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A decade ago, it became feasible to store multi-terabyte databases in main memory. These in-memory databases (IMDBs) profit from DRAM's low latency and high throughput as well as from the removal of costly abstractions used in disk-based systems, such as the buffer cache. However, as the DRAM technology approaches physical limits, scaling these databases becomes difficult. Non-volatile memory (NVM) addresses this challenge. This new type of memory is persistent, has more capacity than DRAM (4x), and does not suffer from its density-inhibiting limitations. Yet, as NVM has a higher latency (5-15x) and a lower throughput (0.35x), it cannot fully replace DRAM.
IMDBs thus need to navigate the trade-off between the two memory tiers. We present a solution to this optimization problem. Leveraging information about access frequencies and patterns, our solution utilizes NVM's additional capacity while minimizing the associated access costs. Unlike buffer cache-based implementations, our tiering abstraction does not add any costs when reading data from DRAM. As such, it can act as a drop-in replacement for existing IMDBs. Our contributions are as follows:
(1) As the foundation for our research, we present Hyrise, an open-source, columnar IMDB that we re-engineered and re-wrote from scratch. Hyrise enables realistic end-to-end benchmarks of SQL workloads and offers query performance which is competitive with other research and commercial systems. At the same time, Hyrise is easy to understand and modify as repeatedly demonstrated by its uses in research and teaching.
(2) We present a novel memory management framework for different memory and storage tiers. By encapsulating the allocation and access methods of these tiers, we enable existing data structures to be stored on different tiers with no modifications to their implementation. Besides DRAM and NVM, we also support and evaluate SSDs and have made provisions for upcoming technologies such as disaggregated memory.
(3) To identify the parts of the data that can be moved to (s)lower tiers with little performance impact, we present a tracking method that identifies access skew both in the row and column dimensions and that detects patterns within consecutive accesses. Unlike existing methods that have substantial associated costs, our access counters exhibit no identifiable overhead in standard benchmarks despite their increased accuracy.
(4) Finally, we introduce a tiering algorithm that optimizes the data placement for a given memory budget. In the TPC-H benchmark, this allows us to move 90% of the data to NVM while the throughput is reduced by only 10.8% and the query latency is increased by 11.6%. With this, we outperform approaches that ignore the workload's access skew and access patterns and increase the query latency by 20% or more.
Individually, our contributions provide novel approaches to current challenges in systems engineering and database research. Combining them allows IMDBs to scale past the limits of DRAM while continuing to profit from the benefits of in-memory computing.
Subdividing space through interfaces leads to many space partitions that are relevant to soft matter self-assembly. Prominent examples include cellular media, e.g. soap froths, which are bubbles of air separated by interfaces of soap and water, but also more complex partitions such as bicontinuous minimal surfaces.
Using computer simulations, this thesis analyses soft matter systems in terms of the relationship between the physical forces between the system's constituents and the structure of the resulting interfaces or partitions. The focus is on two systems, copolymeric self-assembly and the so-called Quantizer problem, where the driving force of structure formation, the minimisation of the free-energy, is an interplay of surface area minimisation and stretching contributions, favouring cells of uniform thickness.
In the first part of the thesis we address copolymeric phase formation with sharp interfaces. We analyse a columnar copolymer system "forced" to assemble on a spherical surface, where the perfect solution, the hexagonal tiling, is topologically prohibited. For a system of three-armed copolymers, the resulting structure is described by solutions of the so-called Thomson problem, the search of minimal energy configurations of repelling charges on a sphere. We find three intertwined Thomson problem solutions on a single sphere, occurring at a probability depending on the radius of the substrate.
We then investigate the formation of amorphous and crystalline structures in the Quantizer system, a particulate model with an energy functional without surface tension that favours spherical cells of equal size. We find that quasi-static equilibrium cooling allows the Quantizer system to crystallise into a BCC ground state, whereas quenching and non-equilibrium cooling, i.e. cooling at slower rates then quenching, leads to an approximately hyperuniform, amorphous state. The assumed universality of the latter, i.e. independence of energy minimisation method or initial configuration, is strengthened by our results. We expand the Quantizer system by introducing interface tension, creating a model that we find to mimic polymeric micelle systems: An order-disorder phase transition is observed with a stable Frank-Caspar phase.
The second part considers bicontinuous partitions of space into two network-like domains, and introduces an open-source tool for the identification of structures in electron microscopy images. We expand a method of matching experimentally accessible projections with computed projections of potential structures, introduced by Deng and Mieczkowski (1998). The computed structures are modelled using nodal representations of constant-mean-curvature surfaces. A case study conducted on etioplast cell membranes in chloroplast precursors establishes the double Diamond surface structure to be dominant in these plant cells. We automate the matching process employing deep-learning methods, which manage to identify structures with excellent accuracy.
While estimated numbers of past and future climate migrants are alarming, the growing empirical evidence suggests that the association between adverse climate-related events and migration is not universally positive. This dissertation seeks to advance our understanding of when and how climate migration emerges by analyzing heterogeneous climatic influences on migration in low- and middle-income countries. To this end, it draws on established economic theories of migration, datasets from physical and social sciences, causal inference techniques and approaches from systematic literature review. In three of its five chapters, I estimate causal effects of processes of climate change on inequality and migration in India and Sub-Saharan Africa. By employing interaction terms and by analyzing sub-samples of data, I explore how these relationships differ for various segments of the population. In the remaining two chapters, I present two systematic literature reviews. First, I undertake a comprehensive meta-regression analysis of the econometric climate migration literature to summarize general climate migration patterns and explain the conflicting findings. Second, motivated by the broad range of approaches in the field, I examine the literature from a methodological perspective to provide best practice guidelines for studying climate migration empirically. Overall, the evidence from this dissertation shows that climatic influences on human migration are highly heterogeneous. Whether adverse climate-related impacts materialize in migration depends on the socio-economic characteristics of the individual households, such as wealth, level of education, agricultural dependence or access to adaptation technologies and insurance. For instance, I show that while adverse climatic shocks are generally associated with an increase in migration in rural India, they reduce migration in the agricultural context of Sub-Saharan Africa, where the average wealth levels are much lower so that households largely cannot afford the upfront costs of moving. I find that unlike local climatic shocks which primarily enhance internal migration to cities and hence accelerate urbanization, shocks transmitted via agricultural producer prices increase migration to neighboring countries, likely due to the simultaneous decrease in real income in nearby urban areas. These findings advance our current understanding by showing when and how economic agents respond to climatic events, thus providing explicit contexts and mechanisms of climate change effects on migration in the future. The resulting collection of findings can guide policy interventions to avoid or mitigate any present and future welfare losses from climate change-related migration choices.
Writing travel, writing life
(2022)
The book compares the texts of three Swiss authors: Ella Maillart, Annemarie Schwarzenbach and Nicolas Bouvier. The focus is on their trip from Genève to Kabul that Ella Maillart and Annemarie Schwarzenbach made together in 1939/1940 and Nicolas Bouvier 1953/1954 with the artist Thierry Vernet. The comparison shows the strong connection between the journey and life and between ars vivendi and travel literature.
This book also gives an overview of and organises the numerous terms, genres, and categories that already exist to describe various travel texts and proposes the new term travelling narration. The travelling narration looks at the text from a narratological perspective that distinguishes the author, narrator, and protagonist within the narration.
In the examination, ten motifs could be found to characterise the travelling narration: Culture, Crossing Borders, Freedom, Time and Space, the Aesthetics of Landscapes, Writing and Reading, the Self and/as the Other, Home, Religion and Spirituality as well as the Journey. The importance of each individual motif does not only apply in the 1930s or 1950s but also transmits important findings for living together today and in the future.
Flares are magnetically driven explosions that occur in the atmospheres of all main sequence stars that possess an outer convection zone. Flaring activity is rooted in the magnetic dynamo that operates deep in the stellar interior, propagates through all layers of the atmosphere from the corona to the photosphere, and emits electromagnetic radiation from radio bands to X-ray. Eventually, this radiation, and associated eruptions of energetic particles, are ejected out into interplanetary space, where they impact planetary atmospheres, and dominate the space weather environments of young star-planet systems.
Thanks to the Kepler and the Transit Exoplanet Survey Satellite (TESS) missions, flare observations have become accessible for millions of stars and star-planet systems. The goal of this thesis is to use these flares as multifaceted messengers to understand stellar magnetism across the main sequence, investigate planetary habitability, and explore how close-in planets can affect the host star.
Using space based observations obtained by the Kepler/K2 mission, I found that flaring activity declines with stellar age, but this decline crucially depends on stellar mass and rotation. I calibrated the age of the stars in my sample using their membership in open clusters from zero age main sequence to solar age. This allowed me to reveal the rapid transition from an active, saturated flaring state to a more quiescent, inactive flaring behavior in early M dwarfs at about 600-800 Myr. This result is an important observational constraint on stellar activity evolution that I was able to de-bias using open clusters as an activity-independent age indicator.
The TESS mission quickly superseded Kepler and K2 as the main source of flares in low mass M dwarfs. Using TESS 2-minute cadence light curves, I developed a new technique for flare localization and discovered, against the commonly held belief, that flares do not occur uniformly across their stellar surface: In fast rotating fully convective stars, giant flares are preferably located at high latitudes. This bears implications for both our understanding of magnetic field emergence in these stars, and the impact on the exoplanet atmospheres: A planet that orbits in the equatorial plane of its host may be spared from the destructive effects of these poleward emitting flares.
AU Mic is an early M dwarf, and the most actively flaring planet host detected to date. Its innermost companion, AU Mic b is one of the most promising targets for a first observation of flaring star-planet interactions. In these interactions, the planet influences the star, as opposed to space weather, where the planet is always on the receiving side. The effect reflects the properties of the magnetosphere shared by planet and star, as well as the so far inaccessible magnetic properties of planets. In the about 50 days of TESS monitoring data of AU Mic, I searched for statistically robust signs of flaring interactions with AU Mic b as flares that occur in surplus of the star's intrinsic activity. I found the strongest yet still marginal signal in recurring excess flaring in phase with the orbital period of AU Mic b. If it reflects true signal, I estimate that extending the observing time by a factor of 2-3 will yield a statistically significant detection. Well within the reach of future TESS observations, this additional data may bring us closer to robustly detecting this effect than we have ever been.
This thesis demonstrates the immense scientific value of space based, long baseline flare monitoring, and the versatility of flares as a carrier of information about the magnetism of star-planet systems. Many discoveries still lay in wait in the vast archives that Kepler and TESS have produced over the years. Flares are intense spotlights into the magnetic structures in star-planet systems that are otherwise far below our resolution limits. The ongoing TESS mission, and soon PLATO, will further open the door to in-depth understanding of small and dynamic scale magnetic fields on low mass stars, and the space weather environment they effect.
Due to the major role of greenhouse gas emissions in global climate change, the development of non-fossil energy technologies is essential. Deep geothermal energy represents such an alternative, which offers promising properties such as a high base load capability and a large untapped potential. The present work addresses barite precipitation within geothermal systems and the associated reduction in rock permeability, which is a major obstacle to maintaining high efficiency. In this context, hydro-geochemical models are essential to quantify and predict the effects of precipitation on the efficiency of a system.
The objective of the present work is to quantify the induced injectivity loss using numerical and analytical reactive transport simulations. For the calculations, the fractured-porous reservoirs of the German geothermal regions North German Basin (NGB) and Upper Rhine Graben (URG) are considered.
Similar depth-dependent precipitation potentials could be determined for both investigated regions (2.8-20.2 g/m3 fluid). However, the reservoir simulations indicate that the injectivity loss due to barite deposition in the NGB is significant (1.8%-6.4% per year) and the longevity of the system is affected as a result; this is especially true for deeper reservoirs (3000 m). In contrast, simulations of URG sites indicate a minor role of barite (< 0.1%-1.2% injectivity loss per year). The key differences between the investigated regions are reservoir thicknesses and the presence of fractures in the rock, as well as the ionic strength of the fluids. The URG generally has fractured-porous reservoirs with much higher thicknesses, resulting in a greater distribution of precipitates in the subsurface. Furthermore, ionic strengths are higher in the NGB, which accelerates barite precipitation, causing it to occur more concentrated around the wellbore. The more concentrated the precipitates occur around the wellbore, the higher the injectivity loss.
In this work, a workflow was developed within which numerical and analytical models can be used to estimate and quantify the risk of barite precipitation within the reservoir of geothermal systems. A key element is a newly developed analytical scaling score that provides a reliable estimate of induced injectivity loss. The key advantage of the presented approach compared to fully coupled reservoir simulations is its simplicity, which makes it more accessible to plant operators and decision makers. Thus, in particular, the scaling score can find wide application within geothermal energy, e.g., in the search for potential plant sites and the estimation of long-term efficiency.
Climate change is one of the greatest challenges to humanity in this century, and most noticeable consequences are expected to be impacts on the water cycle – in particular the distribution and availability of water, which is fundamental for all life on Earth. In this context, it is essential to better understand where and when water is available and what processes influence variations in water storages. While estimates of the overall terrestrial water storage (TWS) variations are available from the GRACE satellites, these represent the vertically integrated signal over all water stored in ice, snow, soil moisture, groundwater and surface water bodies. Therefore, complementary observational data and hydrological models are still required to determine the partitioning of the measured signal among different water storages and to understand the underlying processes. However, the application of large-scale observational data is limited by their specific uncertainties and the incapacity to measure certain water fluxes and storages. Hydrological models, on the other hand, vary widely in their structure and process-representation, and rarely incorporate additional observational data to minimize uncertainties that arise from their simplified representation of the complex hydrologic cycle.
In this context, this thesis aims to contribute to improving the understanding of global water storage variability by combining simple hydrological models with a variety of complementary Earth observation-based data. To this end, a model-data integration approach is developed, in which the parameters of a parsimonious hydrological model are calibrated against several observational constraints, inducing GRACE TWS, simultaneously, while taking into account each data’s specific strengths and uncertainties. This approach is used to investigate 3 specific aspects that are relevant for modelling and understanding the composition of large-scale TWS variations.
The first study focusses on Northern latitudes, where snow and cold-region processes define the hydrological cycle. While the study confirms previous findings that seasonal dynamics of TWS are dominated by the cyclic accumulation and melt of snow, it reveals that inter-annual TWS variations on the contrary, are determined by variations in liquid water storages. Additionally, it is found to be important to consider the impact of compensatory effects of spatially heterogeneous hydrological variables when aggregating the contribution of different storage components over large areas. Hence, the determinants of TWS variations are scale-dependent and underlying driving mechanism cannot be simply transferred between spatial and temporal scales. These findings are supported by the second study for the global land areas beyond the Northern latitudes as well.
This second study further identifies the considerable impact of how vegetation is represented in hydrological models on the partitioning of TWS variations. Using spatio-temporal varying fields of Earth observation-based data to parameterize vegetation activity not only significantly improves model performance, but also reduces parameter equifinality and process uncertainties. Moreover, the representation of vegetation drastically changes the contribution of different water storages to overall TWS variability, emphasizing the key role of vegetation for water allocation, especially between sub-surface and delayed water storages. However, the study also identifies parameter equifinality regarding the decay of sub-surface and delayed water storages by either evapotranspiration or runoff, and thus emphasizes the need for further constraints hereof.
The third study focuses on the role of river water storage, in particular whether it is necessary to include computationally expensive river routing for model calibration and validation against the integrated GRACE TWS. The results suggest that river routing is not required for model calibration in such a global model-data integration approach, due to the larger influence other observational constraints, and the determinability of certain model parameters and associated processes are identified as issues of greater relevance. In contrast to model calibration, considering river water storage derived from routing schemes can already significantly improve modelled TWS compared to GRACE observations, and thus should be considered for model evaluation against GRACE data.
Beyond these specific findings that contribute to improved understanding and modelling of large-scale TWS variations, this thesis demonstrates the potential of combining simple modeling approaches with diverse Earth observational data to improve model simulations, overcome inconsistencies of different observational data sets, and identify areas that require further research. These findings encourage future efforts to take advantage of the increasing number of diverse global observational data.
Sustainable urban growth
(2022)
This dissertation explores the determinants for sustainable and socially optimalgrowth in a city. Two general equilibrium models establish the base for this evaluation, each adding its puzzle piece to the urban sustainability discourse and examining the role of non-market-based and market-based policies for balanced growth and welfare improvements in different theory settings. Sustainable urban growth either calls for policy actions or a green energy transition. Further, R&D market failures can pose severe challenges to the sustainability of urban growth and the social optimality of decentralized allocation decisions. Still, a careful (holistic) combination of policy instruments can achieve sustainable growth and even be first best.
The motivation for this work was the question of reliability and robustness of seismic tomography. The problem is that many earth models exist which can describe the underlying ground motion records equally well. Most algorithms for reconstructing earth models provide a solution, but rarely quantify their variability. If there is no way to verify the imaged structures, an interpretation is hardly reliable. The initial idea was to explore the space of equivalent earth models using Bayesian inference. However, it quickly became apparent that the rigorous quantification of tomographic uncertainties could not be accomplished within the scope of a dissertation.
In order to maintain the fundamental concept of statistical inference, less complex problems from the geosciences are treated instead. This dissertation aims to anchor Bayesian inference more deeply in the geosciences and to transfer knowledge from applied mathematics. The underlying idea is to use well-known methods and techniques from statistics to quantify the uncertainties of inverse problems in the geosciences. This work is divided into three parts:
Part I introduces the necessary mathematics and should be understood as a kind of toolbox. With a physical application in mind, this section provides a compact summary of all methods and techniques used. The introduction of Bayesian inference makes the beginning. Then, as a special case, the focus is on regression with Gaussian processes under linear transformations. The chapters on the derivation of covariance functions and the approximation of non-linearities are discussed in more detail.
Part II presents two proof of concept studies in the field of seismology. The aim is to present the conceptual application of the introduced methods and techniques with moderate complexity. The example about traveltime tomography applies the approximation of non-linear relationships. The derivation of a covariance function using the wave equation is shown in the example of a damped vibrating string. With these two synthetic applications, a consistent concept for the quantification of modeling uncertainties has been developed.
Part III presents the reconstruction of the Earth's archeomagnetic field. This application uses the whole toolbox presented in Part I and is correspondingly complex. The modeling of the past 1000 years is based on real data and reliably quantifies the spatial modeling uncertainties. The statistical model presented is widely used and is under active development.
The three applications mentioned are intentionally kept flexible to allow transferability to similar problems. The entire work focuses on the non-uniqueness of inverse problems in the geosciences. It is intended to be of relevance to those interested in the concepts of Bayesian inference.
Plate tectonics describes the movement of rigid plates at the surface of the Earth as well as their complex deformation at three types of plate boundaries: 1) divergent boundaries such as rift zones and mid-ocean ridges, 2) strike-slip boundaries where plates grind past each other, such as the San Andreas Fault, and 3) convergent boundaries that form large mountain ranges like the Andes. The generally narrow deformation zones that bound the plates exhibit complex strain patterns that evolve through time. During this evolution, plate boundary deformation is driven by tectonic forces arising from Earth’s deep interior and from within the lithosphere, but also by surface processes, which erode topographic highs and deposit the resulting sediment into regions of low elevation. Through the combination of these factors, the surface of the Earth evolves in a highly dynamic way with several feedback mechanisms. At divergent boundaries, for example, tensional stresses thin the lithosphere, forcing uplift and subsequent erosion of rift flanks, which creates a sediment source. Meanwhile, the rift center subsides and becomes a topographic low where sediments accumulate. This mass transfer from foot- to hanging wall plays an important role during rifting, as it prolongs the activity of individual normal faults. When rifting continues, continents are eventually split apart, exhuming Earth’s mantle and creating new oceanic crust. Because of the complex interplay between deep tectonic forces that shape plate boundaries and mass redistribution at the Earth’s surface, it is vital to understand feedbacks between the two domains and how they shape our planet.
In this study I aim to provide insight on two primary questions: 1) How do divergent and strike-slip plate boundaries evolve? 2) How is this evolution, on a large temporal scale and a smaller structural scale, affected by the alteration of the surface through erosion and deposition? This is done in three chapters that examine the evolution of divergent and strike-slip plate boundaries using numerical models. Chapter 2 takes a detailed look at the evolution of rift systems using two-dimensional models. Specifically, I extract faults from a range of rift models and correlate them through time to examine how fault networks evolve in space and time. By implementing a two-way coupling between the geodynamic code ASPECT and landscape evolution code FastScape, I investigate how the fault network and rift evolution are influenced by the system’s erosional efficiency, which represents many factors like lithology or climate. In Chapter 3, I examine rift evolution from a three-dimensional perspective. In this chapter I study linkage modes for offset rifts to determine when fast-rotating plate-boundary structures known as continental microplates form. Chapter 4 uses the two-way numerical coupling between tectonics and landscape evolution to investigate how a strike-slip boundary responds to large sediment loads, and whether this is sufficient to form an entirely new type of flexural strike-slip basin.
This study explores the identity of the Bene Israel caste from India and its assimilation into Israeli society. The large immigration from India to Israel started in the early 1950s and continued until the early 1970s. Initially, these immigrants struggled hard as they faced many problems such as the language barrier, cultural differences, a new climate, geographical isolation, and racial discrimination. This analysis focuses on the three major aspects of the integration process involving the Bene Israel: economic, socio-cultural and political. The study covers the period from the early fifties to the present.
I will focus on the origin of the Bene Israel, which has evolved after their immigration to Israel; from a Hindu–Muslim lifestyle and customs they integrated into the Jewish life of Israel. Despite its ethnographic nature, this study has theological implications as it is an encounter between Jewish monotheism and Indian polytheism.
All the western scholars who researched the Bene Israel community felt impelled to rely on information received by community members themselves. No written historical evidence recorded Bene Israel culture and origin. Only during the nineteenth century onwards, after the intrusion of western Jewish missionaries, were Jewish books translated into Marathi . Missionary activities among the Bene Israel served as a catalyst for the Bene Israel themselves to investigate their historical past . Haeem Samuel Kehimkar (1830-1908), a Bene Israel teacher, wrote notes on the history of the Bene Israel in India in Marathi in 1897. Brenda Ness wrote in her dissertation:
The results [of the missionary activities] are several works about the community in English and Marathi by Bene-Israel authors which have appeared during the last century. These are, for the most part, not documented; they consist of much theorizing on accepted tradition and tend to be apologetic in nature.
There can be no philosophical explanation or rational justification for an entire community to leave their motherland India, and enter into a process of annihilation of its own free will. I see this as a social and cultural suicide. In craving for a better future in Israel, the Indian Bene Israel community pays an enormously heavy price as a people that are today discarded by the East and disowned by the West: because they chose to become something that they never were and never could be. As it is written, “know where you came from, and where you are going.” A community with an ancient history from a spiritual culture has completely lost its identity and self-esteem.
In concluding this dissertation, I realize the dilemma with which I have confronted the members of the Bene Israel community which I have reviewed after strenuous and constant self-examination. I chose to evolve the diversifications of the younger generations urges towards acceptance, and wish to clarify my intricate analysis of this controversial community. The complexity of living in a Jewish State, where citizens cannot fulfill their basic desires, like matrimony, forced an entire community to conceal their true identity and perjure themselves to blend in, for the sake of national integration. Although scholars accepted their new claims, the skepticism of the rabbinate authorities prevails, and they refuse to marry them to this day, suspecting they are an Indian caste.
In the present thesis I investigate the lattice dynamics of thin film hetero structures of magnetically ordered materials upon femtosecond laser excitation as a probing and manipulation scheme for the spin system. The quantitative assessment of laser induced thermal dynamics as well as generated picosecond acoustic pulses and their respective impact on the magnetization dynamics of thin films is a challenging endeavor. All the more, the development and implementation of effective experimental tools and comprehensive models are paramount to propel future academic and technological progress.
In all experiments in the scope of this cumulative dissertation, I examine the crystal lattice of nanoscale thin films upon the excitation with femtosecond laser pulses. The relative change of the lattice constant due to thermal expansion or picosecond strain pulses is directly monitored by an ultrafast X-ray diffraction (UXRD) setup with a femtosecond laser-driven plasma X-ray source (PXS). Phonons and spins alike exert stress on the lattice, which responds according to the elastic properties of the material, rendering the lattice a versatile sensor for all sorts of ultrafast interactions. On the one hand, I investigate materials with strong magneto-elastic properties; The highly magnetostrictive rare-earth compound TbFe2, elemental Dysprosium or the technological relevant Invar material FePt. On the other hand I conduct a comprehensive study on the lattice dynamics of Bi1Y2Fe5O12 (Bi:YIG), which exhibits high-frequency coherent spin dynamics upon femtosecond laser excitation according to the literature. Higher order standing spinwaves (SSWs) are triggered by coherent and incoherent motion of atoms, in other words phonons, which I quantified with UXRD. We are able to unite the experimental observations of the lattice and magnetization dynamics qualitatively and quantitatively. This is done with a combination of multi-temperature, elastic, magneto-elastic, anisotropy and micro-magnetic modeling.
The collective data from UXRD, to probe the lattice, and time-resolved magneto-optical Kerr effect (tr-MOKE) measurements, to monitor the magnetization, were previously collected at different experimental setups. To improve the precision of the quantitative assessment of lattice and magnetization dynamics alike, our group implemented a combination of UXRD and tr-MOKE in a singular experimental setup, which is to my knowledge, the first of its kind. I helped with the conception and commissioning of this novel experimental station, which allows the simultaneous observation of lattice and magnetization dynamics on an ultrafast timescale under identical excitation conditions. Furthermore, I developed a new X-ray diffraction measurement routine which significantly reduces the measurement time of UXRD experiments by up to an order of magnitude. It is called reciprocal space slicing (RSS) and utilizes an area detector to monitor the angular motion of X-ray diffraction peaks, which is associated with lattice constant changes, without a time-consuming scan of the diffraction angles with the goniometer. RSS is particularly useful for ultrafast diffraction experiments, since measurement time at large scale facilities like synchrotrons and free electron lasers is a scarce and expensive resource. However, RSS is not limited to ultrafast experiments and can even be extended to other diffraction techniques with neutrons or electrons.
In this thesis, I present my contributions to the field of ultrafast molecular spectroscopy. Using the molecule 2-thiouracil as an example, I use ultrashort x-ray pulses from free- electron lasers to study the relaxation dynamics of gas-phase molecular samples. Taking advantage of the x-ray typical element- and site-selectivity, I investigate the charge flow and geometrical changes in the excited states of 2-thiouracil.
In order to understand the photoinduced dynamics of molecules, knowledge about the ground-state structure and the relaxation after photoexcitation is crucial. Therefore, a part of this thesis covers the electronic ground-state spectroscopy of mainly 2-thiouracil to provide the basis for the time-resolved experiments. Many of the previously published studies that focused on the gas-phase time-resolved dynamics of thionated uracils after UV excitation relied on information from solution phase spectroscopy to determine the excitation energies. This is not an optimal strategy as solvents alter the absorption spec- trum and, hence, there is no guarantee that liquid-phase spectra resemble the gas-phase spectra. Therefore, I measured the UV-absorption spectra of all three thionated uracils to provide a gas-phase reference and, in combination with calculations, we determined the excited states involved in the transitions.
