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On a planetary scale human populations need to adapt to both socio-economic and environmental problems amidst rapid global change. This holds true for coupled human-environment (socio-ecological) systems in rural and urban settings alike. Two examples are drylands and urban coasts. Such socio-ecological systems have a global distribution. Therefore, advancing the knowledge base for identifying socio-ecological adaptation needs with local vulnerability assessments alone is infeasible: The systems cover vast areas, while funding, time, and human resources for local assessments are limited. They are lacking in low an middle-income countries (LICs and MICs) in particular.
But places in a specific socio-ecological system are not only unique and complex – they also exhibit similarities. A global patchwork of local rural drylands vulnerability assessments of human populations to socio-ecological and environmental problems has already been reduced to a limited number of problem structures, which typically cause vulnerability. However, the question arises whether this is also possible in urban socio-ecological systems. The question also arises whether these typologies provide added value in research beyond global change. Finally, the methodology employed for drylands needs refining and standardizing to increase its uptake in the scientific community. In this dissertation, I set out to fill these three gaps in research.
The geographical focus in my dissertation is on LICs and MICs, which generally have lower capacities to adapt, and greater adaptation needs, regarding rapid global change. Using a spatially explicit indicator-based methodology, I combine geospatial and clustering methods to identify typical configurations of key factors in case studies causing vulnerability to human populations in two specific socio-ecological systems. Then I use statistical and analytical methods to interpret and appraise both the typical configurations and the global typologies they constitute.
First, I improve the indicator-based methodology and then reanalyze typical global problem structures of socio-ecological drylands vulnerability with seven indicator datasets. The reanalysis confirms the key tenets and produces a more realistic and nuanced typology of eight spatially explicit problem structures, or vulnerability profiles: Two new profiles with typically high natural resource endowment emerge, in which overpopulation has led to medium or high soil erosion. Second, I determine whether the new drylands typology and its socio-ecological vulnerability concept advance a thematically linked scientific debate in human security studies: what drives violent conflict in drylands? The typology is a much better predictor for conflict distribution and incidence in drylands than regression models typically used in peace research. Third, I analyze global problem structures typically causing vulnerability in an urban socio-ecological system - the rapidly urbanizing coastal fringe (RUCF) – with eleven indicator datasets. The RUCF also shows a robust typology, and its seven profiles show huge asymmetries in vulnerability and adaptive capacity. The fastest population increase, lowest income, most ineffective governments, most prevalent poverty, and lowest adaptive capacity are all typically stacked in two profiles in LICs. This shows that beyond local case studies tropical cyclones and/or coastal flooding are neither stalling rapid population growth, nor urban expansion, in the RUCF. I propose entry points for scaling up successful vulnerability reduction strategies in coastal cities within the same vulnerability profile.
This dissertation shows that patchworks of local vulnerability assessments can be generalized to structure global socio-ecological vulnerabilities in both rural and urban socio-ecological systems according to typical problems. In terms of climate-related extreme events in the RUCF, conflicting problem structures and means to deal with them are threatening to widen the development gap between LICs and high-income countries unless successful vulnerability reduction measures are comprehensively scaled up. The explanatory power for human security in drylands warrants further applications of the methodology beyond global environmental change research in the future. Thus, analyzing spatially explicit global typologies of socio-ecological vulnerability is a useful complement to local assessments: The typologies provide entry points for where to consider which generic measures to reduce typical problem structures – including the countless places without local assessments. This can save limited time and financial resources for adaptation under rapid global change.
Interactions and feedbacks between tectonics, climate, and upper plate architecture control basin geometry, relief, and depositional systems. The Andes is part of a longlived continental margin characterized by multiple tectonic cycles which have strongly modified the Andean upper plate architecture. In the Andean retroarc, spatiotemporal variations in the structure of the upper plate and tectonic regimes have resulted in marked along-strike variations in basin geometry, stratigraphy, deformational style, and mountain belt morphology. These along-strike variations include high-elevation plateaus (Altiplano and Puna) associated with a thin-skin fold-and-thrust-belt and thick-skin deformation in broken foreland basins such as the Santa Barbara system and the Sierras Pampeanas. At the confluence of the Puna Plateau, the Santa Barbara system and the Sierras Pampeanas, major along-strike changes in upper plate architecture, mountain belt morphology, basement exhumation, and deformation style can be recognized. I have used a source to sink approach to unravel the spatiotemporal tectonic evolution of the Andean retroarc between 26 and 28°S. I obtained a large low-temperature thermochronology data set from basement units which includes apatite fission track, apatite U-Th-Sm/He, and zircon U-Th/He (ZHe) cooling ages. Stratigraphic descriptions of Miocene units were temporally constrained by U-Pb LA-ICP-MS zircon ages from interbedded pyroclastic material.
Modeled ZHe ages suggest that the basement of the study area was exhumed during the Famatinian orogeny (550-450 Ma), followed by a period of relative tectonic quiescence during the Paleozoic and the Triassic. The basement experienced horst exhumation during the Cretaceous development of the Salta rift. After initial exhumation, deposition of thick Cretaceous syn-rift strata caused reheating of several basement blocks within the Santa Barbara system. During the Eocene-Oligocene, the Andean compressional setting was responsible for the exhumation of several disconnected basement blocks. These exhumed blocks were separated by areas of low relief, in which humid climate and low erosion rates facilitated the development of etchplains on the crystalline basement. The exhumed basement blocks formed an Eocene to Oligocene broken foreland basin in the back-bulge depozone of the Andean foreland. During the Early Miocene, foreland basin strata filled up the preexisting Paleogene topography. The basement blocks in lower relief positions were reheated; associated geothermal gradients were higher than 25°C/km. Miocene volcanism was responsible for lateral variations on the amount of reheating along the Campo-Arenal basin. Around 12 Ma, a new deformational phase modified the drainage network and fragmented the lacustrine system. As deformation and rock uplift continued, the easily eroded sedimentary cover was efficiently removed and reworked by an ephemeral fluvial system, preventing the development of significant relief. After ~6 Ma, the low erodibility of the basement blocks which began to be exposed caused relief increase, leading to the development of stable fluvial systems. Progressive relief development modified atmospheric circulation, creating a rainfall gradient. After 3 Ma, orographic rainfall and high relief lead to the development of proximal fluvial-gravitational depositional systems in the surrounding basins.
Aluminum oxide is an Earth-abundant geological material, and its interaction with water is of crucial importance for geochemical and environmental processes. Some aluminum oxide surfaces are also known to be useful in heterogeneous catalysis, while the surface chemistry of aqueous oxide interfaces determines the corrosion, growth and dissolution of such materials. In this doctoral work, we looked mainly at the (0001) surface of α-Al 2 O 3 and its reactivity towards water. In particular, a great focus of this work is dedicated to simulate and address the vibrational spectra of water adsorbed on the α-alumina(0001) surface in various conditions and at different coverages. In fact, the main source of comparison and inspiration for this work comes from the collaboration with the “Interfacial Molecular Spectroscopy” group led by Dr. R. Kramer Campen at the Fritz-Haber Institute of the MPG in Berlin. The expertise of our project partners in surface-sensitive Vibrational Sum Frequency (VSF) generation spectroscopy was crucial to develop and adapt specific simulation schemes used in this work. Methodologically, the main approach employed in this thesis is Ab Initio Molecular Dynamics (AIMD) based on periodic Density Functional Theory (DFT) using the PBE functional with D2 dispersion correction. The analysis of vibrational frequencies from both a static and a dynamic, finite-temperature perspective offers the ability to investigate the water / aluminum oxide interface in close connection to experiment.
The first project presented in this work considers the characterization of dissociatively adsorbed deuterated water on the Al-terminated (0001) surface. This particular structure is known from both experiment and theory to be the thermodynamically most stable surface termination of α-alumina in Ultra-High Vacuum (UHV) conditions. Based on experiments performed by our colleagues at FHI, different adsorption sites and products have been proposed and identified for D 2 O. While previous theoretical investigations only looked at vibrational frequencies of dissociated OD groups by staticNormal Modes Analysis (NMA), we rather employed a more sophisticated approach to directly assess vibrational spectra (like IR and VSF) at finite temperature from AIMD. In this work, we have employed a recent implementation which makes use of velocity-velocity autocorrelation functions to simulate such spectral responses of O-H(D) bonds. This approach allows for an efficient and qualitatively accurate estimation of Vibrational Densities of States (VDOS) as well as IR and VSF spectra, which are then tested against experimental spectra from our collaborators.
In order to extend previous work on unimolecularly dissociated water on α-Al 2 O 3 , we then considered a different system, namely, a fully hydroxylated (0001) surface, which results from the reconstruction of the UHV-stable Al-terminated surface at high water contents. This model is then further extended by considering a hydroxylated surface with additional water molecules, forming a two-dimensional layer which serves as a potential template to simulate an aqueous interface in environmental conditions. Again, employing finite-temperature AIMD trajectories at the PBE+D2 level, we investigated the behaviour of both hydroxylated surface (HS) and the water-covered structure derived from it (known as HS+2ML). A full range of spectra, from VDOS to IR and VSF, is then calculated using the same methodology, as described above. This is the main focus of the second project, reported in Chapter 5. In this case, comparison between theoretical spectra and experimental data is definitely good. In particular, we underline the nature of high-frequency resonances observed above 3700 cm −1 in VSF experiments to be associated with surface OH-groups, known as “aluminols” which are a key fingerprint of the fully hydroxylated surface.
In the third and last project, which is presented in Chapter 6, the extension of VSF spectroscopy experiments to the time-resolved regime offered us the opportunity to investigate vibrational energy relaxation at the α-alumina / water interface. Specifically, using again DFT-based AIMD simulations, we simulated vibrational lifetimes for surface aluminols as experimentally detected via pump-probe VSF. We considered the water-covered HS model as a potential candidate to address this problem. The vibrational (IR) excitation and subsequent relaxation is performed by means of a non-equilibrium molecular dynamics scheme. In such a scheme, we specifically looked at the O-H stretching mode of surface aluminols. Afterwards, the analysis of non-equilibrium trajectories allows for an estimation of relaxation times in the order of 2-4 ps which are in overall agreement with measured ones.
The aim of this work has been to provide, within a consistent theoretical framework, a better understanding of vibrational spectroscopy and dynamics for water on the α-alumina(0001) surface,ranging from very low water coverage (similar to the UHV case) up to medium-high coverages, resembling the hydroxylated oxide in environmental moist conditions.
The natural abundance of Coiled Coil (CC) motifs in cytoskeleton and extracellular matrix proteins suggests that CCs play an important role as passive (structural) and active (regulatory) mechanical building blocks. CCs are self-assembled superhelical structures consisting of 2-7 α-helices. Self-assembly is driven by hydrophobic and ionic interactions, while the helix propensity of the individual helices contributes additional stability to the structure. As a direct result of this simple sequence-structure relationship, CCs serve as templates for protein design and sequences with a pre-defined thermodynamic stability have been synthesized de novo. Despite this quickly increasing knowledge and the vast number of possible CC applications, the mechanical function of CCs has been largely overlooked and little is known about how different CC design parameters determine the mechanical stability of CCs. Once available, this knowledge will open up new applications for CCs as nanomechanical building blocks, e.g. in biomaterials and nanobiotechnology.
With the goal of shedding light on the sequence-structure-mechanics relationship of CCs, a well-characterized heterodimeric CC was utilized as a model system. The sequence of this model system was systematically modified to investigate how different design parameters affect the CC response when the force is applied to opposing termini in a shear geometry or separated in a zipper-like fashion from the same termini (unzip geometry). The force was applied using an atomic force microscope set-up and dynamic single-molecule force spectroscopy was performed to determine the rupture forces and energy landscape properties of the CC heterodimers under study. Using force as a denaturant, CC chain separation is initiated by helix uncoiling from the force application points. In the shear geometry, this allows uncoiling-assisted sliding parallel to the force vector or dissociation perpendicular to the force vector. Both competing processes involve the opening of stabilizing hydrophobic (and ionic) interactions. Also in the unzip geometry, helix uncoiling precedes the rupture of hydrophobic contacts.
In a first series of experiments, the focus was placed on canonical modifications in the hydrophobic core and the helix propensity. Using the shear geometry, it was shown that both a reduced core packing and helix propensity lower the thermodynamic and mechanical stability of the CC; however, with different effects on the energy landscape of the system. A less tightly packed hydrophobic core increases the distance to the transition state, with only a small effect on the barrier height. This originates from a more dynamic and less tightly packed core, which provides more degrees of freedom to respond to the applied force in the direction of the force vector. In contrast, a reduced helix propensity decreases both the distance to the transition state and the barrier height. The helices are ‘easier’ to unfold and the remaining structure is less thermodynamically stable so that dissociation perpendicular to the force axis can occur at smaller deformations.
Having elucidated how canonical sequence modifications influence CC mechanics, the pulling geometry was investigated in the next step. Using one and the same sequence, the force application points were exchanged and two different shear and one unzipping geometry were compared. It was shown that the pulling geometry determines the mechanical stability of the CC. Different rupture forces were observed in the different shear as well as in the unzipping geometries, suggesting that chain separation follows different pathways on the energy landscape. Whereas the difference between CC shearing and unzipping was anticipated and has also been observed for other biological structures, the observed difference for the two shear geometries was less expected. It can be explained with the structural asymmetry of the CC heterodimer. It is proposed that the direction of the α-helices, the different local helix propensities and the position of a polar asparagine in the hydrophobic core are responsible for the observed difference in the chain separation pathways. In combination, these factors are considered to influence the interplay between processes parallel and perpendicular to the force axis.
To obtain more detailed insights into the role of helix stability, helical turns were reinforced locally using artificial constraints in the form of covalent and dynamic ‘staples’. A covalent staple bridges to adjacent helical turns, thus protecting them against uncoiling. The staple was inserted directly at the point of force application in one helix or in the same terminus of the other helix, which did not experience the force directly. It was shown that preventing helix uncoiling at the point of force application reduces the distance to the transition state while slightly increasing the barrier height. This confirms that helix uncoiling is critically important for CC chain separation. When inserted into the second helix, this stabilizing effect is transferred across the hydrophobic core and protects the force-loaded turns against uncoiling. If both helices were stapled, no additional increase in mechanical stability was observed. When replacing the covalent staple with a dynamic metal-coordination bond, a smaller decrease in the distance to the transition was observed, suggesting that the staple opens up while the CC is under load.
Using fluorinated amino acids as another type of non-natural modification, it was investigated how the enhanced hydrophobicity and the altered packing at the interface influences CC mechanics. The fluorinated amino acid was inserted into one central heptad of one or both α-helices. It was shown that this substitution destabilized the CC thermodynamically and mechanically. Specifically, the barrier height was decreased and the distance to the transition state increased. This suggests that a possible stabilizing effect of the increased hydrophobicity is overruled by a disturbed packing, which originates from a bad fit of the fluorinated amino acid into the local environment. This in turn increases the flexibility at the interface, as also observed for the hydrophobic core substitution described above. In combination, this confirms that the arrangement of the hydrophobic side chains is an additional crucial factor determining the mechanical stability of CCs.
In conclusion, this work shows that knowledge of the thermodynamic stability alone is not sufficient to predict the mechanical stability of CCs. It is the interplay between helix propensity and hydrophobic core packing that defines the sequence-structure-mechanics relationship. In combination, both parameters determine the relative contribution of processes parallel and perpendicular to the force axis, i.e. helix uncoiling and uncoiling-assisted sliding as well as dissociation. This new mechanistic knowledge provides insight into the mechanical function of CCs in tissues and opens up the road for designing CCs with pre-defined mechanical properties. The library of mechanically characterized CCs developed in this work is a powerful starting point for a wide spectrum of applications, ranging from molecular force sensors to mechanosensitive crosslinks in protein nanostructures and synthetic extracellular matrix mimics.
The growing energy demand of the modern economies leads to the increased consumption of fossil fuels in form of coal, oil, and natural gases, as the mains sources. The combustion of these carbon-based fossil fuels is inevitably producing greenhouse gases, especially CO2. Approaches to tackle the CO2 problem are to capture it from the combustion sources or directly from air, as well as to avoid CO2 production in energy consuming sources (e.g., in the refrigeration sector). In the former, relatively low CO2 concentrations and competitive adsorption of other gases is often leading to low CO2 capacities and selectivities. In both approaches, the interaction of gas molecules with porous materials plays a key role. Porous carbon materials possess unique properties including electric conductivity, tunable porosity, as well as thermal and chemical stability. Nevertheless, pristine carbon materials offer weak polarity and thus low CO2 affinity. This can be overcome by nitrogen doping, which enhances the affinity of carbon materials towards acidic or polar guest molecules (e.g., CO2, H2O, or NH3). In contrast to heteroatom-free materials, such carbon materials are in most cases “noble”, that is, they oxidize other matter rather than being oxidized due to the very positive working potential of their electrons. The challenging task here is to achieve homogenous distribution of significant nitrogen content with similar bonding motives throughout the carbon framework and a uniform pore size/distribution to maximize host-guest interactions. The aim of this thesis is the development of novel synthesis pathways towards nitrogen-doped nanoporous noble carbon materials with precise design on a molecular level and understanding of their structure-related performance in energy and environmental applications, namely gas adsorption and electrochemical energy storage.
A template-free synthesis approach towards nitrogen-doped noble microporous carbon materials with high pyrazinic nitrogen content and C2N-type stoichiometry was established via thermal condensation of a hexaazatriphenylene derivative. The materials exhibited high uptake of guest molecules, such as H2O and CO2 at low concentrations, as well as moderate CO2/N2 selectivities. In the following step, the CO2/N2 selectivity was enhanced towards molecular sieving of CO2 via kinetic size exclusion of N2. The precise control over the condensation degree, and thus, atomic construction and porosity of the resulting materials led to remarkable CO2/N2 selectivities, CO2 capacities, and heat of CO2 adsorption. The ultrahydrophilic nature of the pore walls and the narrow microporosity of these carbon materials served as ideal basis for the investigation of interface effects with more polar guest molecules than CO2, namely H2O and NH3.
