insulin resistance. Transcriptomic analysis of gWAT shows an up
regulation of genes involved in macroautophagy. Confirmatory, expression of microtubuleassociated protein 1A/1B light chain 3B (LC3), as a protein marker of autophagy, and direct measurement of lysosomal activity is increased in the gWAT of male Hsp60+/- mice.
In summary, this thesis revealed a novel gene-nutrient interaction. The reduction of the crucial chaperone HSP60 did not have large effects in mice fed a NCD, but impacted metabolism during DIO in a sex-specific manner, where, despite opposing body weight and
body composition phenotypes, both female and male Hsp60+/- mice show signs of protection from high fat diet-induced systemic insulin resistance.
Plants possess cell wall, a polysaccharide exoskeleton which encompasses all plant cells. Cell wall gives plant cells mechanical support, defines their shape, enables growth and water transport through a plant. It also has important role in communication with the external environment. Regulation of plant cell wall biosynthesis and cell and organ morphogenesis depends on cell’s ability to detect mechanical signals originating both from the external environment and from internal plant tissues. Thanks to the presence of the cell wall, all living plant cells develop constant internal pressure generated by the active water uptake, known as turgor pressure, which enables them to grow. Thus, actively growing cells in the tissue are exerting mechanical stress to each other. In order to properly coordinate cell growth, tissue morphogenesis and maintain cell-to-cell adhesion, plant cell have to detect these mechanical signals. That is performed by a group of still not well enough characterized plant mechanosensitive proteins. Mechanosensors are proteins capable of detecting changes in mechanical stress patterns and translating them into physiological and developmental outputs. One of plant mechanosensitive proteins, DEFECTIVE KERNEL1 (DEK1) has shown to be a very important in proper plant development. DEK1 bears similarity with animal cysteine proteases of Calpain superfamily. DEK1 is very important for plant development since all null alleles are embryo lethal. During the last 20 years of DEK1 studies, this protein has proven to be a very difficult for different molecular and biochemical manipulations. As a consequence, very little is known about its direct target proteins. Wang and co-workers (2003) and Johnson and co-workers (2008) have given a valuable contribution to biochemical understanding of DEK1 by determining that it functions as Cys-protease in similar way as animal calpains. However, a lot of indirect knowledge was gathered about the effects of disruption and modulation of DEK1 activity. DEK1 is important for proper organ development, epidermal specification, and maintenance. However, some studies have inferred that DEK1 affects expression of different cell wall related genes, and it regulates cell-to-cell adhesion in epidermal cells. This led to two extensive studies (Amanda et al., 2016, 2017) which demonstrated importance of DEK1 in regulation leaf epidermal cell walls in A. thaliana mature leaves and inflorescence stems. These studies demonstrated that DEK1 also influences cell wall thickness and cell-to-cell adhesion and that it could potentially regulate cell growth and expansion. Building up on this research, we decided to try to further characterize molecular and biomechanical aspects of DEK1 mediated cell wall regulation, with special emphasis on regulation of cellulose synthesis. We used two mutant lines, with modulated DEK1 activity, a constitutive overexpressor for DEK1 CALPAIN domain and a point mutant in CALPAIN domain, dek1-4. In Chapter 3 we demonstrated that DEK1 regulates dynamics of Cellulose Synthase Complexes (CSCs). Both lines showed decreased crystalline cellulose contents. This led us to investigate if velocity of CSCs in cotyledons, was affected, since it is known that changes in cellulose contents are often caused by defects in CSC. We found that bothDEK1 modulated lines we used have significantly decreased velocity of CSCs. We have also examined plasma membrane turnover rates of CSCs and found out that after photo-bleaching OE CALPAIN has much faster recovery rates compared to Col-0 wild type, while dek1-4 has lower exocytotic rates of CSCs, and much longer life-time of CSCs inserted into the plasma membrane. These results suggested that DEK1 regulates different aspects of CSC dynamics, possibly through interaction with different regulatory proteins. Decrease in cellulose contents we observed in DEK1 modulated lines, prompted us to investigate how this reflects biomechanics and structural properties of epidermal cotyledon cell walls of DEK1 modulated lines, which is described in Chapter 4. To achieve this, we developed a novel microdissection method for isolation and mechanical and structural characterization of native epidermal cell wall monolayers using atomic force microscopy (AFM). AFM force spectroscopy assays showed that both DEK1 modulated lines had stiffer cell walls compared to Col-0. This was awkward since we initially detected decrease in crystalline cellulose which implied decrease in cell wall stiffness. However, subsequent