In contrast to the UV absorption, the literature on the x-ray spectroscopy of thionated uracil is sparse. Thus, we measured static photoelectron, Auger-Meitner and x-ray absorption spectra on the sulfur L edge before or parallel to the time-resolved experiments we performed at FLASH (DESY, Hamburg). In addition, (so far unpublished) measurements were performed at the synchrotron SOLEIL (France) which have been included in this thesis and show the spin-orbit splitting of the S 2p photoline and its satellite which was not observed at the free-electron laser.
The relaxation of 2-thiouracil has been studied extensively in recent years with ultrafast visible and ultraviolet methods showing the ultrafast nature of the molecular process after photoexcitation. Ultrafast spectroscopy probing the core-level electrons provides a complementary approach to common optical ultrafast techniques. The method inherits its local sensitivity from the strongly localised core electrons. The core energies and core-valence transitions are strongly affected by local valence charge and geometry changes, and past studies have utilised this sensitivity to investigate the molecular process reflected by the ultrafast dynamics. We have built an apparatus that provides the requirements to perform time-resolved x-ray spectroscopy on molecules in the gas phase. With the apparatus, we performed UV-pump x-ray-probe electron spectroscopy on the S 2p edge of 2-thiouracil using the free-electron laser FLASH2. While the UV triggers the relaxation dynamics, the x-ray probes the single sulfur atom inside the molecule. I implemented photoline self-referencing for the photoelectron spectral analysis. This minimises the spectral jitter of the FEL, which is due to the underlying self-amplified spontaneous emission (SASE) process. With this approach, we were not only able to study dynamical changes in the binding energy of the electrons but also to detect an oscillatory behaviour in the shift of the observed photoline, which we associate with non-adiabatic dynamics involving several electronic states. Moreover, we were able to link the UV-induced shift in binding energy to the local charge flow at the sulfur which is directly connected to the electronic state. Furthermore, the analysis of the Auger-Meitner electrons shows that energy shifts observed at early stages of the photoinduced relaxation are related to the geometry change in the molecule. More specifically, the observed increase in kinetic energy of the Auger-Meitner electrons correlates with a previously predicted C=S bond stretch.
One aspect of achieving a more sustainable chemical industry is the minimization of the usage of solvents and chemicals. Thus, optimization and development of chemical processes for large-scale production is favourably performed in small batches. The critical step in this approach is upscaling the batches from the small reaction systems to the large reactors mandatory for cost efficient production in an industrial environment. Scaling up the bulk volume always goes along with increasing the surface where the reaction medium is in contact with the confining vessel. Since volume scales proportional with the cubic dimension while the surface scales quadratic, their ratio is size-dependent. The influence of reaction vessel walls can change the reaction performance. A number of phenomena occurring at the surface-liquid interface can affect reaction rates and yields, resulting in possible difficulties in predicting and extrapolating from small size production scale to large industrial processes. The application of levitated droplets as a containerless reaction vessels provides a promising possibility to avoid the above-mentioned issues.
In the presented work, an efficient coupling of acoustically levitated droplets to an ion mobility (IM) spectrometer, operating at ambient conditions, was designed for real-time monitoring of chemical reactions. The design of the system comprises noncontact sampling and ionization of the droplet realised by laser desorption/ionization at 2,94 µm. The scope of the work includes fundamental studies covering understanding of laser irradiation of droplets enclosed in an acoustical field. Understanding of this phenomenon is crucial to comprehending the effects of temporal and spatial resolution of the generated ion plume that influence the resolution of the system.
The set-up includes an acoustic trap, laser irradiation and ion manipulation electrostatic lenses operating at high voltage at ambient pressure. The complexity of the design needs to fully be considered for an effective ion transfer at the interface region between the levitated droplet and IM spectrometer. For sampling and ionization, two distinct laser pulse lengths were evaluated, ns and µs. Irradiation via µs laser pulses provides several advantages: i) the droplet volume is not extensively impinged, as in case of ns laser pulses, allowing the sampling of only the small volume of the droplet; ii) the lower fluence results in less pronounced oscillations of the droplet confined in the acoustic field. The droplet will not be dissipated out of the acoustic field leading to loss of the sample; iii) the mild laser irradiation results in better spatial and temporal ion plume confinement, leading to better resolution of the detected ion packets. Finally, this knowledge allows the application of ion optics necessary to induce ion flow between the droplet suspended in the acoustic field and the IM spectrometer. The ion optics, composed of 2 electrostatic lenses placed in the near vicinity of the droplet, allow effective focusing of the ion plume and its redirection directly to the IM spectrometer entrance. This novel coupling has proved to be successful for detection of some simple molecules ionizable at the 2.94 µm wavelength. To further demonstrate the applicability of the system, a proof-of-principle reaction was selected, fulfilling the requirements of the system, and was subjected to comprehensive investigation of its performance. Herein, the reaction between N-Boc cysteine methyl ester and allyl alcohol has been performed in a batch reactor and on-line monitored via 1H NMR to establish reaction propagation. With the additional assessment, it was confirmed that the thiol-ene coupling can be performed within first 20 minutes of the irradiation with a reaction yield above 50%, proving that the reaction can be applied as a study case to assess the possibilities of the developed system.
Digital transformation (DT) has not only been a major challenge in recent years, it is also supposed to continue to enormously impact our society and economy in the forthcoming decade. On the one hand, digital technologies have emerged, diffusing and determining our private and professional lives. On the other hand, digital platforms have leveraged the potentials of digital technologies to provide new business models. These dynamics have a massive effect on individuals, companies, and entire ecosystems. Digital technologies and platforms have changed the way persons consume or interact with each other. Moreover, they offer companies new opportunities to conduct their business in terms of value creation (e.g., business processes), value proposition (e.g., business models), or customer interaction (e.g., communication channels), i.e., the three dimensions of DT. However, they also can become a threat for a company's competitiveness or even survival. Eventually, the emergence, diffusion, and employment of digital technologies and platforms bear the potential to transform entire markets and ecosystems.
Against this background, IS research has explored and theorized the phenomena in the context of DT in the past decade, but not to its full extent. This is not surprising, given the complexity and pervasiveness of DT, which still requires far more research to further understand DT with its interdependencies in its entirety and in greater detail, particularly through the IS perspective at the confluence of technology, economy, and society. Consequently, the IS research discipline has determined and emphasized several relevant research gaps for exploring and understanding DT, including empirical data, theories as well as knowledge of the dynamic and transformative capabilities of digital technologies and platforms for both organizations and entire industries.
Hence, this thesis aims to address these research gaps on the IS research agenda and consists of two streams. The first stream of this thesis includes four papers that investigate the impact of digital technologies on organizations. In particular, these papers study the effects of new technologies on firms (paper II.1) and their innovative capabilities (II.2), the nature and characteristics of data-driven business models (II.3), and current developments in research and practice regarding on-demand healthcare (II.4). Consequently, the papers provide novel insights on the dynamic capabilities of digital technologies along the three dimensions of DT. Furthermore, they offer companies some opportunities to systematically explore, employ, and evaluate digital technologies to modify or redesign their organizations or business models.
The second stream comprises three papers that explore and theorize the impact of digital platforms on traditional companies, markets, and the economy and society at large. At this, paper III.1 examines the implications for the business of traditional insurance companies through the emergence and diffusion of multi-sided platforms, particularly in terms of value creation, value proposition, and customer interaction. Paper III.2 approaches the platform impact more holistically and investigates how the ongoing digital transformation and "platformization" in healthcare lastingly transform value creation in the healthcare market. Paper III.3 moves on from the level of single businesses or markets to the regulatory problems that result from the platform economy for economy and society, and proposes appropriate regulatory approaches for addressing these problems. Hence, these papers bring new insights on the table about the transformative capabilities of digital platforms for incumbent companies in particular and entire ecosystems in general.
Altogether, this thesis contributes to the understanding of the impact of DT on organizations and markets through the conduction of multiple-case study analyses that are systematically reflected with the current state of the art in research. On this empirical basis, the thesis also provides conceptual models, taxonomies, and frameworks that help describing, explaining, or predicting the impact of digital technologies and digital platforms on companies, markets and the economy or society at large from an interdisciplinary viewpoint.
Accurately solving classification problems nowadays is likely to be the most relevant machine learning task. Binary classification separating two classes only is algorithmically simpler but has fewer potential applications as many real-world problems are multi-class. On the reverse, separating only a subset of classes simplifies the classification task. Even though existing multi-class machine learning algorithms are very flexible regarding the number of classes, they assume that the target set Y is fixed and cannot be restricted once the training is finished. On the other hand, existing state-of-the-art production environments are becoming increasingly interconnected with the advance of Industry 4.0 and related technologies such that additional information can simplify the respective classification problems. In light of this, the main aim of this thesis is to introduce dynamic classification that generalizes multi-class classification such that the target class set can be restricted arbitrarily to a non-empty class subset M of Y at any time between two consecutive predictions.
This task is solved by a combination of two algorithmic approaches. First, classifier calibration, which transforms predictions into posterior probability estimates that are intended to be well calibrated. The analysis provided focuses on monotonic calibration and in particular corrects wrong statements that appeared in the literature. It also reveals that bin-based evaluation metrics, which became popular in recent years, are unjustified and should not be used at all. Next, the validity of Platt scaling, which is the most relevant parametric calibration approach, is analyzed in depth. In particular, its optimality for classifier predictions distributed according to four different families of probability distributions as well its equivalence with Beta calibration up to a sigmoidal preprocessing are proven. For non-monotonic calibration, extended variants on kernel density estimation and the ensemble method EKDE are introduced. Finally, the calibration techniques are evaluated using a simulation study with complete information as well as on a selection of 46 real-world data sets.
Building on this, classifier calibration is applied as part of decomposition-based classification that aims to reduce multi-class problems to simpler (usually binary) prediction tasks. For the involved fusing step performed at prediction time, a new approach based on evidence theory is presented that uses classifier calibration to model mass functions. This allows the analysis of decomposition-based classification against a strictly formal background and to prove closed-form equations for the overall combinations. Furthermore, the same formalism leads to a consistent integration of dynamic class information, yielding a theoretically justified and computationally tractable dynamic classification model. The insights gained from this modeling are combined with pairwise coupling, which is one of the most relevant reduction-based classification approaches, such that all individual predictions are combined with a weight. This not only generalizes existing works on pairwise coupling but also enables the integration of dynamic class information.
Lastly, a thorough empirical study is performed that compares all newly introduced approaches to existing state-of-the-art techniques. For this, evaluation metrics for dynamic classification are introduced that depend on corresponding sampling strategies. Thereafter, these are applied during a three-part evaluation. First, support vector machines and random forests are applied on 26 data sets from the UCI Machine Learning Repository. Second, two state-of-the-art deep neural networks are evaluated on five benchmark data sets from a relatively recent reference work. Here, computationally feasible strategies to apply the presented algorithms in combination with large-scale models are particularly relevant because a naive application is computationally intractable. Finally, reference data from a real-world process allowing the inclusion of dynamic class information are collected and evaluated. The results show that in combination with support vector machines and random forests, pairwise coupling approaches yield the best results, while in combination with deep neural networks, differences between the different approaches are mostly small to negligible. Most importantly, all results empirically confirm that dynamic classification succeeds in improving the respective prediction accuracies. Therefore, it is crucial to pass dynamic class information in respective applications, which requires an appropriate digital infrastructure.
Enhanced geothermal systems (EGS) are considered a cornerstone of future sustainable energy production. In such systems, high-pressure fluid injections break the rock to provide pathways for water to circulate in and heat up. This approach inherently induces small seismic events that, in rare cases, are felt or can even cause damage. Controlling and reducing the seismic impact of EGS is crucial for a broader public acceptance. To evaluate the applicability of hydraulic fracturing (HF) in EGS and to improve the understanding of fracturing processes and the hydromechanical relation to induced seismicity, six in-situ, meter-scale HF experiments with different injection schemes were performed under controlled conditions in crystalline rock in a depth of 410 m at the Äspö Hard Rock Laboratory (Sweden).
I developed a semi-automated, full-waveform-based detection, classification, and location workflow to extract and characterize the acoustic emission (AE) activity from the continuous recordings of 11 piezoelectric AE sensors. Based on the resulting catalog of 20,000 AEs, with rupture sizes of cm to dm, I mapped and characterized the fracture growth in great detail. The injection using a novel cyclic injection scheme (HF3) had a lower seismic impact than the conventional injections. HF3 induced fewer AEs with a reduced maximum magnitude and significantly larger b-values, implying a decreased number of large events relative to the number of small ones. Furthermore, HF3 showed an increased fracture complexity with multiple fractures or a fracture network. In contrast, the conventional injections developed single, planar fracture zones (Publication 1).
An independent, complementary approach based on a comparison of modeled and observed tilt exploits transient long-period signals recorded at the horizontal components of two broad-band seismometers a few tens of meters apart from the injections. It validated the efficient creation of hydraulic fractures and verified the AE-based fracture geometries. The innovative joint analysis of AEs and tilt signals revealed different phases of the fracturing process, including the (re-)opening, growth, and aftergrowth of fractures, and provided evidence for the reactivation of a preexisting fault in one of the experiments (Publication 2). A newly developed network-based waveform-similarity analysis applied to the massive AE activity supports the latter finding.
To validate whether the reduction of the seismic impact as observed for the cyclic injection schemes during the Äspö mine-scale experiments is transferable to other scales, I additionally calculated energy budgets for injection experiments from previously conducted laboratory tests and from a field application. Across all three scales, the cyclic injections reduce the seismic impact, as depicted by smaller maximum magnitudes, larger b-values, and decreased injection efficiencies (Publication 3).
The echo chamber model describes the development of groups in heterogeneous social networks. By heterogeneous social network we mean a set of individuals, each of whom represents exactly one opinion. The existing relationships between individuals can then be represented by a graph. The echo chamber model is a time-discrete model which, like a board game, is played in rounds. In each round, an existing relationship is randomly and uniformly selected from the network and the two connected individuals interact. If the opinions of the individuals involved are sufficiently similar, they continue to move closer together in their opinions, whereas in the case of opinions that are too far apart, they break off their relationship and one of the individuals seeks a new relationship. In this paper we examine the building blocks of this model. We start from the observation that changes in the structure of relationships in the network can be described by a system of interacting particles in a more abstract space.
These reflections lead to the definition of a new abstract graph that encompasses all possible relational configurations of the social network. This provides us with the geometric understanding necessary to analyse the dynamic components of the echo chamber model in Part III. As a first step, in Part 7, we leave aside the opinions of the inidividuals and assume that the position of the edges changes with each move as described above, in order to obtain a basic understanding of the underlying dynamics. Using Markov chain theory, we find upper bounds on the speed of convergence of an associated Markov chain to its unique stationary distribution and show that there are mutually identifiable networks that are not apparent in the dynamics under analysis, in the sense that the stationary distribution of the associated Markov chain gives equal weight to these networks.
In the reversible cases, we focus in particular on the explicit form of the stationary distribution as well as on the lower bounds of the Cheeger constant to describe the convergence speed.
The final result of Section 8, based on absorbing Markov chains, shows that in a reduced version of the echo chamber model, a hierarchical structure of the number of conflicting relations can be identified.
We can use this structure to determine an upper bound on the expected absorption time, using a quasi-stationary distribution. This hierarchy of structure also provides a bridge to classical theories of pure death processes. We conclude by showing how future research can exploit this link and by discussing the importance of the results as building blocks for a full theoretical understanding of the echo chamber model. Finally, Part IV presents a published paper on the birth-death process with partial catastrophe. The paper is based on the explicit calculation of the first moment of a catastrophe. This first part is entirely based on an analytical approach to second degree recurrences with linear coefficients. The convergence to 0 of the resulting sequence as well as the speed of convergence are proved. On the other hand, the determination of the upper bounds of the expected value of the population size as well as its variance and the difference between the determined upper bound and the actual value of the expected value. For these results we use almost exclusively the theory of ordinary nonlinear differential equations.
The increasing introduction of non-native plant species may pose a threat to local biodiversity. However, the basis of successful plant invasion is not conclusively understood, especially since these plant species can adapt to the new range within a short period of time despite impoverished genetic diversity of the starting populations. In this context, DNA methylation is considered promising to explain successful adaptation mechanisms in the new habitat. DNA methylation is a heritable variation in gene expression without changing the underlying genetic information. Thus, DNA methylation is considered a so-called epigenetic mechanism, but has been studied in mainly clonally reproducing plant species or genetic model plants. An understanding of this epigenetic mechanism in the context of non-native, predominantly sexually reproducing plant species might help to expand knowledge in biodiversity research on the interaction between plants and their habitats and, based on this, may enable more precise measures in conservation biology.
For my studies, I combined chemical DNA demethylation of field-collected seed material from predominantly sexually reproducing species and rearing offsping under common climatic conditions to examine DNA methylation in an ecological-evolutionary context. The contrast of chemically treated (demethylated) plants, whose variation in DNA methylation was artificially reduced, and untreated control plants of the same species allowed me to study the impact of this mechanism on adaptive trait differentiation and local adaptation. With this experimental background, I conducted three studies examining the effect of DNA methylation in non-native species along a climatic gradient and also between climatically divergent regions.
The first study focused on adaptive trait differentiation in two invasive perennial goldenrod species, Solidago canadensis sensu latu and S. gigantea AITON, along a climate gradient of more than 1000 km in length in Central Europe. I found population differences in flowering timing, plant height, and biomass in the temporally longer-established S. canadensis, but only in the number of regrowing shoots for S. gigantea. While S. canadensis did not show any population structure, I was able to identify three genetic groups along this climatic gradient in S. gigantea. Surprisingly, demethylated plants of both species showed no change in the majority of traits studied. In the subsequent second study, I focused on the longer-established goldenrod species S. canadensis and used molecular analyses to infer spatial epigenetic and genetic population differences in the same specimens from the previous study. I found weak genetic but no epigenetic spatial variation between populations. Additionally, I was able to identify one genetic marker and one epigenetic marker putatively susceptible to selection. However, the results of this study reconfirmed that the epigenetic mechanism of DNA methylation appears to be hardly involved in adaptive processes within the new range in S. canadensis.
Finally, I conducted a third study in which I reciprocally transplanted short-lived plant species between two climatically divergent regions in Germany to investigate local adaptation at the plant family level. For this purpose, I used four plant families (Amaranthaceae, Asteraceae, Plantaginaceae, Solanaceae) and here I additionally compared between non-native and native plant species. Seeds were transplanted to regions with a distance of more than 600 kilometers and had either a temperate-oceanic or a temperate-continental climate. In this study, some species were found to be maladapted to their own local conditions, both in non-native and native plant species alike. In demethylated individuals of the plant species studied, DNA methylation had inconsistent but species-specific effects on survival and biomass production. The results of this study highlight that DNA methylation did not make a substantial contribution to local adaptation in the non-native as well as native species studied.
In summary, my work showed that DNA methylation plays a negligible role in both adaptive trait variation along climatic gradients and local adaptation in non-native plant species that either exhibit a high degree of genetic variation or rely mainly on sexual reproduction with low clonal propagation. I was able to show that the adaptive success of these non-native plant species can hardly be explained by DNA methylation, but could be a possible consequence of multiple introductions, dispersal corridors and meta-population dynamics. Similarly, my results illustrate that the use of plant species that do not predominantly reproduce clonally and are not model plants is essential to characterize the effect size of epigenetic mechanisms in an ecological-evolutionary context.
Successful communication is often explored by people throughout their life courses. To effectively transfer one’s own information to others, people employ various linguistic tools, such as word order information, prosodic cues, and lexical choices. The exploration of these linguistic cues is known as the study of information structure (IS). Moreover, an important issue in the language acquisition of children is the investigation of how they acquire IS. This thesis seeks to improve our understanding of how children acquire different tools (i.e., prosodical cues, syntactical cues, and the focus particle only) of focus marking in a cross linguistic perspective.
In the first study, following Szendrői and her colleagues (2017)- the sentence-picture verification task- was performed to investigate whether three- to five-year-old Mandarin-speaking children as well as Mandarin-speaking adults could apply prosodic information to recognize focus in sentences. More, in the second study, not only Mandarin-speaking adults and Mandarin-speaking children but also German-speaking adults and German-speaking children were included to confirm the assumption that children could have adult-like performance in understanding sentence focus by identifying language specific cues in their mother tongue from early onwards. In this study, the same paradigm- the sentence-picture verification task- as in the first study was employed together with the eye-tracking method. Finally, in the last study, an issue of whether five-year-old Mandarin-speaking children could understand the pre-subject only sentence was carried out and again whether prosodic information would help them to better understand this kind of sentences.
The overall results seem to suggest that Mandarin-speaking children from early onwards could make use of the specific linguistic cues in their ambient language. That is, in Mandarin, a Topic-prominent and tone language, the word order information plays a more important rule than the prosodic information and even three-year-old Mandarin-speaking children could follow the word order information. More, although it seems that German-speaking children could follow the prosodic information, they did not have the adult-like performance in the object-accented condition. A feasible reason for this result is that there are more possibilities of marking focus in German, such as flexible word order, prosodic information, focus particles, and thus it would take longer time for German-speaking children to manage these linguistic tools. Another important empirical finding regarding the syntactically-marked focus in German is that it seems that the cleft construction is not a valid focus construction and this result corroborates with the previous observations (Dufter, 2009). Further, eye-tracking method did help to uncover how the parser direct their attention for recognizing focus. In the final study, it is showed that with explicit verbal context Mandarin-speaking children could understand the pre-subject only sentence and the study brought a better understanding of the acquisition of the focus particle- only with the Mandarin-speaking children.
Different lake systems might reflect different climate elements of climate changes, while the responses of lake systems are also divers, and are not completely understood so far. Therefore, a comparison of lakes in different climate zones, during the high-amplitude and abrupt climate fluctuations of the Last Glacial to Holocene transition provides an exceptional opportunity to investigate distinct natural lake system responses to different abrupt climate changes. The aim of this doctoral thesis was to reconstruct climatic and environmental fluctuations down to (sub-) annual resolution from two different lake systems during the Last Glacial-Interglacial transition (~17 and 11 ka). Lake Gościąż, situated in the temperate central Poland, developed in the Allerød after recession of the Last Glacial ice sheets. The Dead Sea is located in the Levant (eastern Mediterranean) within a steep gradient from sub-humid to hyper-arid climate, and formed in the mid-Miocene. Despite their differences in sedimentation processes, both lakes form annual laminations (varves), which are crucial for studies of abrupt climate fluctuations. This doctoral thesis was carried out within the DFG project PALEX-II (Paleohydrology and Extreme Floods from the Dead Sea ICDP Core) that investigates extreme hydro-meteorological events in the ICDP core in relation to climate changes, and ICLEA (Virtual Institute of Integrated Climate and Landscape Evolution Analyses) that intends to better the understanding of climate dynamics and landscape evolutions in north-central Europe since the Last Glacial. Further, it contributes to the Helmholtz Climate Initiative REKLIM (Regional Climate Change and Humans) Research Theme 3 “Extreme events across temporal and spatial scales” that investigates extreme events using climate data, paleo-records and model-based simulations. The three main aims were to (1) establish robust chronologies of the lakes, (2) investigate how major and abrupt climate changes affect the lake systems, and (3) to compare the responses of the two varved lakes to these hemispheric-scale climate changes.
Robust chronologies are a prerequisite for high-resolved climate and environmental reconstructions, as well as for archive comparisons. Thus, addressing the first aim, the novel chronology of Lake Gościąż was established by microscopic varve counting and Bayesian age-depth modelling in Bacon for a non-varved section, and was corroborated by independent age constrains from 137Cs activity concentration measurements, AMS radiocarbon dating and pollen analysis. The varve chronology reaches from the late Allerød until AD 2015, revealing more Holocene varves than a previous study of Lake Gościąż suggested. Varve formation throughout the complete Younger Dryas (YD) even allowed the identification of annually- to decadal-resolved leads and lags in proxy responses at the YD transitions.
The lateglacial chronology of the Dead Sea (DS) was thus far mainly based on radiocarbon and U/Th-dating. In the unique ICDP core from the deep lake centre, continuous search for cryptotephra has been carried out in lateglacial sediments between two prominent gypsum deposits – the Upper and Additional Gypsum Units (UGU and AGU, respectively). Two cryptotephras were identified with glass analyses that correlate with tephra deposits from the Süphan and Nemrut volcanoes indicating that the AGU is ~1000 years younger than previously assumed, shifting it into the YD, and the underlying varved interval into the Bølling/Allerød, contradicting previous assumptions.
Using microfacies analyses, stable isotopes and temperature reconstructions, the second aim was achieved at Lake Gościąż. The YD lake system was dynamic, characterized by higher aquatic bioproductivity, more re-suspended material and less anoxia than during the Allerød and Early Holocene, mainly influenced by stronger water circulation and catchment erosion due to stronger westerly winds and less lake sheltering. Cooling at the YD onset was ~100 years longer than the final warming, while environmental proxies lagged the onset of cooling by ~90 years, but occurred contemporaneously during the termination of the YD. Chironomid-based temperature reconstructions support recent studies indicating mild YD summer temperatures. Such a comparison of annually-resolved proxy responses to both abrupt YD transitions is rare, because most European lake archives do not preserve varves during the YD.
To accomplish the second aim at the DS, microfacies analyses were performed between the UGU (~17 ka) and Holocene onset (~11 ka) in shallow- (Masada) and deep-water (ICDP core) environments. This time interval is marked by a huge but fluctuating lake level drop and therefore the complete transition into the Holocene is only recorded in the deep-basin ICDP core. In this thesis, this transition was investigated for the first time continuously and in detail. The final two pronounced lake level drops recorded by deposition of the UGU and AGU, were interrupted by one millennium of relative depositional stability and a positive water budget as recorded by aragonite varve deposition interrupted by only a few event layers. Further, intercalation of aragonite varves between the gypsum beds of the UGU and AGU shows that these generally dry intervals were also marked by decadal- to centennial-long rises in lake level. While continuous aragonite varves indicate decadal-long stable phases, the occurrence of thicker and more frequent event layers suggests general more instability during the gypsum units. These results suggest a pattern of complex and variable hydroclimate at different time scales during the Lateglacial at the DS.
The third aim was accomplished based on the individual studies above that jointly provide an integrated picture of different lake responses to different climate elements of hemispheric-scale abrupt climate changes during the Last Glacial-Interglacial transition. In general, climatically-driven facies changes are more dramatic in the DS than at Lake Gościąż. Further, Lake Gościąż is characterized by continuous varve formation nearly throughout the complete profile, whereas the DS record is widely characterized by extreme event layers, hampering the establishment of a continuous varve chronology. The lateglacial sedimentation in Lake Gościąż is mainly influenced by westerly winds and minor by changes in catchment vegetation, whereas the DS is primarily influenced by changes in winter precipitation, which are caused by temperature variations in the Mediterranean. Interestingly, sedimentation in both archives is more stable during the Bølling/Allerød and more dynamic during the YD, even when sedimentation processes are different.