H2O vapor physisorption measurements, as well as NH3-temperature programmed desorption and thermal response measurements showed exceptionally high affinity towards H2O vapor and NH3 gas. Another series of nitrogen-doped carbon materials was synthesized by direct condensation of a pyrazine-fused conjugated microporous polymer and their structure-related performance in electrochemical energy storage, namely as anode materials for sodium-ion battery, was investigated.
All in all, the findings in this thesis exemplify the value of molecularly designed nitrogen-doped carbon materials with remarkable heteroatom content implemented as well-defined structure motives. The simultaneous adjustment of the porosity renders these materials suitable candidates for fundamental studies about the interactions between nitrogen-doped carbon materials and different guest species.
Im Rahmen dieser Arbeit wird anhand von neuartigen Materialien das Potential der Europium-Lumineszenz für die strukturelle Analyse dargestellt. Bei diesen Materialien handelt es sich zum einen um Nanopartikel mit Matrizes aus mehreren Metall-Mischoxiden und Dotierungen durch die Sonde Europium und zum anderen um Metallorganische Netzwerke (MOFs), die mit Neodym , Samarium- und Europium-Ionen beladen sind.
Die Synthese der aus der Kombination von Metalloxiden enthaltenen Nanopartikel ist unter milden Bedingungen mithilfe von speziell dafür hergestellten Reagenzien erfolgt und hat zu sehr kleinen, amorphen Nanopartikeln geführt. Durch eine nachfolgende Temperaturbehandlung hat sich die Kristallinität erhöht. Damit verbunden haben sich auch die Kristallstruktur sowie die Position des Dotanden Europium verändert.
Während die etablierte Methode der Röntgendiffraktometrie einen Blick auf das Kristallgitter als Gesamtes ermöglicht, so trifft die Lumineszenz des Europiums durch die Sichtbarkeit einzelner Stark-Aufspaltungen Aussagen über dessen lokale Symmetrien. Die Symmetrie wird durch Sauerstofffehlstellen verändert, welche die Sauerstoffleitfähigkeit der Nanopartikel beeinflussen. Diese ist für die Anwendung als Katalysatoren in industriellen Prozessen und ebenso als Sensoren und Therapeutika in biologischen Systemen von Bedeutung.
Zur ersten katalytischen Charakterisierung werden die Proben mittels Temperatur-programmierter Reduktion untersucht. Des Weiteren werden die Mischoxid-Nanopartikel auch hinsichtlich ihrer Verwendbarkeit als Matrix in Aufkonversionsprozessen untersucht.
Die Metallorganischen Netzwerke eignen sich aufgrund ihrer mikroporösen Struktur für Anwendungen in der Speicherung gleichermaßen von Nutzgasen wie auch von Schadstoffen. Ebenfalls ist eine biologische Anwendung denkbar, die insbesondere den Bereich der drug delivery-Reagenzien betrifft.
Erfolgt in die mikroporösen Strukturen der Metallorganischen Netzwerke die Einlagerung von Lanthanoid-Ionen, so können diese bei der entsprechenden Kombination als Weißlicht-Emittierer fungieren. Dabei ist neben den Verhältnissen zwischen den Lanthanoid-Ionen auch die genaue Position innerhalb des Netzwerks sowie die Distanz zu anderen Ionen von Interesse. Zur Untersuchung dieser Fragestellungen wird die Umgebungssensitivität der Europium-Lumineszenz ausgenutzt. Die auf diese Weise festgestellte Formiat-Bildung hängt von zahlreichen Parametern ab.
Insgesamt stellt sich die im Rahmen dieser Arbeit verwendete Methodik des Einsatzes von Europium als strukturelle Sonde in höchstem Maße vielseitig dar und zeigt seine größte Stärke in der Kombination mit weiteren Methoden der Strukturanalytik. Die auf diese Weise genauestens charakterisierten neuartigen Materialien können nun gezielt und anwendungsfokussiert weiterentwickelt werden.
Electrets are dielectrics with quasi-permanent electric charge and/or dipoles, sometimes can be regarded as an electric analogy to a magnet. Since the discovery of the excellent charge retention capacity of poly(tetrafluoro ethylene) and the invention of the electret microphone, electrets have grown out of a scientific curiosity to an important application both in science and technology. The history of electret research goes hand in hand with the quest for new materials with better capacity at charge and/or dipole retention. To be useful, electrets normally have to be charged/poled to render them electro-active. This process involves electric-charge deposition and/or electric dipole orientation within the dielectrics ` surfaces and bulk. Knowledge of the spatial distribution of electric charge and/or dipole polarization after their deposition and subsequent decay is crucial in the task to improve their stability in the dielectrics.
Likewise, for dielectrics used in electrical insulation applications, there are also needs for accumulated space-charge and polarization spatial profiling. Traditionally, space-charge accumulation and large dipole polarization within insulating dielectrics is considered undesirable and harmful to the insulating dielectrics as they might cause dielectric loss and could lead to internal electric field distortion and local field enhancement. High local electric field could trigger several aging processes and reduce the insulating dielectrics' lifetime. However, with the advent of high-voltage DC transmission and high-voltage capacitor for energy storage, these are no longer the case. There are some overlapped between the two fields of electrets and electric insulation. While quasi-permanently trapped electric-charge and/or large remanent dipole polarization are the requisites for electret operation, stably trapped electric charge in electric insulation helps reduce electric charge transport and overall reduced electric conductivity. Controlled charge trapping can help in preventing further charge injection and accumulation as well as serving as field grading purpose in insulating dielectrics whereas large dipole polarization can be utilized in energy storage applications.
In this thesis, the Piezoelectrically-generated Pressure Steps (PPSs) were employed as a nondestructive method to probe the electric-charge and dipole polarization distribution in a range of thin film (several hundred micron) polymer-based materials, namely polypropylene (PP), low-density polyethylene/magnesium oxide (LDPE/MgO) nanocomposites and poly(vinylidene fluoride-co- trifluoro ethylene) (P(VDF-TrFE)) copolymer. PP film surface-treated with phosphoric acid to introduce surfacial isolated nanostructures serves as example of 2-dimensional nano-composites whereas LDPE/MgO serves as the case of 3-dimensional nano-composites with MgO nano-particles dispersed in LDPE polymer matrix. It is evidenced that the nanoparticles on the surface of acid-treated PP and in the bulk of LDPE/MgO nanocomposites improve charge trapping capacity of the respective material and prevent further charge injection and transport and that the enhanced charge trapping capacity makes PP and LDPE/MgO nanocomposites potential materials for both electret and electrical insulation applications. As for PVDF and VDF-based copolymers, the remanent spatial polarization distribution depends critically on poling method as well as specific parameters used in the respective poling method. In this work, homogeneous polarization poling of P(VDF-TrFE) copolymers with different VDF-contents have been attempted with hysteresis cyclical poling. The behaviour of remanent polarization growth and spatial polarization distribution are reported and discussed. The Piezoelectrically-generated Pressure Steps (PPSs) method has proven as a powerful method for the charge storage and transport characterization of a wide range of polymer material from nonpolar, to polar, to polymer nanocomposites category.
The identification of vulnerabilities in IT infrastructures is a crucial problem in enhancing the security, because many incidents resulted from already known vulnerabilities, which could have been resolved. Thus, the initial identification of vulnerabilities has to be used to directly resolve the related weaknesses and mitigate attack possibilities. The nature of vulnerability information requires a collection and normalization of the information prior to any utilization, because the information is widely distributed in different sources with their unique formats. Therefore, the comprehensive vulnerability model was defined and different sources have been integrated into one database. Furthermore, different analytic approaches have been designed and implemented into the HPI-VDB, which directly benefit from the comprehensive vulnerability model and especially from the logical preconditions and postconditions.
Firstly, different approaches to detect vulnerabilities in both IT systems of average users and corporate networks of large companies are presented. Therefore, the approaches mainly focus on the identification of all installed applications, since it is a fundamental step in the detection. This detection is realized differently depending on the target use-case. Thus, the experience of the user, as well as the layout and possibilities of the target infrastructure are considered. Furthermore, a passive lightweight detection approach was invented that utilizes existing information on corporate networks to identify applications.
In addition, two different approaches to represent the results using attack graphs are illustrated in the comparison between traditional attack graphs and a simplistic graph version, which was integrated into the database as well. The implementation of those use-cases for vulnerability information especially considers the usability. Beside the analytic approaches, the high data quality of the vulnerability information had to be achieved and guaranteed. The different problems of receiving incomplete or unreliable information for the vulnerabilities are addressed with different correction mechanisms. The corrections can be carried out with correlation or lookup mechanisms in reliable sources or identifier dictionaries. Furthermore, a machine learning based verification procedure was presented that allows an automatic derivation of important characteristics from the textual description of the vulnerabilities.
Risiken für Cyberressourcen können durch unbeabsichtigte oder absichtliche Bedrohungen entstehen. Dazu gehören Insider-Bedrohungen von unzufriedenen oder nachlässigen Mitarbeitern und Partnern, eskalierende und aufkommende Bedrohungen aus aller Welt, die stetige Weiterentwicklung der Angriffstechnologien und die Entstehung neuer und zerstörerischer Angriffe. Informationstechnik spielt mittlerweile in allen Bereichen des Lebens eine entscheidende Rolle, u. a. auch im Bereich des Militärs. Ein ineffektiver Schutz von Cyberressourcen kann hier Sicherheitsvorfälle und Cyberattacken erleichtern, welche die kritischen Vorgänge stören, zu unangemessenem Zugriff, Offenlegung, Änderung oder Zerstörung sensibler Informationen führen und somit die nationale Sicherheit, das wirtschaftliche Wohlergehen sowie die öffentliche Gesundheit und Sicherheit gefährden. Oftmals ist allerdings nicht klar, welche Bedrohungen konkret vorhanden sind und welche der kritischen Systemressourcen besonders gefährdet ist.
In dieser Dissertation werden verschiedene Analyseverfahren für Bedrohungen in militärischer Informationstechnik vorgeschlagen und in realen Umgebungen getestet. Dies bezieht sich auf Infrastrukturen, IT-Systeme, Netze und Anwendungen, welche Verschlusssachen (VS)/Staatsgeheimnisse verarbeiten, wie zum Beispiel bei militärischen oder Regierungsorganisationen. Die Besonderheit an diesen Organisationen ist das Konzept der Informationsräume, in denen verschiedene Datenelemente, wie z. B. Papierdokumente und Computerdateien, entsprechend ihrer Sicherheitsempfindlichkeit eingestuft werden, z. B. „STRENG GEHEIM“, „GEHEIM“, „VS-VERTRAULICH“, „VS-NUR-FÜR-DEN-DIENSTGEBRAUCH“ oder „OFFEN“.
Die Besonderheit dieser Arbeit ist der Zugang zu eingestuften Informationen aus verschiedenen Informationsräumen und der Prozess der Freigabe dieser. Jede in der Arbeit entstandene Veröffentlichung wurde mit Angehörigen in der Organisation besprochen, gegengelesen und freigegeben, so dass keine eingestuften Informationen an die Öffentlichkeit gelangen.
Die Dissertation beschreibt zunächst Bedrohungsklassifikationsschemen und Angreiferstrategien, um daraus ein ganzheitliches, strategiebasiertes Bedrohungsmodell für Organisationen abzuleiten. Im weiteren Verlauf wird die Erstellung und Analyse eines Sicherheitsdatenflussdiagramms definiert, welches genutzt wird, um in eingestuften Informationsräumen operationelle Netzknoten zu identifizieren, die aufgrund der Bedrohungen besonders gefährdet sind. Die spezielle, neuartige Darstellung ermöglicht es, erlaubte und verbotene Informationsflüsse innerhalb und zwischen diesen Informationsräumen zu verstehen.
Aufbauend auf der Bedrohungsanalyse werden im weiteren Verlauf die Nachrichtenflüsse der operationellen Netzknoten auf Verstöße gegen Sicherheitsrichtlinien analysiert und die Ergebnisse mit Hilfe des Sicherheitsdatenflussdiagramms anonymisiert dargestellt. Durch Anonymisierung der Sicherheitsdatenflussdiagramme ist ein Austausch mit externen Experten zur Diskussion von Sicherheitsproblematiken möglich.
Der dritte Teil der Arbeit zeigt, wie umfangreiche Protokolldaten der Nachrichtenflüsse dahingehend untersucht werden können, ob eine Reduzierung der Menge an Daten möglich ist. Dazu wird die Theorie der groben Mengen aus der Unsicherheitstheorie genutzt. Dieser Ansatz wird in einer Fallstudie, auch unter Berücksichtigung von möglichen auftretenden Anomalien getestet und ermittelt, welche Attribute in Protokolldaten am ehesten redundant sind.
Medical imaging plays an important role in disease diagnosis, treatment planning, and clinical monitoring. One of the major challenges in medical image analysis is imbalanced training data, in which the class of interest is much rarer than the other classes. Canonical machine learning algorithms suppose that the number of samples from different classes in the training dataset is roughly similar or balance. Training a machine learning model on an imbalanced dataset can introduce unique challenges to the learning problem.
A model learned from imbalanced training data is biased towards the high-frequency samples. The predicted results of such networks have low sensitivity and high precision. In medical applications, the cost of misclassification of the minority class could be more than the cost of misclassification of the majority class. For example, the risk of not detecting a tumor could be much higher than referring to a healthy subject to a doctor. The current Ph.D. thesis introduces several deep learning-based approaches for handling class imbalanced problems for learning multi-task such as disease classification and semantic segmentation.
At the data-level, the objective is to balance the data distribution through re-sampling the data space: we propose novel approaches to correct internal bias towards fewer frequency samples. These approaches include patient-wise batch sampling, complimentary labels, supervised and unsupervised minority oversampling using generative adversarial networks for all.
On the other hand, at algorithm-level, we modify the learning algorithm to alleviate the bias towards majority classes. In this regard, we propose different generative adversarial networks for cost-sensitive learning, ensemble learning, and mutual learning to deal with highly imbalanced imaging data.
We show evidence that the proposed approaches are applicable to different types of medical images of varied sizes on different applications of routine clinical tasks, such as disease classification and semantic segmentation. Our various implemented algorithms have shown outstanding results on different medical imaging challenges.
In the era of social networks, internet of things and location-based services, many online services produce a huge amount of data that have valuable objective information, such as geographic coordinates and date time. These characteristics (parameters) in the combination with a textual parameter bring the challenge for the discovery of geospatiotemporal knowledge. This challenge requires efficient methods for clustering and pattern mining in spatial, temporal and textual spaces.
In this thesis, we address the challenge of providing methods and frameworks for geospatiotemporal data analytics. As an initial step, we address the challenges of geospatial data processing: data gathering, normalization, geolocation, and storage. That initial step is the basement to tackle the next challenge -- geospatial clustering challenge. The first step of this challenge is to design the method for online clustering of georeferenced data. This algorithm can be used as a server-side clustering algorithm for online maps that visualize massive georeferenced data. As the second step, we develop the extension of this method that considers, additionally, the temporal aspect of data. For that, we propose the density and intensity-based geospatiotemporal clustering algorithm with fixed distance and time radius.
Each version of the clustering algorithm has its own use case that we show in the thesis.
In the next chapter of the thesis, we look at the spatiotemporal analytics from the perspective of the sequential rule mining challenge. We design and implement the framework that transfers data into textual geospatiotemporal data - data that contain geographic coordinates, time and textual parameters. By this way, we address the challenge of applying pattern/rule mining algorithms in geospatiotemporal space. As the applicable use case study, we propose spatiotemporal crime analytics -- discovery spatiotemporal patterns of crimes in publicly available crime data.
The second part of the thesis, we dedicate to the application part and use case studies. We design and implement the application that uses the proposed clustering algorithms to discover knowledge in data. Jointly with the application, we propose the use case studies for analysis of georeferenced data in terms of situational and public safety awareness.
Interlocutors typically link their utterances to the discourse environment and enrich communication by linguistic (e.g., information packaging) and extra-linguistic (e.g., eye gaze, gestures) means to optimize information transfer. Psycholinguistic studies underline that ‒for meaning computation‒ listeners profit from linguistic and visual cues that draw their focus of attention to salient information. This dissertation is the first work that examines how linguistic compared to visual salience cues influence sentence comprehension using the very same experimental paradigms and materials, that is, German subject-before-object (SO) and object-before-subject (OS) sentences, across the two cue modalities. Linguistic salience was induced by indicating a referent as the aboutness topic. Visual salience was induced by implicit (i.e., unconscious) or explicit (i.e., shared) manipulations of listeners’ attention to a depicted referent.
In Study 1, a selective, facilitative impact of linguistic salience on the context-sensitive OS word order was found using offline comprehensibility judgments. More precisely, during online sentence processing, this impact was characterized by a reduced sentence-initial Late positivity which reflects reduced processing costs for updating the current mental representation of discourse. This facilitative impact of linguistic salience was not replicated by means of an implicit visual cue (Study 2) shown to modulate word order preferences during sentence production. However, a gaze shift to a depicted referent as an indicator of shared attention eased sentence-initial processing similar to linguistic salience as revealed by reduced reading times (Study 3). Yet, this cue did not modulate the strong subject-antecedent preference during later pronoun resolution like linguistic salience. Taken together, these findings suggest a significant impact of linguistic and visual salience cues on sentence comprehension, which substantiates that both the information delivered via language and via the visual environment is integrated into the mental representation of the discourse; but, the way how salience is induced is crucial to its impact.