high-resolution AFM imaging has revealed that DEK1 modulate lines cells walls have their cellulose microfibrils organized in thicker bundles than Col-0. Also, polysaccharide composition analysis has revealed that DEK1 modulated lines have increased abundance of pectins, which could also be responsible for the observed increase in cell wall stiffness. Previous work has shown that different dek1 mutants and modulated lines have defects in cell-to-cell adhesion. This implied that DEK1 may be involved in sensing and/or maintaining cell wall integrity (CWI). We performed several growth assays to determine role of DEK1 in CWI, which is described in Chapter 5. We performed cellulose synthesis perturbation assays with cellulose synthesis inhibitor Isoxaben and obtained very interesting results. While OE CALPAIN plants were hypersensitive to Isoxaben, dek1-4 has shown complete insensitivity. Furthermore, a regular CWI maintenance response, reported in A. thaliana as result of compromised CWI, ectopic lignification in seedlings’ roots was absent in both DEK1 modulated lines we examined. We detected interesting growth response of DEK1 lines to NaCl and mannitol treatments as well. Although these findings are pointing out that DEK1 could be part of CWI signalling pathways, more experiments are necessary to fully elucidate possible role of DEK1 in CWI sensing and/or maintenance pathways, especially to check if DEK1 is interacting with Catharanthus roseus Receptor Like Kinase group of CWI sensors. Studies on 4-month old short day grown DEK1 modulated lines, have shown defects in branching, with development of fasciated stem branches in a DEK1 modulated line overexpressing CALPAIN domain (Amanda et al., 2017). This result pointed out to a possibility that DEK1 may regulate organ morphogenesis and patterning at the level of shoot apical meristem (SAM). Work towards elucidating role of DEK1 in SAM maintenance and organ patterning is detailed in Chapter 6. We determined that OE CALPAIN had significantly larger central zone of SAM as well as larger individual SAM cells in central zone, as well as higher distribution of cell sizes, implying possible cell expansion defects. dek1-4 did not exhibited changes in SAM central zone size or individual stem cell size, but it seemed that it had increased number of stem cells in SAM central zone. Both DEK1 lines had perturbation of phyllotaxis on SAM level, with disturbed divergence angles between floral primordia. Disturbed phyllotaxis was also observed between siliques, in mature plants. In addition to this, OE CALPAIN has exhibited occurrence of multiple (up to four) siliques growing from a single stem node. All this is pointing out that DEK1 might participate in hormone-signalling in the SAM.. DEK1 is a highly intriguing protein. However, since it is a unigene, and in addition to that, a regulatory protease, it probably participates in multiple signalling pathways, which makes understanding its function much more complicated.
The objective of this book is to provide ICAO, States, competent authorities and aerodrome operators with a comprehensive overview of legal challenges related to international aerodrome planning. Answers to derived legal questions as well as recommendations thereafter shall help to enhance regulatory systems and to establish a safer aerodrome environment worldwide. Compliant aerodrome planning has an immense impact on the safety of passengers, personnel, aircraft – and of course the airport. Achieving a high safety standard is crucial, as many incidents and accidents in aviation happen at or in the vicinity of airports. Currently, more than 40% of the ICAO Member States do not fully comply with international legal requirements for aerodrome planning. Representatives of ICAO and States, as well as aerodrome and authority personnel, will understand why compliance with the different legal facets of aerodrome planning is challenging and learn how shortcomings can be solved.
Intentionality in Sellars
(2021)
This book argues that Sellars’ theory of intentionality can be understood as an advancement of a transcendental philosophical approach. It shows how Sellars develops his theory of intentionality through his engagement with the theoretical philosophy of Immanuel Kant.
The book delivers a provocative reinterpretation of one of the most problematic and controversial concepts of Sellars' philosophy: the picturing-relation. Sellars' theory of intentionality addresses the question of how to reconcile two aspects that seem opposed: the non-relational theory of intellectual and linguistic content and a causal-transcendental theory of representation inspired by the philosophy of the early Wittgenstein. The author explains how both parts cohere in a transcendental account of finite knowledge. He claims that this can only be achieved by reading Sellars as committed to a transcendental methodology inspired by Kant. In a final step, he brings his interpretation to bear on the contemporary metaphilosophical debate on pragmatism and expressivism.
Intentionality in Sellars will be of interest to scholars of Sellars and Kant, as well as researchers working in philosophy of mind, epistemology, and the history of nineteenth- and twentieth-century philosophy.