In summary, this doctoral thesis presents seasonally-resolved records from two lake archives during the Lateglacial (ca 17-11 ka) to investigate the impact of abrupt climate changes in different lake systems. New age constrains from the identification of volcanic glass shards in the lateglacial sediments of the DS allowed the first lithology-based interpretation of the YD in the DS record and its comparison to Lake Gościąż. This highlights the importance of the construction of a robust chronology, and provides a first step for synchronization of the DS with other eastern Mediterranean archives. Further, climate reconstructions from the lake sediments showed variability on different time scales in the different archives, i.e. decadal- to millennial fluctuations in the lateglacial DS, and even annual variations and sub-decadal leads and lags in proxy responses during the rapid YD transitions in Lake Gościąż. This showed the importance of a comparison of different lake archives to better understand the regional and local impacts of hemispheric-scale climate variability. An unprecedented example is demonstrated here of how different lake systems show different lake responses and also react to different climate elements of abrupt climate changes. This further highlights the importance of the understanding of the respective lake system for climate reconstructions.
The heterogeneity of today's state-of-the-art computer architectures is confronting application developers with an immense degree of complexity which results from two major challenges. First, developers need to acquire profound knowledge about the programming models or the interaction models associated with each type of heterogeneous system resource to make efficient use thereof. Second, developers must take into account that heterogeneous system resources always need to exchange data with each other in order to work on a problem together. However, this data exchange is always associated with a certain amount of overhead, which is why the amounts of data exchanged should be kept as low as possible.
This thesis proposes three programming abstractions to lessen the burdens imposed by these major challenges with the goal of making heterogeneous system resources accessible to a wider range of application developers. The lib842 compression library provides the first method for accessing the compression and decompression facilities of the NX-842 on-chip compression accelerator available in IBM Power CPUs from user space applications running on Linux. Addressing application development of scale-out GPU workloads, the CloudCL framework makes the resources of GPU clusters more accessible by hiding many aspects of distributed computing while enabling application developers to focus on the aspects of the data parallel programming model associated with GPUs. Furthermore, CloudCL is augmented with transparent data compression facilities based on the lib842 library in order to improve the efficiency of data transfers among cluster nodes. The improved data transfer efficiency provided by the integration of transparent data compression yields performance improvements ranging between 1.11x and 2.07x across four data-intensive scale-out GPU workloads. To investigate the impact of programming abstractions for data placement in NUMA systems, a comprehensive evaluation of the PGASUS framework for NUMA-aware C++ application development is conducted. On a wide range of test systems, the evaluation demonstrates that PGASUS does not only improve the developer experience across all workloads, but that it is also capable of outperforming NUMA-agnostic implementations with average performance improvements of 1.56x.
Based on these programming abstractions, this thesis demonstrates that by providing a sufficient degree of abstraction, the accessibility of heterogeneous system resources can be improved for application developers without occluding performance-critical properties of the underlying hardware.
A task-based parallel elliptic solver for numerical relativity with discontinuous Galerkin methods
(2022)
Elliptic partial differential equations are ubiquitous in physics. In numerical relativity---the study of computational solutions to the Einstein field equations of general relativity---elliptic equations govern the initial data that seed every simulation of merging black holes and neutron stars. In the quest to produce detailed numerical simulations of these most cataclysmic astrophysical events in our Universe, numerical relativists resort to the vast computing power offered by current and future supercomputers. To leverage these computational resources, numerical codes for the time evolution of general-relativistic initial value problems are being developed with a renewed focus on parallelization and computational efficiency. Their capability to solve elliptic problems for accurate initial data must keep pace with the increasing detail of the simulations, but elliptic problems are traditionally hard to parallelize effectively.
In this thesis, I develop new numerical methods to solve elliptic partial differential equations on computing clusters, with a focus on initial data for orbiting black holes and neutron stars. I develop a discontinuous Galerkin scheme for a wide range of elliptic equations, and a stack of task-based parallel algorithms for their iterative solution. The resulting multigrid-Schwarz preconditioned Newton-Krylov elliptic solver proves capable of parallelizing over 200 million degrees of freedom to at least a few thousand cores, and already solves initial data for a black hole binary about ten times faster than the numerical relativity code SpEC. I also demonstrate the applicability of the new elliptic solver across physical disciplines, simulating the thermal noise in thin mirror coatings of interferometric gravitational-wave detectors to unprecedented accuracy. The elliptic solver is implemented in the new open-source SpECTRE numerical relativity code, and set up to support simulations of astrophysical scenarios for the emerging era of gravitational-wave and multimessenger astronomy.
The geomagnetic main field is vital for live on Earth, as it shields our habitat against the solar wind and cosmic rays. It is generated by the geodynamo in the Earth’s outer core and has a rich dynamic on various timescales. Global models of the field are used to study the interaction of the field and incoming charged particles, but also to infer core dynamics and to feed numerical simulations of the geodynamo. Modern satellite missions, such as the SWARM or the CHAMP mission, support high resolution reconstructions of the global field. From the 19 th century on, a global network of magnetic observatories has been established. It is growing ever since and global models can be constructed from the data it provides. Geomagnetic field models that extend further back in time rely on indirect observations of the field, i.e. thermoremanent records such as burnt clay or volcanic rocks and sediment records from lakes and seas. These indirect records come with (partially very large) uncertainties, introduced by the complex measurement methods and the dating procedure.
Focusing on thermoremanent records only, the aim of this thesis is the development of a new modeling strategy for the global geomagnetic field during the Holocene, which takes the uncertainties into account and produces realistic estimates of the reliability of the model. This aim is approached by first considering snapshot models, in order to address the irregular spatial distribution of the records and the non-linear relation of the indirect observations to the field itself. In a Bayesian setting, a modeling algorithm based on Gaussian process regression is developed and applied to binned data. The modeling algorithm is then extended to the temporal domain and expanded to incorporate dating uncertainties. Finally, the algorithm is sequentialized to deal with numerical challenges arising from the size of the Holocene dataset.
The central result of this thesis, including all of the aspects mentioned, is a new global geomagnetic field model. It covers the whole Holocene, back until 12000 BCE, and we call it ArchKalmag14k. When considering the uncertainties that are produced together with the model, it is evident that before 6000 BCE the thermoremanent database is not sufficient to support global models. For times more recent, ArchKalmag14k can be used to analyze features of the field under consideration of posterior uncertainties. The algorithm for generating ArchKalmag14k can be applied to different datasets and is provided to the community as an open source python package.
Text collections, such as corpora of books, research articles, news, or business documents are an important resource for knowledge discovery. Exploring large document collections by hand is a cumbersome but necessary task to gain new insights and find relevant information. Our digitised society allows us to utilise algorithms to support the information seeking process, for example with the help of retrieval or recommender systems. However, these systems only provide selective views of the data and require some prior knowledge to issue meaningful queries and asses a system’s response. The advancements of machine learning allow us to reduce this gap and better assist the information seeking process. For example, instead of sighting countless business documents by hand, journalists and investigator scan employ natural language processing techniques, such as named entity recognition. Al-though this greatly improves the capabilities of a data exploration platform, the wealth of information is still overwhelming. An overview of the entirety of a dataset in the form of a two-dimensional map-like visualisation may help to circumvent this issue. Such overviews enable novel interaction paradigms for users, which are similar to the exploration of digital geographical maps. In particular, they can provide valuable context by indicating how apiece of information fits into the bigger picture.This thesis proposes algorithms that appropriately pre-process heterogeneous documents and compute the layout for datasets of all kinds. Traditionally, given high-dimensional semantic representations of the data, so-called dimensionality reduction algorithms are usedto compute a layout of the data on a two-dimensional canvas. In this thesis, we focus on text corpora and go beyond only projecting the inherent semantic structure itself. Therefore,we propose three dimensionality reduction approaches that incorporate additional information into the layout process: (1) a multi-objective dimensionality reduction algorithm to jointly visualise semantic information with inherent network information derived from the underlying data; (2) a comparison of initialisation strategies for different dimensionality reduction algorithms to generate a series of layouts for corpora that grow and evolve overtime; (3) and an algorithm that updates existing layouts by incorporating user feedback provided by pointwise drag-and-drop edits. This thesis also contains system prototypes to demonstrate the proposed technologies, including pre-processing and layout of the data and presentation in interactive user interfaces.
It is estimated that data scientists spend up to 80% of the time exploring, cleaning, and transforming their data. A major reason for that expenditure is the lack of knowledge about the used data, which are often from different sources and have heterogeneous structures. As a means to describe various properties of data, metadata can help data scientists understand and prepare their data, saving time for innovative and valuable data analytics. However, metadata do not always exist: some data file formats are not capable of storing them; metadata were deleted for privacy concerns; legacy data may have been produced by systems that were not designed to store and handle meta- data. As data are being produced at an unprecedentedly fast pace and stored in diverse formats, manually creating metadata is not only impractical but also error-prone, demanding automatic approaches for metadata detection.
In this thesis, we are focused on detecting metadata in CSV files – a type of plain-text file that, similar to spreadsheets, may contain different types of content at arbitrary positions. We propose a taxonomy of metadata in CSV files and specifically address the discovery of three different metadata: line and cell type, aggregations, and primary keys and foreign keys.
Data are organized in an ad-hoc manner in CSV files, and do not follow a fixed structure, which is assumed by common data processing tools. Detecting the structure of such files is a prerequisite of extracting information from them, which can be addressed by detecting the semantic type, such as header, data, derived, or footnote, of each line or each cell. We propose the supervised- learning approach Strudel to detect the type of lines and cells. CSV files may also include aggregations. An aggregation represents the arithmetic relationship between a numeric cell and a set of other numeric cells. Our proposed AggreCol algorithm is capable of detecting aggregations of five arithmetic functions in CSV files. Note that stylistic features, such as font style and cell background color, do not exist in CSV files. Our proposed algorithms address the respective problems by using only content, contextual, and computational features.
Storing a relational table is also a common usage of CSV files. Primary keys and foreign keys are important metadata for relational databases, which are usually not present for database instances dumped as plain-text files. We propose the HoPF algorithm to holistically detect both constraints in relational databases. Our approach is capable of distinguishing true primary and foreign keys from a great amount of spurious unique column combinations and inclusion dependencies, which can be detected by state-of-the-art data profiling algorithms.
Biofilms are complex living materials that form as bacteria get embedded in a matrix of self-produced protein and polysaccharide fibres. The formation of a network of extracellular biopolymer fibres contributes to the cohesion of the biofilm by promoting cell-cell attachment and by mediating biofilm-substrate interactions. This sessile mode of bacteria growth has been well studied by microbiologists to prevent the detrimental effects of biofilms in medical and industrial settings. Indeed, biofilms are associated with increased antibiotic resistance in bacterial infections, and they can also cause clogging of pipelines or promote bio-corrosion. However, biofilms also gained interest from biophysics due to their ability to form complex morphological patterns during growth. Recently, the emerging field of engineered living materials investigates biofilm mechanical properties at multiple length scales and leverages the tools of synthetic biology to tune the functions of their constitutive biopolymers.
This doctoral thesis aims at clarifying how the morphogenesis of Escherichia coli (E. coli) biofilms is influenced by their growth dynamics and mechanical properties. To address this question, I used methods from cell mechanics and materials science. I first studied how biological activity in biofilms gives rise to non-uniform growth patterns. In a second study, I investigated how E. coli biofilm morphogenesis and its mechanical properties adapt to an environmental stimulus, namely the water content of their substrate. Finally, I estimated how the mechanical properties of E. coli biofilms are altered when the bacteria express different extracellular biopolymers.
On nutritive hydrogels, micron-sized E. coli cells can build centimetre-large biofilms. During this process, bacterial proliferation and matrix production introduce mechanical stresses in the biofilm, which release through the formation of macroscopic wrinkles and delaminated buckles. To relate these biological and mechanical phenomena, I used time-lapse fluorescence imaging to track cell and matrix surface densities through the early and late stages of E. coli biofilm growth. Colocalization of high cell and matrix densities at the periphery precede the onset of mechanical instabilities at this annular region. Early growth is detected at this outer annulus, which was analysed by adding fluorescent microspheres to the bacterial inoculum. But only when high rates of matrix production are present in the biofilm centre, does overall biofilm spreading initiate along the solid-air interface. By tracking larger fluorescent particles for a long time, I could distinguish several kinematic stages of E. coli biofilm expansion and observed a transition from non-linear to linear velocity profiles, which precedes the emergence of wrinkles at the biofilm periphery. Decomposing particle velocities to their radial and circumferential components revealed a last kinematic stage, where biofilm movement is mostly directed towards the radial delaminated buckles, which verticalize. The resulting compressive strains computed in these regions were observed to substantially deform the underlying agar substrates. The co-localization of higher cell and matrix densities towards an annular region and the succession of several kinematic stages are thus expected to promote the emergence of mechanical instabilities at the biofilm periphery. These experimental findings are predicted to advance future modelling approaches of biofilm morphogenesis.
E. coli biofilm morphogenesis is further anticipated to depend on external stimuli from the environment. To clarify how the water could be used to tune biofilm material properties, we quantified E. coli biofilm growth, wrinkling dynamics and rigidity as a function of the water content of the nutritive substrates. Time-lapse microscopy and computational image analysis revealed that substrates with high water content promote biofilm spreading kinetics, while substrates with low water content promote biofilm wrinkling. The wrinkles observed on biofilm cross-sections appeared more bent on substrates with high water content, while they tended to be more vertical on substrates with low water content. Both wet and dry biomass, accumulated over 4 days of culture, were larger in biofilms cultured on substrates with high water content, despite extra porosity within the matrix layer. Finally, the micro-indentation analysis revealed that substrates with low water content supported the formation of stiffer biofilms. This study shows that E. coli biofilms respond to the water content of their substrate, which might be used for tuning their material properties in view of further applications.
Biofilm material properties further depend on the composition and structure of the matrix of extracellular proteins and polysaccharides. In particular, E. coli biofilms were suggested to present tissue-like elasticity due to a dense fibre network consisting of amyloid curli and phosphoethanolamine-modified cellulose. To understand the contribution of these components to the emergent mechanical properties of E. coli biofilms, we performed micro-indentation on biofilms grown from bacteria of several strains. Besides showing higher dry masses, larger spreading diameters and slightly reduced water contents, biofilms expressing both main matrix components also presented high rigidities in the range of several hundred kPa, similar to biofilms containing only curli fibres. In contrast, a lack of amyloid curli fibres provides much higher adhesive energies and more viscoelastic fluid-like material behaviour. Therefore, the combination of amyloid curli and phosphoethanolamine-modified cellulose fibres implies the formation of a composite material whereby the amyloid curli fibres provide rigidity to E. coli biofilms, whereas the phosphoethanolamine-modified cellulose rather acts as a glue. These findings motivate further studies involving purified versions of these protein and polysaccharide components to better understand how their interactions benefit biofilm functions.
All three studies depict different aspects of biofilm morphogenesis, which are interrelated. The first work reveals the correlation between non-uniform biological activities and the emergence of mechanical instabilities in the biofilm. The second work acknowledges the adaptive nature of E. coli biofilm morphogenesis and its mechanical properties to an environmental stimulus, namely water. Finally, the last study reveals the complementary role of the individual matrix components in the formation of a stable biofilm material, which not only forms complex morphologies but also functions as a protective shield for the bacteria it contains. Our experimental findings on E. coli biofilm morphogenesis and their mechanical properties can have further implications for fundamental and applied biofilm research fields.
Plants can be primed to survive the exposure to a severe heat stress (HS) by prior exposure to a mild HS. The information about the priming stimulus is maintained by the plant for several days. This maintenance of acquired thermotolerance, or HS memory, is genetically separable from the acquisition of thermotolerance itself and several specific regulatory factors have been identified in recent years.
On the molecular level, HS memory correlates with two types of transcriptional memory, type I and type II, that characterize a partially overlapping subset of HS-inducible genes. Type I transcriptional memory or sustained induction refers to the sustained transcriptional induction above non-stressed expression levels of a gene for a prolonged time period after the end of the stress exposure. Type II transcriptional memory refers to an altered transcriptional response of a gene after repeated exposure to a stress of similar duration and intensity. In particular, enhanced re-induction refers to a transcriptional pattern in which a gene is induced to a significantly higher degree after the second stress exposure than after the first.
This thesis describes the functional characterization of a novel positive transcriptional regulator of type I transcriptional memory, the heat shock transcription factor HSFA3, and compares it to HSFA2, a known positive regulator of type I and type II transcriptional memory. It investigates type I transcriptional memory and its dependence on HSFA2 and HSFA3 for the first time on a genome-wide level, and gives insight on the formation of heteromeric HSF complexes in response to HS. This thesis confirms the tight correlation between transcriptional memory and H3K4 hyper-methylation, reported here in a case study that aimed to reduce H3K4 hyper-methylation of the type II transcriptional memory gene APX2 by CRISPR/dCas9-mediated epigenome editing. Finally, this thesis gives insight into the requirements for a heat shock transcription factor to function as a positive regulator of transcriptional memory, both in terms of its expression profile and protein abundance after HS and the contribution of individual functional domains.
In summary, this thesis contributes to a more detailed understanding of the molecular processes underlying transcriptional memory and therefore HS memory, in Arabidopsis thaliana.
Cosmic rays (CRs) are a ubiquitous and an important component of astrophysical environments such as the interstellar medium (ISM) and intracluster medium (ICM). Their plasma physical interactions with electromagnetic fields strongly influence their transport properties. Effective models which incorporate the microphysics of CR transport are needed to study the effects of CRs on their surrounding macrophysical media. Developing such models is challenging because of the conceptional, length-scale, and time-scale separation between the microscales of plasma physics and the macroscales of the environment. Hydrodynamical theories of CR transport achieve this by capturing the evolution of CR population in terms of statistical moments. In the well-established one-moment hydrodynamical model for CR transport, the dynamics of the entire CR population are described by a single statistical quantity such as the commonly used CR energy density. In this work, I develop a new hydrodynamical two-moment theory for CR transport that expands the well-established hydrodynamical model by including the CR energy flux as a second independent hydrodynamical quantity. I detail how this model accounts for the interaction between CRs and gyroresonant Alfvén waves. The small-scale magnetic fields associated with these Alfvén waves scatter CRs which fundamentally alters CR transport along large-scale magnetic field lines. This leads to the effects of CR streaming and diffusion which are both captured within the presented hydrodynamical theory. I use an Eddington-like approximation to close the hydrodynamical equations and investigate the accuracy of this closure-relation by comparing it to high-order approximations of CR transport. In addition, I develop a finite-volume scheme for the new hydrodynamical model and adapt it to the moving-mesh code Arepo. This scheme is applied using a simulation of a CR-driven galactic wind. I investigate how CRs launch the wind and perform a statistical analysis of CR transport properties inside the simulated circumgalactic medium (CGM). I show that the new hydrodynamical model can be used to explain the morphological appearance of a particular type of radio filamentary structures found inside the central molecular zone (CMZ). I argue that these harp-like features are synchrotron-radiating CRs which are injected into braided magnetic field lines by a point-like source such as a stellar wind of a massive star or a pulsar. Lastly, I present the finite-volume code Blinc that uses adaptive mesh refinement (AMR) techniques to perform simulations of radiation and magnetohydrodynamics (MHD). The mesh of Blinc is block-structured and represented in computer memory using a graph-based approach. I describe the implementation of the mesh graph and how a diffusion process is employed to achieve load balancing in parallel computing environments. Various test problems are used to verify the accuracy and robustness of the employed numerical algorithms.
Li and B in ascending magmas: an experimental study on their mobility and isotopic fractionation
(2022)
This research study focuses on the behaviour of Li and B during magmatic ascent, and decompression-driven degassing related to volcanic systems. The main objective of this dissertation is to determine whether it is possible to use the diffusion properties of the two trace elements as a tool to trace magmatic ascent rate. With this objective, diffusion-couple and decompression experiments have been performed in order to study Li and B mobility in intra-melt conditions first, and then in an evolving system during decompression-driven degassing.
Synthetic glasses were prepared with rhyolitic composition and an initial water content of 4.2 wt%, and all the experiments were performed using an internally heated pressure vessel, in order to ensure a precise control on the experimental parameters such as temperature and pressure.
Diffusion-couple experiments were performed with a fix pressure 300 MPa. The temperature was varied in the range of 700-1250 °C with durations between 0 seconds and 24 hours. The diffusion-couple results show that Li diffusivity is very fast and starts already at very low temperature. Significant isotopic fractionation occurs due to the faster mobility of 6Li compared to 7Li. Boron diffusion is also accelerated by the presence of water, but the results of the isotopic ratios are unclear, and further investigation would be necessary to well constrain the isotopic fractionation process of boron in hydrous silicate melts. The isotopic ratios results show that boron isotopic fractionation might be affected by the speciation of boron in the silicate melt structure, as 10B and 11B tend to have tetrahedral and trigonal coordination, respectively.
Several decompression experiments were performed at 900 °C and 1000 °C, with pressures going from 300 MPa to 71-77 MPa and durations of 30 minutes, two, five and ten hours, in order to trigger water exsolution and the formation of vesicles in the sample. Textural observations and the calculation of the bubble number density confirmed that the bubble size and distribution after decompression is directly proportional to the decompression rate.
The overall SIMS results of Li and B show that the two trace elements tend to progressively decrease their concentration with decreasing decompression rates. This is explained because for longer decompression times, the diffusion of Li and B into the bubbles has more time to progress and the melt continuously loses volatiles as the bubbles expand their volumes.
For fast decompression, Li and B results show a concentration increase with a δ7Li and δ11B decrease close to the bubble interface, related to the sudden formation of the gas bubble, and the occurrence of a diffusion process in the opposite direction, from the bubble meniscus to the unaltered melt. When the bubble growth becomes dominant and Li and B start to exsolve into the gas phase, the silicate melt close to the bubble gets depleted in Li and B, because of a stronger diffusion of the trace elements into the bubble.
Our data are being applied to different models, aiming to combine the dynamics of bubble nucleation and growth with the evolution of trace elements concentration and isotopic ratios. Here, first considerations on these models will be presented, giving concluding remarks on this research study. All in all, the final remarks constitute a good starting point for further investigations. These results are a promising base to continue to study this process, and Li and B can indeed show clear dependences on decompression-related magma ascent rates in volcanic systems.
As of late, epidemiological studies have highlighted a strong association of dairy intake with lower disease risk, and similarly with an increased amount of odd-chain fatty acids (OCFA). While the OCFA also demonstrate inverse associations with disease incidence, the direct dietary sources and mode of action of the OCFA remain poorly understood.
The overall aim of this thesis was to determine the impact of two main fractions of dairy, milk fat and milk protein, on OCFA levels and their influence on health outcomes under high-fat (HF) diet conditions. Both fractions represent viable sources of OCFA, as milk fats contain a significant amount of OCFA and milk proteins are high in branched chain amino acids (BCAA), namely valine (Val) and isoleucine (Ile), which can produce propionyl-CoA (Pr-CoA), a precursor for endogenous OCFA synthesis, while leucine (Leu) does not. Additionally, this project sought to clarify the specific metabolic effects of the OCFA heptadecanoic acid (C17:0).
Both short-term and long-term feeding studies were performed using male C57BL/6JRj mice fed HF diets supplemented with milk fat or C17:0, as well as milk protein or individual BCAA (Val; Leu) to determine their influences on OCFA and metabolic health. Short-term feeding revealed that both milk fractions induce OCFA in vivo, and the increases elicited by milk protein could be, in part, explained by Val intake. In vitro studies using primary hepatocytes further showed an induction of OCFA after Val treatment via de novo lipogenesis and increased α-oxidation. In the long-term studies, both milk fat and milk protein increased hepatic and circulating OCFA levels; however, only milk protein elicited protective effects on adiposity and hepatic fat accumulation—likely mediated by the anti-obesogenic effects of an increased Leu intake. In contrast, Val feeding did not increase OCFA levels nor improve obesity, but rather resulted in glucotoxicity-induced insulin resistance in skeletal muscle mediated by its metabolite 3-hydroxyisobutyrate (3-HIB). Finally, while OCFA levels correlated with improved health outcomes, C17:0 produced negligible effects in preventing HF-diet induced health impairments.
The results presented herein demonstrate that the beneficial health outcomes associated with dairy intake are likely mediated through the effects of milk protein, while OCFA levels are likely a mere association and do not play a significant causal role in metabolic health under HF conditions. Furthermore, the highly divergent metabolic effects of the two BCAA, Leu and Val, unraveled herein highlight the importance of protein quality.
The complex hierarchical structure of bone undergoes a lifelong remodeling process, where it adapts to mechanical needs. Hereby, bone resorption by osteoclasts and bone formation by osteoblasts have to be balanced to sustain a healthy and stable organ. Osteocytes orchestrate this interplay by sensing mechanical strains and translating them into biochemical signals. The osteocytes are located in lacunae and are connected to one another and other bone cells via cell processes through small channels, the canaliculi. Lacunae and canaliculi form a network (LCN) of extracellular spaces that is able to transport ions and enables cell-to-cell communication. Osteocytes might also contribute to mineral homeostasis by direct interactions with the surrounding matrix. If the LCN is acting as a transport system, this should be reflected in the mineralization pattern. The central hypothesis of this thesis is that osteocytes are actively changing their material environment. Characterization methods of material science are used to achieve the aim of detecting traces of this interaction between osteocytes and the extracellular matrix. First, healthy murine bones were characterized. The properties analyzed were then compared with three murine model systems: 1) a loading model, where a bone of the mouse was loaded during its life time; 2) a healing model, where a bone of the mouse was cut to induce a healing response; and 3) a disease model, where the Fbn1 gene is dysfunctional causing defects in the formation of the extracellular tissue.
The measurement strategy included routines that make it possible to analyze the organization of the LCN and the material components (i.e., the organic collagen matrix and the mineral particles) in the same bone volumes and compare the spatial distribution of different data sets. The three-dimensional network architecture of the LCN is visualized by confocal laser scanning microscopy (CLSM) after rhodamine staining and is then subsequently quantified. The calcium content is determined via quantitative backscattered electron imaging (qBEI), while small- and wide-angle X-ray scattering (SAXS and WAXS) are employed to determine the thickness and length of local mineral particles.
First, tibiae cortices of healthy mice were characterized to investigate how changes in LCN architecture can be attributed to interactions of osteocytes with the surrounding bone matrix. The tibial mid-shaft cross-sections showed two main regions, consisting of a band with unordered LCN surrounded by a region with ordered LCN. The unordered region is a remnant of early bone formation and exhibited short and thin mineral particles. The surrounding, more aligned bone showed ordered and dense LCN as well as thicker and longer mineral particles. The calcium content was unchanged between the two regions.
In the mouse loading model, the left tibia underwent two weeks of mechanical stimulation, which results in increased bone formation and decreased resorption in skeletally mature mice. Here the specific research question addressed was how do bone material characteristics change at (re)modeling sites? The new bone formed in response to mechanical stimulation showed similar properties in terms of the mineral particles, like the ordered calcium region but lower calcium content compared to the right, non-loaded control bone of the same mice. There was a clear, recognizable border between mature and newly formed bone. Nevertheless, some canaliculi went through this border connecting the LCN of mature and newly formed bone.