With the emergence of the Internet of things (IoT), plenty of battery-powered and energy-harvesting devices are being deployed to fulfill sensing and actuation tasks in a variety of application areas, such as smart homes, precision agriculture, smart cities, and industrial automation. In this context, a critical issue is that of denial-of-sleep attacks. Such attacks temporarily or permanently deprive battery-powered, energy-harvesting, or otherwise energy-constrained devices of entering energy-saving sleep modes, thereby draining their charge. At the very least, a successful denial-of-sleep attack causes a long outage of the victim device. Moreover, to put battery-powered devices back into operation, their batteries have to be replaced. This is tedious and may even be infeasible, e.g., if a battery-powered device is deployed at an inaccessible location. While the research community came up with numerous defenses against denial-of-sleep attacks, most present-day IoT protocols include no denial-of-sleep defenses at all, presumably due to a lack of awareness and unsolved integration problems. After all, despite there are many denial-of-sleep defenses, effective defenses against certain kinds of denial-of-sleep attacks are yet to be found.
The overall contribution of this dissertation is to propose a denial-of-sleep-resilient medium access control (MAC) layer for IoT devices that communicate over IEEE 802.15.4 links. Internally, our MAC layer comprises two main components. The first main component is a denial-of-sleep-resilient protocol for establishing session keys among neighboring IEEE 802.15.4 nodes. The established session keys serve the dual purpose of implementing (i) basic wireless security and (ii) complementary denial-of-sleep defenses that belong to the second main component. The second main component is a denial-of-sleep-resilient MAC protocol. Notably, this MAC protocol not only incorporates novel denial-of-sleep defenses, but also state-of-the-art mechanisms for achieving low energy consumption, high throughput, and high delivery ratios. Altogether, our MAC layer resists, or at least greatly mitigates, all denial-of-sleep attacks against it we are aware of. Furthermore, our MAC layer is self-contained and thus can act as a drop-in replacement for IEEE 802.15.4-compliant MAC layers. In fact, we implemented our MAC layer in the Contiki-NG operating system, where it seamlessly integrates into an existing protocol stack.
Carbonfasern haben sich in der Luft- und Raumfahrt etabliert und gewinnen in Alltagsanwendungen wie dem Automobilbereich, Windkraft- und Sportbereich durch ihre hohen Zugfestigkeiten, insbesondere ihrer hohen E-Moduli, und ihrer geringen Dichte immer mehr an Bedeutung. Auf Grund ihrer hohen Kosten, welche sich zur Hälfte aus der Precursorherstellung, inklusive seiner Synthese und seinem Verspinnprozess, dem Lösungsspinnverfahren, ergeben, erhalten zunehmend alternative und schmelzspinnbare Precursoren Interesse. Für die Carbonfaserherstellung wird fast ausschließlich Polyacrylnitril (PAN) verwendet, das vor dem Schmelzen irreversible exotherme Zyklisierungsreaktionen aufweist, welchen sich seine Zersetzung anschließt. Eine Möglichkeit der Reduzierung der Schmelztemperatur von Polymeren ist die Einbringung von Comonomeren zur Erhöhung des freien Volumens und die Reduzierung der intermolekularen Wechselwirkungen als interne Weichmacher. Wie am Fraunhofer IAP gezeigt wurde, kann mittels 2-Methoxyethylacrylat (MEA) die Schmelztemperatur zu neuartigen PAN-basierten Precursoren verringert werden. Um den PAN-co-MEA-Precursor für die nachfolgenden Prozessschritte der Carbonfaserherstellung zu verwenden, müssen die thermoplastischen Fasern in thermisch stabile Fasern ohne thermoplastisches Verhalten überführt werden. Es wurde ein neuer Prozessschritt (Prästabilisierung) eingeführt, welcher unter alkalischen Bedingungen zur Abspaltung der Comonomerseitenkette führt. Neben der Esterhydrolyse finden Reaktionen statt, welche an diesem Material noch nicht hinreichend untersucht wurden. Weiterhin stellt sich die Frage nach der Kinetik der Prästabilisierung und der Ermittlung einer geeigneten Prozessführung.
Hierzu wurde die Prästabilisierung in den Labormaßstab überführt und die möglichen Zusammensetzungen des aus DMSO und einer KOH-Lösung bestehenden Reaktionsmediums evaluiert. Weiterhin wurde die Behandlung bei verschiedenen Prästabilisierungszeiten von maximal 30 min und Temperaturen von 40, 50 und 60 °C durchgeführt, um primär mittels NMR-Spektroskopie die chemischen Strukturänderungen aufzuklären. Die Esterhydrolyse des Comonomers, welche zur Abspaltung des 2-Methoxyethanols führt, wurde mittels 1H-NMR-spektroskopischer Untersuchungen detektiert.
Es wurde ein Modell aufgestellt, das die chemisch-physikalischen Strukturänderungen während der Prästabilisierung aufzeigt. Die zuerst ablaufende Reaktion ist die Esterhydrolyse am Comonomer, welche vom Faserrand nach innen verläuft und durch die Präsenz des DMSO in Kombination mit der KOH-Lösung (Superbase) initiiert wird. Der zeitliche Reaktionsverlauf der Esterhydrolyse kann in drei Bereiche eingeteilt werden. Der erste Bereich ab dem Prästabilisierungsbeginn wird durch die Diffusion der basischen Anionen in die Faser, der zweite Bereich durch die Reaktion an der Estergruppe des Comonomers und der dritte Bereich durch letzte Reaktionen im Faserinneren und diffusiven Prozessen der Produkte und Edukte charakterisiert. Der zweite Bereich kann mit einer Reaktion pseudo 1. Ordnung abgebildet werden, da in diesem Bereich bereits eine ausreichende Diffusion der Edukte in die Faser stattgefunden hat. Bei 50 °C spielt die Diffusion im ersten Bereich im Vergleich zur Reaktion eine untergeordnete Rolle. Mit Erhöhung der Temperatur auf 60 °C kann eine im Verhältnis geringere Diffusions- als Reaktionsgeschwindigkeit beobachtet werden. Die Nebenreaktionen wurden mittels 13C-CP/MAS-NMR-spektroskopischen, elementaranlaytischen Untersuchungen sowie Doppelbrechungsmessungen charakterisiert. Während der alkalischen Esterhydrolyse beginnt die Reduzierung der Nitrilgruppen unter der Bildung von primären Carbonsäureamiden und Carbonsäuren. Zur Beschreibung dieser Umsetzung wurde eine Methode entwickelt, welche die Addition von 13C-CP/MAS-NMR-Spektren der Modellsubstanzen PAN, PAM und PAA beinhaltet. Weitere stattfindende Reaktionen sind die Bildung von konjugierten Doppelbindungen, welche insbesondere auf eine Zyklisierung der Nitrile hinweisen. Die nasschemisch initiierte Zyklisierung der Nitrilgruppen kann zu kürzeren Stabilisierungszeiten und einem besser kontrollierbaren Stabilisierungsprozess durch geringere Wärmefreisetzung und schlussendlich zu einer Kostenersparnis des gesamten Verfahrens führen. Die Umsetzung der Nitrilgruppen konnte mit einer Reaktion pseudo 1. Ordnung gut abgebildet werden. DMSO initiiert die Esterhydrolyse, wobei die KOH-Konzentration einen höheren Einfluss auf die Reaktionsgeschwindigkeit der Ester- und Nitrilhydrolyse als die DMSO-Konzentration besitzt. Beide Reaktionen zeigen eine vergleichbare Abhängigkeit von der Temperatur. Die Erhöhung der Prästabilisierungszeit und der KOH- bzw. DMSO-Konzentration führt zur Migration niedermolekularer Bestandteile des Fasermaterials an die Oberfläche und der Bildung punktueller Ablagerungen bis hin zu miteinander verbundenen Einzelfasern. Eine weitere Erhöhung der Prästabilisierungszeit bzw. der Konzentration führt zu einem steigenden Carbonsäureanteil und zur Quellung des Fasermaterials, wodurch die Ablagerungen in das Reaktionsmedium diffundieren. Die Ablagerungen enthalten Chlor, welches durch den Waschvorgang mit HCl in das Materialsystem gelangt ist und durch Parameteranpassungen reduziert wurde. Die schmelzbaren Fasern konnten durch die Prästabilisierung erfolgreich über eine Kern-Mantel-Struktur in nicht-thermoplastische Fasern überführt werden.
Zur Ermittlung eines geeigneten Prozessfensters für nachfolgende thermische Beanspruchungen der prästabilisierten Fasern wurden drei Kriterien identifiziert, anhand welcher die Evaluation erfolgte. Das erste Kriterium beinhaltet die Notwendigkeit der vollständigen Aufhebung der thermoplastischen Eigenschaft der Fasern. Als zweites Kriterium diente die Fasermorphologie. Anhand von REM-Aufnahmen wurden Faserbündel mit separierten Einzelfasern ohne Ablagerungen für die nachfolgende Stabilisierung ausgewählt. Das dritte Kriterium bezieht sich auf eine möglichst geringe Umsetzung der Nitrilgruppen, um Prästabilisierungsbedingungen mit Nebenreaktionen zu vermeiden.
Aus den Untersuchungen konnte eine Prästabilisierungstemperatur von 60 °C als geeignet identifiziert werden. Weiterhin führen hoch alkalische Zusammensetzungen des Reaktionsmediums mit KOH-Konzentrationen von 1, 1,5 und 2 M, vorzugsweise 1,5 M und 50 vol% DMSO mit Reaktionszeiten von unter 10 min zu geeigneten Fasern. Ein MEA-Anteil unterhalb von 2 mol% bewirkt eine Überführung in die Unschmelzbarkeit. Thermisch stabile und für die nachfolgende Stabilisierung geeignete Fasern besitzen weiterhin 68 – 80 mol% Nitrilgruppen, 20 – 25 mol% Carbonsäuren, bis zu 15 mol% primäre Carbonsäureamide und zyklisierte Strukturen.
Due to advances in science and technology towards smaller and more powerful processing units, the fabrication of micrometer sized machines for different tasks becomes more and more possible. Such micro-robots could revolutionize medical treatment of diseases and shall support to work on other small machines. Nevertheless, scaling down robots and other devices is a challenging task and will probably remain limited in near future. Over the past decade the concept of bio-hybrid systems has proved to be a promising approach in order to advance the further development of micro-robots. Bio-hybrid systems combine biological cells with artificial components, thereby benefiting from the functionality of living biological cells. Cell-driven micro-transport is one of the most prominent applications in the emerging field of these systems. So far, micrometer sized cargo has been successfully transported by means of swimming bacterial cells. The potential of motile adherent cells as transport systems has largely remained unexplored.
This thesis concentrates on the social amoeba Dictyostelium discoideum as a potential candidate for an amoeboid bio-hybrid transport system. The use of this model organism comes with several advantages. Due to the unspecific properties of Dictyostelium adhesion, a wide range of different cargo materials can be used for transport. As amoeboid cells exceed bacterial cells in size by one order of magnitude, also the size of an object carried by a single cell can also be much larger for an amoeba. Finally it is possible to guide the cell-driven transport based on the chemotactic behavior of the amoeba. Since cells undergo a developmentally induced chemotactic aggregation, cargo could be assembled in a self-organized manner into a cluster. It is also possible to impose an external chemical gradient to guide the amoeboid transport system to a desired location.
To establish Dictyostelium discoideum as a possible candidate for bio-hybrid transport systems, this thesis will first investigate the movement of single cells. Secondly, the interaction of cargo and cells will be studied. Eventually, a conceptional proof will be conducted, that the cheomtactic behavior can be exploited either to transport a cargo self-organized or through an external chemical source.
With the growth of information technology, patient attitudes are shifting – away from passively receiving care towards actively taking responsibility for their well- being. Handling doctor-patient relationships collaboratively and providing patients access to their health information are crucial steps in empowering patients. In mental healthcare, the implicit consensus amongst practitioners has been that sharing medical records with patients may have an unpredictable, harmful impact on clinical practice. In order to involve patients more actively in mental healthcare processes, Tele-Board MED (TBM) allows for digital collaborative documentation in therapist-patient sessions. The TBM software system offers a whiteboard-inspired graphical user interface that allows therapist and patient to jointly take notes during the treatment session. Furthermore, it provides features to automatically reuse the digital treatment session notes for the creation of treatment session summaries and clinical case reports. This thesis presents the development of the TBM system and evaluates its effects on 1) the fulfillment of the therapist’s duties of clinical case documentation, 2) patient engagement in care processes, and 3) the therapist-patient relationship. Following the design research methodology, TBM was developed and tested in multiple evaluation studies in the domains of cognitive behavioral psychotherapy and addiction care. The results show that therapists are likely to use TBM with patients if they have a technology-friendly attitude and when its use suits the treatment context. Support in carrying out documentation duties as well as fulfilling legal requirements contributes to therapist acceptance. Furthermore, therapists value TBM as a tool to provide a discussion framework and quick access to worksheets during treatment sessions. Therapists express skepticism, however, regarding technology use in patient sessions and towards complete record transparency in general. Patients expect TBM to improve the communication with their therapist and to offer a better recall of discussed topics when taking a copy of their notes home after the session. Patients are doubtful regarding a possible distraction of the therapist and usage in situations when relationship-building is crucial. When applied in a clinical environment, collaborative note-taking with TBM encourages patient engagement and a team feeling between therapist and patient. Furthermore, it increases the patient’s acceptance of their diagnosis, which in turn is an important predictor for therapy success. In summary, TBM has a high potential to deliver more than documentation support and record transparency for patients, but also to contribute to a collaborative doctor-patient relationship. This thesis provides design implications for the development of digital collaborative documentation systems in (mental) healthcare as well as recommendations for a successful implementation in clinical practice.
The foreland of the Andes in South America is characterised by distinct along strike changes in surface deformational styles. These styles are classified into two end-members, the thin-skinned and the thick-skinned style. The superficial expression of thin-skinned deformation is a succession of narrowly spaced hills and valleys, that form laterally continuous ranges on the foreland facing side of the orogen. Each of the hills is defined by a reverse fault that roots in a basal décollement surface within the sedimentary cover, and acted as thrusting ramp to stack the sedimentary pile. Thick-skinned deformation is morphologically characterised by spatially disparate, basement-cored mountain ranges. These mountain ranges are uplifted along reactivated high-angle crustal-scale discontinuities, such as suture zones between different tectonic terranes.
Amongst proposed causes for the observed variation are variations in the dip angle of the Nazca plate, variation in sediment thickness, lithospheric thickening, volcanism or compositional differences. The proposed mechanisms are predominantly based on geological observations or numerical thermomechanical modelling, but there has been no attempt to understand the mechanisms from a point of data-integrative 3D modelling. The aim of this dissertation is therefore to understand how lithospheric structure controls the deformational behaviour. The integration of independent data into a consistent model of the lithosphere allows to obtain additional evidence that helps to understand the causes for the different deformational styles. Northern Argentina encompasses the transition from the thin-skinned fold-and-thrust belt in Bolivia, to the thick-skinned Sierras Pampeanas province, which makes this area a well suited location for such a study. The general workflow followed in this study first involves data-constrained structural- and density-modelling in order to obtain a model of the study area. This model was then used to predict the steady-state thermal field, which was then used to assess the present-day rheological state in northern Argentina.
The structural configuration of the lithosphere in northern Argentina was determined by means of data-integrative, 3D density modelling verified by Bouguer gravity. The model delineates the first-order density contrasts in the lithosphere in the uppermost 200 km, and discriminates bodies for the sediments, the crystalline crust, the lithospheric mantle and the subducting Nazca plate. To obtain the intra-crustal density structure, an automated inversion approach was developed and applied to a starting structural model that assumed a homogeneously dense crust. The resulting final structural model indicates that the crustal structure can be represented by an upper crust with a density of 2800 kg/m³, and a lower crust of 3100 kg/m³. The Transbrazilian Lineament, which separates the Pampia terrane from the Río de la Plata craton, is expressed as a zone of low average crustal densities.
In an excursion, we demonstrate in another study, that the gravity inversion method developed to obtain intra-crustal density structures, is also applicable to obtain density variations in the uppermost lithospheric mantle. Densities in such sub-crustal depths are difficult to constrain from seismic tomographic models due to smearing of crustal velocities. With the application to the uppermost lithospheric mantle in the north Atlantic, we demonstrate in Tan et al. (2018) that lateral density trends of at least 125\,km width are robustly recovered by the inversion method, thereby providing an important tool for the delineation of subcrustal density trends.
Due to the genetic link between subduction, orogenesis and retroarc foreland basins the question rises whether the steady-state assumption is valid in such a dynamic setting. To answer this question, I analysed (i) the impact of subduction on the conductive thermal field of the overlying continental plate, (ii) the differences between the transient and steady-state thermal fields of a geodynamic coupled model. Both studies indicate that the assumption of a thermal steady-state is applicable in most parts of the study area. Within the orogenic wedge, where the assumption cannot be applied, I estimated the transient thermal field based on the results of the conducted analyses.
Accordingly, the structural model that had been obtained in the first step, could be used to obtain a 3D conductive steady-state thermal field. The rheological assessment based on this thermal field indicates that the lithosphere of the thin-skinned Subandean ranges is characterised by a relatively strong crust and a weak mantle. Contrarily, the adjacent foreland basin consists of a fully coupled, very strong lithosphere. Thus, shortening in northern Argentina can only be accommodated within the weak lithosphere of the orogen and the Subandean ranges. The analysis suggests that the décollements of the fold-and-thrust belt are the shallow continuation of shear zones that reside in the ductile sections of the orogenic crust. Furthermore, the localisation of the faults that provide strain transfer between the deeper ductile crust and the shallower décollement is strongly influenced by crustal weak zones such as foliation. In contrast to the northern foreland, the lithosphere of the thick-skinned Sierras Pampeanas is fully coupled and characterised by a strong crust and mantle. The high overall strength prevents the generation of crustal-scale faults by tectonic stresses. Even inherited crustal-scale discontinuities, such as sutures, cannot sufficiently reduce the strength of the lithosphere in order to be reactivated. Therefore, magmatism that had been identified to be a precursor of basement uplift in the Sierras Pampeanas, is the key factor that leads to the broken foreland of this province. Due to thermal weakening, and potentially lubrication of the inherited discontinuities, the lithosphere is locally weakened such that tectonic stresses can uplift the basement blocks. This hypothesis explains both the spatially disparate character of the broken foreland, as well as the observed temporal delay between volcanism and basement block uplift.