Additionally, the question should be answered whether the LCN topology and the bone matrix material properties adapt to loading. Although, mechanically stimulated bones did not show differences in calcium content compared to controls, different correlations were found between the local LCN density and the local Ca content depending on whether the bone was loaded or not. These results suggest that the LCN may serve as a mineral reservoir.
For the healing model, the femurs of mice underwent an osteotomy, stabilized with an external fixator and were allowed to heal for 21 days. Thus, the spatial variations in the LCN topology with mineral properties within different tissue types and their interfaces, namely calcified cartilage, bony callus and cortex, could be simultaneously visualized and compared in this model. All tissue types showed structural differences across multiple length scales. Calcium content increased and became more homogeneous from calcified cartilage to bony callus to lamellar cortical bone. The degree of LCN organization increased as well, while the lacunae became smaller, as did the lacunar density between these different tissue types that make up the callus. In the calcified cartilage, the mineral particles were short and thin. The newly formed callus exhibited thicker mineral particles, which still had a low degree of orientation. While most of the callus had a woven-like structure, it also served as a scaffold for more lamellar tissue at the edges. The lamelar bone callus showed thinner mineral particles, but a higher degree of alignment in both, mineral particles and the LCN. The cortex showed the highest values for mineral length, thickness and degree of orientation. At the same time, the lacunae number density was 34% lower and the lacunar volume 40% smaller compared to bony callus. The transition zone between cortical and callus regions showed a continuous convergence of bone mineral properties and lacunae shape. Although only a few canaliculi connected callus and the cortical region, this indicates that communication between osteocytes of both tissues should be possible. The presented correlations between LCN architecture and mineral properties across tissue types may suggest that osteocytes have an active role in mineralization processes of healing.
A mouse model for the disease marfan syndrome, which includes a genetic defect in the fibrillin-1 gene, was investigated. In humans, Marfan syndrome is characterized by a range of clinical symptoms such as long bone overgrowth, loose joints, reduced bone mineral density, compromised bone microarchitecture, and increased fracture rates. Thus, fibrillin-1 seems to play a role in the skeletal homeostasis. Therefore, the present work studied how marfan syndrome alters LCN architecture and the surrounding bone matrix. The mice with marfan syndrome showed longer tibiae than their healthy littermates from an age of seven weeks onwards. In contrast, the cortical development appeared retarded, which was observed across all measured characteristics, i. e. lower endocortical bone formation, looser and less organized lacuno-canalicular network, less collagen orientation, thinner and shorter mineral particles.
In each of the three model systems, this study found that changes in the LCN architecture spatially correlated with bone matrix material parameters. While not knowing the exact mechanism, these results provide indications that osteocytes can actively manipulate a mineral reservoir located around the canaliculi to make a quickly accessible contribution to mineral homeostasis. However, this interaction is most likely not one-sided, but could be understood as an interplay between osteocytes and extra-cellular matrix, since the bone matrix contains biochemical signaling molecules (e.g. non-collagenous proteins) that can change osteocyte behavior. Bone (re)modeling can therefore not only be understood as a method for removing defects or adapting to external mechanical stimuli, but also for increasing the efficiency of possible osteocyte-mineral interactions during bone homeostasis. With these findings, it seems reasonable to consider osteocytes as a target for drug development related to bone diseases that cause changes in bone composition and mechanical properties. It will most likely require the combined effort of materials scientists, cell biologists, and molecular biologists to gain a deeper understanding of how bone cells respond to their material environment.
The deciduous needle tree larch (Larix Mill.) covers more than 80% of the Asian boreal forests. Only a few Larix species constitute the vast forests and these species differ markedly in their ecological traits, most importantly in their ability to grow on and stabilize underlying permafrost. The pronounced dominance of the summergreen larches makes the Asian boreal forests unique, as the rest of the northern hemisphere boreal forests is almost exclusively dominated by evergreen needle-leaf forests. Global warming is impacting the whole world but is especially pronounced in the arctic and boreal regions. Although adapted to extreme climatic conditions, larch forests are sensitive to varying climatic conditions. By their sheer size, changes in Asian larch forests as range shifts or changes in species composition and the resulting vegetation-climate feedbacks are of global relevance. It is however still uncertain if larch forests will persist under the ongoing warming climate or if they will be replaced by evergreen forests. It is therefore of great importance to understand how these ecosystems will react to future climate warmings and if they will maintain their dominance. One step in the better understanding of larch dynamics is to study how the vast dominant forests developed and why they only established in northern Asia. A second step is to study how the species reacted to past changes in the climate.
The first objective of this thesis was to review and identify factors promoting Asian larch dominance. I achieved this by synthesizing and comparing reported larch occurrences and influencing components on the northern hemisphere continents in the present and in the past. The second objective was to find a possibility to directly study past Larix populations in Siberia and specifically their genetic variation, enabling the study of geographic movements. For this, I established chloroplast enrichment by hybridization capture from sedimentary ancient DNA (sedaDNA) isolated from lake sediment records. The third objective was to use the established method to track past larch populations, their glacial refugia during the Last Glacial Maximum (LGM) around 21,000 years before present (ka BP), and their post-glacial migration patterns.
To study larch promoting factors, I compared the present state of larch species ranges, areas of dominance, their bioclimatic niches, and the distribution on different extents and thaw depths of permafrost. The species comparison showed that the bioclimatic niches greatly overlap between the American and Asian species and that it is only in the extremely continental climates in which only the Asian larch species can persist. I revealed that the area of dominance is strongly connected to permafrost extent but less linked to permafrost seasonal thaw depths. Comparisons of the paleorecord of larch between the continents suggest differences in the recolonization history. Outside of northern Asia and Alaska, glacial refugial populations of larch were confined to the southern regions and thus recolonization could only occur as migration from south to north. Alaskan larch populations could not establish wide-range dominant forest which could be related to their own genetically depletion as separated refugial population. In Asia, it is still unclear whether or not the northern refugial populations contributed and enhanced the postglacial colonization or whether they were replaced by populations invading from the south in the course of climate warming. Asian larch dominance is thus promoted partly by adaptions to extremely continental climates and by adaptations to grow on continuous permafrost but could be also connected to differences in glacial survival and recolonization history of Larix species.
Except for extremely rare macrofossil findings of fossilized cones, traditional methods to study past vegetation are not able to distinguish between larch species or populations. Within the scope of this thesis, I therefore established a method to retrieve genetic information of past larch populations to distinguish between species. Using the Larix chloroplast genome as target, I successfully applied the method of DNA target enrichment by hybridization capture on sedaDNA samples from lake records and showed that it is able to distinguish between larch species. I then used the method on samples from lake records from across Siberia dating back up to 50 ka BP. The results allowed me to address the question of glacial survival and post-glacial recolonization mode in Siberian larch species. The analyzed pattern showed that LGM refugia were almost exclusively constituted by L. gmelinii, even in sites of current L. sibirica distribution. For included study sites, L. sibirica migrated into its extant northern distribution area only in the Holocene. Consequently, the post-glacial recolonization of L. sibirica was not enhanced by northern glacial refugia. In case of sites in extant distribution area of L. gmelinii, the absence of a genetic turn-over point to a continuous population rather than an invasion of southern refugia. The results suggest that climate has a strong influence on the distribution of Larix species and that species may also respond differently to future climate warming. Because species differ in their ecological characteristics, species distribution is also relevant with respect to further feedbacks between vegetation and climate.
With this thesis, I give an overview of present and past larch occurrences and evaluate which factors promote their dominance. Furthermore, I provide the tools to study past Larix species and give first important insights into the glacial history of Larix populations.
Stellar interferometry is the only method in observational astronomy for obtaining the highest resolution images of astronomical targets. This method is based on combining light from two or more separate telescopes to obtain the complex visibility that contains information about the brightness distribution of an astronomical source. The applications of stellar interferometry have made significant contributions in the exciting research areas of astronomy and astrophysics, including the precise measurement of stellar diameters, imaging of stellar surfaces, observations of circumstellar disks around young stellar objects, predictions of Einstein's General relativity at the galactic center, and the direct search for exoplanets to name a few. One important related technique is aperture masking interferometry, pioneered in the 1960s, which uses a mask with holes at the re-imaged pupil of the telescope, where the light from the holes is combined using the principle of stellar interferometry. While this can increase the resolution, it comes with a disadvantage. Due to the finite size of the holes, the majority of the starlight (typically > 80 %) is lost at the mask, thus limiting the signal-to-noise ratio (SNR) of the output images. This restriction of aperture masking only to the bright targets can be avoided using pupil remapping interferometry - a technique combining aperture masking interferometry and advances in photonic technologies using single-mode fibers. Due to the inherent spatial filtering properties, the single-mode fibers can be placed at the focal plane of the re-imaged pupil, allowing the utilization of the whole pupil of the telescope to produce a high-dynamic range along with high-resolution images. Thus, pupil remapping interferometry is one of the most promising application areas in the emerging field of astrophotonics.
At the heart of an interferometric facility, a beam combiner exists whose primary function is to combine light to obtain high-contrast fringes. A beam combiner can be as simple as a beam splitter or an anamorphic lens to combine light from 2 apertures (or telescopes) or as complex as a cascade of beam splitters and lenses to combine light for > 2 apertures. However, with the field of astrophotonics, interferometric facilities across the globe are increasingly employing some form of photonics technologies by using single-mode fibers or integrated optics (IO) chips as an efficient way to combine light from several apertures. The state-of-the-art instrument - GRAVITY at the very large telescope interferometer (VLTI) facility uses an IO-based beam combiner device reaching visibilities accuracy of better than < 0.25 %, which is roughly 50× as precise as a few decades back.
Therefore, in the context of IO-based components for applications in stellar interferometry, this Thesis describes the work towards the development of a 3-dimensional (3-D) IO device - a monolithic astrophotonics component containing both the pupil remappers and a discrete beam combiner (DBC). In this work, the pupil remappers are 3-D single-mode waveguides in a glass substrate collecting light from the re-imaged pupil of the telescope and feeding the light to a DBC, where the combination takes place. The DBC is a lattice of 3-D single-mode waveguides, which interact through evanescent coupling. By observing the output power of single-mode waveguides of the DBC, the visibilities are retrieved by using a calibrated transfer matrix ({U}) of the device.
The feasibility of the DBC in retrieving the visibilities theoretically and experimentally had already been studied in the literature but was only limited to laboratory tests with monochromatic light sources. Thus, a part of this work extends these studies by investigating the response of a 4-input DBC to a broad-band light source. Hence, the objectives of this Thesis are the following: 1) Design an IO device for broad-band light operation such that accurate and precise visibilities could be retrieved experimentally at astronomical H-band (1.5-1.65 μm), and 2) Validation of the DBC as a possible beam combination scheme for future interferometric facilities through on-sky testing at the William Herschel Telescope (WHT).
This work consisted of designing three different 3-D IO devices. One of the popular methods for fabricating 3-D photonic components in a glass substrate is ultra-fast laser inscription (ULI). Thus, manufacturing of the designed devices was outsourced to Politecnico di Milano as part of an iterative fabrication process using their state-of-the-art ULI facility. The devices were then characterized using a 2-beam Michelson interferometric setup obtaining both the monochromatic and polychromatic visibilities. The retrieved visibilities for all devices were in good agreement as predicted by the simulation results of a DBC, which confirms both the repeatability of the ULI process and the stability of the Michelson setup, thus fulfilling the first objective.
The best-performing device was then selected for the pupil-remapping of the WHT using a different optical setup consisting of a deformable mirror and a microlens array. The device successfully collected stellar photons from Vega and Altair. The visibilities were retrieved using a previously calibrated {U} but showed significant deviations from the expected results. Based on the analysis of comparable simulations, it was found that such deviations were primarily caused by the limited SNR of the stellar observations, thus constituting a first step towards the fulfillment of the second objective.
Two approaches for the synthesis of prenylated isoflavones were explored: the 2,3-oxidative rearrangement/cross metathesis approach, using hypervalent iodine reagents as oxidants and the Suzuki-Miyaura cross-coupling/cross metathesis approach. Three natural prenylated isoflavones: 5-deoxy-3′-prenylbiochanin A (59), erysubin F (61) and 7-methoxyebenosin (64), and non-natural analogues: 7,4′-dimethoxy-8,3′-diprenylisoflavone (126j) and 4′-hydroxy-7-methoxy-8,3′-diprenylisoflavone (128) were synthesized for the first time via the 2,3-oxidative rearrangement/cross metathesis approach, using mono- or diallylated flavanones as key intermediates. The reaction of flavanones with hypervalent iodine reagents afforded isoflavones via a 2,3-oxidative rearrangement and the corresponding flavone isomers via a 2,3-dehydrogenation. This afforded the synthesis of 7,4′-dimethoxy-8-prenylflavone (127g), 7,4′-dimethoxy-8,3′-diprenylflavone (127j), 7,4′-dihydroxy-8,3′-diprenylflavone (129) and 4′-hydroxy-7-methoxy-8,3′-diprenylflavone (130), the non-natural regioisomers of 7-methoxyebenosin, 126j, erysubin F and 128 respectively. Three natural prenylated isoflavones: 3′-prenylbiochanin A (58), neobavaisoflavone (66) and 7-methoxyneobavaisoflavone (137) were synthesized for the first time using the Suzuki-Miyaura cross-coupling/cross metathesis approach. The structures of 3′-prenylbiochanin A (58) and 5-deoxy-3′-prenylbiochanin A (59) were confirmed by single crystal X-ray diffraction analysis. The 2,3-oxidative rearrangement approach appears to be limited to the substitution pattern on both rings A and B of the flavanone while the Suzuki-Miyaura cross-coupling approach appears to be the most suitable for the synthesis of simple isoflavones or prenylated isoflavones whose prenyl substituents or allyl groups, the substituents that are essential precursors for the prenyl side chains, can be regioselectively introduced after the construction of the isoflavone core.
The chalcone-flavanone hybrids 146, 147 and 148, hybrids of the naturally occurring bioactive flavanones liquiritigenin-7-methyl ether, liquiritigenin and liquiritigenin-4′-methyl ether respectively were also synthesized for the first time, using Matsuda-Heck arylation and allylic/benzylic oxidation as key steps.
The intermolecular interactions of 5-deoxy-3′-prenylbiochanin A (59) and its two closely related precursors 106a and 106b was investigated by single crystal and Hirshfeld surface analyses to comprehend their different physicochemical properties. The results indicate that the presence of strong intermolecular O-H···O hydrogen bonds and an increase in the number of π-stacking interactions increases the melting point and lowers the solubility of isoflavone derivatives. However, the strong intermolecular O-H···O hydrogen bonds have a greater effect than the π-stacking interactions.
5-Deoxy-3′-prenylbiochanin A (59), erysubin F (61) and 7,4′-dihydroxy-8,3′-diprenylflavone (129), were tested against three bacterial strains and one fungal pathogen. All the three compounds were inactive against Salmonella enterica subsp. enterica (NCTC 13349), Escherichia coli (ATCC 25922), and Candida albicans (ATCC 90028), with MIC values greater than 80.0 μM. The diprenylated isoflavone erysubin F (61) and its flavone isomer 129 showed in vitro activity against methicillin-resistant Staphylococcus aureus (MRSA, ATCC 43300) at MIC values of 15.4 and 20.5 μM, respectively. 5-Deoxy-3′-prenylbiochanin A (59) was inactive against this MRSA strain. Erysubin F (61) and its flavone isomer 129 could serve as lead compounds for the development of new alternative drugs for the treatment of MRSA infections.
This cumulative doctoral thesis consists of three empirical studies that examine the role of top-level executives in shaping adverse financial reporting outcomes and other forms of corporate misconduct. The first study examines CEO effects on a wide range of offenses. Using data from enforcement actions by more than 50 U.S. federal agencies, regression re-sults show CEO effects on the likelihood, frequency, and severity of corporate misconduct. The findings hold for financial, labor-related, and environmental offenses; however, CEO effects are more pronounced for non-financial misconduct. Further results show a positive relation between CEO ability and non-financial misconduct, but no relation with financial misconduct, suggesting that higher CEO ability can have adverse consequences for employee welfare and society and public health. The second study focuses on CEO and CFO effects on financial misreporting. Using data on restatements and public enforcement actions, regression results show that the incremental effect of CFOs is economically larger than that of CEOs. This greater economic impact of CFOs is particularly pronounced for fraudulent misreporting. The findings remain consistent across different samples, methods, misreporting measures, and specification choices for the underlying conceptual mechanism, highlighting the important role of the CFO as a key player in the beyond-GAAP setting. The third study reexamines the relation between equity incentives and different reporting outcomes. The literature review reveals large variation in the empirical measures for firm size as standard control variable, equity incentives as key explanatory variables, and the reporting outcome of interest. Regres-sion results show that these design choices have a direct bearing on empirical results, with changes in t-statistics that often exceed typical thresholds for statistical significance. The find-ings hold for aggressive accrual management, earnings management through discretionary accruals, and material misstatements, suggesting that common design choices can have a large impact on whether equity incentives effects are considered significant or not.
In plant cells, subcellular transport of cargo proteins relies to a large extent on post-Golgi transport pathways, many of which are mediated by clathrin-coated vesicles (CCVs). Vesicle formation is facilitated by different factors like accessory proteins and adaptor protein complexes (APs), the latter serving as a bridge between cargo proteins and the coat protein clathrin. One type of accessory proteins is defined by a conserved EPSIN N-TERMINAL HOMOLOGY (ENTH) domain and interacts with APs and clathrin via motifs in the C-terminal part. In Arabidopsis thaliana, there are three closely related ENTH domain proteins (EPSIN1, 2 and 3) and one highly conserved but phylogenetically distant outlier, termed MODIFIED TRANSPORT TO THE VACUOLE1 (MTV1). In case of the trans-Golgi network (TGN) located MTV1, clathrin association and a role in vacuolar transport have been shown previously (Sauer et al. 2013). In contrast, for EPSIN1 and EPSIN2 limited functional and localization data were available; and EPSIN3 remained completely uncharacterized prior to this study (Song et al. 2006; Lee et al. 2007). The molecular details of ENTH domain proteins in plants are still unknown. In order to systematically characterize all four ENTH proteins in planta, we first investigated expression and subcellular localization by analysis of stable reporter lines under their endogenous promotors. Although all four genes are ubiquitously expressed, their subcellular distribution differs markedly. EPSIN1 and MTV1 are located at the TGN, whereas EPSIN2 and EPSIN3 are associated with the plasma membrane (PM) and the cell plate. To examine potential functional redundancy, we isolated knockout T-DNA mutant lines and created all higher order mutant combinations. The clearest evidence for functional redundancy was observed in the epsin1 mtv1 double mutant, which is a dwarf displaying overall growth reduction. These findings are in line with the TGN localization of both MTV1 and EPS1. In contrast, loss of EPSIN2 and EPSIN3 does not result in a growth phenotype compared to wild type, however, a triple knockout of EPSIN1, EPSIN2 and EPSIN3 shows partially sterile plants. We focused mainly on the epsin1 mtv1 double mutant and addressed the functional role of these two genes in clathrin-mediated vesicle transport by comprehensive molecular, biochemical, and genetic analyses. Our results demonstrate that EPSIN1 and MTV1 promote vacuolar transport and secretion of a subset of cargo. However, they do not seem to be involved in endocytosis and recycling. Importantly, employing high-resolution imaging, genetic and biochemical experiments probing the relationship of the AP complexes, we found that EPSIN1/AP1 and MTV1/AP4 define two spatially and molecularly distinct subdomains of the TGN. The AP4 complex is essential for MTV1 recruitment to the TGN, whereas EPSIN1 is independent of AP4 but presumably acts in an AP1-dependent framework. Our findings suggest that this ENTH/AP pairing preference is conserved between animals and plants.
Current business organizations want to be more efficient and constantly evolving to find ways to retain talent. It is well established that visionary leadership plays a vital role in organizational success and contributes to a better working environment. This study aims to determine the effect of visionary leadership on employees' perceived job satisfaction. Specifically, it investigates whether the mediators meaningfulness at work and commitment to the leader impact the relationship. I take support from job demand resource theory to explain the overarching model used in this study and broaden-and-build theory to leverage the use of mediators.
To test the hypotheses, evidence was collected in a multi-source, time-lagged design field study of 95 leader-follower dyads. The data was collected in a three-wave study, each survey appearing after one month. Data on employee perception of visionary leadership was collected in T1, data for both mediators were collected in T2, and employee perception of job satisfaction was collected in T3. The findings display that meaningfulness at work and commitment to the leader play positive intervening roles (in the form of a chain) in the indirect influence of visionary leadership on employee perceptions regarding job satisfaction.
This research offers contributions to literature and theory by first broadening the existing knowledge on the effects of visionary leadership on employees. Second, it contributes to the literature on constructs meaningfulness at work, commitment to the leader, and job satisfaction. Third, it sheds light on the mediation mechanism dealing with study variables in line with the proposed model. Fourth, it integrates two theories, job demand resource theory and broaden-and-build theory providing further evidence. Additionally, the study provides practical implications for business leaders and HR practitioners.
Overall, my study discusses the potential of visionary leadership behavior to elevate employee outcomes. The study aligns with previous research and answers several calls for further research on visionary leadership, job satisfaction, and mediation mechanism with meaningfulness at work and commitment to the leader.
Why do exercises in collaborative governance often witness more impasse than advantage? This cumulative dissertation undertakes a micro-level analysis of collaborative governance to tackle this research puzzle. It situates micropolitics at the very center of analysis: a wide range of activities, interventions, and tactics used by actors – be they conveners, facilitators, or participants – to shape the collaborative exercise. It is by focusing on these daily minutiae, and on the consequences that they bring along, the study argues, that we can better understand why and how collaboration can become stuck or unproductive. To do so, the foundational part of this dissertation (Article 1) uses power as a sensitizing concept to investigate the micro-dynamics that shape collaboration. It develops an analytical approach to advance the study of collaborative governance at the empirical level under a power-sensitive and process-oriented perspective. The subsequent articles follow the dissertation's red thread of investigating the micropolitics of collaborative governance by showing facilitation artefacts' interrelatedness and contribution to the potential success or failure of collaborative arrangements (Article 2); and by examining the specialized knowledge, skills and practices mobilized when designing a collaborative process (Article 3). The work is based on an abductive research approach, tacking back and forth between empirical data and theory, and offers a repertoire of concepts – from analytical terms (designed and emerging interaction orders, flows of power, arenas for power), to facilitation practices (scripting, situating, and supervising) and types of knowledge (process expertise) – to illustrate and study the detailed and constant work (and rework) that surrounds collaborative arrangements. These concepts sharpen the way researchers can look at, observe, and understand collaborative processes at a micro level. The thesis thereby elucidates the subtleties of power, which may be overlooked if we focus only on outcomes rather than the processes that engender them, and supports efforts to identify potential sources of impasse.
Duplicate detection describes the process of finding multiple representations of the same real-world entity in the absence of a unique identifier, and has many application areas, such as customer relationship management, genealogy and social sciences, or online shopping. Due to the increasing amount of data in recent years, the problem has become even more challenging on the one hand, but has led to a renaissance in duplicate detection research on the other hand.
This thesis examines the effects and opportunities of transitive relationships on the duplicate detection process. Transitivity implies that if record pairs ⟨ri,rj⟩ and ⟨rj,rk⟩ are classified as duplicates, then also record pair ⟨ri,rk⟩ has to be a duplicate. However, this reasoning might contradict with the pairwise classification, which is usually based on the similarity of objects. An essential property of similarity, in contrast to equivalence, is that similarity is not necessarily transitive.
First, we experimentally evaluate the effect of an increasing data volume on the threshold selection to classify whether a record pair is a duplicate or non-duplicate. Our experiments show that independently of the pair selection algorithm and the used similarity measure, selecting a suitable threshold becomes more difficult with an increasing number of records due to an increased probability of adding a false duplicate to an existing cluster. Thus, the best threshold changes with the dataset size, and a good threshold for a small (possibly sampled) dataset is not necessarily a good threshold for a larger (possibly complete) dataset. As data grows over time, earlier selected thresholds are no longer a suitable choice, and the problem becomes worse for datasets with larger clusters.
Second, we present with the Duplicate Count Strategy (DCS) and its enhancement DCS++ two alternatives to the standard Sorted Neighborhood Method (SNM) for the selection of candidate record pairs. DCS adapts SNMs window size based on the number of detected duplicates and DCS++ uses transitive dependencies to save complex comparisons for finding duplicates in larger clusters. We prove that with a proper (domain- and data-independent!) threshold, DCS++ is more efficient than SNM without loss of effectiveness.
Third, we tackle the problem of contradicting pairwise classifications. Usually, the transitive closure is used for pairwise classifications to obtain a transitively closed result set. However, the transitive closure disregards negative classifications. We present three new and several existing clustering algorithms and experimentally evaluate them on various datasets and under various algorithm configurations. The results show that the commonly used transitive closure is inferior to most other clustering algorithms, especially for the precision of results. In scenarios with larger clusters, our proposed EMCC algorithm is, together with Markov Clustering, the best performing clustering approach for duplicate detection, although its runtime is longer than Markov Clustering due to the subexponential time complexity. EMCC especially outperforms Markov Clustering regarding the precision of the results and additionally has the advantage that it can also be used in scenarios where edge weights are not available.
Biomimicry is the art of mimicking nature to overcome a particular technical or scientific challenge. The approach studies how evolution has found solutions to the most complex problems in nature. This makes it a powerful method for science. In combination with the rapid development of manufacturing and information technologies into the digital age, structures and material that were before thought to be unrealizable can now be created with simple sketch and the touch of a button. This doctoral thesis had as its primary goal to investigate how digital tools, such as programming, modelling, 3D-Design tools and 3D-Printing, with the help from biomimicry, could lead to new analysis methods in science and new medical devices in medicine.
The Electrical Discharge Machining (EDM) process is applied commonly to deform or mold hard metals that are difficult to work using normal machinery. A workpiece submerged in an electrolyte is deformed while being in close vicinity to an electrode. When high voltage is put between the workpiece and the electrode it will cause sparks that create cavitations on the substrate which in turn removes material and is flushed away by the electrolyte. Usually, such surfaces are analysed based on roughness, in this work another method using a novel curvature analysis method is presented as an alternative. In addition, to better understand how the surface changes during process time of the EDM process, a digital impact model was created which created craters on ridges on an originally flat substrate. These substrates were then analysed using the curvature analysis method at different processing times of the modelling. It was found that a substrate reaches an equilibrium at around 10000 impacts. The proposed curvature analysis method has potential to be used in the design of new cell culture substrates for stem cell.
The Venus flytrap can shut its jaws at an amazing speed. The shutting mechanism may be interesting to use in science and is an example of a so-called mechanical bi-stable system – there are two stable states. In this work two truncated pyramid structures were modelled using a non-linear mechanical model called the Chained Beam Constraint Model (CBCM). The structure with a slope angle of 30 degrees is not bi-stable and the structure with a slope angle of 45 degrees is bi-stable. Developing this idea further by using PEVA, which has a shape-memory effect, the structure which is not bi-stable could be programmed to be bi-stable and then turned off again. This could be used as an energy storage system. Another species which has interesting mechanism is the tapeworm. Some species of this animal has a crown of hooks and suckers located on its side. The parasite commonly is found in mammals in the lower intestine and attaches to the walls by using its suckers. When the tapeworm has found a suitable spot, it ejects its hooks and permanently attaches to the wall. This function could be used in minimally invasive medicine to have better control of implants during the implantation process. By using the CBCM model and a 3D-printer capable of tuning how hard or soft a printed part is, a design strategy was developed to investigate how one could create a device that mimics the tapeworm. In the end a prototype was created which was able attach to a pork loin at an under pressure of 20 kPa and to ejects its hooks at an under pressure of 50 kPa or above.
These three projects is an exhibit of how digital tools and biomimicry can be used together to come up with applicable solutions in science and in medicine.
Polyglot programming allows developers to use multiple programming languages within the same software project. While it is common to use more than one language in certain programming domains, developers also apply polyglot programming for other purposes such as to re-use software written in other languages. Although established approaches to polyglot programming come with significant limitations, for example, in terms of performance and tool support, developers still use them to be able to combine languages.
Polyglot virtual machines (VMs) such as GraalVM provide a new level of polyglot programming, allowing languages to directly interact with each other. This reduces the amount of glue code needed to combine languages, results in better performance, and enables tools such as debuggers to work across languages. However, only a little research has focused on novel tools that are designed to support developers in building software with polyglot VMs. One reason is that tool-building is often an expensive activity, another one is that polyglot VMs are still a moving target as their use cases and requirements are not yet well understood.
In this thesis, we present an approach that builds on existing self-sustaining programming systems such as Squeak/Smalltalk to enable exploratory programming, a practice for exploring and gathering software requirements, and re-use their extensive tool-building capabilities in the context of polyglot VMs. Based on TruffleSqueak, our implementation for the GraalVM, we further present five case studies that demonstrate how our approach helps tool developers to design and build tools for polyglot programming. We further show that TruffleSqueak can also be used by application developers to build and evolve polyglot applications at run-time and by language and runtime developers to understand the dynamic behavior of GraalVM languages and internals. Since our platform allows all these developers to apply polyglot programming, it can further help to better understand the advantages, use cases, requirements, and challenges of polyglot VMs. Moreover, we demonstrate that our approach can also be applied to other polyglot VMs and that insights gained through it are transferable to other programming systems.
We conclude that our research on tools for polyglot programming is an important step toward making polyglot VMs more approachable for developers in practice. With good tool support, we believe polyglot VMs can make it much more common for developers to take advantage of multiple languages and their ecosystems when building software.
Functional traits determine biomass dynamics, coexistence and energetics in plankton food webs
(2022)
Plankton food webs are the basis of marine and limnetic ecosystems. Especially aquatic ecosystems of high biodiversity provide important ecosystem services for humankind as providers of food, coastal protection, climate regulation, and tourism. Understanding the dynamics of biomass and coexistence in these food webs is a first step to understanding the ecosystems. It also lays the foundation for the development of management strategies for the maintenance of the marine and freshwater biodiversity despite anthropogenic influences.
Natural food webs are highly complex, and thus often equally complex methods are needed to analyse and understand them well. Models can help to do so as they depict simplified parts of reality. In the attempt to get a broader understanding of the complex food webs, diverse methods are used to investigate different questions.
In my first project, we compared the energetics of a food chain in two versions of an allometric trophic network model. In particular, we solved the problem of unrealistically high trophic transfer efficiencies (up to 70%) by accounting for both basal respiration and activity respiration, which decreased the trophic transfer efficiency to realistic values of ≤30%. Next in my second project I turned to plankton food webs and especially phytoplankton traits. Investigating a long-term data set from Lake Constance we found evidence for a trade-off between defence and growth rate in this natural phytoplankton community. I continued working with this data set in my third project focusing on ciliates, the main grazer of phytoplankton in spring. Boosted regression trees revealed that temperature and predators have the highest influence on net growth rates of ciliates. We finally investigated in my fourth project a food web model inspired by ciliates to explore the coexistence of plastic competitors and to study the new concept of maladaptive switching, which revealed some drawbacks of plasticity: faster adaptation led to higher maladaptive switching towards undefended phenotypes which reduced autotroph biomass and coexistence and increased consumer biomass.
It became obvious that even well-established models should be critically questioned as it is important not to forget reality on the way to a simplistic model. The results showed furthermore that long-term data sets are necessary as they can help to disentangle complex natural processes. Last, one should keep in mind that the interplay between models and experiments/ field data can deliver fruitful insights about our complex world.
More than a century ago the phenomenon of non-Mendelian inheritance (NMI), defined as any type of inheritance pattern in which traits do not segregate in accordance with Mendel’s laws, was first reported. In the plant kingdom three genomic compartments, the nucleus, chloroplast, and mitochondrion, can participate in such a phenomenon. High-throughput sequencing (HTS) proved to be a key technology to investigate NMI phenomena by assembling and/or resequencing entire genomes. However, generation, analysis and interpretation of such datasets remain challenging by the multi-layered biological complexity. To advance our knowledge in the field of NMI, I conducted three studies involving different HTS technologies and implemented two new algorithms to analyze them.
In the first study I implemented a novel post-assembly pipeline, called Semi-Automated Graph-Based Assembly Curator (SAGBAC), which visualizes non-graph-based assemblies as graphs, identifies recombinogenic repeat pairs (RRPs), and reconstructs plant mitochondrial genomes (PMG) in a semiautomated workflow. We applied this pipeline to assemblies of three Oenothera species resulting in a spatially folded and circularized model. This model was confirmed by PCR and Southern blot analyses and was used to predict a defined set of 70 PMG isoforms. With Illumina Mate Pair and PacBio RSII data, the stoichiometry of the RRPs was determined quantitatively differing up to three-fold.
In the second study I developed a post-multiple sequence alignment algorithm, called correlation mapping (CM), which correlates segment-wise numbers of nucleotide changes to a numeric ascertainable phenotype. We applied this algorithm to 14 wild type and 18 mutagenized plastome assemblies within the Oenothera genus and identified two genes, accD and ycf2 that may cause the competitive behavior of plastid genotypes as plastids can be biparental inherited in Oenothera. Moreover, lipid composition of the plastid envelope membrane is affected by polymorphisms within these two genes.
For the third study, I programmed a pipeline to investigate a NMI phenomenon, known as paramutation, in tomato by analyzing DNA and bisulfite sequencing data as well as microarray data. We identified the responsible gene (Solyc02g0005200) and were able to fully repress its caused phenotype by heterologous complementation with a paramutation insensitive transgene of the Arabidopsis thaliana orthologue. Additionally, a suppressor mutant shows a globally altered DNA methylation pattern and carries a large deletion leading to a gene fusion involving a histone deacetylase.
In conclusion, my developed and implemented algorithms and data analysis pipelines are suitable to investigate NMI and led to novel insights about such phenomena by reconstructing PMGs (SAGBAC) as a requirement to study mitochondria-associated phenotypes, by identifying genes (CM) causing interplastidial competition as well by applying a DNA/Bisulfite-seq analysis pipeline to shed light in a transgenerational epigenetic inheritance phenomenon.
Hydraulic-driven fractures play a key role in subsurface energy technologies across several scales. By injecting fluid at high hydraulic pressure into rock with intrinsic low permeability, in-situ stress field and fracture development pattern can be characterised as well as rock permeability can be enhanced. Hydraulic fracturing is a commercial standard procedure for enhanced oil and gas production of rock reservoirs with low permeability in petroleum industry. However, in EGS utilization, a major geological concern is the unsolicited generation of earthquakes due to fault reactivation, referred to as induced seismicity, with a magnitude large enough to be felt on the surface or to damage facilities and buildings. Furthermore, reliable interpretation of hydraulic fracturing tests for stress measurement is a great challenge for the energy technologies. Therefore, in this cumulative doctoral thesis the following research questions are investigated. (1): How do hydraulic fractures grow in hard rock at various scales?; (2): Which parameters control hydraulic fracturing and hydro-mechanical coupling?; and (3): How can hydraulic fracturing in hard rock be modelled?
In the laboratory scale study, several laboratory hydraulic fracturing experiments are investigated numerically using Irazu2D that were performed on intact cubic Pocheon granite samples from South Korea applying different injection protocols. The goal of the laboratory experiments is to test the concept of cyclic soft stimulation which may enable sustainable permeability enhancement (Publication 1).
In the borehole scale study, hydraulic fracturing tests are reported that were performed in boreholes located in central Hungary to determine the in-situ stress for a geological site investigation. At depth of about 540 m, the recorded pressure versus time curves in mica schist with low dip angle foliation show atypical evolution. In order to provide explanation for this observation, a series of discrete element computations using Particle Flow Code 2D are performed (Publication 2).
In the reservoir scale study, the hydro-mechanical behaviour of fractured crystalline rock due to one of the five hydraulic stimulations at the Pohang Enhanced Geothermal site in South Korea is studied. Fluid pressure perturbation at faults of several hundred-meter lengths during hydraulic stimulation is simulated using FracMan (Publication 3).
The doctoral research shows that the resulting hydraulic fracturing geometry will depend “locally”, i.e. at the length scale of representative elementary volume (REV) and below that (sub-REV), on the geometry and strength of natural fractures, and “globally”, i.e. at super-REV domain volume, on far-field stresses. Regarding hydro-mechanical coupling, it is suggested to define separate coupling relationship for intact rock mass and natural fractures. Furthermore, the relative importance of parameters affecting the magnitude of formation breakdown pressure, a parameter characterising hydro-mechanical coupling, is defined. It can be also concluded that there is a clear gap between the capacity of the simulation software and the complexity of the studied problems. Therefore, the computational time of the simulation of complex hydraulic fracture geometries must be reduced while maintaining high fidelity simulation results. This can be achieved either by extending the computational resources via parallelization techniques or using time scaling techniques. The ongoing development of used numerical models focuses on tackling these methodological challenges.
The main goal of this dissertation is to experimentally investigate how focus is realised, perceived, and processed by native Turkish speakers, independent of preconceived notions of positional restrictions. Crucially, there are various issues and scientific debates surrounding focus in the Turkish language in the existing literature (chapter 1). It is argued in this dissertation that two factors led to the stagnant literature on focus in Turkish: the lack of clearly defined, modern understandings of information structure and its fundamental notion of focus, and the ongoing and ill-defined debate surrounding the question of whether there is an immediately preverbal focus position in Turkish. These issues gave rise to specific research questions addressed across this dissertation. Specifically, we were interested in how the focus dimensions such as focus size (comparing narrow constituent and broad sentence focus), focus target (comparing narrow subject and narrow object focus), and focus type (comparing new-information and contrastive focus) affect Turkish focus realisation and, in turn, focus comprehension when speakers are provided syntactic freedom to position focus as they see fit.
To provide data on these core goals, we presented three behavioural experiments based on a systematic framework of information structure and its notions (chapter 2): (i) a production task with trigger wh-questions and contextual animations manipulated to elicit the focus dimensions of interest (chapter 3), (ii) a timed acceptability judgment task in listening to the recorded answers in our production task (chapter 4), and (iii) a self-paced reading task to gather on-line processing data (chapter 5).
Based on the results of the conducted experiments, multiple conclusions are made in this dissertation (chapter 6). Firstly, this dissertation demonstrated empirically that there is no focus position in Turkish, neither in the sense of a strict focus position language nor as a focally loaded position facilitating focus perception and/or processing. While focus is, in fact, syntactically variable in the Turkish preverbal area, this is a consequence of movement triggered by other IS aspects like topicalisation and backgrounding, and the observational markedness of narrow subject focus compared to narrow object focus. As for focus type in Turkish, this dimension is not associated with word order in production, perception, or processing. Significant acoustic correlates of focus size (broad sentence focus vs narrow constituent focus) and focus target (narrow subject focus vs narrow object focus) were observed in fundamental frequency and intensity, representing focal boost, (postfocal) deaccentuation, and the presence or absence of a phrase-final rise in the prenucleus, while the perceivability of these effects remains to be investigated. In contrast, no acoustic correlates of focus type in simple, three-word transitive structures were observed, with focus types being interchangeable in mismatched question-answer pairs. Overall, the findings of this dissertation highlight the need for experimental investigations regarding focus in Turkish, as theoretical predictions do not necessarily align with experimental data. As such, the fallacy of implying causation from correlation should be strictly kept in mind, especially when constructions coincide with canonical structures, such as the immediately preverbal position in narrow object foci. Finally, numerous open questions remain to be explored, especially as focus and word order in Turkish are multifaceted. As shown, givenness is a confounding factor when investigating focus types, while thematic role assignment potentially confounds word order preferences. Further research based on established, modern information structure frameworks is needed, with chapter 5 concluding with specific recommendations for such future research.
Salt deposits offer a variety of usage types. These include the mining of rock salt and potash salt as important raw materials, the storage of energy in man-made underground caverns, and the disposal of hazardous substances in former mines. The most serious risk with any of these usage types comes from the contact with groundwater or surface water. It causes an uncontrolled dissolution of salt rock, which in the worst case can result in the flooding or collapse of underground facilities. Especially along potash seams, cavernous structures can spread quickly, because potash salts show a much higher solubility than rock salt. However, as their chemical behavior is quite complex, previous models do not account for these highly soluble interlayers. Therefore, the objective of the present thesis is to describe the evolution of cavernous structures along potash seams in space and time in order to improve hazard mitigation during the utilization of salt deposits.
The formation of cavernous structures represents an interplay of chemical and hydraulic processes. Hence, the first step is to systematically investigate the dissolution and precipitation reactions that occur when water and potash salt come into contact. For this purpose, a geochemical reaction model is used. The results show that the minerals are only partially dissolved, resulting in a porous sponge like structure. With the saturation of the solution increasing, various secondary minerals are formed, whose number and type depend on the original rock composition. Field data confirm a correlation between the degree of saturation and the distance from the center of the cavern, where solution is entering. Subsequently, the reaction model is coupled with a flow and transport code and supplemented by a novel approach called ‘interchange’. The latter enables the exchange of solution and rock between areas of different porosity and mineralogy, and thus ultimately the growth of the cavernous structure. By means of several scenario analyses, cavern shape, growth rate and mineralogy are systematically investigated, taking also heterogeneous potash seams into account. The results show that basically four different cases can be distinguished, with mixed forms being a frequent occurrence in nature. The classification scheme is based on the dimensionless numbers Péclet and Damköhler, and allows for a first assessment of the hazard potential. In future, the model can be applied to any field case, using measurement data for calibration.
The presented research work provides a reactive transport model that is able to spatially and temporally characterize the propagation of cavernous structures along potash seams for the first time. Furthermore, it allows to determine thickness and composition of transition zones between cavern center and unaffected salt rock. The latter is particularly important in potash mining, so that natural cavernous structures can be located at an early stage and the risk of mine flooding can thus be reduced. The models may also contribute to an improved hazard prevention in the construction of storage caverns and the disposal of hazardous waste in salt deposits. Predictions regarding the characteristics and evolution of cavernous structures enable a better assessment of potential hazards, such as integrity or stability loss, as well as of suitable mitigation measures.
Complex networks like the Internet or social networks are fundamental parts of our everyday lives. It is essential to understand their structural properties and how these networks are formed. A game-theoretic approach to network design problems has become of high interest in the last decades. The reason is that many real-world networks are the outcomes of decentralized strategic behavior of independent agents without central coordination. Fabrikant, Luthra, Maneva, Papadimitriou, and Schenker proposed a game-theoretic model aiming to explain the formation of the Internet-like networks. In this model, called the Network Creation Game, agents are associated with nodes of a network. Each agent seeks to maximize her centrality by establishing costly connections to other agents. The model is relatively simple but shows a high potential in modeling complex real-world networks. In this thesis, we contribute to the line of research on variants of the Network Creation Games. Inspired by real-world networks, we propose and analyze several novel network creation models. We aim to understand the impact of certain realistic modeling assumptions on the structure of the created networks and the involved agents’ behavior.
The first natural additional objective that we consider is the network’s robustness. We consider a game where the agents seek to maximize their centrality and, at the same time, the stability of the created network against random edge failure.
Our second point of interest is a model that incorporates an underlying geometry. We consider a network creation model where the agents correspond to points in some underlying space and where edge lengths are equal to the distances between the endpoints in that space. The geometric setting captures many physical real-world networks like transport networks and fiber-optic communication networks.
We focus on the formation of social networks and consider two models that incorporate particular realistic behavior observed in real-world networks. In the first model, we embed the anti-preferential attachment link formation. Namely, we assume that the cost of the connection is proportional to the popularity of the targeted agent. Our second model is based on the observation that the probability of two persons to connect is inversely proportional to the length of their shortest chain of mutual acquaintances.
For each of the four models above, we provide a complete game-theoretical analysis. In particular, we focus on distinctive structural properties of the equilibria, the hardness of computing a best response, the quality of equilibria in comparison to the centrally designed socially optimal networks. We also analyze the game dynamics, i.e., the process of sequential strategic improvements by the agents, and analyze the convergence to an equilibrium state and its properties.
The index theorem for elliptic operators on a closed Riemannian manifold by Atiyah and Singer has many applications in analysis, geometry and topology, but it is not suitable for a generalization to a Lorentzian setting.
In the case where a boundary is present Atiyah, Patodi and Singer provide an index theorem for compact Riemannian manifolds by introducing non-local boundary conditions obtained via the spectral decomposition of an induced boundary operator, so called APS boundary conditions. Bär and Strohmaier prove a Lorentzian version of this index theorem for the Dirac operator on a manifold with boundary by utilizing results from APS and the characterization of the spectral flow by Phillips. In their case the Lorentzian manifold is assumed to be globally hyperbolic and spatially compact, and the induced boundary operator is given by the Riemannian Dirac operator on a spacelike Cauchy hypersurface. Their results show that imposing APS boundary conditions for these boundary operator will yield a Fredholm operator with a smooth kernel and its index can be calculated by a formula similar to the Riemannian case.
Back in the Riemannian setting, Bär and Ballmann provide an analysis of the most general kind of boundary conditions that can be imposed on a first order elliptic differential operator that will still yield regularity for solutions as well as Fredholm property for the resulting operator. These boundary conditions can be thought of as deformations to the graph of a suitable operator mapping APS boundary conditions to their orthogonal complement.
This thesis aims at applying the boundary conditions found by Bär and Ballmann to a Lorentzian setting to understand more general types of boundary conditions for the Dirac operator, conserving Fredholm property as well as providing regularity results and relative index formulas for the resulting operators. As it turns out, there are some differences in applying these graph-type boundary conditions to the Lorentzian Dirac operator when compared to the Riemannian setting. It will be shown that in contrast to the Riemannian case, going from a Fredholm boundary condition to its orthogonal complement works out fine in the Lorentzian setting. On the other hand, in order to deduce Fredholm property and regularity of solutions for graph-type boundary conditions, additional assumptions for the deformation maps need to be made.
The thesis is organized as follows. In chapter 1 basic facts about Lorentzian and Riemannian spin manifolds, their spinor bundles and the Dirac operator are listed. These will serve as a foundation to define the setting and prove the results of later chapters.
Chapter 2 defines the general notion of boundary conditions for the Dirac operator used in this thesis and introduces the APS boundary conditions as well as their graph type deformations. Also the role of the wave evolution operator in finding Fredholm boundary conditions is analyzed and these boundary conditions are connected to notion of Fredholm pairs in a given Hilbert space.
Chapter 3 focuses on the principal symbol calculation of the wave evolution operator and the results are used to proof Fredholm property as well as regularity of solutions for suitable graph-type boundary conditions. Also sufficient conditions are derived for (pseudo-)local boundary conditions imposed on the Dirac operator to yield a Fredholm operator with a smooth solution space.
In the last chapter 4, a few examples of boundary conditions are calculated applying the results of previous chapters. Restricting to special geometries and/or boundary conditions, results can be obtained that are not covered by the more general statements, and it is shown that so-called transmission conditions behave very differently than in the Riemannian setting.
Boolean Satisfiability (SAT) is one of the problems at the core of theoretical computer science. It was the first problem proven to be NP-complete by Cook and, independently, by Levin. Nowadays it is conjectured that SAT cannot be solved in sub-exponential time. Thus, it is generally assumed that SAT and its restricted version k-SAT are hard to solve. However, state-of-the-art SAT solvers can solve even huge practical instances of these problems in a reasonable amount of time.
Why is SAT hard in theory, but easy in practice? One approach to answering this question is investigating the average runtime of SAT. In order to analyze this average runtime the random k-SAT model was introduced. The model generates all k-SAT instances with n variables and m clauses with uniform probability. Researching random k-SAT led to a multitude of insights and tools for analyzing random structures in general. One major observation was the emergence of the so-called satisfiability threshold: A phase transition point in the number of clauses at which the generated formulas go from asymptotically almost surely satisfiable to asymptotically almost surely unsatisfiable. Additionally, instances around the threshold seem to be particularly hard to solve.
In this thesis we analyze a more general model of random k-SAT that we call non-uniform random k-SAT. In contrast to the classical model each of the n Boolean variables now has a distinct probability of being drawn. For each of the m clauses we draw k variables according to the variable distribution and choose their signs uniformly at random. Non-uniform random k-SAT gives us more control over the distribution of Boolean variables in the resulting formulas. This allows us to tailor distributions to the ones observed in practice. Notably, non-uniform random k-SAT contains the previously proposed models random k-SAT, power-law random k-SAT and geometric random k-SAT as special cases.
We analyze the satisfiability threshold in non-uniform random k-SAT depending on the variable probability distribution. Our goal is to derive conditions on this distribution under which an equivalent of the satisfiability threshold conjecture holds. We start with the arguably simpler case of non-uniform random 2-SAT. For this model we show under which conditions a threshold exists, if it is sharp or coarse, and what the leading constant of the threshold function is. These are exactly the three ingredients one needs in order to prove or disprove the satisfiability threshold conjecture. For non-uniform random k-SAT with k=3 we only prove sufficient conditions under which a threshold exists. We also show some properties of the variable probabilities under which the threshold is sharp in this case. These are the first results on the threshold behavior of non-uniform random k-SAT.
Knowledge-intensive business processes are flexible and data-driven. Therefore, traditional process modeling languages do not meet their requirements: These languages focus on highly structured processes in which data plays a minor role. As a result, process-oriented information systems fail to assist knowledge workers on executing their processes. We propose a novel case management approach that combines flexible activity-centric processes with data models, and we provide a joint semantics using colored Petri nets. The approach is suited to model, verify, and enact knowledge-intensive processes and can aid the development of information systems that support knowledge work.
Knowledge-intensive processes are human-centered, multi-variant, and data-driven. Typical domains include healthcare, insurances, and law. The processes cannot be fully modeled, since the underlying knowledge is too vast and changes too quickly. Thus, models for knowledge-intensive processes are necessarily underspecified. In fact, a case emerges gradually as knowledge workers make informed decisions. Knowledge work imposes special requirements on modeling and managing respective processes. They include flexibility during design and execution, ad-hoc adaption to unforeseen situations, and the integration of behavior and data. However, the predominantly used process modeling languages (e.g., BPMN) are unsuited for this task.
Therefore, novel modeling languages have been proposed. Many of them focus on activities' data requirements and declarative constraints rather than imperative control flow. Fragment-Based Case Management, for example, combines activity-centric imperative process fragments with declarative data requirements. At runtime, fragments can be combined dynamically, and new ones can be added. Yet, no integrated semantics for flexible activity-centric process models and data models exists.
In this thesis, Wickr, a novel case modeling approach extending fragment-based Case Management, is presented. It supports batch processing of data, sharing data among cases, and a full-fledged data model with associations and multiplicity constraints. We develop a translational semantics for Wickr targeting (colored) Petri nets. The semantics assert that a case adheres to the constraints in both the process fragments and the data models. Among other things, multiplicity constraints must not be violated. Furthermore, the semantics are extended to multiple cases that operate on shared data. Wickr shows that the data structure may reflect process behavior and vice versa. Based on its semantics, prototypes for executing and verifying case models showcase the feasibility of Wickr. Its applicability to knowledge-intensive and to data-centric processes is evaluated using well-known requirements from related work.
Localisation of deformation is a ubiquitous feature in continental rift dynamics and observed across drastically different time and length scales. This thesis comprises one experimental and two numerical modelling studies investigating strain localisation in (1) a ductile shear zone induced by a material heterogeneity and (2) in an active continental rift setting. The studies are related by the fact that the weakening mechanisms on the crystallographic and grain size scale enable bulk rock weakening, which fundamentally enables the formation of shear zones, continental rifts and hence plate tectonics. Aiming to investigate the controlling mechanisms on initiation and evolution of a shear zone, the torsion experiments of the experimental study were conducted in a Patterson type apparatus with strong Carrara marble cylinders with a weak, planar Solnhofen limestone inclusion. Using state-of-the-art numerical modelling software, the torsion experiments were simulated to answer questions regarding localisation procedure like stress distribution or the impact of rheological weakening. 2D numerical models were also employed to integrate geophysical and geological data to explain characteristic tectonic evolution of the Southern and Central Kenya Rift. Key elements of the numerical tools are a randomized initial strain distribution and the usage of strain softening. During the torsion experiments, deformation begins to localise at the limestone inclusion tips in a process zone, which propagates into the marble matrix with increasing deformation until a ductile shear zone is established. Minor indicators for coexisting brittle deformation are found close to the inclusion tip and presumed to slightly facilitate strain localisation besides the dominant ductile deformation processes. The 2D numerical model of the torsion experiment successfully predicts local stress concentration and strain rate amplification ahead of the inclusion in first order agreement with the experimental results. A simple linear parametrization of strain weaking enables high accuracy reproduction of phenomenological aspects of the observed weakening. The torsion experiments suggest that loading conditions do not affect strain localisation during high temperature deformation of multiphase material with high viscosity contrasts. A numerical simulation can provide a way of analysing the process zone evolution virtually and extend the examinable frame. Furthermore, the nested structure and anastomosing shape of an ultramylonite band was mimicked with an additional second softening step. Rheological weakening is necessary to establish a shear zone in a strong matrix around a weak inclusion and for ultramylonite formation.
Such strain weakening laws are also incorporated into the numerical models of the
Southern and Central Kenya Rift that capture the characteristic tectonic evolution. A three-stage early rift evolution is suggested that starts with (1) the accommodation of strain by a single border fault and flexure of the hanging-wall crust, after which (2) faulting in the hanging-wall and the basin centre increases before (3) the early-stage asymmetry is lost and basinward localisation of deformation occurs. Along-strike variability of rifts can be produced by modifying the initial random noise distribution. In summary, the three studies address selected aspects of the broad range of mechanisms and processes that fundamentally enable the deformation of rock and govern the localisation patterns across the scales. In addition to the aforementioned results, the first and second manuscripts combined, demonstrate a procedure to find new or improve on existing numerical formulations for specific rheologies and their dynamic weakening. These formulations are essential in addressing rock deformation from the grain to the global scale. As within the third study of this thesis, where geodynamic controls on the evolution of a rift were examined and acquired by the integration of geological and geophysical data into a numerical model.