This dissertation provides for the first time a data-driven 3D model that is consistent with geophysical data and geological observations, and that is able to causally link the thermo-rheological structure of the lithosphere to the observed variation of surface deformation styles in the retroarc foreland of northern Argentina.
Untersuchungen an neuartigen sauerstoffsubstituierten Donoren und Akzeptoren für Singulettsauerstoff
(2019)
Im Verlauf dieser Arbeit wurden Aromaten wie Naphthaline und Anthracene mit Singulettsauerstoff, einer reaktiven Form des gewöhnlichen Sauerstoffs, zu sogenannten Endoperoxiden umgesetzt. Die hier eingesetzten Systeme wurden mit funktionellen Gruppen modifiziert, die über eine Sauerstoffbrücke mit dem Aromaten verknüpft sind. Die daraus entstandenen Endoperoxide sind meist besonders labil und konnten in dieser Arbeit isoliert und umfassend untersucht werden.
Hierbei wurde zum einen das Reaktionsverhalten untersucht. Es konnte gezeigt werden, dass die Aromaten in Abhängigkeit ihrer funktionellen Gruppen unterschiedlich schnell mit Singulettsauerstoff reagieren. Die so ermittelten Reaktivitäten wurden zusätzlich durch theoretische Berechnungen gestützt.
Die resultierenden Endoperoxide wurden unter verschiedenen Bedingungen wie erhöhter Temperatur oder einem sauren bzw. basischen Milieu auf ihre Stabilität hin untersucht. Dabei konnte gezeigt werden, dass die auf Naphthalinen basierenden Endoperoxiden den gebundenen Singulettsauerstoff in guten Ausbeuten oft schon bei sehr niedrigen Temperaturen (−40 bis 0 °C) freisetzen. Diese Verbindungen können daher als milde Quellen dieser reaktiven Sauerstoffspezies eingesetzt werden. Weiterhin konnten bei den Anthracenendoperoxiden Zerfallsmechanismen aufgeklärt und andere reaktive Sauerstoffspezies wie Wasserstoffperoxid oder Persäuren nachgewiesen werden.
Zu den Modifikationen der Aromaten gehören auch Glucosereste. Dadurch könnten sich die hier hergestellten Endoperoxide als vielversprechende Verbindungen in der Krebstherapie herausstellen, da Krebszellen deutlich stärker als gesunde Zellen kohlenhydratreiche Verbindungen für ihren Stoffwechsel benötigen. Bei der Spaltung von Endoperoxiden mit Glucosesubstituenten werden ebenfalls reaktive Sauerstoffspezies frei, die so zum Zelltod führen könnten.
Partial melting is a first order process for the chemical differentiation of the crust (Vielzeuf et al., 1990). Redistribution of chemical elements during melt generation crucially influences the composition of the lower and upper crust and provides a mechanism to concentrate and transport chemical elements that may also be of economic interest. Understanding of the diverse processes and their controlling factors is therefore not only of scientific interest but also of high economic importance to cover the demand for rare metals.
The redistribution of major and trace elements during partial melting represents a central step for the understanding how granite-bound mineralization develops (Hedenquist and Lowenstern, 1994). The partial melt generation and mobilization of ore elements (e.g. Sn, W, Nb, Ta) into the melt depends on the composition of the sedimentary source and melting conditions. Distinct source rocks have different compositions reflecting their deposition and alteration histories. This specific chemical “memory” results in different mineral assemblages and melting reactions for different protolith compositions during prograde metamorphism (Brown and Fyfe, 1970; Thompson, 1982; Vielzeuf and Holloway, 1988). These factors do not only exert an important influence on the distribution of chemical elements during melt generation, they also influence the volume of melt that is produced, extraction of the melt from its source, and its ascent through the crust (Le Breton and Thompson, 1988). On a larger scale, protolith distribution and chemical alteration (weathering), prograde metamorphism with partial melting, melt extraction, and granite emplacement are ultimately depending on a (plate-)tectonic control (Romer and Kroner, 2016). Comprehension of the individual stages and their interaction is crucial in understanding how granite-related mineralization forms, thereby allowing estimation of the mineralization potential of certain areas. Partial melting also influences the isotope systematics of melt and restite. Radiogenic and stable isotopes of magmatic rocks are commonly used to trace back the source of intrusions or to quantify mixing of magmas from different sources with distinct isotopic signatures (DePaolo and Wasserburg, 1979; Lesher, 1990; Chappell, 1996). These applications are based on the fundamental requirement that the isotopic signature in the melt reflects that of the bulk source from which it is derived. Different minerals in a protolith may have isotopic compositions of radiogenic isotopes that deviate from their whole rock signature (Ayres and Harris, 1997; Knesel and Davidson, 2002). In particular, old minerals with a distinct parent-to-daughter (P/D) ratio are expected to have a specific radiogenic isotope signature. As the partial melting reaction only involves selective phases in a protolith, the isotopic signature of the melt reflects that of the minerals involved in the melting reaction and, therefore, should be different from the bulk source signature. Similar considerations hold true for stable isotopes.
A reliable inference of networks from data is of key interest in many scientific fields. Several methods have been suggested in the literature to reliably determine links in a network. These techniques rely on statistical methods, typically controlling the number of false positive links, but not considering false negative links. In this thesis new methodologies to improve network inference are suggested. Initial analyses demonstrate the impact of falsepositive and false negative conclusions about the presence or absence of links on the resulting inferred network. Consequently, revealing the importance of making well-considered choices leads to suggest new approaches to enhance existing network reconstruction methods.
A simulation study, presented in Chapter 3, shows that different values to balance false positive and false negative conclusions about links should be used in order to reliably estimate network characteristics. The existence of type I and type II errors in the reconstructed network, also called biased network, is accepted. Consequently, an analytic method that describes the influence of these two errors on the network structure is explored. As a result of this analysis, an analytic formula of the density of the biased vertex degree distribution is found (Chapter 4).
In the inverse problem, the vertex degree distribution of the true underlying network is analytically reconstructed, assuming the probabilities of type I and type II errors. Chapters 4-5 show that the method is robust to incorrect estimates of α and β within reasonable limits. In Chapter 6, an iterative procedure to enhance this method is presented in the case of large errors on the estimates of α and β.
The investigations presented so far focus on the influence of false positive and false negative links on the network characteristics. In Chapter 7, the analysis is reversed - the study focuses on the influence of network characteristics on the probability of type I and type II errors, in the case of networks of coupled oscillators. The probabilities of α and β are influenced by the shortest path length and the detour degree, respectively. These results have been used to improve the network reconstruction, when the true underlying network is not known a priori, introducing a novel and advanced concept of threshold.
Einleitung
Die Implantation einer Knie- oder Hüft-Totalendoprothese (TEP) ist eine der häufigsten operativen Eingriffe. Im Anschluss an die Operation und die postoperative Rehabilitation stellt die Bewegungstherapie einen wesentlichen Bestandteil der Behandlung zur Verbesserung der Gelenkfunktion und der Lebensqualität dar. In strukturschwachen Gebieten werden entsprechende Angebote nur in unzureichender Dichte vorgehalten. Zudem zeichnet sich ein flächendeckender Fachkräftemangel im Bereich der Physiotherapie ab. Die Tele-Nachsorge bietet daher einen innovativen Ansatz für die postrehabilitative Versorgung der Patienten. Das Ziel der vorliegenden Untersuchung war die Überprüfung der Wirksamkeit einer interaktiven Tele-Nachsorgeintervention für Patienten mit Knie- oder Hüft-TEP im Vergleich zur herkömmlichen Versorgung (usual care). Dazu wurden die Funktionalität und die berufliche Wiedereingliederung untersucht.
Methode
Zwischen August 2016 und August 2017 wurden 111 Patienten (54,9 ± 6,8 Jahre, 54,3 % weiblich) zu Beginn ihrer stationären Anschlussheilbehandlung nach Implantation einer Knie- oder Hüft-TEP in diese randomisiert, kontrolliert, multizentrische Studie eingeschlossen. Nach Entlassung aus der orthopädischen Anschlussrehabilitation (Baseline) führte die Interventionsgruppe (IG) ein dreimonatiges interaktives Training über ein Telerehabilitationssystem durch. Hierfür erstellte ein betreuender Physiotherapeut einen individuellen Trainingsplan aus 38 Übungen zur Verbesserung der Kraft sowie der posturalen Kontrolle. Zur Anpassung des Trainingsplans übermittelte das System dem Physiotherapeuten Daten zur Quantität sowie zur Qualität des Trainings. Die Kontrollgruppe (KG) konnte die herkömmlichen Versorgungsangebote nutzen. Zur Beurteilung der Wirksamkeit der Intervention wurde die Differenz der Verbesserung im 6MWT zwischen der IG und der KG nach drei Monaten als primärer Endpunkt definiert. Als sekundäre Endpunkte wurden die Return-to-Work-Rate sowie die funktionelle Mobilität mittels des Stair Ascend Tests, des Five-Times-Sit-to-Stand Test und des Timed Up and Go Tests untersucht. Weiterhin wurden die gesundheitsbezogene Lebensqualität mit dem Short-Form 36 (SF-36) und die gelenkbezogenen Einschränkungen mit dem Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) evaluiert. Der primäre und die sekundären Endpunkte wurden anhand von baseline-adjustierten Kovarianzanalysen im intention-to-treat-Ansatz ausgewertet. Zusätzlich wurde die Teilnahme an Nachsorgeangeboten und die Adhärenz der Interventionsgruppe an der Tele-Nachsorge erfasst und evaluiert.
Ergebnisse
Zum Ende der Intervention wiesen beide Gruppen einen statistisch signifikanten Anstieg ihrer 6MWT Strecke auf (p < 0,001). Zu diesem Zeitpunkt legten die Teilnehmer der IG im Mittel 530,8 ± 79,7 m, die der KG 514,2 ± 71,2 m zurück. Dabei betrug die Differenz der Verbesserung der Gehstrecke in der IG 88,3 ± 57,7 m und in der KG 79,6 ± 48,7 m. Damit zeigt der primäre Endpunkt keine signifikanten Gruppenunterschiede (p = 0,951). Bezüglich der beruflichen Wiedereingliederung konnte jedoch eine signifikant höhere Rate in der IG (64,6 % versus 46,2 %; p = 0,014) festgestellt werden. Für die sekundären Endpunkte der funktionellen Mobilität, der Lebensqualität und der gelenkbezogenen Beschwerden belegen die Ergebnisse eine Gleichwertigkeit beider Gruppen zum Ende der Intervention.
Schlussfolgerung
Die telemedizinisch assistierte Bewegungstherapie für Knie- oder Hüft-TEP Patienten ist der herkömmlichen Versorgung zur Nachsorge hinsichtlich der erzielten Verbesserungen der funktionellen Mobilität, der gesundheitsbezogenen Lebensqualität und der gelenkbezogenen Beschwerden gleichwertig. In dieser Patientenpopulation ließen sich klinisch relevante Verbesserungen unabhängig von der Form der Bewegungstherapie erzielen. Im Hinblick auf die berufliche Wiedereingliederung zeigte sich eine signifikant höhere Rate in der Interventionsgruppe. Die telemedizinisch assistierte Bewegungstherapie scheint eine geeignete Versorgungsform der Nachsorge zu sein, die orts- und zeitunabhängig durchgeführt werden kann und somit den Bedürfnissen berufstätiger Patienten entgegenkommt und in den Alltag der Patienten integriert werden kann. Die Tele-Nachsorge sollte daher als optionale und komplementäre Form der postrehabilitativen Nachsorge angeboten werden. Auch im Hinblick auf den zunehmenden Fachkräftemangel im Bereich der Physiotherapie und bestehende Versorgungslücken in strukturschwachen Gebieten kann der Einsatz der Tele-Nachsorge innovative und bedarfsgerechte Lösungsansätze bieten.
The goal of this thesis is to broaden the empirical basis for a better, comprehensive understanding
of massive star evolution, star formation and feedback at low metallicity. Low metallicity massive stars are a key to understand the early universe. Quantitative information on metal-poor massive stars was sparse before. The quantitative spectroscopic studies of massive star populations associated with large-scale ISM structures were not performed at low metallicity before, but are important to investigate star-formation histories and feedback in detail. Much of this work relies on spectroscopic observations with VLT-FLAMES of ~500 OB stars in the Magellanic Clouds. When available, the optical spectroscopy was complemented by UV spectra from the HST, IUE, and FUSE archives. The two representative young stellar populations that have been studied are associated with the superbubble N 206 in the Large Magellanic Cloud (LMC) and with the supergiant shell SMC-SGS 1 in the Wing of the Small Magellanic Cloud (SMC), respectively. We performed spectroscopic analyses of the massive stars using the nonLTE Potsdam Wolf-Rayet (PoWR) model atmosphere code. We estimated the stellar, wind, and feedback parameters of the individual massive stars and established their statistical distributions.
The mass-loss rates of N206 OB stars are consistent with theoretical expectations for LMC metallicity. The most massive and youngest stars show nitrogen enrichment at their surface and are found to be slower rotators than the rest of the sample. The N 206 complex has undergone star formation episodes since more than 30 Myr, with a current star formation rate higher than average in the LMC. The spatial age distribution of stars across the complex possibly indicates triggered star formation due to the expansion of the superbubble. Three very massive, young Of stars in the region dominate the ionizing and mechanical feedback among hundreds of other OB stars in the sample. The current stellar wind feedback rate from the two WR stars in the complex is comparable to that released by the whole OB sample. We see only a minor fraction of this stellar wind feedback converted into X-ray emission. In this LMC complex, stellar winds and supernovae equally contribute to the total energy feedback, which eventually powered the central superbubble. However, the total energy input accumulated over the time scale of the superbubble significantly exceeds the observed energy content of the complex. The lack of energy along with the morphology of the complex suggests a leakage of hot gas from the superbubble.
With a detailed spectroscopic study of massive stars in SMC-SGS 1, we provide the stellar and wind parameters of a large sample of OB stars at low metallicity, including those in the lower mass-range. The stellar rotation velocities show a broad, tentatively bimodal distribution, with Be stars being among the fastest. A few very luminous O stars are found close to the main sequence, while all other, slightly evolved stars obey a strict luminosity limit. Considering additional massive stars in evolved stages, with published parameters and located all over the SMC, essentially confirms this picture. The comparison with single-star evolutionary tracks suggests a dichotomy in the fate of massive stars in the SMC. Only stars with an initial mass below 30 solar masses seem to evolve from the main sequence to the cool side of the HRD to become a red supergiant and to explode as type II-P supernova. In contrast, more massive stars appear to stay always hot and might evolve quasi chemically homogeneously, finally collapsing to relatively massive black holes. However, we find no indication that chemical mixing is correlated with rapid rotation. We measured the key parameters of stellar feedback and established the links between the rates of star formation and supernovae. Our study demonstrates that in metal-poor environments stellar feedback is dominated by core-collapse supernovae in combination with winds and ionizing radiation supplied by a few of the most massive stars. We found indications of the stochastic mode of star formation, where the resulting stellar population is fully capable of producing large-scale structures such as the supergiant shell SMC-SGS 1 in the Wing. The low level of feedback in metal-poor stellar populations allows star formation episodes to persist over long timescales.
Our study showcases the importance of quantitative spectroscopy of massive stars with adequate stellar-atmosphere models in order to understand star-formation, evolution, and feedback. The stellar population analyses in the LMC and SMC make us understand that massive stars and their impact can be very different depending on their environment. Obviously, due to their different metallicity, the massive stars in the LMC and the SMC follow different evolutionary paths. Their winds differ significantly, and the key feedback agents are different. As a consequence, the star formation can proceed in different modes.
C-Arylglykoside und Chalkone
(2019)
Im bis heute andauernden Zeitalter der wissenschaftlichen Medizin, konnte ein breites Spektrum von Wirkstoffen zur Behandlung diverser Krankheiten zusammengetragen werden. Dennoch hat es sich die organische Synthesechemie zur Aufgabe gemacht, dieses Spektrum auf neuen oder bekannten Wegen und aus verschiedenen Gründen zu erweitern. Zum einen ist das Vorkommen bestimmter Verbindungen in der Natur häufig limitiert, sodass synthetische Methoden immer öfter an Stelle eines weniger nachhaltigen Abbaus treten. Zum anderen kann durch Derivatisierung und Wirkstoffanpassung die physiologische Wirkung oder die Bioverfügbarkeit eines Wirkstoffes erhöht werden. In dieser Arbeit konnten einige Vertreter der bekannten Wirkstoffklassen C-Arylglykoside und Chalkone durch den Schlüsselschritt der Palladium-katalysierten MATSUDA-HECK-Reaktion synthetisiert werden.