Humankind and their environment need to be protected from the harmful effects of spent nuclear fuel, and therefore disposal in deep geological formations is favoured worldwide. Suitability of potential host rocks is evaluated, among others, by the retention capacity with respect to radionuclides. Safety assessments are based on the quantification of radionuclide migration lengths with numerical simulations as experiments cannot cover the required temporal (1 Ma) and spatial scales (>100 m).
Aim of the present thesis is to assess the migration of uranium, a geochemically complex radionuclide, in the potential host rock Opalinus Clay. Radionuclide migration in clay formations is governed by diffusion due to their low permeability and retarded by sorption. Both processes highly depend on pore water geochemistry and mineralogy that vary between different facies. Diffusion is quantified with the single-component (SC) approach using one diffusion coefficient for all species and the process-based multi-component (MC) option. With this, each species is assigned its own diffusion coefficient and the interaction with the diffuse double layer is taken into account. Sorption is integrated via a bottom-up approach using mechanistic surface complexation models and cation exchange. Therefore, reactive transport simulations are conducted with the geochemical code PHREEQC to quantify uranium migration, i.e. diffusion and sorption, as a function of mineralogical and geochemical heterogeneities on the host rock scale.
Sorption processes are facies dependent. Migration lengths vary between the Opalinus Clay facies by up to 10 m. Thereby, the geochemistry of the pore water, in particular the partial pressure of carbon dioxide (pCO2), is more decisive for the sorption capacity than the amount of clay minerals. Nevertheless, higher clay mineral quantities compensate geochemical variations. Consequently, sorption processes must be quantified as a function of pore water geochemistry in contact with the mineral assemblage.
Uranium diffusion in the Opalinus Clay is facies independent. Speciation is dominated by aqueous ternary complexes of U(VI) with calcium and carbonate. Differences in the migration lengths between SC and MC diffusion are with +/-5 m negligible. Further, the application of the MC approach highly depends on the quality and availability of the underlying data. Therefore, diffusion processes can be adequately quantified with the SC approach using experimentally determined diffusion coefficients.
The hydrogeological system governs pore water geochemistry within the formation rather than the mineralogy. Diffusive exchange with the adjacent aquifers established geochemical gradients over geological time scales that can enhance migration by up to 25 m. Consequently, uranium sorption processes must be quantified following the identified priority: pCO2 > hydrogeology > mineralogy.
The presented research provides a workflow and orientation for other potential disposal sites with similar pore water geochemistry due to the identified mechanisms and dependencies. With a maximum migration length of 70 m, the retention capacity of the Opalinus Clay with respect to uranium is sufficient to fulfill the German legal minimum requirement of a thickness of at least 100 m.
This paper examines the function that cross-cultural competence (3C) has for NATO in a military context while focusing on two member states and their armed forces: the United States and Germany. Three dimensions were established to analyze 3C internally and externally: dimension A, dealing with 3C within the military organization; dimension B, focusing on 3C in a coalition environment/multicultural NATO contingent, for example while on a mission/training exercise abroad; and dimension C, covering 3C and NATO missions abroad with regard to interaction with the local population.
When developing the research design, the cultural studies-based theory of hegemony constructed by Antonio Gramsci was applied to a comprehensive document analysis of 3C coursework and regulations as well as official documents in order to establish a typification for cross-cultural competence.
As the result, 3C could be categorized as Type I – Ethical 3C, Type II – Hegemonic 3C, and Type III – Dominant 3C. Attributes were assigned according to each type. To validate the established typification, qualitative surveys were conducted with NATO (ACT), the U.S. Armed Forces (USCENTCOM), and the German Armed Forces (BMVg). These interviews validated the typification and revealed a varied approach to 3C in the established dimensions. It became evident that dimensions A and B indicated a prevalence of Type III, which greatly impacts the work atmosphere and effectiveness for NATO (ACT). In contrast, dimension C revealed the use of postcolonial mechanisms by NATO forces, such as applying one’s value systems to other cultures and having the appearance of an occupying force when 3C is not applied (Type I-II). In general, the function of each 3C type in the various dimensions could be determined.
In addition, a comparative study of the document analysis and the qualitative surveys resulted in a canon for culture-general skills. Regarding the determined lack of coherence in 3C correlating with a demonstrably negative impact on effectiveness and efficiency as well as interoperability, a NATO standard in the form of a standardization agreement (STANAG) was suggested based on the aforementioned findings, with a focus on: empathy, cross-cultural awareness, communication skills (including active listening), flexibility and adaptability, and interest. Moreover, tolerance of ambiguity and teachability, patience, observation skills, and perspective-taking could be considered significant. Suspending judgment and respect are also relevant skills here.
At the same time, the document analysis also revealed a lack of coherency and consistency in 3C education and interorganizational alignment. In particular, the documents examined for the U.S. Forces indicated divergent approaches. Furthermore, the interview analysis disclosed a large discrepancy in part between doctrine and actual implementation with regard to the NATO Forces.
Aldehyde oxidases (AOXs) (E.C. 1.2.3.1) are molybdoflavo-enzymes belonging to the xanthine oxidase (XO) family. AOXs in mammals contain one molybdenum cofactor (Moco), one flavin adenine dinucleotide (FAD) and two [2Fe-2S] clusters, the presence of which is essential for the activity of the enzyme. Human aldehyde oxidase (hAOX1) is a cytosolic enzyme mainly expressed in the liver. hAOX1is involved in the metabolism of xenobiotics. It oxidizes aldehydes to their corresponding carboxylic acids and hydroxylates N-heterocyclic compounds. Since these functional groups are widely present in therapeutics, understanding the behaviour of hAOX1 has important implications in medicine. During the catalytic cycle of hAOX1, the substrate is oxidized at Moco and electrons are internally transferred to FAD via the FeS clusters. An electron acceptor juxtaposed to the FAD receives the electrons and re-oxidizes the enzyme for the next catalytic cycle. Molecular oxygen is the endogenous electron acceptor of hAOX1 and in doing so it is reduced and produces reactive oxygen species (ROS) including hydrogen peroxide (H2O2) and superoxide (O2.-). The production of ROS has patho-physiological importance, as ROS can have a wide range of effects on cell components including the enzyme itself.
In this thesis, we have shown that hAOX1 loses its activity over multiple cycles of catalysis due to endogenous ROS production and have identified a cysteine rich motif that protects hAOX1 from the ROS damaging effects. We have also shown that a sulfido ligand, which is bound at Moco and is essential for the catalytic activity of the enzyme, is vulnerable during turnover. The ROS produced during the course of the reaction are also able to remove this sulfido ligand from Moco. ROS, in addition, oxidize particular cysteine residues. The combined effects of ROS on the sulfido ligand and on specific cysteine residues in the enzyme result in its inactivation. Furthermore, we report that small reducing agents containing reactive sulfhydryl groups, in a selective manner, inactivate some of the mammalian AOXs by modifying the sulfido ligand at Moco. The mechanism of ROS production by hAOX1 is another scope that has been investigated as part of the work in this thesis. We have shown that the ratio of type of ROS, i.e. hydrogen peroxide (H2O2) and superoxide (O2.-), produced by hAOX1 is determined by a particular position on a flexible loop that locates in close proximity of FAD. The size of the cavity at the ROS producing site, i.e. the N5 position of the FAD isoalloxazine ring, kinetically affects the amount of each type of ROS generated by hAOX1. Taken together, hAOX1 is an enzyme with emerging importance in pharmacological and medical studies, not only due to its involvement in drug metabolism, but also due to ROS production which has physiological and pathological implications.
What are the consequences of unemployment and precarious employment for individuals' health in Europe? What are the moderating factors that may offset (or increase) the health consequences of labor-market risks? How do the effects of these risks vary across different contexts, which differ in their institutional and cultural settings? Does gender, regarded as a social structure, play a role, and how? To answer these questions is the aim of my cumulative thesis. This study aims to advance our knowledge about the health consequences that unemployment and precariousness cause over the life course. In particular, I investigate how several moderating factors, such as gender, the family, and the broader cultural and institutional context, may offset or increase the impact of employment instability and insecurity on individual health.
In my first paper, 'The buffering role of the family in the relationship between job loss and self-perceived health: Longitudinal results from Europe, 2004-2011', I and my co-authors measure the causal effect of job loss on health and the role of the family and welfare states (regimes) as moderating factors. Using EU-SILC longitudinal data (2004-2011), we estimate the probability of experiencing 'bad health' following a transition to unemployment by applying linear probability models and undertake separate analyses for men and women. Firstly, we measure whether changes in the independent variable 'job loss' lead to changes in the dependent variable 'self-rated health' for men and women separately. Then, by adding into the model different interaction terms, we measure the moderating effect of the family, both in terms of emotional and economic support, and how much it varies across different welfare regimes. As an identification strategy, we first implement static fixed-effect panel models, which control for time-varying observables and indirect health selection—i.e., constant unobserved heterogeneity. Secondly, to control for reverse causality and path dependency, we implement dynamic fixed-effect panel models, adding a lagged dependent variable to the model.
We explore the role of the family by focusing on close ties within households: we consider the presence of a stable partner and his/her working status as a source of social and economic support. According to previous literature, having a partner should reduce the stress from adverse events, thanks to the symbolic and emotional dimensions that such a relationship entails, regardless of any economic benefits. Our results, however, suggest that benefits linked to the presence of a (female) partner also come from the financial stability that (s)he can provide in terms of a second income. Furthermore, we find partners' employment to be at least as important as the mere presence of the partner in reducing the negative effect of job loss on the individual's health by maintaining the household's standard of living and decreasing economic strain on the family. Our results are in line with previous research, which has highlighted that some people cope better than others with adverse life circumstances, and the support provided by the family is a crucial resource in that regard.
We also reported an important interaction between the family and the welfare state in moderating the health consequences of unemployment, showing how the compensation effect of the family varies across welfare regimes. The family plays a decisive role in cushioning the adverse consequences of labor market risks in Southern and Eastern welfare states, characterized by less developed social protection systems and –especially the Southern – high level of familialism.
The first paper also found important gender differences concerning job loss, family and welfare effects. Of particular interest is the evidence suggesting that health selection works differently for men and women, playing a more prominent role for women than for men in explaining the relationship between job loss and self-perceived health. The second paper, 'Gender roles and selection mechanisms across contexts: A comparative analysis of the relationship between unemployment, self-perceived health, and gender.' investigates more in-depth the gender differential in health driven by unemployment.
Being a highly contested issue in literature, we aim to study whether men are more penalized than women or the other way around and the mechanisms that may explain the gender difference. To do that, we rely on two theoretical arguments: the availability of alternative roles and social selection. The first argument builds on the idea that men and women may compensate for the detrimental health consequences of unemployment through the commitment to 'alternative roles,' which can provide for the resources needed to fulfill people's socially constructed needs. Notably, the availability of alternative options depends on the different positions that men and women have in society.
Further, we merge the availability of the 'alternative roles' argument with the health selection argument. We assume that health selection could be contingent on people's social position as defined by gender and, thus, explain the gender differential in the relationship between unemployment and health. Ill people might be less reluctant to fall or remain (i.e., self-select) in unemployment if they have alternative roles. In Western societies, women generally have more alternative roles than men and thus more discretion in their labor market attachment. Therefore, health selection should be stronger for them, explaining why unemployment is less menace for women than for their male counterparts.
Finally, relying on the idea of different gender regimes, we extended these arguments to comparison across contexts. For example, in contexts where being a caregiver is assumed to be women's traditional and primary roles and the primary breadwinner role is reserved to men, unemployment is less stigmatized, and taking up alternative roles is more socially accepted for women than for men (Hp.1). Accordingly, social (self)selection should be stronger for women than for men in traditional contexts, where, in the case of ill-health, the separation from work is eased by the availability of alternative roles (Hp.2).
By focusing on contexts that are representative of different gender regimes, we implement a multiple-step comparative approach. Firstly, by using EU-SILC longitudinal data (2004-2015), our analysis tests gender roles and selection mechanisms for Sweden and Italy, representing radically different gender regimes, thus providing institutional and cultural variation. Then, we limit institutional heterogeneity by focusing on Germany and comparing East- and West-Germany and older and younger cohorts—for West-Germany (SOEP data 1995-2017). Next, to assess the differential impact of unemployment for men and women, we compared (unemployed and employed) men with (unemployed and employed) women. To do so, we calculate predicted probabilities and average marginal effect from two distinct random-effects probit models. Our first step is estimating random-effects models that assess the association between unemployment and self-perceived health, controlling for observable characteristics. In the second step, our fully adjusted model controls for both direct and indirect selection. We do this using dynamic correlated random-effects (CRE) models. Further, based on the fully adjusted model, we test our hypotheses on alternative roles (Hp.1) by comparing several contexts – models are estimated separately for each context. For this hypothesis, we pool men and women and include an interaction term between unemployment and gender, which has the advantage to allow for directly testing whether gender differences in the effect of unemployment exist and are statistically significant. Finally, we test the role of selection mechanisms (Hp.2), using the KHB method to compare coefficients across nested nonlinear models. Specifically, we test the role of selection for the relationship between unemployment and health by comparing the partially-adjusted and fully-adjusted models. To allow selection mechanisms to operate differently between genders, we estimate separate models for men and women.
We found support to our first hypotheses—the context where people are embedded structures the relationship between unemployment, health, and gender. We found no gendered effect of unemployment on health in the egalitarian context of Sweden. Conversely, in the traditional context of Italy, we observed substantive and statistically significant gender differences in the effect of unemployment on bad health, with women suffering less than men. We found the same pattern for comparing East and West Germany and younger and older cohorts in West Germany.
On the contrary, our results did not support our theoretical argument on social selection. We found that in Sweden, women are more selected out of employment than men. In contrast, in Italy, health selection does not seem to be the primary mechanism behind the gender differential—Italian men and women seem to be selected out of employment to the same extent. Namely, we do not find any evidence that health selection is stronger for women in more traditional countries (Hp2), despite the fact that the institutional and the cultural context would offer them a more comprehensive range of 'alternative roles' relative to men. Moreover, our second hypothesis is also rejected in the second and third comparisons, where the cross-country heterogeneity is reduced to maximize cultural differences within the same institutional context. Further research that addresses selection into inactivity is needed to evaluate the interplay between selection and social roles across gender regimes.
While the health consequences of unemployment have been on the research agenda for a pretty long time, the interest in precarious employment—defined as the linking of the vulnerable worker to work that is characterized by uncertainty and insecurity concerning pay, the stability of the work arrangement, limited access to social benefits, and statutory protections—has emerged only later. Since the 80s, scholars from different disciplines have raised concerns about the social consequences of de-standardization of employment relationships. However, while work has become undoubtedly more precarious, very little is known about its causal effect on individual health and the role of gender as a moderator. These questions are at the core of my third paper : 'Bad job, bad health? A longitudinal analysis of the interaction between precariousness, gender and self-perceived health in Germany'. Herein, I investigate the multidimensional nature of precarious employment and its causal effect on health, particularly focusing on gender differences.
With this paper, I aim at overcoming three major shortcomings of earlier studies: The first one regards the cross-sectional nature of data that prevents the authors from ruling out unobserved heterogeneity as a mechanism for the association between precarious employment and health. Indeed, several unmeasured individual characteristics—such as cognitive abilities—may confound the relationship between precarious work and health, leading to biased results. Secondly, only a few studies have directly addressed the role of gender in shaping the relationship. Moreover, available results on the gender differential are mixed and inconsistent: some found precarious employment being more detrimental for women's health, while others found no gender differences or stronger negative association for men. Finally, previous attempts to an empirical translation of the employment precariousness (EP) concept have not always been coherent with their theoretical framework. EP is usually assumed to be a multidimensional and continuous phenomenon; it is characterized by different dimensions of insecurity that may overlap in the same job and lead to different "degrees of precariousness." However, researchers have predominantly focused on one-dimensional indicators—e.g., temporary employment, subjective job insecurity—to measure EP and study the association with health. Besides the fact that this approach partially grasps the phenomenon's complexity, the major problem is the inconsistency of evidence that it has produced. Indeed, this line of inquiry generally reveals an ambiguous picture, with some studies finding substantial adverse effects of temporary over permanent employment, while others report only minor differences.
To measure the (causal) effect of precarious work on self-rated health and its variation by gender, I focus on Germany and use four waves from SOEP data (2003, 2007, 2011, and 2015). Germany is a suitable context for my study. Indeed, since the 1980s, the labor market and welfare system have been restructured in many ways to increase the German economy's competitiveness in the global market. As a result, the (standard) employment relationship has been de-standardized: non-standard and atypical employment arrangements—i.e., part-time work, fixed-term contracts, mini-jobs, and work agencies—have increased over time while wages have lowered, even among workers with standard work. In addition, the power of unions has also fallen over the last three decades, leaving a large share of workers without collective protection. Because of this process of de-standardization, the link between wage employment and strong social rights has eroded, making workers more powerless and more vulnerable to labor market risks than in the past. EP refers to this uneven distribution of power in the employment relationship, which can be detrimental to workers' health. Indeed, by affecting individuals' access to power and other resources, EP puts precarious workers at risk of experiencing health shocks and influences their ability to gain and accumulate health advantages (Hp.1).
Further, the focus on Germany allows me to investigate my second research question on the gender differential. Germany is usually regarded as a traditionalist gender regime: a context characterized by a configuration of roles. Here, being a caregiver is assumed to be women's primary role, whereas the primary breadwinner role is reserved for men. Although many signs of progress have been made over the last decades towards a greater equalization of opportunities and more egalitarianism, the breadwinner model has barely changed towards a modified version. Thus, women usually take on the double role of workers (the so-called secondary earner) and caregivers, and men still devote most of their time to paid work activities. Moreover, the overall upward trend towards more egalitarian gender ideologies has leveled off over the last decades, moving notably towards more traditional gender ideologies.
In this setting, two alternative hypotheses are possible. Firstly, I assume that the negative relationship between EP and health is stronger for women than for men. This is because women are systematically more disadvantaged than men in the public and private spheres of life, having less access to formal and informal sources of power. These gender-related power asymmetries may interact with EP-related power asymmetries resulting in a stronger effect of EP on women's health than on men's health (Hp.2).
An alternative way of looking at the gender differential is to consider the interaction that precariousness might have with men's and women's gender identities. According to this view, the negative relationship between EP and health is weaker for women than for men (Hp.2a). In a society with a gendered division of labor and a strong link between masculine identities and stable and well-rewarded job—i.e., a job that confers the role of primary family provider—a male worker with precarious employment might violate the traditional male gender role. Men in precarious jobs may perceive themselves (and by others) as possessing a socially undesirable characteristic, which conflicts with the stereotypical idea of themselves as the male breadwinner. Engaging in behaviors that contradict stereotypical gender identity may decrease self-esteem and foster feelings of inferiority, helplessness, and jealousy, leading to poor health.
I develop a new indicator of EP that empirically translates a definition of EP as a multidimensional and continuous phenomenon. I assume that EP is a latent construct composed of seven dimensions of insecurity chosen according to the theory and previous empirical research: Income insecurity, social insecurity, legal insecurity, employment insecurity, working-time insecurity, representation insecurity, worker's vulnerability. The seven dimensions are proxied by eight indicators available in the four waves of the SOEP dataset. The EP composite indicator is obtained by performing a multiple correspondence analysis (MCA) on the eight indicators. This approach aims to construct a summary scale in which all dimensions contribute jointly to the measured experience of precariousness and its health impact.
Further, the relationship between EP and 'general self-perceived health' is estimated by applying ordered probit random-effects estimators and calculating average marginal effect (further AME). Then, to control for unobserved heterogeneity, I implement correlated random-effects models that add to the model the within-individual means of the time-varying independent variables. To test the significance of the gender differential, I add an interaction term between EP and gender in the fully adjusted model in the pooled sample.
My correlated random-effects models showed EP's negative and substantial 'effect' on self-perceived health for both men and women. Although nonsignificant, the evidence seems in line with previous cross-sectional literature. It supports the hypothesis that employment precariousness could be detrimental to workers' health. Further, my results showed the crucial role of unobserved heterogeneity in shaping the health consequences of precarious employment. This is particularly important as evidence accumulates, yet it is still mostly descriptive.
Moreover, my results revealed a substantial difference among men and women in the relationship between EP and health: when EP increases, the risk of experiencing poor health increases much more for men than for women. This evidence falsifies previous theory according to whom the gender differential is contingent on the structurally disadvantaged position of women in western societies. In contrast, they seem to confirm the idea that men in precarious work could experience role conflict to a larger extent than women, as their self-standard is supposed to be the stereotypical breadwinner worker with a good and well-rewarded job. Finally, results from the multiple correspondence analysis contribute to the methodological debate on precariousness, showing that a multidimensional and continuous indicator can express a latent variable of EP.
All in all, complementarities are revealed in the results of unemployment and employment precariousness, which have two implications: Policy-makers need to be aware that the total costs of unemployment and precariousness go far beyond the economic and material realm penetrating other fundamental life domains such as individual health. Moreover, they need to balance the trade-off between protecting adequately unemployed people and fostering high-quality employment in reaction to the highlighted market pressures. In this sense, the further development of a (universalistic) welfare state certainly helps mitigate the adverse health effects of unemployment and, therefore, the future costs of both individuals' health and welfare spending. In addition, the presence of a working partner is crucial for reducing the health consequences of employment instability. Therefore, policies aiming to increase female labor market participation should be promoted, especially in those contexts where the welfare state is less developed.
Moreover, my results support the significance of taking account of a gender perspective in health research. The findings of the three articles show that job loss, unemployment, and precarious employment, in general, have adverse effects on men's health but less or absent consequences for women's health. Indeed, this suggests the importance of labor and health policies that consider and further distinguish the specific needs of the male and female labor force in Europe. Nevertheless, a further implication emerges: the health consequences of employment instability and de-standardization need to be investigated in light of the gender arrangements and the transforming gender relationships in specific cultural and institutional contexts. My results indeed seem to suggest that women's health advantage may be a transitory phenomenon, contingent on the predominant gendered institutional and cultural context. As the structural difference between men's and women's position in society is eroded, egalitarianism becomes the dominant normative status, so will probably be the gender difference in the health consequences of job loss and precariousness. Therefore, while gender equality in opportunities and roles is a desirable aspect for contemporary societies and a political goal that cannot be postponed further, this thesis raises a further and maybe more crucial question: What kind of equality should be pursued to provide men and women with both good life quality and equal chances in the public and private spheres? In this sense, I believe that social and labor policies aiming to reduce gender inequality in society should focus on improving women's integration into the labor market, implementing policies targeting men, and facilitating their involvement in the private sphere of life. Equal redistribution of social roles could activate a crucial transformation of gender roles and the cultural models that sustain and still legitimate gender inequality in Western societies.
An important goal in biotechnology and (bio-) medical research is the isolation of single cells from a heterogeneous cell population. These specialised cells are of great interest for bioproduction, diagnostics, drug development, (cancer) therapy and research. To tackle emerging questions, an ever finer differentiation between target cells and non-target cells is required. This precise differentiation is a challenge for a growing number of available methods.
Since the physiological properties of the cells are closely linked to their morphology, it is beneficial to include their appearance in the sorting decision. For established methods, this represents a non addressable parameter, requiring new methods for the identification and isolation of target cells. Consequently, a variety of new flow-based methods have been developed and presented in recent years utilising 2D imaging data to identify target cells within a sample. As these methods aim for high throughput, the devices developed typically require highly complex fluid handling techniques, making them expensive while offering limited image quality.
In this work, a new continuous flow system for image-based cell sorting was developed that uses dielectrophoresis to precisely handle cells in a microchannel. Dielectrophoretic forces are exerted by inhomogeneous alternating electric fields on polarisable particles (here: cells). In the present system, the electric fields can be switched on and off precisely and quickly by a signal generator. In addition to the resulting simple and effective cell handling, the system is characterised by the outstanding quality of the image data generated and its compatibility with standard microscopes. These aspects result in low complexity, making it both affordable and user-friendly.
With the developed cell sorting system, cells could be sorted reliably and efficiently according to their cytosolic staining as well as morphological properties at different optical magnifications. The achieved purity of the target cell population was up to 95% and about 85% of the sorted cells could be recovered from the system. Good agreement was achieved between the results obtained and theoretical considerations. The achieved throughput of the system was up to 12,000 cells per hour. Cell viability studies indicated a high biocompatibility of the system.
The results presented demonstrate the potential of image-based cell sorting using dielectrophoresis. The outstanding image quality and highly precise yet gentle handling of the cells set the system apart from other technologies. This results in enormous potential for processing valuable and sensitive cell samples.
Fiber-based microfluidics has undergone many innovative developments in recent years, with exciting examples of portable, cost-effective and easy-to-use detection systems already being used in diagnostic and analytical applications. In water samples, Legionella are a serious risk as human pathogens. Infection occurs through inhalation of aerosols containing Legionella cells and can cause severe pneumonia and may even be fatal. In case of Legionella contamination of water-bearing systems or Legionella infection, it is essential to find the source of the contamination as quickly as possible to prevent further infections. In drinking, industrial and wastewater monitoring, the culture-based method is still the most commonly used technique to detect Legionella contamination. In order to improve the laboratory-dependent determination, the long analysis times of 10-14 days as well as the inaccuracy of the measured values in colony forming units (CFU), new innovative ideas are needed. In all areas of application, for example in public, commercial or private facilities, rapid and precise analysis is required, ideally on site.
In this PhD thesis, all necessary single steps for a rapid DNA-based detection of Legionella were developed and characterized on a fiber-based miniaturized platform. In the first step, a fast, simple and device-independent chemical lysis of the bacteria and extraction of genomic DNA was established. Subsequently, different materials were investigated with respect to their non-specific DNA retention. Glass fiber filters proved to be particularly suitable, as they allow recovery of the DNA sample from the fiber material in combination with dedicated buffers and exhibit low autofluorescence, which was important for fluorescence-based readout.
A fiber-based electrophoresis unit was developed to migrate different oligonucleotides within a fiber matrix by application of an electric field. A particular advantage over lateral flow assays is the targeted movement, even after the fiber is saturated with liquid. For this purpose, the entire process of fiber selection, fiber chip patterning, combination with printed electrodes, and testing of retention and migration of different DNA samples (single-stranded, double-stranded and genomic DNA) was performed. DNA could be pulled across the fiber chip in an electric field of 24 V/cm within 5 minutes, remained intact and could be used for subsequent detection assays e.g., polymerase chain reaction (PCR) or fluorescence in situ hybridization (FISH). Fiber electrophoresis could also be used to separate DNA from other components e.g., proteins or cell lysates or to pull DNA through multiple layers of the glass microfiber. In this way, different fragments experienced a moderate, size-dependent separation. Furthermore, this arrangement offers the possibility that different detection reactions could take place in different layers at a later time. Electric current and potential measurements were collected to investigate the local distribution of the sample during migration. While an increase in current signal at high concentrations indicated the presence of DNA samples, initial experiments with methylene blue stained DNA showed a temporal sequence of signals, indicating sample migration along the chip.
For the specific detection of a Legionella DNA, a FISH-based detection with a molecular beacon probe was tested on the glass microfiber. A specific region within the 16S rRNA gene of Legionella spp. served as a target. For this detection, suitable reaction conditions and a readout unit had to be set up first. Subsequently, the sensitivity of the probe was tested with the reverse complementary target sequence and the specificity with several DNA fragments that differed from the target sequence. Compared to other DNA sequences of similar length also found in Legionella pneumophila, only the target DNA was specifically detected on the glass microfiber. If a single base exchange is present or if two bases are changed, the probe can no longer distinguish between the DNA targets and non-targets. An analysis with this specificity can be achieved with other methods such as melting point determination, as was also briefly indicated here. The molecular beacon probe could be dried on the glass microfiber and stored at room temperature for more than three months, after which it was still capable of detecting the target sequence. Finally, the feasibility of fiber-based FISH detection for genomic Legionella DNA was tested. Without further processing, the probe was unable to detect its target sequence in the complex genomic DNA. However, after selecting and application of appropriate restriction enzymes, specific detection of Legionella DNA against other aquatic pathogens with similar fragment patterns as Acinetobacter haemolyticus was possible.
Bio-sourced adsorbing poly(2-oxazoline)s mimicking mussel glue proteins for antifouling applications
(2022)
Nature developed countless systems for many applications. In maritime environments, several organisms established extra-ordinary mechanisms to attach to surfaces. Over the past years, the scientific interest to employ those mechanisms for coatings and long-lasting adhering materials gained significant attention.
This work describes the synthesis of bio-inspired adsorbing copoly(2-oxazoline)s for surface coatings with protein repelling effects, mimicking mussel glue proteins. From a set of methoxy substituted phenyl, benzyl, and cinnamyl acids, 2-oxazoline monomers were synthesized. All synthesized 2-oxazolines were analyzed by FT-IR spectroscopy, NMR spectroscopy, and EI mass spectrometry. With those newly synthesized 2-oxazoline monomers and 2-ethyl-2-oxazoline, kinetic studies concerning homo- and copolymerization in a microwave reactor were conducted. The success of the polymerization reactions was demonstrated by FT-IR spectroscopy, NMR spectroscopy, MALDI-TOF mass spectrometry, and size exclusion chromatography (SEC). The copolymerization of 2-ethyl-2-oxazoline with a selection of methoxy-substituted 2-oxazolines resulted in water-soluble copolymers. To release the adsorbing catechol and cationic units, the copoly(2-oxazoline)s were modified. The catechol units were (partially) released by a methyl aryl ether cleavage reaction. A subsequent partial acidic hydrolysis of the ethyl unit resulted in mussel glue protein-inspired catechol and cation-containing copolymers. The modified copolymers were analyzed by NMR spectroscopy, UV-VIS spectroscopy, and SEC. The catechol- and cation-containing copolymers and their precursors were examined by a Quartz Crystal Microbalance with Dissipation (QCM-D), so study the adsorption performance on gold, borosilicate, iron, and polystyrene surfaces. An exemplary study revealed that a catechol and cation-containing copoly(2-oxazoline)-coated gold surface exhibits strong protein repelling properties.
The development of novel programmable materials aiming to control friction in real-time holds potential to facilitate innovative lubrication solutions for reducing wear and energy losses. This work describes the integration of light-responsiveness into two lubricating materials, silicon oils and polymer brush surfaces.
The first part focusses on the assessment on 9-anthracene ester-terminated polydimethylsiloxanes (PDMS-A) and, in particular, on the variability of rheological properties and the implications that arise with UV-light as external trigger. The applied rheometer setup contains an UV-transparent quartz-plate, which enables radiation and simultaneous measurement of the dynamic moduli. UV-A radiation (354 nm) triggers the cycloaddition reaction between the terminal functionalities of linear PDMS, resulting in chain extension. The newly-formed anthracene dimers cleave by UV-C radiation (254 nm) or at elevated temperatures (T > 130 °C). The sequential UV-A radiation and thermal reprogramming over three cycles demonstrate high conversions and reproducible programming of rheological properties. In contrast, the photochemical back reaction by UV-C is incomplete and can only partially restore the initial rheological properties. The dynamic moduli increase with each cycle in photochemical programming, presumably resulting from a chain segment re-arrangement as a result of the repeated partial photocleavage and subsequent chain length-dependent dimerization. In addition, long periods of radiation cause photooxidative degradation, which damages photo-responsive functions and consequently reduces the programming range. The absence of oxygen, however, reduces undesired side reactions. Anthracene-functionalized PDMS and native PDMS mix depending on the anthracene ester content and chain length, respectively, and allow fine-tuning of programmable rheological properties. The work shows the influence of mixing conditions during the photoprogramming step on the rheological properties, indicating that material property gradients induced by light attenuation along the beam have to be considered. Accordingly, thin lubricant films are suggested as potential application for light-programmable silicon fluids.
The second part compares strategies for the grafting of spiropyran (SP) containing copolymer brushes from Si wafers and evaluates the light-responsiveness of the surfaces. Pre-experiments on the kinetics of the thermally initiated RAFT copolymerization of 2-hydroxyethyl acrylate (HEA) and spiropyran acrylate (SPA) in solution show, first, a strong retardation by SP and, second, the dependence of SPA polymerization on light. Surprisingly, the copolymerization of SPA is inhibited in the dark. These findings contribute to improve the synthesis of polar, spiropyran-containing copolymers. The comparison between initiator systems for the grafting-from approach indicates PET-RAFT superior to thermally initiated RAFT, suggesting a more efficient initiation of surface-bound CTA by light. Surface-initiated polymerization via PET-RAFT with an initiator system of EosinY (EoY) and ascorbic acid (AscA) facilitates copolymer synthesis from HEA and 5-25 mol% SPA. The resulting polymer film with a thickness of a few nanometers was detected by atomic force microscopy (AFM) and ellipsometry. Water contact angle (CA) measurements demonstrate photo-switchable surface polarity, which is attributed to the photoisomerization between non-polar spiropyran and zwitterionic merocyanine isomer. Furthermore, the obtained spiropyran brushes show potential for further studies on light-programmable properties. In this context, it would be interesting to investigate whether swollen spiropyran-containing polymers change their configuration and thus their film thickness under the influence of light. In addition, further experiments using an AFM or microtribometer should evaluate whether light-programmable solvation enables a change in frictional properties between polymer brush surfaces.
The negative impact of crude oil on the environment has led to a necessary transition toward alternative, renewable, and sustainable resources. In this regard, lignocellulosic biomass (LCB) is a promising renewable and sustainable alternative to crude oil for the production of fine chemicals and fuels in a so-called biorefinery process. LCB is composed of polysaccharides (cellulose and hemicellulose), as well as aromatics (lignin). The development of a sustainable and economically advantageous biorefinery depends on the complete and efficient valorization of all components. Therefore, in the new generation of biorefinery, the so-called biorefinery of type III, the LCB feedstocks are selectively deconstructed and catalytically transformed into platform chemicals. For this purpose, the development of highly stable and efficient catalysts is crucial for progress toward viability in biorefinery. Furthermore, a modern and integrated biorefinery relies on process and reactor design, toward more efficient and cost-effective methodologies that minimize waste. In this context, the usage of continuous flow systems has the potential to provide safe, sustainable, and innovative transformations with simple process integration and scalability for biorefinery schemes.
This thesis addresses three main challenges for future biorefinery: catalyst synthesis, waste feedstock valorization, and usage of continuous flow technology. Firstly, a cheap, scalable, and sustainable approach is presented for the synthesis of an efficient and stable 35 wt.-% Ni catalyst on highly porous nitrogen-doped carbon support (35Ni/NDC) in pellet shape. Initially, the performance of this catalyst was evaluated for the aqueous phase hydrogenation of LCB-derived compounds such as glucose, xylose, and vanillin in continuous flow systems. The 35Ni/NDC catalyst exhibited high catalytic performances in three tested hydrogenation reactions, i.e., sorbitol, xylitol, and 2-methoxy-4-methylphenol with yields of 82 mol%, 62 mol%, and 100 mol% respectively. In addition, the 35Ni/NDC catalyst exhibited remarkable stability over a long time on stream in continuous flow (40 h). Furthermore, the 35Ni/NDC catalyst was combined with commercially available Beta zeolite in a dual–column integrated process for isosorbide production from glucose (yield 83 mol%).
Finally, 35Ni/NDC was applied for the valorization of industrial waste products, namely sodium lignosulfonate (LS) and beech wood sawdust (BWS) in continuous flow systems. The LS depolymerization was conducted combining solvothermal fragmentation of water/alcohol mixtures (i.e.,methanol/water and ethanol/water) with catalytic hydrogenolysis/hydrogenation (SHF). The depolymerization was found to occur thermally in absence of catalyst with a tunable molecular weight according to temperature. Furthermore, the SHF generated an optimized cumulative yield of lignin-derived phenolic monomers of 42 mg gLS-1. Similarly, a solvothermal and reductive catalytic fragmentation (SF-RCF) of BWS was conducted using MeOH and MeTHF as a solvent. In this case, the optimized total lignin-derived phenolic monomers yield was found of 247 mg gKL-1.
The world energy consumption has constantly increased every year due to economic development and population growth. This inevitably caused vast amount of CO2 emission, and the CO2 concentration in the atmosphere keeps increasing with economic growth. To reduce CO2 emission, various methods have been developed but there are still many bottlenecks to be solved. Solvents easily absorbing CO2 such as monoethanol-amine (MEA) and diethanolamine, for example, have limitations of solvent loss, amine degradation, vulnerability to heat and toxicity, and the high cost of regeneration which is especially caused due to chemisorption process. Though some of these drawbacks can be compensated through physisorption with zeolites and metal-organic frameworks (MOFs) by displaying significant adsorption selectivity and capacity even in ambient conditions, limitations for these materials still exist. Zeolites demand relatively high regeneration energy and have limited adsorption kinetics due to the exceptionally narrow pore structure. MOFs have low stability against heat and moisture and high manufacturing cost.
Nanoporous carbons have recently received attention as an attractive functional porous material due to their unique properties. These materials are crucial in many applications of modern science and industry such as water and air purification, catalysis, gas separation, and energy storage/conversion due to their high chemical and thermal stability, and in particular electronic conductivity in combination with high specific surface areas. Nanoporous carbons can be used to adsorb environmental pollutants or small gas molecules such as CO2 and to power electrochemical energy storage devices such as batteries and fuel cells. In all fields, their pore structure or electrical properties can be modified depending on their purposes.
This thesis provides an in-depth look at novel nanoporous carbons from the synthetic and the application point of view. The interplay between pore structure, atomic construction, and the adsorption properties of nanoporous carbon materials are investigated. Novel nanoporous carbon materials are synthesized by using simple precursor molecules containing heteroatoms through a facile
templating method. The affinity, and in turn the adsorption capacity, of carbon materials toward polar gas molecules (CO2 and H2O) is enhanced by the modification of their chemical construction. It is also shown that these properties are important in electrochemical energy storage, here especially for supercapacitors with aqueous electrolytes which are basically based on the physisorption of ions on carbon surfaces. This shows that nanoporous carbons can be a “functional” material with specific physical or chemical interactions with guest species just like zeolites and MOFs.
The synthesis of sp2-conjugated materials with high heteroatom content from a mixture of citrazinic acid and melamine in which heteroatoms are already bonded in specific motives is illustrated. By controlling the removal procedure of the salt-template and the condensation temperature, the role of salts in the formation of porosity and as coordination sites for the stabilization of heteroatoms is proven. A high amount of nitrogen of up to 20 wt. %, oxygen contents of up to 19 wt.%, and a high CO2/N2 selectivity with maximum CO2 uptake at 273 K of 5.31 mmol g–1 are achieved. Besides, the further controlled thermal condensation of precursor molecules and advanced functional properties on applications of the synthesized porous carbons are described. The materials have different porosity and atomic construction exhibiting a high nitrogen content up to 25 wt. % as well as a high porosity with a specific surface area of more than 1800 m2 g−1, and a high performance in selective CO2 gas adsorption of 62.7. These pore structure as well as properties of surface affect to water adsorption with a remarkably high Qst of over 100 kJ mol−1 even higher than that of zeolites or CaCl2 well known as adsorbents. In addition to that, the pore structure of HAT-CN-derived carbon materials during condensation in vacuum is fundamentally understood which is essential to maximize the utilization of porous system in materials showing significant difference in their pore volume of 0.5 cm3 g−1 and 0.25 cm3 g−1 without and with vacuum, respectively.
The molecular designs of heteroatom containing porous carbon derived from abundant and simple molecules are introduced in the presented thesis. Abundant precursors that already containing high amount of nitrogen or oxygen are beneficial to achieve enhanced interaction with adsorptives. The physical and chemical properties of these heteroatom-doped porous carbons are affected by mainly two parameters, that is, the porosity from the pore structure and the polarity from the atomic composition on the surface. In other words, controlling the porosity as well as the polarity of the carbon materials is studied to understand interactions with different guest species which is a fundamental knowledge for the utilization on various applications.
Neural conversation models aim to predict appropriate contributions to a (given) conversation by using neural networks trained on dialogue data. A specific strand focuses on non-goal driven dialogues, first proposed by Ritter et al. (2011): They investigated the task of transforming an utterance into an appropriate reply. Then, this strand evolved into dialogue system approaches using long dialogue histories and additional background context. Contributing meaningful and appropriate to a conversation is a complex task, and therefore research in this area has been very diverse: Serban et al. (2016), for example, looked into utilizing variable length dialogue histories, Zhang et al. (2018) added additional context to the dialogue history, Wolf et al. (2019) proposed a model based on pre-trained Self-Attention neural networks (Vasvani et al., 2017), and Dinan et al. (2021) investigated safety issues of these approaches. This trend can be seen as a transformation from trying to somehow carry on a conversation to generating appropriate replies in a controlled and reliable way.
In this thesis, we first elaborate the meaning of appropriateness in the context of neural conversation models by drawing inspiration from the Cooperative Principle (Grice, 1975). We first define what an appropriate contribution has to be by operationalizing these maxims as demands on conversation models: being fluent, informative, consistent towards given context, coherent and following a social norm. Then, we identify different targets (or intervention points) to achieve the conversational appropriateness by investigating recent research in that field.
In this thesis, we investigate the aspect of consistency towards context in greater detail, being one aspect of our interpretation of appropriateness.
During the research, we developed a new context-based dialogue dataset (KOMODIS) that combines factual and opinionated context to dialogues. The KOMODIS
dataset is publicly available and we use the data in this thesis to gather new insights in context-augmented dialogue generation.
We further introduced a new way of encoding context within Self-Attention based neural networks. For that, we elaborate the issue of space complexity from knowledge graphs,
and propose a concise encoding strategy for structured context inspired from graph neural networks (Gilmer et al., 2017) to reduce the space complexity of the additional context. We discuss limitations of context-augmentation for neural conversation models, explore the characteristics of knowledge graphs, and explain how we create and augment knowledge graphs for our experiments.
Lastly, we analyzed the potential of reinforcement and transfer learning to improve context-consistency for neural conversation models. We find that current reward functions need to be more precise to enable the potential of reinforcement learning, and that sequential transfer learning can improve the subjective quality of generated dialogues.
In this thesis, the dependencies of charge localization and itinerance in two classes of aromatic molecules are accessed: pyridones and porphyrins. The focus lies on the effects of isomerism, complexation, solvation, and optical excitation, which are concomitant with different crucial biological applications of specific members of these groups of compounds. Several porphyrins play key roles in the metabolism of plants and animals. The nucleobases, which store the genetic information in the DNA and RNA are pyridone derivatives. Additionally, a number of vitamins are based on these two groups of substances.
This thesis aims to answer the question of how the electronic structure of these classes of molecules is modified, enabling the versatile natural functionality. The resulting insights into the effect of constitutional and external factors are expected to facilitate the design of new processes for medicine, light-harvesting, catalysis, and environmental remediation.
The common denominator of pyridones and porphyrins is their aromatic character. As aromaticity was an early-on topic in chemical physics, the overview of relevant theoretical models in this work also mirrors the development of this scientific field in the 20th century. The spectroscopic investigation of these compounds has long been centered on their global, optical transition between frontier orbitals.
The utilization and advancement of X-ray spectroscopic methods characterizing the local electronic structure of molecular samples form the core of this thesis. The element selectivity of the near-edge X-ray absorption fine structure (NEXAFS) is employed to probe the unoccupied density of states at the nitrogen site, which is key for the chemical reactivity of pyridones and porphyrins. The results contribute to the growing database of NEXAFS features and their interpretation, e.g., by advancing the debate on the porphyrin N K-edge through systematic experimental and theoretical arguments. Further, a state-of-the-art laser pump – NEXAFS probe scheme is used to characterize the relaxation pathway of a photoexcited porphyrin on the atomic level.
Resonant inelastic X-ray scattering (RIXS) provides complementary results by accessing the highest occupied valence levels including symmetry information. It is shown that RIXS is an effective experimental tool to gain detailed information on charge densities of individual species in tautomeric mixtures. Additionally, the hRIXS and METRIXS high-resolution RIXS spectrometers, which have been in part commissioned in the course of this thesis, will gain access to the ultra-fast and thermal chemistry of pyridones, porphyrins, and many other compounds.
With respect to both classes of bio-inspired aromatic molecules, this thesis establishes that even though pyridones and porphyrins differ largely by their optical absorption bands and hydrogen bonding abilities, they all share a global stabilization of local constitutional changes and relevant external perturbation. It is because of this wide-ranging response that pyridones and porphyrins can be applied in a manifold of biological and technical processes.
Struggle for existence
(2022)
In this project, I sought to understand how Palestinian claim-making in the West Bank is possible within the context of continuing Israeli occupation and repression by the Palestinian political leadership. I explored the questions of what channels non-state actors use to advance their claims, what opportunities they have for making these claims, and what challenges they face. This exploration covers the time period from the Oslo Accords in the mid-1990s to the so-called Great March of Return in 2018.
I demonstrated that Palestinians used different modes and strategies of resistance in the past century, as the area of what today is Israel/Palestine has historically been a target for foreign penetration. Yet, the Oslo agreements between the Israeli government and the Palestinian leadership have ended Palestinians’ decentralized and pluralist social governance, reinforced Israeli rule in the Palestinian territories, promoted continuing dispossession and segregation of Palestinians, and further restricted their rights and their claim-making opportunities until this day. Therefore, today, Palestinian society in the West Bank is characterized by fragmentation, geographical and societal segregation, and double repression by Israeli occupation and Palestinian Authority (PA) policies. What is more, Palestinian claim-making is legally curtailed due to the establishment of different geographical entities in which Palestinians are subjugated to different forms of Israeli rule and regulations.
I argue that the concepts of civil society and acts of citizenship, which are often used to describe non-state actors’ rights-seeking activities, fall short on understanding and describing Palestinian claim-making in the West Bank comprehensively. By determining their boundaries, the concept of acts of subjecthood evolved as a novel theoretical approach within the research process and as a means of claim-making within repressive contexts where claim makers’ rights are curtailed and opportunities for rights-seeking activities are few. Thereby, this study applies a new theoretical framework to the conflict in Israel/Palestine and contributes to a better understanding of rights-seeking activities within the West Bank. Further, I argue that Palestinian acts of subjecthood against hostile Israeli rule in the West Bank are embedded within the comprehensive structure of settler colonialism. As a form of colonialism that aims at replacing an indigenous population, Israeli settler colonialism in the West Bank manifests itself in restrictions of Palestinian movement, settlement constructions, home demolitions, violence, and detentions.
By using grounded theory and inductive reasoning as methodological approaches, I was able to make generalizations about the state of Palestinian claim-making. These generalizations are based on the analysis of secondary materials and data collected via face-to-face and video interviews with non-state actors in Israel/Palestine. The conducted research shows that there is not a single measure or a standalone condition that hinders Palestinian claim-making, but a complex and comprehensive structure that, on the one hand, shrinks Palestinian living space by occupation and destruction and, on the other hand, diminishes Palestinian civic space by limiting the fundamental rights to organize and build social movements to change the status Palestinians live in.
Although the concrete, tangible outcomes of Palestinian acts of subjecthood are marginal, they contribute to strengthening and perpetuating Palestinian’s long history of resistance against Israeli oppression. With a lack of adherence to international law, the neglect of UN resolutions by the Israeli government, the continuous defeats of rights organizations in Israeli courts, and the repression of institutions based in the West Bank by PA and occupation policies, Palestinian acts of subjecthood cannot overturn current power structures. Nevertheless, the ongoing persistence of non-state actors claiming rights, as well as the pop-up of new initiatives and youth movements are all essential for strengthening Palestinians’ resilience and documenting current injustices. Therefore, they can build the pillars for social change in the future.
Das Ziel der vorliegenden Dissertation war es zu untersuchen, wie palästinensisches claim-making, also die Artikulation von Forderungen bzw. die Geltendmachung von bestimmten Rechten, vor dem Hintergrund der anhaltenden israelischen Besatzung und Repressalien durch die palästinensische politische Führung im Westjordanland durchgesetzt werden kann. Dabei soll der Frage nachgegangen werden, welche Kanäle nichtstaatliche Akteure nutzen, um ihre Ansprüche geltend zu machen, welche Möglichkeiten sich ihnen dafür bieten und vor welchen Herausforderungen sie stehen. Der Untersuchungszeitraum erstreckt sich dabei vom Osloer Friedensprozess Mitte der 1990er Jahre bis hin zum sogenannten Great March of Return im Jahr 2018.
Die im Gebiet des heutigen Israel/Palästina lebenden PalästinenserInnen bedienten sich in Zeiten ausländischer Einflussnahme, z.B. während der britischen Besatzung im vergangenen Jahrhundert, verschiedenster Widerstandsformen und -strategien. Jedoch haben die Osloer Abkommen zwischen der israelischen Regierung und der palästinensischen Führung die dezentrale und partizipative Mobilisierung der palästinensischen Gesellschaft erschwert, die andauernde Enteignung von PalästinenserInnen begünstigt und ihre Rechte bis zum heutigen Tag weiter eingeschränkt. Die heutige palästinensische Gesellschaft im Westjordanland ist daher durch Zersplitterung, geografische und gesellschaftliche Segregation und doppelte Un-terdrückung durch die israelische Besatzung sowie die Palästinensische Autonomiebehörde gekennzeichnet. Zudem führt die Etablierung verschiedener geografischer Entitäten, in denen PalästinenserInnen unterschiedlichen Formen israelischer Herrschaft, Regularien und Ein-griffsrechten unterworfen sind, dazu, dass palästinensisches claim-making auch formalrecht-lich eingeschränkt ist.
Um die Aktivitäten nichtstaatlicher Akteure in diesem Kontext beschreiben zu können, wer-den häufig das Konzept der Zivilgesellschaft oder das der acts of citizenship herangezogen. In der vorliegenden Arbeit wird jedoch argumentiert, dass diese Konzepte nur bedingt auf den Status Quo im Westjordanland anwendbar sind und palästinensisches claim-making nicht hinreichend verstehen und beschreiben können. Im Laufe des Forschungsprozesses hat sich daher das Konzept der acts of subjecthood als neuer theoretischer Ansatz herausgebildet, der claim-making in repressiven Kontexten beschreibt, in denen nichtstaatliche Akteure nur geringen Handlungsspielraum haben, ihre Forderungen durchsetzen zu können. Durch diese „Theorie-Brille“ ermöglicht meine Forschung einen neuartigen Blick auf den israelisch-palästinensischen Konflikt und trägt auf diese Weise zu einem besseren Verständnis von claim-making-Aktivitäten im Westjordanland bei. Darüber hinaus bettet die vorliegende Ar-beit acts of subjecthood in den größeren Kontext des Siedlungskolonialismus ein. Dieser beschreibt eine Form des Kolonialismus, die darauf abzielt, eine einheimische Bevölkerung durch die der Kolonialmacht zu ersetzen. Im Westjordanland manifestiert sich der israelische Siedlungskolonialismus in der Einschränkung der Bewegungsfreiheit von PalästinenserIn-nen, dem Bau von Siedlungen, der Zerstörung von Häusern, Gewalt und Inhaftierungen.
Die Verwendung der Grounded Theory und des induktiven Denkens als methodische Ansätze ermöglichte es, verallgemeinerbare Aussagen zum Zustand palästinensischen claim-makings treffen zu können. Diese Verallgemeinerungen beruhen auf der Analyse von Sekundärquellen und Daten, die im Rahmen von Interviews mit VertreterInnen nichtstaatlicher Organisationen in Israel/Palästina erhoben wurden. Die durchgeführte Analyse macht deutlich, dass nicht eine einzelne Maßnahme oder Bedingung palästinensisches claim-making behindert, sondern eine komplexe, vielschichtige und zielgerichtet implementierte Struktur. Diese verringert einerseits den Lebensraum von PalästinenserInnen durch Besatzung und Zerstörung und schränkt andererseits den zivilen Raum ein, indem sie ihnen grundlegende Rechte und fundamentale Freiheiten verwehrt.
Obwohl die konkreten Auswirkungen palästinensischer acts of subjecthood marginal sind, tragen sie dazu bei, den Widerstand gegen politische Unterdrückung zu stärken und fortzusetzen. Angesichts der Verletzung von Völkerrecht und der Missachtung zahlreicher UN-Resolutionen durch die israelische Regierung, der Niederlagen von Menschenrechtsorganisationen vor israelischen Gerichten, der Unterdrückung von Institutionen im Westjordanland durch die Palästinensische Autonomiebehörde und die Besatzungspolitik können acts of subjecthood die derzeitigen Machtstrukturen nicht aufbrechen. Dennoch sind die anhaltende Beharrlichkeit nichtstaatlicher Akteure, Forderungen zu artikulieren und Rechte einzufordern und die Gründung neuer Initiativen und Organisationen essenziell für die Stärkung gesellschaftlicher Resilienz sowie die Dokumentation von Ungerechtigkeiten und Rechtsverletzungen. Diese Akteure legen so den Grundstein für einen möglichen gesellschaftspolitischen Wandel in der Zukunft.
High-mountain regions provide valuable ecosystem services, including food, water, and energy production, to more than 900 million people worldwide. Projections hold, that this population number will rapidly increase in the next decades, accompanied by a continued urbanisation of cities located in mountain valleys. One of the manifestations of this ongoing socio-economic change of mountain societies is a rise in settlement areas and transportation infrastructure while an increased power need fuels the construction of hydropower plants along rivers in the high-mountain regions of the world. However, physical processes governing the cryosphere of these regions are highly sensitive to changes in climate and a global warming will likely alter the conditions in the headwaters of high-mountain rivers. One of the potential implications of this change is an increase in frequency and magnitude of outburst floods – highly dynamic flows capable of carrying large amounts of water and sediments. Sudden outbursts from lakes formed behind natural dams are complex geomorphological processes and are often part of a hazard cascade. In contrast to other types of natural hazards in high-alpine areas, for example landslides or avalanches, outburst floods are highly infrequent. Therefore, observations and data describing for example the mode of outburst or the hydraulic properties of the downstream propagating flow are very limited, which is a major challenge in contemporary (glacial) lake outburst flood research. Although glacial lake outburst floods (GLOFs) and landslide-dammed lake outburst floods (LLOFs) are rare, a number of documented events caused high fatality counts and damage. The highest documented losses due to outburst floods since the start of the 20th century were induced by only a few high-discharge events. Thus, outburst floods can be a significant hazard to downvalley communities and infrastructure in high-mountain regions worldwide.