Dazu wurden im Fall der C-Arylglykoside zunächst ungesättigte Kohlenhydrate (Glykale) über eine Ruthenium-katalysierte Zyklisierungsreaktion dargestellt. Diese wurden im Anschluss mit unterschiedlich substituierten Diazoniumsalzen in der oben erwähnten Palladium-katalysierten Kupplungsreaktion zur Reaktion gebracht. Bei der Auswertung der analytischen Daten konnte festgestellt werden, dass stets die trans-Diastereomere gebildet wurden. Im Anschluss konnte gezeigt werden, dass die Doppelbindungen dieser Verbindungen durch Hydrierung, Dihydroxylierung oder Epoxidierung funktionalisiert werden können. Auf diesem Wege konnte u. a. eine dem Diabetesmedikament Dapagliflozin ähnliche Verbindung hergestellt werden.
Im zweiten Teil der Arbeit wurden Arylallylchromanone durch die MATSUDA-HECK-Reaktion von verschiedenen 8-Allylchromanonen mit Diazoniumsalzen dargestellt. Dabei konnte beobachtet werden, dass eine MOM-Schutzgruppe in 7-Position der Moleküle die Darstellung von Produktgemischen unterdrückt und jeweils nur eine der möglichen Verbindungen gebildet wird. Die Lage der Doppelbindung konnte mittels 2D-NMR-Untersuchungen lokalisiert werden. In Kooperation mit der theoretischen Chemie sollte durch Berechnungen untersucht werden, wie die beobachteten Verbindungen entstehen. Durch eine auftretende Wechselwirkung innerhalb des Moleküls konnte allerdings keine explizite Aussage getroffen werden.
Im Anschluss sollten die erhaltenen Verbindungen in einer allylischen Oxidation zu Chalkonen umgesetzt werden. Die Ruthenium-katalysierten Methoden zeigten u. a. keine Eignung. Es konnte allerdings eine metallfreie, Mikrowellen-unterstützte Methode erfolgreich erprobt werden, sodass die Darstellung einiger Vertreter dieser physiologisch aktiven Stoffklasse gelang.
Das Preußische Erbrecht in der Judikatur des Berliner Obertribunals in den Jahren 1836 bis 1865
(2019)
Die Dissertation befasst sich mit dem Allgemeinen Preußischen Landrecht von 1794 und der hierzu ergangenen Rechtsprechung des Berliner Obertribunals. Im Fokus der Untersuchung stehen die erbrechtlichen Regelungen des Landrechts und deren Anwendung sowie Auslegung in der Judikatur des höchsten preußischen Gerichts. Der Forschungsgegenstand ergibt sich aus dem im Landrecht kodifizierten speziellen Gesetzesverständnisses. Nach diesem sollte die Gesetzesauslegung durch die Rechtsprechung auf ein Minimum, nämlich die Auslegung allein anhand des Wortlauts der Regelung reduziert werden, um dem absolutistischen Regierungsanspruch der preußischen Monarchen, namentlich Friedrich des Großen, hinreichend Rechnung zu tragen. In diesem Kontext wird der Frage nachgegangen, inwieweit das preußische Obertribunal das im Landrecht statuierte „Auslegungsverbot“ beachtet hat und in welchen Fällen sich das Gericht von der Vorgabe emanzipierte und weitere Auslegungsmethoden anwendete und sich so eine unabhängige Rechtsprechung entwickeln konnte.
Die Arbeit gliedert sich in drei Hauptabschnitte. Im Anschluss an die Einleitung, in der zunächst die rechtshistorische Bedeutung des Landrechts und des Erbrechts sowie der Untersuchungsgegenstand umrissen werden, folgt die Darstellung der Entstehungsgeschichte des Landrechts und des Berliner Obertribunals.
Hieran schließt sich in einem dritten Abschnitt eine Analyse der erbrechtlichen Vorschriften des Landrechts an. In dieser wird auf die Entstehungsgeschichte der verschiedenen erbrechtlichen Institute wie beispielsweise der gesetzlichen und gewillkürten Erbfolge, dem Pflichtteilsrecht etc., unter Berücksichtigung des zeitgenössischen wissenschaftlichen Diskurses eingegangen.
Im vierten Abschnitt geht es um die Judikate des Berliner Obertribunals aus den Jahren 1836-1865 in denen die zuvor dargestellten erbrechtlichen Regelungen entscheidungserheblich waren. Dabei wird der Forschungsfrage, inwieweit das Obertribunal das im Landrecht statuierte Auslegungsverbot beachtet hat und in welchen Fällen es von diesem abwich bzw. weitere Auslegungsmethoden anwendete, konkret nachgegangen wird. Insgesamt werden 26 Entscheidungen des Obertribunals unter dem Aspekt der Auslegungspraxis, der Kontinuität und der Beschleunigung der Rechtsprechung analysiert und ausgewertet.
Vom Monomer zum Glykopolymer
(2019)
Glykopolymere sind synthetische und natürlich vorkommende Polymere, die eine Glykaneinheit in der Seitenkette des Polymers tragen. Glykane sind durch die Glykan-Protein-Wechselwirkung verantwortlich für viele biologische Prozesse. Die Beteiligung der Glykanen in diesen biologischen Prozessen ermöglicht das Imitieren und Analysieren der Wechselwirkungen durch geeignete Modellverbindungen, z.B. der Glykopolymere. Dieses System der Glykan-Protein-Wechselwirkung soll durch die Glykopolymere untersucht und studiert werden, um die spezifische und selektive Bindung der Proteine an die Glykopolymere nachzuweisen. Die Proteine, die in der Lage sind, Kohlenhydratstrukturen selektiv zu binden, werden Lektine genannt.
In dieser Dissertationsarbeit wurden verschiedene Glykopolymere synthetisiert. Dabei sollte auf einen effizienten und kostengünstigen Syntheseweg geachtet werden.
Verschiedene Glykopolymere wurden durch funktionalisierte Monomere mit verschiedenen Zuckern, wie z.B. Mannose, Laktose, Galaktose oder N-Acetyl-Glukosamin als funktionelle Gruppe, hergestellt. Aus diesen funktionalisierten Glykomonomeren wurden über ATRP und RAFT-Polymerisation Glykopolymere synthetisiert.
Die erhaltenen Glykopolymere wurden in Diblockcopolymeren als hydrophiler Block angewendet und die Selbstassemblierung in wässriger Lösung untersucht. Die Polymere formten in wässriger Lösung Mizellen, bei denen der Zuckerblock an der Oberfläche der Mizellen sitzt. Die Mizellen wurden mit einem hydrophoben Fluoreszenzfarbstoff beladen, wodurch die CMC der Mizellenbildung bestimmt werden konnte.
Außerdem wurden die Glykopolymere als Oberflächenbeschichtung über „Grafting from“ mit SI-ATRP oder über „Grafting to“ auf verschiedene Oberflächen gebunden. Durch die glykopolymerbschichteten Oberflächen konnte die Glykan Protein Wechselwirkung über spektroskopische Messmethoden, wie SPR- und Mikroring Resonatoren untersucht werden. Hierbei wurde die spezifische und selektive Bindung der Lektine an die Glykopolymere nachgewiesen und die Bindungsstärke untersucht.
Die synthetisierten Glykopolymere könnten durch Austausch der Glykaneinheit für andere Lektine adressierbar werden und damit ein weites Feld an anderen Proteinen erschließen. Die bioverträglichen Glykopolymere wären alternativen für den Einsatz in biologischen Prozessen als Transporter von Medikamenten oder Farbstoffe in den Körper. Außerdem könnten die funktionalisierten Oberflächen in der Diagnostik zum Erkennen von Lektinen eingesetzt werden. Die Glykane, die keine selektive und spezifische Bindung zu Proteinen eingehen, könnten als antiadsorptive Oberflächenbeschichtung z.B. in der Zellbiologie eingesetzt werden.
Seit 2003 hat sich das politische Bild des Irak stark verändert. Dadurch begann der Prozess der Neugestaltung der irakischen Rechtsordnung. Die irakische Verfassung von 2005 legt erstmalig in der Geschichte des Irak den Islam und die Demokratie als zwei nebeneinander zu beachtende Grundprinzipien bei der Gesetzgebung fest. Trotz dieser signifikanten Veränderung im irakischen Rechtssystem und erheblicher Entwicklungen im internationalen Privat- und Zivilverfahrensrecht (IPR/IZVR) im internationalen Vergleich gilt die hauptsächlich im irakischen Zivilgesetzbuch (ZGB) von 1951 enthaltene gesetzliche Regelung des IPR/IZVR im Irak weiterhin. Deshalb entstand diese Arbeit für eine Reformierung des irakischen IPR/IZVR.
Die Arbeit gilt als erste umfassende wissenschaftliche Untersuchung, die sich mit dem jetzigen Inhalt und der zukünftigen Reformierung des irakischen internationalen Privatrecht- und Zivilverfahrensrechts (IPR/IZVR) beschäftigt.
Die Verfasserin vermittelt einen Gesamtüberblick über das jetzt geltende irakische internationale Privat- und Zivilverfahrensrecht mit gelegentlicher punktueller und stichwortartiger Heranziehung des deutschen, islamischen, türkischen und tunesischen Rechts, zeigt dessen Schwachstellen auf und unterbreitet entsprechende Reformvorschläge.
Wegen der besonderen Bedeutung des internationalen Vertragsrechts für die Wirtschaft im Irak und auch zum Teil für Deutschland gibt die Verfasserin einen genaueren Überblick über das irakische internationale Vertragsrecht und bekräftigt gleichzeitig dessen Reformbedürftigkeit.
Die Darstellung der wichtigen Entwicklungen im deutsch-europäischen, im traditionellen islamischen Recht und im türkischen und tunesischen internationalen Privat- und Zivilverfahrensrecht im zweiten Kapitel dienen als Grundlage, auf die bei der Reformierung des irakischen IPR/ IZVR zurück gegriffen werden kann. Da die Kenntnisse des islamischen Rechts nicht zwingend zum Rechtsstudium gehören, wird das islamische Recht dazu in Bezug auf seine Entstehung und die Rechtsquellen dargestellt.
Am Ende der Arbeit wird ein Entwurf eines föderalen Gesetzes zum internationalen Privatrecht im Irak katalogisiert, der sich im Rahmen der irakischen Verfassung gleichzeitig mit dem Islam und der Demokratie vereinbaren lässt.
Die Anfechtbarkeit und die Feststellbarkeit der Mutterschaft de lege lata und de lege ferenda
(2019)
Der althergebrachte Grundsatz, wonach das Kind von der Frau abstammt, welche es geboren hat, ist durch die moderne Fortpflanzungsmedizin ins Wanken geraten. Dennoch ordnet § 1591 BGB das Kind unanfechtbar der Geburtsmutter zu. Rechtliche und genetische Mutterschaft fallen deshalb dauerhaft auseinander, wenn das Kind im Wege der Leihmutterschaft oder nach einer Eizell- bzw. Embryospende zur Welt kommt. Die auf diese Methoden der artifiziellen Reproduktion bezogenen, im Inland bestehenden Verbote halten Paare mit Kinderwunsch nicht davon ab, auf entsprechende Angebote im Ausland zurückzugreifen. Daraus resultierende kollisions- und verfassungsrechtliche Probleme sind Gegenstand der vorliegenden Arbeit.
Für den Bereich der Leihmutterschaft wird der Frage nachgegangen, ob die mit dem Anfechtungsausschluss verfolgten Ziele des Gesetzgebers die damit einhergehenden Beeinträchtigungen grundrechtlich geschützter Rechtspositionen von genetischer Mutter und Kind rechtfertigen können. Besonderes Augenmerk liegt auf dem von Art. 6 Abs. 2 S. 1 GG geschützten Interesse von leiblichen Eltern und Kindern, die verfahrensrechtliche Möglichkeit zu erhalten, rechtlich einander zugeordnet zu werden. Dieses Interesse wird den Zielen des Gesetzgebers, der mit dem Anfechtungsausschluss die Rechte von Leihmüttern und Kindern zu schützen beabsichtigt, im Rahmen einer umfassenden Verhältnismäßigkeitsprüfung gegenübergestellt.
In den Konstellationen der Eizell- und Embryospende tritt schwerpunktmäßig das Recht des Kindes auf Kenntnis der eigenen Abstammung in den Vordergrund und mit ihm die Frage, ob sich daraus eine Verpflichtung des Gesetzgebers ableiten lässt, den Tatbestand von § 1598a BGB so zu erweitern, dass die vermuteten genetischen Eltern für den Bereich der artifiziellen Reproduktion in den Kreis der Klärungsverpflichteten aufgenommen werden.
Neben diesen Schwerpunkten werden viele weitere Probleme angesprochen. Im Ergebnis mündet die Arbeit in einen Vorschlag für die Legislative.
Der historische Spielfilm zählt zu den populärsten Formen geschichtskultureller Artikulation. Als solche ist er Gegenstand kontroverser Diskussionen über einen angemessenen didaktischen Umgang. Vor diesem Hintergrund ist es das Ziel der vorliegenden Arbeit, ein integratives, theoretisch und empirisch abgesichertes Analysemodell zu entwickeln, das nach den Tiefenstrukturen historischen Erzählens im Medium des Spielfilms fragt und dabei unterschiedliche Erscheinungsformen historischer Spielfilme berücksichtigt. Die Überlegungen bewegen sich deshalb in einem interdisziplinären Spannungsfeld von Theorien zum historischen Erzählen und Konzepten der Literatur- und Filmwissenschaft. Die Diskussion und Synthese dieser unterschiedlichen Konzepte geht dabei – auf der Grundlage einer großen Materialbasis – vom Gegenstand aus und ist induktiv angelegt. Als Orientierung für die praktische Arbeit werden am Ende der einzelnen Kapitel Toolkits entwickelt, die zu einer vertieften Auseinandersetzung mit historischen Spielfilmen anregen sollen.
The thesis comprises three experimental studies, which were carried out to unravel the short- as well as the long-term mechanical properties of shale rocks. Short-term mechanical properties such as compressive strength and Young’s modulus were taken from recorded stress-strain curves of constant strain rate tests. Long-term mechanical properties are represented by the time– dependent creep behavior of shales. This was obtained from constant stress experiments, where the test duration ranged from a couple minutes up to two weeks. A profound knowledge of the mechanical behavior of shales is crucial to reliably estimate the potential of a shale reservoir for an economical and sustainable extraction of hydrocarbons (HC). In addition, healing of clay-rich forming cap rocks involving creep and compaction is important for underground storage of carbon dioxide and nuclear waste.
Chapter 1 introduces general aspects of the research topic at hand and highlights the motivation for conducting this study. At present, a shift from energy recovered from conventional resources e.g., coal towards energy provided by renewable resources such as wind or water is a big challenge. Gas recovered from unconventional reservoirs (shale plays) is considered a potential bridge technology.
In Chapter 2, short-term mechanical properties of two European mature shale rocks are presented, which were determined from constant strain rate experiments performed at ambient and in situ deformation conditions (confining pressure, pc ≤ 100 MPa, temperature, T ≤ 125 °C, representing pc, T - conditions at < 4 km depth) using a Paterson– type gas deformation apparatus. The investigated shales were mainly from drill core material of Posidonia (Germany) shale and weathered material of Bowland (United Kingdom) shale. The results are compared with mechanical properties of North American shales. Triaxial compression tests performed perpendicular to bedding revealed semibrittle deformation behavior of Posidonia shale with pronounced inelastic deformation. This is in contrast to Bowland shale samples that deformed brittle and displayed predominantly elastic deformation. The static Young’s modulus, E, and triaxial compressive strength, σTCS, determined from recorded stress-strain curves strongly depended on the applied confining pressure and sample composition, whereas the influence of temperature and strain rate on E and σTCS was minor. Shales with larger amounts of weak minerals (clay, mica, total organic carbon) yielded decreasing E and σTCS. This may be related to a shift from deformation supported by a load-bearing framework of hard phases (e.g., quartz) towards deformation of interconnected weak minerals, particularly for higher fractions of about 25 – 30 vol% weak phases. Comparing mechanical properties determined at reservoir conditions with mechanical data applying effective medium theories revealed that E and σTCS of Posidonia and Bowland shale are close to the lower (Reuss) bound. Brittleness B is often quoted as a measure indicating the response of a shale formation to stimulation and economic production. The brittleness, B, of Posidonia and Bowland shale, estimated from E, is in good agreement with the experimental results. This correlation may be useful to predict B from sonic logs, from which the (dynamic) Young’s modulus can be retrieved.
Chapter 3 presents a study of the long-term creep properties of an immature Posidonia shale. Constant stress experiments (σ = const.) were performed at elevated confining pressures (pc = 50 – 200 MPa) and temperatures (T = 50 – 200 °C) to simulate reservoir pc, T - conditions. The Posidonia shale samples were acquired from a quarry in South Germany. At stresses below ≈ 84 % compressive strength of Posidonia shale, at high temperature and low confining pressure, samples showed pronounced transient (primary) creep with high deformation rates in the semibrittle regime. Sample deformation was mainly accommodated by creep of weak sample constituents and pore space reduction. An empirical power law relation between strain and time, which also accounts for the influence of pc, T and σ on creep strain was formulated to describe the primary creep phase. Extrapolation of the results to a creep period of several years, which is the typical time interval for a large production decline, suggest that fracture closure is unlikely at low stresses. At high stresses as expected for example at the contact between the fracture surfaces and proppants added during stimulation measures, subcritical crack growth may lead to secondary and tertiary creep. An empirical power law is suggested to describe secondary creep of shale rocks as a function of stress, pressure and temperature. The predicted closure rates agree with typical production decline curves recorded during the extraction of hydrocarbons. At the investigated conditions, the creep behavior of Posidonia shale was found to correlate with brittleness, calculated from sample composition.
In Chapter 4 the creep properties of mature Posidonia and Bowland shales are presented. The observed long-term creep behavior is compared to the short-term behavior determined in Chapter 2. Creep experiments were performed at simulated reservoir conditions of pc = 50 – 115 MPa and T = 75 – 150 °C. Similar to the mechanical response of immature Posidonia shale samples investigated in Chapter 3, creep strain rates of mature Bowland and Posidonia shales were enhanced with increasing stress and temperature and decreasing confining pressures. Depending on applied deformation conditions, samples displayed either only a primary (decelerating) or in addition also a secondary (quasi-steady state) and subsequently a tertiary (accelerating) creep phase before failure. At the same deformation conditions, creep strain of Posidonia shale, which is rich in weak constituents, is tremendously higher than of quartz-rich Bowland shale. Typically, primary creep strain is again mostly accommodated by deformation of weak minerals and local pore space reduction. At the onset of tertiary creep most of the deformation was accommodated by micro crack growth. A power law was used to characterize the primary creep phase of Posidonia and Bowland shale. Primary creep strain of shale rocks is inversely correlated to triaxial compressive strength and brittleness, as described in Chapter 2.
Chapter 5 provides a synthesis of the experimental findings and summarizes the major results of the studies presented in Chapters 2 – 4 and potential applications in the Exploration & Production industry.
Chapter 6 gives a brief outlook on potential future experimental research that would help to further improve our understanding of processes leading to fracture closure involving proppant embedment in unconventional shale gas reservoirs. Such insights may allow to improve stimulation techniques aimed at maintaining economical extraction of hydrocarbons over several years.
The current thesis examined how second language (L2) speakers of German predict upcoming input during language processing. Early research has shown that the predictive abilities of L2 speakers relative to L1 speakers are limited, resulting in the proposal of the Reduced Ability to Generate Expectations (RAGE) hypothesis. Considering that prediction is assumed to facilitate language processing in L1 speakers and probably plays a role in language learning, the assumption that L1/L2 differences can be explained in terms of different processing mechanisms is a particularly interesting approach. However, results from more recent studies on the predictive processing abilities of L2 speakers have indicated that the claim of the RAGE hypothesis is too broad and that prediction in L2 speakers could be selectively limited. In the current thesis, the RAGE hypothesis was systematically put to the test.
In this thesis, German L1 and highly proficient late L2 learners of German with Russian as L1 were tested on their predictive use of one or more information sources that exist as cues to sentence interpretation in both languages, to test for selective limits. The results showed that, in line with previous findings, L2 speakers can use the lexical-semantics of verbs to predict the upcoming noun. Here the level of prediction was more systematically controlled for than in previous studies by using verbs that restrict the selection of upcoming nouns to the semantic category animate or inanimate. Hence, prediction in L2 processing is possible. At the same time, this experiment showed that the L2 group was slower/less certain than the L1 group. Unlike previous studies, the experiment on case marking demonstrated that L2 speakers can use this morphosyntactic cue for prediction. Here, the use of case marking was tested by manipulating the word order (Dat > Acc vs. Acc > Dat) in double object constructions after a ditransitive verb. Both the L1 and the L2 group showed a difference between the two word order conditions that emerged within the critical time window for an anticipatory effect, indicating their sensitivity towards case. However, the results for the post-critical time window pointed to a higher uncertainty in the L2 group, who needed more time to integrate incoming information and were more affected by the word order variation than the L1 group, indicating that they relied more on surface-level information. A different cue weighting was also found in the experiment testing whether participants predict upcoming reference based on implicit causality information. Here, an additional child L1 group was tested, who had a lower memory capacity than the adult L2 group, as confirmed by a digit span task conducted with both learner groups. Whereas the children were only slightly delayed compared to the adult L1 group and showed the same effect of condition, the L2 speakers showed an over-reliance on surface-level information (first-mention/subjecthood). Hence, the pattern observed resulted more likely from L1/L2 differences than from resource deficits.
The reviewed studies and the experiments conducted show that L2 prediction is affected by a range of factors. While some of the factors can be attributed to more individual differences (e.g., language similarity, slower processing) and can be interpreted by L2 processing accounts assuming that L1 and L2 processing are basically the same, certain limits are better explained by accounts that assume more substantial L1/L2 differences. Crucially, the experimental results demonstrate that the RAGE hypothesis should be refined: Although prediction as a fast-operating mechanism is likely to be affected in L2 speakers, there is no indication that prediction is the dominant source of L1/L2 differences. The results rather demonstrate that L2 speakers show a different weighting of cues and rely more on semantic and surface-level information to predict as well as to integrate incoming information.
The present dissertation about teachers’ cultural diversity beliefs and culturally responsive practices includes a general introduction (Chapter 1), a systematic literature review (Chapter 2), three empirical studies (Chapter 3, 4, and 5) and it ends with a general discussion and conclusion (Chapter 6). The major focus of investigation laid in creating a deeper understanding of teachers’ beliefs about cultural diversity and how those beliefs are related to teaching practices, which could or could not be considered to be culturally responsive. In this dissertation, I relied on insights from theoretical perspectives that derived from the field of psychology such as social cognitive theory and intergroup ideologies, as well as from the field of multicultural education such as culturally responsive teaching.
In Chapter 1, I provide the background of this dissertation, with contextual information regarding the German educational system, the theoretical framework used and the main research objectives of each study.
In Chapter 2, I conducted a systematic review of the existing international studies on trainings addressing cultural diversity beliefs with pre-service teachers. More specifically, the aims of the systematic literature review were (1) to provide a description of main components and contextual characteristics of teacher trainings targeting cultural diversity beliefs, (2) report the training effects, and (3) detail the methodological strengths and weaknesses of these studies. By examining the main components and contextual characteristics of teacher trainings, the effects on beliefs about cultural diversity as well as the methodological strengths and weaknesses of these studies in a single review, I took an integrated approach to these three processes. To review the final pool of studies (N = 36) I used a descriptive and narrative approach, relying primarily on the use of words and text to summarise and explain findings of the synthesis.
The three empirical studies that follow, all highlight aspects of how far and how teacher beliefs about cultural diversity translate into real-world practices in schools. In Chapter 3, to expand the validity of culturally responsive teaching to the German context, I aimed at verifying the dimensional structure of German version of the Culturally Responsive Classroom Management Self-Efficacy Scale (CRCMSES; Siwatu, Putman, Starker-Glass, & Lewis, 2015). I conducted Exploratory and Confirmatory Factor Analysis, and run correlations between the subscales of the CRCMSES and a measure of cultural diversity- related stress. Data (n = 504) used for the first empirical study (Chapter 3) were collected in the InTePP-project (Inclusive Teaching Professionalization Panel) in which pre-service teachers’ competencies and beliefs were assessed longitudinally at two universities: the University of Potsdam and the University of Cologne.
In the second empirical study, which forms Chapter 4, the focus is on teachers’ practices resembling school approaches to cultural diversity. In this study, I investigated two research questions: (1a) What types of descriptive norms regarding cultural diversity are perceived by teachers and students with and without an immigrant background and (1b) what is their degree of congruence? Additionally, I was also interested in how are teachers’ and students’ perceptions of descriptive norms about cultural diversity related to practices and artefacts in the physical and virtual school environment? Data for the second empirical study (Chapter 4) were previously collected in a dissertation project of doctor Maja Schachner funded by the federal program “ProExzellenz” of the Free State of Thuringia. Adopting a mixed-methods research design I conducted a secondary analysis of data from teachers’ (n = 207) and students’ (n = 1,644) gathered in 22 secondary schools in south-west Germany. Additional sources of data in this study were based on pictures of school interiors (hall and corridors) and sixth-grade classrooms’ walls (n = 2,995), and screenshots from each school website (n = 6,499).
Chapter 5 addresses the question of how culturally responsive teaching, teacher cultural diversity beliefs, and self-reflection on own teaching are related. More specifically, in this study I addressed two research questions: (1) How does CRT relate to teachers’ beliefs about incorporating cultural diversity content into daily teaching and learning activities? And (2) how does the level of teachers’ self-reflection on their own teaching relate to CRT?
For this last empirical chapter, I conducted a multiple case study with four ethnic German teachers who work in one culturally and ethnically diverse high school in Berlin, using classroom video observations and post-observation interviews.
In the final chapter (Chapter 6), I summarised the main findings of the systematic literature review and three empirical studies, and discuss their scientific and practical implications.
This dissertation makes a significant contribution to the field of educational science to understanding culturally responsive teaching in terms of its measurement, focus on both beliefs and practices and the link between the two, and theoretical, practical, and future study implications.
The present work is a compilation of three original research articles submitted (or already published) in international peer-reviewed venues of the field of speech science. These three articles address the topics of fundamental motor laws in speech and dynamics of corresponding speech movements:
1. Kuberski, Stephan R. and Adamantios I. Gafos (2019). "The speed-curvature power law in tongue movements of repetitive speech". PLOS ONE 14(3). Public Library of Science. doi: 10.1371/journal.pone.0213851.
2. Kuberski, Stephan R. and Adamantios I. Gafos (In press). "Fitts' law in tongue movements of repetitive speech". Phonetica: International Journal of Phonetic Science. Karger Publishers. doi: 10.1159/000501644
3. Kuberski, Stephan R. and Adamantios I. Gafos (submitted). "Distinct phase space topologies of identical phonemic sequences". Language. Linguistic Society of America.
The present work introduces a metronome-driven speech elicitation paradigm in which participants were asked to utter repetitive sequences of elementary consonant-vowel syllables. This paradigm, explicitly designed to cover speech rates from a substantially wider range than has been explored so far in previous work, is demonstrated to satisfy the important prerequisites for assessing so far difficult to access aspects of speech. Specifically, the paradigm's extensive speech rate manipulation enabled elicitation of a great range of movement speeds as well as movement durations and excursions of the relevant effectors. The presence of such variation is a prerequisite to assessing whether invariant relations between these and other parameters exist and thus provides the foundation for a rigorous evaluation of the two laws examined in the first two contributions of this work.
In the data resulting from this paradigm, it is shown that speech movements obey the same fundamental laws as movements from other domains of motor control do. In particular, it is demonstrated that speech strongly adheres to the power law relation between speed and curvature of movement with a clear speech rate dependency of the power law's exponent. The often-sought or reported exponent of one third in the statement of the law is unique to a subclass of movements which corresponds to the range of faster rates under which a particular utterance is produced. For slower rates, significantly larger values than one third are observed. Furthermore, for the first time in speech this work uncovers evidence for the presence of Fitts' law. It is shown that, beyond a speaker-specific speech rate, speech movements of the tongue clearly obey Fitts' law by emergence of its characteristic linear relation between movement time and index of difficulty. For slower speech rates (when temporal pressure is small), no such relation is observed. The methods and datasets obtained in the two assessment above provide a rigorous foundation both for addressing implications for theories and models of speech as well as for better understanding the status of speech movements in the context of human movements in general.
All modern theories of language rely on a fundamental segmental hypothesis according to which the phonological message of an utterance is represented by a sequence of segments or phonemes. It is commonly assumed that each of these phonemes can be mapped to some unit of speech motor action, a so-called speech gesture.
For the first time here, it is demonstrated that the relation between the phonological description of simple utterances and the corresponding speech motor action is non-unique. Specifically, by the extensive speech rate manipulation in the herein used experimental paradigm it is demonstrated that speech exhibits clearly distinct dynamical organizations underlying the production of simple utterances. At slower speech rates, the dynamical organization underlying the repetitive production of elementary /CV/ syllables can be described by successive concatenations of closing and opening gestures, each with its own equilibrium point. As speech rate increases, the equilibria of opening and closing gestures are not equally stable yielding qualitatively different modes of organization with either a single equilibrium point of a combined opening-closing gesture or a periodic attractor unleashed by the disappearance of both equilibria. This observation, the non-uniqueness of the dynamical organization underlying what on the surface appear to be identical phonemic sequences, is an entirely new result in the domain of speech. Beyond that, the demonstration of periodic attractors in speech reveals that dynamical equilibrium point models do not account for all possible modes of speech motor behavior.
This dissertation is concerned with the relation between qualitative phonological organization in the form of syllabic structure and continuous phonetics, that is, the spatial and temporal dimensions of vocal tract action that express syllabic structure. The main claim of the dissertation is twofold. First, we argue that syllabic organization exerts multiple effects on the spatio-temporal properties of the segments that partake in that organization. That is, there is no unique or privileged exponent of syllabic organization. Rather, syllabic organization is expressed in a pleiotropy of phonetic indices. Second, we claim that a better understanding of the relation between qualitative phonological organization and continuous phonetics is reached when one considers how the string of segments (over which the nature of the phonological organization is assessed) responds to perturbations (scaling of phonetic variables) of localized properties (such as durations) within that string. Specifically, variation in phonetic variables and more specifically prosodic variation is a crucial key to understanding the nature of the link between (phonological) syllabic organization and the phonetic spatio-temporal manifestation of that organization. The effects of prosodic variation on segmental properties and on the overlap between the segments, we argue, offer the right pathway to discover patterns related to syllabic organization. In our approach, to uncover evidence for global organization, the sequence of segments partaking in that organization as well as properties of these segments or their relations with one another must be somehow locally varied. The consequences of such variation on the rest of the sequence can then be used to unveil the span of organization. When local perturbations to segments or relations between adjacent segments have effects that ripple through the rest of the sequence, this is evidence that organization is global. If instead local perturbations stay local with no consequences for the rest of the whole, this indicates that organization is local.
The public encounter
(2019)
This thesis puts the citizen-state interaction at its center. Building on a comprehensive model incorporating various perspectives on this interaction, I derive selected research gaps. The three articles, comprising this thesis, tackle these gaps. A focal role plays the citizens’ administrative literacy, the relevant competences and knowledge necessary to successfully interact with public organizations. The first article elaborates on the different dimensions of administrative literacy and develops a survey instrument to assess these. The second study shows that public employees change their behavior according to the competences that citizens display during public encounters. They treat citizens preferentially that are well prepared and able to persuade them of their application’s potential. Thereby, they signal a higher success potential for bureaucratic success criteria which leads to the employees’ cream-skimming behavior. The third article examines the dynamics of employees’ communication strategies when recovering from a service failure. The study finds that different explanation strategies yield different effects on the client’s frustration. While accepting the responsibility and explaining the reasons for a failure alleviates the frustration and anger, refusing the responsibility leads to no or even reinforcing effects on the client’s frustration. The results emphasize the different dynamics that characterize the nature of citizen-state interactions and how they establish their short- and long-term outcomes.
The increasing age of worldwide population is a major contributor for the rising prevalence of major pathologies and disease, such as type 2 diabetes, mediated by massive insulin resistance and a decline in functional beta-cell mass, highly associated with an elevated incidence of obesity. Thus, the impact of aging under physiological conditions and in combination with diet-induced metabolic stress on characteristics of pancreatic islets and beta-cells, with the focus on functionality and structural integrity, were investigated in the present dissertation.
Primarily induced by malnutrition due to chronic and excess intake of high caloric diets, containing large amounts of carbohydrates and fats, obesity followed by systemic inflammation and peripheral insulin resistance occurs over time, initiating metabolic stress conditions. Elevated insulin demands initiate an adaptive response by beta-cell mass expansion due to increased proliferation, but prolonged stress conditions drive beta-cell failure and loss. Aging has been also shown to affect beta-cell functionality and morphology, in particular by proliferative limitations. However, most studies in rodents were performed under beta-cell challenging conditions, such as high-fat diet interventions. Thus, in the first part of the thesis (publication I), a characterization of age-related alterations on pancreatic islets and beta-cells was performed by using plasma samples and pancreatic tissue sections of standard diet-fed C57BL/6J wild-type mice in several age groups (2.5, 5, 10, 15 and 21 months).
Aging was accompanied by decreased but sustained islet proliferative potential as well as an induction of cellular senescence. This was associated with a progressive islet expansion to maintain normoglycemia throughout lifespan. Moreover, beta-cell function and mass were not impaired although the formation and accumulation of AGEs occurred, located predominantly in the islet vasculature, accompanied by an induction of oxidative and nitrosative (redox) stress.
The nutritional behavior throughout human lifespan; however, is not restricted to a balanced diet. This emphasizes the significance to investigate malnutrition by the intake of high-energy diets, inducing metabolic stress conditions that synergistically with aging might amplify the detrimental effects on endocrine pancreas. Using diabetes-prone NZO mice aged 7 weeks, fed a dietary regimen of carbohydrate restriction for different periods (young mice - 11 weeks, middle-aged mice - 32 weeks) followed by a carbohydrate intervention for 3 weeks, offered the opportunity to distinguish the effects of diet-induced metabolic stress in different ages on the functionality and integrity of pancreatic islets and their beta-cells (publication II, manuscript).
Interestingly, while young NZO mice exhibited massive hyperglycemia in response to diet-induced metabolic stress accompanied by beta-cell dysfunction and apoptosis, middle-aged animals revealed only moderate hyperglycemia by the maintenance of functional beta-cells. The loss of functional beta-cell mass in islets of young mice was associated with reduced expression of PDX1 transcription factor, increased endocrine AGE formation and related redox stress as well as TXNIP-dependent induction of the mitochondrial death pathway. Although the amounts of secreted insulin and the proliferative potential were comparable in both age groups, islets of middle-aged mice exhibited sustained PDX1 expression, almost regular insulin secretory function, increased capacity for cell cycle progression as well as maintained redox potential.
The results of the present thesis indicate a loss of functional beta-cell mass in young diabetes-prone NZO mice, occurring by redox imbalance and induction of apoptotic signaling pathways. In contrast, aging under physiological conditions in C57BL/6J mice and in combination with diet-induced metabolic stress in NZO mice does not appear to have adverse effects on the functionality and structural integrity of pancreatic islets and beta-cells, associated with adaptive responses on changing metabolic demands. However, considering the detrimental effects of aging, it has to be assumed that the compensatory potential of mice might be exhausted at a later point of time, finally leading to a loss of functional beta-cell mass and the onset and progression of type 2 diabetes.
The polygenic, diabetes-prone NZO mouse is a suitable model for the investigation of human obesity-associated type 2 diabetes. However, mice at advanced age attenuated the diabetic phenotype or do not respond to the dietary stimuli. This might be explained by the middle age of mice, corresponding to the human age of about 38-40 years, in which the compensatory mechanisms of pancreatic islets and beta cells towards metabolic stress conditions are presumably more active.
Earthquake swarms are characterized by large numbers of events occurring in a short period of time within a confined source volume and without significant mainshock aftershock pattern as opposed to tectonic sequences. Intraplate swarms in the absence of active volcanism usually occur in continental rifts as for example in the Eger Rift zone in North West Bohemia, Czech Republic. A common hypothesis links event triggering to pressurized fluids. However, the exact causal chain is often poorly understood since the underlying geotectonic processes are slow compared to tectonic sequences. The high event rate during active periods challenges standard seismological routines as these are often designed for single events and therefore costly in terms of human resources when working with phase picks or computationally costly when exploiting full waveforms.
This methodological thesis develops new approaches to analyze earthquake swarm seismicity as well as the underlying seismogenic volume. It focuses on the region of North West (NW) Bohemia, a well studied, well monitored earthquake swarm region.
In this work I develop and test an innovative approach to detect and locate earthquakes using deep convolutional neural networks. This technology offers great potential as it allows to efficiently process large amounts of data which becomes increasingly important given that seismological data storage grows at increasing pace. The proposed deep neural network trained on NW Bohemian earthquake swarm records is able to locate 1000 events in less than 1 second using full waveforms while approaching precision of double difference relocated catalogs. A further technological novelty is that the trained filters of the deep neural network’s first layer can be repurposed to function as a pattern matching event detector without additional training on noise datasets. For further methodological development and benchmarking, I present a new toolbox to generate realistic earthquake cluster catalogs as well as synthetic full waveforms of those clusters in an automated fashion. The input is parameterized using constraints on source volume geometry, nucleation and frequency-magnitude relations. It harnesses recorded noise to produce highly realistic synthetic data for benchmarking and development. This tool is used to study and assess detection performance in terms of magnitude of completeness Mc of a full waveform detector applied to synthetic data of a hydrofracturing experiment at the Wysin site, Poland.
Finally, I present and demonstrate a novel approach to overcome the masking effects of wave propagation between earthquake and stations and to determine source volume attenuation directly in the source volume where clustered earthquakes occur. The new event couple spectral ratio approach exploits high frequency spectral slopes of two events sharing the greater part of their rays. Synthetic tests based on the toolbox mentioned before show that this method is able to infer seismic wave attenuation within the source volume at high spatial resolution. Furthermore, it is independent from the distance towards a station as well as the complexity of the attenuation and velocity structure outside of the source volume of swarms. The application to recordings of the NW Bohemian earthquake swarm shows increased P phase attenuation within the source volume (Qp < 100) based on results at a station located close to the village Luby (LBC). The recordings of a station located in epicentral proximity, close to Nový Kostel (NKC), show a relatively high complexity indicating that waves arriving at that station experience more scattering than signals recorded at other stations. The high level of complexity destabilizes the inversion. Therefore, the Q estimate at NKC is not reliable and an independent proof of the high attenuation finding given the geometrical and frequency constraints is still to be done. However, a high attenuation in the source volume of NW Bohemian swarms has been postulated before in relation to an expected, highly damaged zone bearing CO 2 at high pressure.
The methods developed in the course of this thesis yield the potential to improve our understanding regarding the role of fluids and gases in intraplate event clustering.
Frailty and sarcopenia share some underlying characteristics like loss of muscle mass, low muscle strength, and low physical performance. Imaging parameters and functional examinations mainly assess frailty and sarcopenia criteria; however, these measures can have limitations in clinical settings. Therefore, finding suitable biomarkers that reflect a catabolic muscle state e.g. an elevated muscle protein turnover as suggested in frailty, are becoming more relevant concerning frailty diagnosis and risk assessment.
3-Methylhistidine (3-MH) and its ratios 3-MH-to-creatinine (3-MH/Crea) and 3 MH-to-estimated glomerular filtration rate (3-MH/eGFR) are under discussion as possible biomarkers for muscle protein turnover and might support the diagnosis of frailty. However, there is some skepticism about the reliability of 3-MH measures since confounders such as meat and fish intake might influence 3-MH plasma concentrations. Therefore, the influence of dietary habits and an intervention with white meat on plasma 3-MH was determined in young and healthy individuals. In another study, the cross-sectional associations of plasma 3-MH, 3-MH/Crea and 3-MH/eGFR with the frailty status (robust, pre-frail and frail) were investigated.
Oxidative stress (OS) is a possible contributor to frailty development, and high OS levels as well as low micronutrient levels are associated with the frailty syndrome. However, data on simultaneous measures of OS biomarkers together with micronutrients are lacking in studies including frail, pre-frail and robust individuals. Therefore, cross-sectional associations of protein carbonyls (PrCarb), 3-nitrotyrosine (3-NT) and several micronutrients with the frailty status were determined.
A validated UPLC-MS/MS (ultra-performance liquid chromatography tandem mass spectrometry) method for the simultaneous quantification of 3-MH and 1-MH (1 methylhistidine, as marker for meat and fish consumption) was presented and used for further analyses. Omnivores showed higher plasma 3-MH and 1-MH concentrations than vegetarians and a white meat intervention resulted in an increase in plasma 3-MH, 3 MH/Crea, 1-MH and 1-MH/Crea in omnivores. Elevated 3-MH and 3-MH/Crea levels declined significantly within 24 hours after this white meat intervention. Thus, 3-MH and 3-MH/Crea might be used as biomarker for muscle protein turnover when subjects did not consume meat 24 hours prior to blood samplings.
Plasma 3-MH, 3-MH/Crea and 3-MH/eGFR were higher in frail individuals than in robust individuals. Additionally, these biomarkers were positively associated with frailty in linear regression models, and higher odds to be frail were found for every increase in 3 MH and 3-MH/eGFR quintile in multivariable logistic regression models adjusted for several confounders. This was the first study using 3-MH/eGFR and it is concluded that plasma 3-MH, 3-MH/Crea and 3-MH/eGFR might be used to identify frail individuals or individuals at higher risk to be frail, and that there might be threshold concentrations or ratios to support these diagnoses.
Higher vitamin D3, lutein/zeaxanthin, γ-tocopherol, α-carotene, β-carotene, lycopene and β-cryptoxanthin concentrations and additionally lower PrCarb concentrations were found in robust compared to frail individuals in multivariate linear models. Frail subjects had higher odds to be in the lowest than in the highest tertile for vitamin D3 α-tocopherol, α-carotene, β-carotene, lycopene, lutein/zeaxanthin, and β cryptoxanthin, and had higher odds to be in the highest than in the lowest tertile for PrCarb than robust individuals in multivariate logistic regression models. Thus, a low micronutrient together with a high PrCarb status is associated with pre-frailty and frailty.
Sinkholes and depressions are typical landforms of karst regions. They pose a considerable natural hazard to infrastructure, agriculture, economy and human life in affected areas worldwide. The physio-chemical processes of sinkholes and depression formation are manifold, ranging from dissolution and material erosion in the subsurface to mechanical subsidence/failure of the overburden. This thesis addresses the mechanisms leading to the development of sinkholes and depressions by using complementary methods: remote sensing, distinct element modelling and near-surface geophysics.
In the first part, detailed information about the (hydro)-geological background, ground structures, morphologies and spatio-temporal development of sinkholes and depressions at a very active karst area at the Dead Sea are derived from satellite image analysis, photogrammetry and geologic field surveys. There, clusters of an increasing number of sinkholes have been developing since the 1980s within large-scale depressions and are distributed over different kinds of surface materials: clayey mud, sandy-gravel alluvium and lacustrine evaporites (salt). The morphology of sinkholes differs depending in which material they form: Sinkholes in sandy-gravel alluvium and salt are generally deeper and narrower than sinkholes in the interbedded evaporite and mud deposits. From repeated aerial surveys, collapse precursory features like small-scale subsidence, individual holes and cracks are identified in all materials. The analysis sheds light on the ongoing hazardous subsidence process, which is driven by the base-level fall of the Dead Sea and by the dynamic formation of subsurface water channels.
In the second part of this thesis, a novel, 2D distinct element geomechanical modelling approach with the software PFC2D-V5 to simulating individual and multiple cavity growth and sinkhole and large-scale depression development is presented. The approach involves a stepwise material removal technique in void spaces of arbitrarily shaped geometries and is benchmarked by analytical and boundary element method solutions for circular cavities. Simulated compression and tension tests are used to calibrate model parameters with bulk rock properties for the materials of the field site. The simulations show that cavity and sinkhole evolution is controlled by material strength of both overburden and cavity host material, the depth and relative speed of the cavity growth and the developed stress pattern in the subsurface. Major findings are: (1) A progressively deepening differential subrosion with variable growth speed yields a more fragmented stress pattern with stress interaction between the cavities. It favours multiple sinkhole collapses and nesting within large-scale depressions. (2) Low-strength materials do not support large cavities in the material removal zone, and subsidence is mainly characterised by gradual sagging into the material removal zone with synclinal bending. (3) High-strength materials support large cavity formation, leading to sinkhole formation by sudden collapse of the overburden. (4) Large-scale depression formation happens either by coalescence of collapsing holes, block-wise brittle failure, or gradual sagging and lateral widening.
The distinct element based approach is compared to results from remote sensing and geophysics at the field site. The numerical simulation outcomes are generally in good agreement with derived morphometrics, documented surface and subsurface structures as well as seismic velocities. Complementary findings on the subrosion process are provided from electric and seismic measurements in the area.
Based on the novel combination of methods in this thesis, a generic model of karst landform evolution with focus on sinkhole and depression formation is developed. A deepening subrosion system related to preferential flow paths evolves and creates void spaces and subsurface conduits. This subsequently leads to hazardous subsidence, and the formation of sinkholes within large-scale depressions. Finally, a monitoring system for shallow natural hazard phenomena consisting of geodetic and geophysical observations is proposed for similarly affected areas.
Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells
(2019)
Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell’s cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C.
A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts.
Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8%.
Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9% relative to 26.5% absolute. The results also reveal general guidelines for further performance gains of the technology.
Die vorliegende Forschungsarbeit untersucht den Umgang mit Dilemmata von Topmanagern. Dilemmata sind ein alltägliches Geschäft im Topmanagement. Die entsprechenden Akteure sind daher immer wieder mit diesen konfrontiert und mit ihnen umzugehen, gehört gewissermaßen zu ihrer Berufsbeschreibung. Hinzu kommen Dilemmata im nicht direkt geschäftlichen Bereich, wie zum Beispiel jene zwischen Familien- und Arbeitszeit. Doch stellt dieses Feld ein kaum untersuchtes Forschungsgebiet dar. Während Dilemmata in anderen Bereichen eine zunehmende Aufmerksamkeit erfuhren, wurden deren Besonderheiten im Topmanagement genauso wenig differenziert betrachtet wie zugehörige Umgangsweisen. Theorie und Praxis stellen bezüglich Dilemmata von Topmanagern vor allem einen Gegensatz dar, beziehungsweise fehlt es an einer theoretischen Fundierung der Empirie. Diesem Umstand wird mittels dieser Studie begegnet. Auf der Grundlage einer differenzierten und breiten Erfassung von Theorien zu Dilemmata, so diese auch noch nicht auf Topmanager bezogen wurden, und einer empirischen Erhebung, die im Mittelpunkt dieser Arbeit stehen, soll das Feld Dilemmata von Topmanagern der Forschung geöffnet werden. Empirische Grundlage sind vor allem narrative Interviews mit Topmanagern über ihre Dilemmata-Wahrnehmung, ausgemachte Ursachen, Umgangsweisen und Resultate. Dies erlaubt es, Topmanagertypen sowie Dilemmata-Arten, mit denen sie konfrontiert sind oder waren, analytisch herauszuarbeiten. Angesichts der Praxisrelevanz von Dilemmata von Topmanagern wird jedoch nicht nur ein theoretisches Modell zu dieser Thematik erarbeitet, es werden auch Reflexionen auf die Praxis in Form von Handlungsempfehlungen vorgenommen. Schließlich gilt es, die allgemeine Theorie zu Dilemmata, ohne konkreten Bezug zu Topmanagern, mit den theoretischen Erkenntnissen dieser Studie auf empirischer Basis zu kontrastieren. Dabei wird im Rahmen der empirischen Erfassung und Auswertung dem Ansatz der Grounded-Theory-Methodologie gefolgt.
The advances in modern geodetic techniques such as the global navigation satellite system (GNSS) and synthetic aperture radar (SAR) provide surface deformation measurements with an unprecedented accuracy and temporal and spatial resolutions even at most remote volcanoes on Earth. Modelling of the high-quality geodetic data is crucial for understanding the underlying physics of volcano deformation processes. Among various approaches, mathematical models are the most effective for establishing a quantitative link between the surface displacements and the shape and strength of deformation sources. Advancing the geodetic data analyses and hence, the knowledge on the Earth’s interior processes, demands sophisticated and efficient deformation modelling approaches. Yet the majority of these models rely on simplistic assumptions for deformation source geometries and ignore complexities such as the Earth’s surface topography and interactions between multiple sources.
This thesis addresses this problem in the context of analytical and numerical volcano deformation modelling. In the first part, new analytical solutions for triangular dislocations (TDs) in uniform infinite and semi-infinite elastic media have been developed. Through a comprehensive investigation, the locations and causes of artefact singularities and numerical instabilities associated with TDs have been determined and these long-standing drawbacks have been addressed thoroughly. This approach has then been extended to rectangular dislocations (RDs) with full rotational degrees of freedom. Using this solution in a configuration of three orthogonal RDs a compound dislocation model (CDM) has been developed. The CDM can represent generalized volumetric and planar deformation sources efficiently. Thus, the CDM is relevant for rapid inversions in early warning systems and can also be used for detailed deformation analyses. In order to account for complex source geometries and realistic topography in the deformation models, in this thesis the boundary element method (BEM) has been applied to the new solutions for TDs. In this scheme, complex surfaces are simulated as a continuous mesh of TDs that may possess any displacement or stress boundary conditions in the BEM calculations. In the second part of this thesis, the developed modelling techniques have been applied to five different real-world deformation scenarios. As the first and second case studies the deformation sources associated with the 2015 Calbuco eruption and 2013–2016 Copahue inflation period have been constrained by using the CDM. The highly anisotropic source geometries in these two cases highlight the importance of using generalized deformation models such as the CDM, for geodetic data inversions. The other three case studies in this thesis involve high-resolution dislocation models and BEM calculations. As the third case, the 2013 pre-explosive inflation of Volcán de Colima has been simulated by using two ellipsoidal cavities, which locate zones of pressurization in the volcano’s lava dome. The fourth case study, which serves as an example for volcanotectonics interactions, the 3-D kinematics of an active ring-fault at Tendürek volcano has been investigated through modelling displacement time series over the 2003–2010 time period. As the fifth example, the deformation sources associated with North Korea’s underground nuclear test in September 2017 have been constrained. These examples demonstrate the advancement and increasing level of complexity and the general applicability of the developed dislocation modelling techniques.
This thesis establishes a unified framework for rapid and high-resolution dislocation modelling, which in addition to volcano deformations can also be applied to tectonic and humanmade deformations.
Floods are among the most costly natural hazards that affect Europe and Germany, demanding a continuous adaptation of flood risk management. While social and economic development in recent years altered the flood risk patterns mainly with regard to an increase in flood exposure, different flood events are further expected to increase in frequency and severity in certain European regions due to climate change. As a result of recent major flood events in Germany, the German flood risk management shifted to more integrated approaches that include private precaution and preparation to reduce the damage on exposed assets. Yet, detailed insights into the preparedness decisions of flood-prone households remain scarce, especially in connection to mental impacts and individual coping strategies after being affected by different flood types.
This thesis aims to gain insights into flash floods as a costly hazard in certain German regions and compares the damage driving factors to the damage driving factors of river floods. Furthermore, psychological impacts as well as the effects on coping and mitigation behaviour of flood-affected households are assessed. In this context, psychological models such as the Protection Motivation Theory (PMT) and methods such as regressions and Bayesian statistics are used to evaluate influencing factors on the mental coping after an event and to identify psychological variables that are connected to intended private flood mitigation. The database consists of surveys that were conducted among affected households after major river floods in 2013 and flash floods in 2016.
The main conclusions that can be drawn from this thesis reveal that the damage patterns and damage driving factors of strong flash floods differ significantly from those of river floods due to a rapid flow origination process, higher flow velocities and flow forces. However, the effects on mental coping of people that have been affected by flood events appear to be weakly influenced by different flood types, but yet show a coherence to the event severity, where often thinking of the respective event is pronounced and also connected to a higher mitigation motivation. The mental coping and preparation after floods is further influenced by a good information provision and a social environment, which encourages a positive attitude towards private mitigation.
As an overall recommendation, approaches for an integrated flood risk management in Germany should be followed that also take flash floods into account and consider psychological characteristics of affected households to support and promote private flood mitigation. Targeted information campaigns that concern coping options and discuss current flood risks are important to better prepare for future flood hazards in Germany.
In light of the debate on the consequences of competitive contracting out of traditionally public services, this research compares two mechanisms used to allocate funds in development cooperation—direct awarding and competitive contracting out—aiming to identify their potential advantages and disadvantages.
The agency theory is applied within the framework of rational-choice institutionalism to study the institutional arrangements that surround two different money allocation mechanisms, identify the incentives they create for the behavior of individual actors in the field, and examine how these then transfer into measurable differences in managerial quality of development aid projects. In this work, project management quality is seen as an important determinant of the overall project success.
For data-gathering purposes, the German development agency, the Gesellschaft für Internationale Zusammenarbeit (GIZ), is used due to its unique way of work. Whereas the majority of projects receive funds via direct-award mechanism, there is a commercial department, GIZ International Services (GIZ IS) that has to compete for project funds.
The data concerning project management practices on the GIZ and GIZ IS projects was gathered via a web-based, self-administered survey of project team leaders. Principal component analysis was applied to reduce the dimensionality of the independent variable to total of five components of project management. Furthermore, multiple regression analysis identified the differences between the separate components on these two project types. Enriched by qualitative data gathered via interviews, this thesis offers insights into everyday managerial practices in development cooperation and identifies the advantages and disadvantages of the two allocation mechanisms.
The thesis first reiterates the responsibility of donors and implementers for overall aid effectiveness. It shows that the mechanism of competitive contracting out leads to better oversight and control of implementers, fosters deeper cooperation between the implementers and beneficiaries, and has a potential to strengthen ownership of recipient countries. On the other hand, it shows that the evaluation quality does not tremendously benefit from the competitive allocation mechanism and that the quality of the component knowledge management and learning is better when direct-award mechanisms are used. This raises questions about the lacking possibilities of actors in the field to learn about past mistakes and incorporate the finings into the future interventions, which is one of the fundamental issues of aid effectiveness. Finally, the findings show immense deficiencies in regard to oversight and control of individual projects in German development cooperation.
Oscillatory systems under weak coupling can be described by the Kuramoto model of phase oscillators. Kuramoto phase oscillators have diverse applications ranging from phenomena such as communication between neurons and collective influences of political opinions, to engineered systems such as Josephson Junctions and synchronized electric power grids. This thesis includes the author's contribution to the theoretical framework of coupled Kuramoto oscillators and to the understanding of non-trivial N-body dynamical systems via their reduced mean-field dynamics.
The main content of this thesis is composed of four parts. First, a partially integrable theory of globally coupled identical Kuramoto oscillators is extended to include pure higher-mode coupling. The extended theory is then applied to a non-trivial higher-mode coupled model, which has been found to exhibit asymmetric clustering. Using the developed theory, we could predict a number of features of the asymmetric clustering with only information of the initial state provided.
The second part consists of an iterated discrete-map approach to simulate phase dynamics. The proposed map --- a Moebius map --- not only provides fast computation of phase synchronization, it also precisely reflects the underlying group structure of the dynamics. We then compare the iterated-map dynamics and various analogous continuous-time dynamics. We are able to replicate known phenomena such as the synchronization transition of the Kuramoto-Sakaguchi model of oscillators with distributed natural frequencies, and chimera states for identical oscillators under non-local coupling.
The third part entails a particular model of repulsively coupled identical Kuramoto-Sakaguchi oscillators under common random forcing, which can be shown to be partially integrable. Via both numerical simulations and theoretical analysis, we determine that such a model cannot exhibit stationary multi-cluster states, contrary to the numerical findings in previous literature. Through further investigation, we find that the multi-clustering states reported previously occur due to the accumulation of discretization errors inherent in the integration algorithms, which introduce higher-mode couplings into the model. As a result, the partial integrability condition is violated.
Lastly, we derive the microscopic cross-correlation of globally coupled non-identical Kuramoto oscillators under common fluctuating forcing. The effect of correlation arises naturally in finite populations, due to the non-trivial fluctuations of the meanfield. In an idealized model, we approximate the finite-sized fluctuation by a Gaussian white noise. The analytical approximation qualitatively matches the measurements in numerical experiments, however, due to other periodic components inherent in the fluctuations of the mean-field there still exist significant inconsistencies.
Species assembly from a regional pool into local metacommunities and how they colonize and coexist over time and space is essential to understand how communities response to their environment including abiotic and biotic factors. In highly disturbed landscapes, connectivity of isolated habitat patches is essential to maintain biodiversity and the entire ecosystem functioning. In northeast Germany, a high density of the small water bodies called kettle holes, are good systems to study metacommunities due to their condition as “aquatic islands” suitable for hygrophilous species that are surrounded by in unsuitable matrix of crop fields. The main objective of this thesis was to infer the main ecological processes shaping plant communities and their response to the environment, from biodiversity patterns and key life-history traits involved in connectivity using ecological and genetic approaches; and to provide first insights of the role of kettle holes harboring wild-bee species as important mobile linkers connecting plant communities in this insular system.
t a community level, I compared plant diversity patterns and trait composition in ephemeral vs. permanent kettle holes). My results showed that types of kettle holes act as environmental filers shaping plant diversity, community-composition and trait-distribution, suggesting species sorting and niche processes in both types of kettle holes. At a population level, I further analyzed the role of dispersal and reproductive strategies of four selected species occurring in permanent kettle holes. Using microsatellites, I found that breeding system (degree of clonality), is the main factor shaping genetic diversity and genetic divergence. Although, higher gene flow and lower genetic differentiation among populations in wind vs. insect pollinated species was also found, suggesting that dispersal mechanisms played a role related to gene flow and connectivity. For most flowering plants, pollinators play an important role connecting communities. Therefore, as a first insight of the potential mobile linkers of these plant communities, I investigated the diversity wild-bees occurring in these kettle holes. My main results showed that local habitat quality (flower resources) had a positive effect on bee diversity, while habitat heterogeneity (number of natural landscape elements surrounding kettle holes 100–300m), was negatively correlated.
This thesis covers from genetic flow at individual and population level to plant community assembly. My results showed how patterns of biodiversity, dispersal and reproduction strategies in plant population and communities can be used to infer ecological processes. In addition, I showed the importance of life-history traits and the relationship between species and their abiotic and biotic interactions. Furthermore, I included a different level of mobile linkers (pollinators) for a better understanding of another level of the system. This integration is essential to understand how communities respond to their surrounding environment and how disturbances such as agriculture, land-use and climate change might affect them. I highlight the need to integrate many scientific areas covering from genes to ecosystems at different spatiotemporal scales for a better understanding, management and conservation of our ecosystems.
Back pain is a problem in adolescent athletes affecting postural control which is an important requirement for physical and daily activities whether under static or dynamic conditions. One leg stance and star excursion balance postural control tests are effective in measuring static and dynamic postural control respectively. These tests have been used in individuals with back pain, athletes and non-athletes without first establishing their reliabilities. In addition to this, there is no published literature investigating dynamic posture in adolescent athletes with back pain using the star excursion balance test. Therefore, the aim of the thesis was to assess deficit in postural control in adolescent athletes with and without back pain using static (one leg stance test) and dynamic postural (SEBT) control tests.
Adolescent athletes with and without back pain participated in the study. Static and dynamic postural control tests were performed using one leg stance and SEBT respectively. The reproducibility of both tests was established. Afterwards, it was determined whether there was an association between static and dynamic posture using the measure of displacement of the centre pressure and reach distance respectively. Finally, it was investigated whether there was a difference in postural control in adolescent athletes with and without back pain using the one leg stance test and the SEBT.
Fair to excellent reliabilities was recorded for the static (one leg stance) and dynamic (star excursion balance) postural control tests in the subjects of interest. No association was found between variables of the static and dynamic tests for the adolescent athletes with and without back pain. Also, no statistically significant difference was obtained between adolescent athletics with and without back pain using the static and dynamic postural control test.
One leg stance test and SEBT can be used as measures of postural control in adolescent athletes with and without back pain. Although static and dynamic postural control might be related, adolescent athletes with and without back pain might be using different mechanisms in controlling their static and dynamic posture. Consequently, static and dynamic postural control in adolescent athletes with back pain was not different from those without back pain. These outcome measures might not be challenging enough to detect deficit in postural control in our study group of interest.
This thesis investigates whether multilingual speakers’ use of grammatical constraints in an additional language (La) is affected by the native (L1) and non-native grammars (L2) of their linguistic repertoire.
Previous studies have used untimed measures of grammatical performance to show that L1 and L2 grammars affect the initial stages of La acquisition. This thesis extends this work by examining whether speakers at intermediate levels of La proficiency, who demonstrate mature untimed/offline knowledge of the target La constraints, are differentially affected by their L1 and L2 knowledge when they comprehend sentences under processing pressure. With this purpose, several groups of La German speakers were tested on word order and agreement phenomena using online/timed measures of grammatical knowledge. Participants had mirror distributions of their prior languages and they were either L1English/L2Spanish speakers or L1Spanish/L2English speakers. Crucially, in half of the phenomena the target La constraint aligned with English but not with Spanish, while in the other half it aligned with Spanish but not with English. Results show that the L1 grammar plays a major role in the use of La constraints under processing pressure, as participants displayed increased sensitivity to La constraints when they aligned with their L1, and reduced sensitivity when they did not. Further, in specific phenomena in which the L2 and La constraints aligned, increased L2 proficiency resulted in an enhanced sensitivity to the La constraint. These findings suggest that both native and non-native grammars affect how speakers use La grammatical constraints under processing pressure. However, L1 and L2 grammars differentially influence on participants’ performance: While L1 constraints seem to be reliably recruited to cope with the processing demands of real-time La use, proficiency in an L2 can enhance sensitivity to La constraints only in specific circumstances, namely when L2 and La constraints align.
This dissertation combines field and geochemical observations and analyses with numerical modeling to understand the formation of vein-hosted Sn-W ore in the Panasqueira deposit of Portugal, which is among the ten largest worldwide. The deposit is located above a granite body that is altered by magmatic-hydrothermal fluids in its upper part (greisen). These fluids are thought to be the source of metals, but that was still under debate. The goal of this study is to determine the composition and temperature of hydrothermal fluids at Panasqueira, and with that information to construct a numerical model of the hydrothermal system. The focus is on analysis of the minerals tourmaline and white mica, which formed during mineralization and are widespread throughout the deposit. Tourmaline occurs mainly in alteration zones around mineralized veins and is less abundant in the vein margins. White mica is more widespread. It is abundant in vein margins as well as alteration zones, and also occurs in the granite greisen. The laboratory work involved in-situ microanalysis of major- and trace elements in tourmaline and white mica, and boron-isotope analysis in both minerals by secondary ion mass spectrometry (SIMS).
The boron-isotope composition of tourmaline and white mica suggests a magmatic source. Comparison of hydrothermally-altered and unaltered rocks from drill cores shows that the ore metals (W, Sn, Cu, and Zn) and As, F, Li, Rb, and Cs were introduced during the alteration. Most of these elements are also enriched in tourmaline and mica, which confirms their potential value as exploration guides to Sn-W ores elsewhere.
The thermal evolution of the hydrothermal system was estimated by B-isotope exchange thermometry and the Ti-in-quartz method. Both methods yielded similar temperatures for the early hydrothermal phase: 430° to 460°C for B-isotopes and 503° ± 24°C for Ti-in-quartz. Mineral pairs from a late fault zone yield significantly lower median temperatures of 250°C. The combined results of thermometry with variations in chemical and B-isotope composition of tourmaline and mica suggest that a similar magmatic-hydrothermal fluid was active at all stages of mineralization. Mineralization in the late stage shows the same B-isotope composition as in the main stage despite a ca. 250°C cooling, which supports a multiple injection model of magmatic-hydrothermal fluids.
Two-dimensional numerical simulations of convection in a multiphase NaCl hydrothermal system were conducted: (a) in order to test a new approach (lower dimensional elements) for flow through fractures and faults and (b) in order to identify conditions for horizontal fluid flow as observed in the flat-lying veins at Panasqueira. The results show that fluid flow over an intrusion (heat and fluid source) develops a horizontal component if there is sufficient fracture connectivity. Late, steep fault zones have been identified in the deposit area, which locally contain low-temperature Zn-Pb mineralization. The model results confirm that the presence of subvertical faults with enhanced permeability play a crucial role in the ascent of magmatic fluids to the surface and the recharge of meteoric waters. Finally, our model results suggest that recharge of meteoric fluids and mixing processes may be important at later stages, while flow of magmatic fluids dominate the early stages of the hydrothermal fluid circulation.
Organic semiconductors are a promising class of materials. Their special properties are the particularly good absorption, low weight and easy processing into thin films. Therefore, intense research has been devoted to the realization of thin film organic solar cells (OPVs). Because of the low dielectric constant of organic semiconductors, primary excitations (excitons) are strongly bound and a type II heterojunction needs to be introduced to split these excitations into free charges. Therefore, most organic solar cells consist of at least an electron donor and electron acceptor material. For such donor acceptor systems mainly three states are relevant; the photoexcited exciton on the donor or acceptor material, the charge transfer state at the donor-acceptor interface and the charge separated state of a free electron and hole. The interplay between these states significantly determines the efficiency of organic solar cells. Due to the high absorption and the low charge carrier mobilities, the active layers are usually thin but also, exciton dissociation and free charge formation proceeds rapidely, which makes the study of carrier dynamics highly challenging.
Therefore, the focus of this work was first to install new experimental setups for the investigation of the charge carrier dynamics in complete devices with superior sensitivity and time resolution and, second, to apply these methods to prototypical photovoltaic materials to address specific questions in the field of organic and hybrid photovoltaics.
Regarding the first goal, a new setup combining transient absorption spectroscopy (TAS) and time delayed collection field (TDCF) was designed and installed in Potsdam. An important part of this work concerned the improvement of the electronic components with respect to time resolution and sensitivity. To this end, a highly sensitive amplifier for driving and detecting the device response in TDCF was developed. This system was then applied to selected organic and hybrid model systems with a particular focus on the understanding of the loss mechanisms that limit the fill factor and short circuit current of organic solar cells.
The first model system was a hybrid photovoltaic material comprising inorganic quantum dots decorated with organic ligands. Measurements with TDCF revealed fast free carrier recombination, in part assisted by traps, while bias-assisted charge extraction measurements showed high mobility. The measured parameters then served as input for a successful description of the device performance with an analytical model.
With a further improvement of the instrumentation, a second topic was the detailed analysis of non-geminate recombination in a disordered polymer:fullerene blend where an important question was the effect of disorder on the carrier dynamics. The measurements revealed that early time highly mobile charges undergo fast non-geminate recombination at the contacts, causing an apparent field dependence of free charge generation in TDCF experiments if not conducted properly. On the other hand, recombination the later time scale was determined by dispersive recombination in the bulk of the active layer, showing the characteristics of carrier dynamics in an exponential density of state distribution. Importantly, the comparison with steady state recombination data suggested a very weak impact of non-thermalized carriers on the recombination properties of the solar cells under application relevant illumination conditions.
Finally, temperature and field dependent studies of free charge generation were performed on three donor-acceptor combinations, with two donor polymers of the same material family blended with two different fullerene acceptor molecules. These particular material combinations were chosen to analyze the influence of the energetic and morphology of the blend on the efficiency of charge generation. To this end, activation energies for photocurrent generation were accurately determined for a wide range of excitation energies. The results prove that the formation of free charge is via thermalized charge transfer states and does not involve hot exciton splitting. Surprisingly, activation energies were of the order of thermal energy at room temperature. This led to the important conclusion that organic solar cells perform well not because of predominate high energy pathways but because the thermalized CT states are weakly bound. In addition, a model is introduced to interconnect the dissociation efficiency of the charge transfer state with its recombination observable with photoluminescence, which rules out a previously proposed two-pool model for free charge formation and recombination. Finally, based on the results, proposals for the further development of organic solar cells are formulated.
Continuous insight into biological processes has led to the development of large-scale, mechanistic systems biology models of pharmacologically relevant networks. While these models are typically designed to study the impact of diverse stimuli or perturbations on multiple system variables, the focus in pharmacological research is often on a specific input, e.g., the dose of a drug, and a specific output related to the drug effect or response in terms of some surrogate marker.
To study a chosen input-output pair, the complexity of the interactions as well as the size of the models hinders easy access and understanding of the details of the input-output relationship.
The objective of this thesis is the development of a mathematical approach, in specific a model reduction technique, that allows (i) to quantify the importance of the different state variables for a given input-output relationship, and (ii) to reduce the dynamics to its essential features -- allowing for a physiological interpretation of state variables as well as parameter estimation in the statistical analysis of clinical data. We develop a model reduction technique using a control theoretic setting by first defining a novel type of time-limited controllability and observability gramians for nonlinear systems. We then show the superiority of the time-limited generalised gramians for nonlinear systems in the context of balanced truncation for a benchmark system from control theory.
The concept of time-limited controllability and observability gramians is subsequently used to introduce a state and time-dependent quantity called the input-response (ir) index that quantifies the importance of state variables for a given input-response relationship at a particular time.
We subsequently link our approach to sensitivity analysis, thus, enabling for the first time the use of sensitivity coefficients for state space reduction. The sensitivity based ir-indices are given as a product of two sensitivity coefficients. This allows not only for a computational more efficient calculation but also for a clear distinction of the extent to which the input impacts a state variable and the extent to which a state variable impacts the output.
The ir-indices give insight into the coordinated action of specific state variables for a chosen input-response relationship.
Our developed model reduction technique results in reduced models that still allow for a mechanistic interpretation in terms of the quantities/state variables of the original system, which is a key requirement in the field of systems pharmacology and systems biology and distinguished the reduced models from so-called empirical drug effect models. The ir-indices are explicitly defined with respect to a reference trajectory and thereby dependent on the initial state (this is an important feature of the measure). This is demonstrated for an example from the field of systems pharmacology, showing that the reduced models are very informative in their ability to detect (genetic) deficiencies in certain physiological entities. Comparing our novel model reduction technique to the already existing techniques shows its superiority.
The novel input-response index as a measure of the importance of state variables provides a powerful tool for understanding the complex dynamics of large-scale systems in the context of a specific drug-response relationship. Furthermore, the indices provide a means for a very efficient model order reduction and, thus, an important step towards translating insight from biological processes incorporated in detailed systems pharmacology models into the population analysis of clinical data.