This thesis focuses on the Greater Himalayan region, a vast mountain belt stretching across 0.89 million km2. Although potentially hundreds of outburst floods have occurred there since the beginning of the 20th century, data on these events is still scarce. Projections of cryospheric change, including glacier-mass wastage and permafrost degradation, will likely result in an overall increase of the water volume stored in meltwater lakes as well as the destabilisation of mountain slopes in the Greater Himalayan region. Thus, the potential for outburst floods to affect the increasingly more densely populated valleys of this mountain belt is also likely to increase in the future. A prime example of one of these valleys is the Pokhara valley in Nepal, which is drained by the Seti Khola, a river crossing one of the steepest topographic gradients in the Himalayas. This valley is also home to Nepal’s second largest, rapidly growing city, Pokhara, which currently has a population of more than half a million people – some of which live in informal settlements within the floodplain of the Seti Khola. Although there is ample evidence for past outburst floods along this river in recent and historic times, these events have hardly been quantified.
The main motivation of my thesis is to address the data scarcity on past and potential future outburst floods in the Greater Himalayan region, both at a regional and at a local scale. For the former, I compiled an inventory of >3,000 moraine-dammed lakes, of which about 1% had a documented sudden failure in the past four decades. I used this data to test whether a number of predictors that have been widely applied in previous GLOF assessments are statistically relevant when estimating past GLOF susceptibility. For this, I set up four Bayesian multi-level logistic regression models, in which I explored the credibility of the predictors lake area, lake-area dynamics, lake elevation, parent-glacier-mass balance, and monsoonality. By using a hierarchical approach consisting of two levels, this probabilistic framework also allowed for spatial variability on GLOF susceptibility across the vast study area, which until now had not been considered in studies of this scale. The model results suggest that in the Nyainqentanglha and Eastern Himalayas – regions with strong negative glacier-mass balances – lakes have been more prone to release GLOFs than in regions with less negative or even stable glacier-mass balances. Similarly, larger lakes in larger catchments had, on average, a higher probability to have had a GLOF in the past four decades. Yet, monsoonality, lake elevation, and lake-area dynamics were more ambiguous. This challenges the credibility of a lake’s rapid growth in surface area as an indicator of a pending outburst; a metric that has been applied to regional GLOF assessments worldwide.
At a local scale, my thesis aims to overcome data scarcity concerning the flow characteristics of the catastrophic May 2012 flood along the Seti Khola, which caused 72 fatalities, as well as potentially much larger predecessors, which deposited >1 km³ of sediment in the Pokhara valley between the 12th and 14th century CE. To reconstruct peak discharges, flow depths, and flow velocities of the 2012 flood, I mapped the extents of flood sediments from RapidEye satellite imagery and used these as a proxy for inundation limits. To constrain the latter for the Mediaeval events, I utilised outcrops of slackwater deposits in the fills of tributary valleys. Using steady-state hydrodynamic modelling for a wide range of plausible scenarios, from meteorological (1,000 m³ s-1) to cataclysmic outburst floods (600,000 m³ s-1), I assessed the likely initial discharges of the recent and the Mediaeval floods based on the lowest mismatch between sedimentary evidence and simulated flood limits. One-dimensional HEC-RAS simulations suggest, that the 2012 flood most likely had a peak discharge of 3,700 m³ s-1 in the upper Seti Khola and attenuated to 500 m³ s-1 when arriving in Pokhara’s suburbs some 15 km downstream.
Simulations of flow in two-dimensions with orders of magnitude higher peak discharges in ANUGA show extensive backwater effects in the main tributary valleys. These backwater effects match the locations of slackwater deposits and, hence, attest for the flood character of Mediaeval sediment pulses. This thesis provides first quantitative proof for the hypothesis, that the latter were linked to earthquake-triggered outbursts of large former lakes in the headwaters of the Seti Khola – producing floods with peak discharges of >50,000 m³ s-1.
Building on this improved understanding of past floods along the Seti Khola, my thesis continues with an analysis of the impacts of potential future outburst floods on land cover, including built-up areas and infrastructure mapped from high-resolution satellite and OpenStreetMap data. HEC-RAS simulations of ten flood scenarios, with peak discharges ranging from 1,000 to 10,000 m³ s-1, show that the relative inundation hazard is highest in Pokhara’s north-western suburbs. There, the potential effects of hydraulic ponding upstream of narrow gorges might locally sustain higher flow depths. Yet, along this reach, informal settlements and gravel mining activities are close to the active channel. By tracing the construction dynamics in two of these potentially affected informal settlements on multi-temporal RapidEye, PlanetScope, and Google Earth imagery, I found that exposure increased locally between three- to twentyfold in just over a decade (2008 to 2021).
In conclusion, this thesis provides new quantitative insights into the past controls on the susceptibility of glacial lakes to sudden outburst at a regional scale and the flow dynamics of propagating flood waves released by past events at a local scale, which can aid future hazard assessments on transient scales in the Greater Himalayan region. My subsequent exploration of the impacts of potential future outburst floods to exposed infrastructure and (informal) settlements might provide valuable inputs to anticipatory assessments of multiple risks in the Pokhara valley.
Microplastics in the environments are estimated to increase in the near future due to increasing consumption of plastic product and also due to further fragmentation in small pieces. The fate and effects of MP once released into the freshwater environment are still scarcely studied, compared to the marine environment. In order to understand possible effect and interaction of MPs in freshwater environment, planktonic zooplankton organisms are very useful for their crucial trophic role. In particular freshwater rotifers are one of the most abundant organisms and they are the interface between primary producers and secondary consumers. The aim of my thesis was to investigate the ingestion and the effect of MPs in rotifers from a more natural scenario and to individuate processes such as the aggregation of MPs, the food dilution effect and the increasing concentrations of MPs that could influence the final outcome of MPs in the environment. In fact, in a near natural scenario MPs interaction with bacteria and algae, aggregations together with the size and concentration are considered drivers of ingestion and effect. The aggregation of MPs makes smaller MPs more available for rotifers and larger MPs less ingested. The negative effect caused by the ingestion of MPs was modulated by their size but also by the quantity and the quality of food that cause variable responses. In fact, rotifers in the environment are subjected to food limitation and the presence of MPs could exacerbate this condition and decrease the population and the reproduction input. Finally, in a scenario incorporating an entire zooplanktonic community, MPs were ingested by most individuals taking into account their feeding mode but also the concentration of MPs, which was found to be essential for the availability of MPs. This study highlights the importance to investigate MPs from a more environmental perspective, this in fact could provide an alternative and realistic view of effect of MPs in the ecosystem.
X-rays are integral to furthering our knowledge of exoplanetary systems. In this work we discuss the use of X-ray observations to understand star-planet interac- tions, mass-loss rates of an exoplanet’s atmosphere and the study of an exoplanet’s atmospheric components using future X-ray spectroscopy.
The low-mass star GJ 1151 was reported to display variable low-frequency radio emission, which is an indication of coronal star-planet interactions with an unseen exoplanet. In chapter 5 we report the first X-ray detection of GJ 1151’s corona based on XMM-Newton data. Averaged over the observation, we detect the star with a low coronal temperature of 1.6 MK and an X-ray luminosity of LX = 5.5 × 1026 erg/s. This is compatible with the coronal assumptions for a sub-Alfvénic star- planet interaction origin of the observed radio signals from this star.
In chapter 6, we aim to characterise the high-energy environment of known ex- oplanets and estimate their mass-loss rates. This work is based on the soft X-ray instrument on board the Spectrum Roentgen Gamma (SRG) mission, eROSITA, along with archival data from ROSAT, XMM-Newton, and Chandra. We use these four X-ray source catalogues to derive X-ray luminosities of exoplanet host stars in the 0.2-2 keV energy band. A catalogue of the mass-loss rates of 287 exoplan- ets is presented, with 96 of these planets characterised for the first time using new eROSITA detections. Of these first time detections, 14 are of transiting exoplanets that undergo irradiation from their host stars that is of a level known to cause ob- servable evaporation signals in other systems, making them suitable for follow-up observations.
In the next generation of space observatories, X-ray transmission spectroscopy of an exoplanet’s atmosphere will be possible, allowing for a detailed look into the atmospheric composition of these planets. In chapter 7, we model sample spectra using a toy model of an exoplanetary atmosphere to predict what exoplanet transit observations with future X-ray missions such as Athena will look like. We then estimate the observable X-ray transmission spectrum for a typical Hot Jupiter-type exoplanet, giving us insights into the advances in X-ray observations of exoplanets in the decades to come.
The doctoral thesis presented provides a comprehensive view of laser-based ablation techniques promoted to new fields of operation, including, but not limited to, size, composition, and concentration analyses. It covers various applications of laser ablation techniques over a wide range of sizes, from single molecules all the way to aerosol particles. The research for this thesis started with broadening and deepening the field of application and the fundamental understanding of liquid-phase IR-MALDI. Here, the hybridization of ion mobility spectrometry and microfluidics was realized by using IR-MALDI as the coupling technique for the first time. The setup was used for monitoring the photocatalytic performance of the E-Z isomerization of olefins. Using this hybrid, measurement times were so drastically reduced that such photocatalyst screenings became a matter of minutes rather than hours. With this on hand, triple measurements screenings could not only be performed within ten minutes, but also with a minimum amount of resources highlighting its potential as a green chemistry alternative to batch-sized reactions. Along the optimizing process of the IR-MALDI source for microfluidics came its application for another liquid sample supply method, the hanging drop. This demarcated one of the first applications of IR-MALDI for the charging of sub-micron particles directly from suspensions via their gas-phase transfer, followed by their characterization with differential mobility analysis. Given the high spectral quality of the data up to octuply charged particles became experimentally accessible, this laid the foundation for deriving a new charge distribution model for IR-MALDI in that size regime. Moving on to even larger analyte sizes, LIBS and LII were employed as ablation techniques for the solid phase, namely the aerosol particles themselves. Both techniques produce light-emitting events and were used to quantify and classify different aerosols. The unique configuration of stroboscopic imaging, photoacoustics, LII, and LIBS measurements opened new realms for analytical synergies and their potential application in industry. The concept of using low fluences, below 100 J/cm2, and high repetition rates of up to 500 Hz for LIBS makes for an excellent phase-selective LIBS setup. This concept was combined with a new approach to the photoacoustic normalization of LIBS. Also, it was possible to acquire statistically relevant amounts of data in a matter of seconds, showing its potential as a real-time optimization technique. On the same time axis, but at much lower fluences, LII was used with a similar methodology to quickly quantify and classify airborne particles of different compositions. For the first time, aerosol particles were evaluated on their LII susceptibility by using a fluence screening approach.
The Arctic nearshore zone plays a key role in the carbon cycle. Organic-rich sediments get eroded off permafrost affected coastlines and can be directly transferred to the nearshore zone. Permafrost in the Arctic stores a high amount of organic matter and is vulnerable to thermo-erosion, which is expected to increase due to climate change. This will likely result in higher sediment loads in nearshore waters and has the potential to alter local ecosystems by limiting light transmission into the water column, thus limiting primary production to the top-most part of it, and increasing nutrient export from coastal erosion. Greater organic matter input could result in the release of greenhouse gases to the atmosphere. Climate change also acts upon the fluvial system, leading to greater discharge to the nearshore zone. It leads to decreasing sea-ice cover as well, which will both increase wave energy and lengthen the open-water season. Yet, knowledge on these processes and the resulting impact on the nearshore zone is scarce, because access to and instrument deployment in the nearshore zone is challenging.
Remote sensing can alleviate these issues in providing rapid data delivery in otherwise non-accessible areas. However, the waters in the Arctic nearshore zone are optically complex, with multiple influencing factors, such as organic rich suspended sediments, colored dissolved organic matter (cDOM), and phytoplankton. The goal of this dissertation was to use remotely sensed imagery to monitor processes related to turbidity caused by suspended sediments in the Arctic nearshore zone. In-situ measurements of water-leaving reflectance and surface water turbidity were used to calibrate a semi-empirical algorithm which relates turbidity from satellite imagery. Based on this algorithm and ancillary ocean and climate variables, the mechanisms underpinning nearshore turbidity in the Arctic were identified at a resolution not achieved before.
The calibration of the Arctic Nearshore Turbidity Algorithm (ANTA) was based on in-situ measurements from the coastal and inner-shelf waters around Herschel Island Qikiqtaruk (HIQ) in the western Canadian Arctic from the summer seasons 2018 and 2019. It performed better than existing algorithms, developed for global applications, in relating turbidity from remotely sensed imagery. These existing algorithms were lacking validation data from permafrost affected waters, and were thus not able to reflect the complexity of Arctic nearshore waters. The ANTA has a higher sensitivity towards the lowest turbidity values, which is an asset for identifying sediment pathways in the nearshore zone. Its transferability to areas beyond HIQ was successfully demonstrated using turbidity measurements matching satellite image recordings from Adventfjorden, Svalbard. The ANTA is a powerful tool that provides robust turbidity estimations in a variety of Arctic nearshore environments.
Drivers of nearshore turbidity in the Arctic were analyzed by combining ANTA results from the summer season 2019 from HIQ with ocean and climate variables obtained from the weather station at HIQ, the ERA5 reanalysis database, and the Mackenzie River discharge. ERA5 reanalysis data were obtained as domain averages over the Canadian Beaufort Shelf. Nearshore turbidity was linearly correlated to wind speed, significant wave height and wave period. Interestingly, nearshore turbidity was only correlated to wind speed at the shelf, but not to the in-situ measurements from the weather station at HIQ. This shows that nearshore turbidity, albeit being of limited spatial extent, gets influenced by the weather conditions multiple kilometers away, rather than in its direct vicinity. The large influence of wave energy on nearshore turbidity indicates that freshly eroded material off the coast is a major contributor to the nearshore sediment load. This contrasts results from the temperate and tropical oceans, where tides and currents are the major drivers of nearshore turbidity. The Mackenzie River discharge was not identified as a driver of nearshore turbidity in 2019, however, the analysis of 30 years of Landsat archive imagery from 1986 to 2016 suggests a direct link between the prevailing wind direction, which heavily influences the Mackenzie River plume extent, and nearshore turbidity around HIQ. This discrepancy could be caused by the abnormal discharge behavior of the Mackenzie River in 2019.
This dissertation has substantially advanced the understanding of suspended sediment processes in the Arctic nearshore zone and provided new monitoring tools for future studies. The presented results will help to understand the role of the Arctic nearshore zone in the carbon cycle under a changing climate.
Extending synchrotron X-ray refraction techniques to the quantitative analysis of metallic materials
(2022)
In this work, two X-ray refraction based imaging methods, namely, synchrotron X-ray refraction radiography (SXRR) and synchrotron X-ray refraction computed tomography (SXRCT), are applied to analyze quantitatively cracks and porosity in metallic materials. SXRR and SXRCT make use of the refraction of X-rays at inner surfaces of the material, e.g., the surfaces of cracks and pores, for image contrast. Both methods are, therefore, sensitive to smaller defects than their absorption based counterparts X-ray radiography and computed tomography. They can detect defects of nanometric size. So far the methods have been applied to the analysis of ceramic materials and fiber reinforced plastics. The analysis of metallic materials requires higher photon energies to achieve sufficient X-ray transmission due to their higher density. This causes smaller refraction angles and, thus, lower image contrast because the refraction index depends on the photon energy. Here, for the first time, a conclusive study is presented exploring the possibility to apply SXRR and SXRCT to metallic materials. It is shown that both methods can be optimized to overcome the reduced contrast due to smaller refraction angles. Hence, the only remaining limitation is the achievable X-ray transmission which is common to all X-ray imaging methods. Further, a model for the quantitative analysis of the inner surfaces is presented and verified.
For this purpose four case studies are conducted each posing a specific challenge to the imaging task. Case study A investigates cracks in a coupon taken from an aluminum weld seam. This case study primarily serves to verify the model for quantitative analysis and prove the sensitivity to sub-resolution features. In case study B, the damage evolution in an aluminum-based particle reinforced metal-matrix composite is analyzed. Here, the accuracy and repeatability of subsequent SXRR measurements is investigated showing that measurement errors of less than 3 % can be achieved. Further, case study B marks the fist application of SXRR in combination with in-situ tensile loading. Case study C is out of the highly topical field of additive manufacturing. Here, porosity in additively manufactured Ti-Al6-V4 is analyzed with a special interest in the pore morphology. A classification scheme based on SXRR measurements is devised which allows to distinguish binding defects from keyhole pores even if the defects cannot be spatially resolved. In case study D, SXRCT is applied to the analysis of hydrogen assisted cracking in steel. Due to the high X-ray attenuation of steel a comparatively high photonenergy of 50 keV is required here. This causes increased noise and lower contrast in the data compared to the other case studies. However, despite the lower data quality a quantitative analysis of the occurance of cracks in dependence of hydrogen content and applied mechanical load is possible.
The Greenland Ice Sheet is the second-largest mass of ice on Earth. Being almost 2000 km long, more than 700 km wide, and more than 3 km thick at the summit, it holds enough ice to raise global sea levels by 7m if melted completely. Despite its massive size, it is particularly vulnerable to anthropogenic climate change: temperatures over the Greenland Ice Sheet have increased by more than 2.7◦C in the past 30 years, twice as much as the global mean temperature. Consequently, the ice sheet has been significantly losing mass since the 1980s and the rate of loss has increased sixfold since then. Moreover, it is one of the potential tipping elements of the Earth System, which might undergo irreversible change once a warming threshold is exceeded. This thesis aims at extending the understanding of the resilience of the Greenland Ice Sheet against global warming by analyzing processes and feedbacks relevant to its centennial to multi-millennial stability using ice sheet modeling.
One of these feedbacks, the melt-elevation-feedback is driven by the temperature rise with decreasing altitudes: As the ice sheet melts, its thickness and surface elevation decrease, exposing the ice surface to warmer air and thus increasing the melt rates even further. The glacial isostatic adjustment (GIA) can partly mitigate this melt-elevation feedback as the bedrock lifts in response to an ice load decrease, forming the negative GIA feedback. In my thesis, I show that the interaction between these two competing feedbacks can lead to qualitatively different dynamical responses of the Greenland Ice Sheet to warming – from permanent loss to incomplete recovery, depending on the feedback parameters. My research shows that the interaction of those feedbacks can initiate self-sustained oscillations of the ice volume while the climate forcing remains constant.
Furthermore, the increased surface melt changes the optical properties of the snow or ice surface, e.g. by lowering their albedo, which in turn enhances melt rates – a process known as the melt-albedo feedback. Process-based ice sheet models often neglect this melt-albedo feedback. To close this gap, I implemented a simplified version of the diurnal Energy Balance Model, a computationally efficient approach that can capture the first-order effects of the melt-albedo feedback, into the Parallel Ice Sheet Model (PISM). Using the coupled model, I show in warming experiments that the melt-albedo feedback almost doubles the ice loss until the year 2300 under the low greenhouse gas emission scenario RCP2.6, compared to simulations where the melt-albedo feedback is neglected,
and adds up to 58% additional ice loss under the high emission scenario RCP8.5. Moreover, I find that the melt-albedo feedback dominates the ice loss until 2300, compared to the melt-elevation feedback.
Another process that could influence the resilience of the Greenland Ice Sheet is the warming induced softening of the ice and the resulting increase in flow. In my thesis, I show with PISM how the uncertainty in Glen’s flow law impacts the simulated response to warming. In a flow line setup at fixed climatic mass balance, the uncertainty in flow parameters leads to a range of ice loss comparable to the range caused by different warming levels.
While I focus on fundamental processes, feedbacks, and their interactions in the first three projects of my thesis, I also explore the impact of specific climate scenarios on the sea level rise contribution of the Greenland Ice Sheet. To increase the carbon budget flexibility, some warming scenarios – while still staying within the limits of the Paris Agreement – include a temporal overshoot of global warming. I show that an overshoot by 0.4◦C increases the short-term and long-term ice loss from Greenland by several centimeters. The long-term increase is driven by the warming at high latitudes, which persists even when global warming is reversed. This leads to a substantial long-term commitment of the sea level rise contribution from the Greenland Ice Sheet.
Overall, in my thesis I show that the melt-albedo feedback is most relevant for the ice loss of the Greenland Ice Sheet on centennial timescales. In contrast, the melt-elevation feedback and its interplay with the GIA feedback become increasingly relevant on millennial timescales. All of these influence the resilience of the Greenland Ice Sheet against global warming, in the near future and on the long term.
The aim of this dissertation was to conduct a larger-scale cross-linguistic empirical investigation of similarity-based interference effects in sentence comprehension.
Interference studies can offer valuable insights into the mechanisms that are involved in long-distance dependency completion.
Many studies have investigated similarity-based interference effects, showing that syntactic and semantic information are employed during long-distance dependency formation (e.g., Arnett & Wagers, 2017; Cunnings & Sturt, 2018; Van Dyke, 2007, Van Dyke & Lewis, 2003; Van Dyke & McElree, 2011). Nevertheless, there are some important open questions in the interference literature that are critical to our understanding of the constraints involved in dependency resolution.
The first research question concerns the relative timing of syntactic and semantic interference in online sentence comprehension. Only few interference studies have investigated this question, and, to date, there is not enough data to draw conclusions with regard to their time course (Van Dyke, 2007; Van Dyke & McElree, 2011).
Our first cross-linguistic study explores the relative timing of syntactic and semantic interference in two eye-tracking reading experiments that implement the study design used in Van Dyke (2007). The first experiment tests English sentences. The second, larger-sample experiment investigates the two interference types in German.
Overall, the data suggest that syntactic and semantic interference can arise simultaneously during retrieval.
The second research question concerns a special case of semantic interference: We investigate whether cue-based retrieval interference can be caused by semantically similar items which are not embedded in a syntactic structure.
This second interference study builds on a landmark study by Van Dyke & McElree (2006). The study design used in their study is unique in that it is able to pin down the source of interference as a consequence of cue overload during retrieval, when semantic retrieval cues do not uniquely match the retrieval target. Unlike most other interference studies, this design is able to rule out encoding interference as an alternative explanation. Encoding accounts postulate that it is not cue overload at the retrieval site but the erroneous encoding of similar linguistic items in memory that leads to interference (Lewandowsky et al., 2008; Oberauer & Kliegl, 2006). While Van Dyke & McElree (2006) reported cue-based retrieval interference from sentence-external distractors, the evidence for this effect was weak. A subsequent study did not show interference of this type (Van Dyke et al., 2014). Given these inconclusive findings, further research is necessary to investigate semantic cue-based retrieval interference.
The second study in this dissertation provides a larger-scale cross-linguistic investigation of cue-based retrieval interference from sentence-external items. Three larger-sample eye-tracking studies in English, German, and Russian tested cue-based interference in the online processing of filler-gap dependencies. This study further extends the previous research by investigating interference in each language under varying task demands (Logačev & Vasishth, 2016; Swets et al., 2008).
Overall, we see some very modest support for proactive cue-based retrieval interference in English. Unexpectedly, this was observed only under a low task demand. In German and Russian, there is some evidence against the interference effect. It is possible that interference is attenuated in languages with richer case marking.
In sum, the cross-linguistic experiments on the time course of syntactic and semantic interference from sentence-internal distractors support existing evidence of syntactic and semantic interference during sentence comprehension. Our data further show that both types of interference effects can arise simultaneously. Our cross-linguistic experiments investigating semantic cue-based retrieval interference from sentence-external distractors suggest that this type of interference may arise only in specific linguistic contexts.
Knowledge graphs are structured repositories of knowledge that store facts
about the general world or a particular domain in terms of entities and
their relationships. Owing to the heterogeneity of use cases that are served
by them, there arises a need for the automated construction of domain-
specific knowledge graphs from texts. While there have been many research
efforts towards open information extraction for automated knowledge graph
construction, these techniques do not perform well in domain-specific settings.
Furthermore, regardless of whether they are constructed automatically from
specific texts or based on real-world facts that are constantly evolving, all
knowledge graphs inherently suffer from incompleteness as well as errors in
the information they hold.
This thesis investigates the challenges encountered during knowledge graph
construction and proposes techniques for their curation (a.k.a. refinement)
including the correction of semantic ambiguities and the completion of missing
facts. Firstly, we leverage existing approaches for the automatic construction
of a knowledge graph in the art domain with open information extraction
techniques and analyse their limitations. In particular, we focus on the
challenging task of named entity recognition for artwork titles and show
empirical evidence of performance improvement with our proposed solution
for the generation of annotated training data.
Towards the curation of existing knowledge graphs, we identify the issue of
polysemous relations that represent different semantics based on the context.
Having concrete semantics for relations is important for downstream appli-
cations (e.g. question answering) that are supported by knowledge graphs.
Therefore, we define the novel task of finding fine-grained relation semantics
in knowledge graphs and propose FineGReS, a data-driven technique that
discovers potential sub-relations with fine-grained meaning from existing pol-
ysemous relations. We leverage knowledge representation learning methods
that generate low-dimensional vectors (or embeddings) for knowledge graphs
to capture their semantics and structure. The efficacy and utility of the
proposed technique are demonstrated by comparing it with several baselines
on the entity classification use case.
Further, we explore the semantic representations in knowledge graph embed-
ding models. In the past decade, these models have shown state-of-the-art
results for the task of link prediction in the context of knowledge graph comple-
tion. In view of the popularity and widespread application of the embedding
techniques not only for link prediction but also for different semantic tasks,
this thesis presents a critical analysis of the embeddings by quantitatively
measuring their semantic capabilities. We investigate and discuss the reasons
for the shortcomings of embeddings in terms of the characteristics of the
underlying knowledge graph datasets and the training techniques used by
popular models.
Following up on this, we propose ReasonKGE, a novel method for generating
semantically enriched knowledge graph embeddings by taking into account the
semantics of the facts that are encapsulated by an ontology accompanying the
knowledge graph. With a targeted, reasoning-based method for generating
negative samples during the training of the models, ReasonKGE is able to
not only enhance the link prediction performance, but also reduce the number
of semantically inconsistent predictions made by the resultant embeddings,
thus improving the quality of knowledge graphs.
It is well-known that individuals with aphasia (IWA) have difficulties understanding sentences that involve non-adjacent dependencies, such as object relative clauses or passives (Caplan, Baker, & Dehaut, 1985; Caramazza & Zurif, 1976). A large body of research supports the view that IWA’s grammatical system is intact, and that comprehension difficulties in aphasia are caused by a processing deficit, such as a delay in lexical access and/or in syntactic structure building (e.g., Burkhardt, Piñango, & Wong, 2003; Caplan, Michaud, & Hufford, 2015; Caplan, Waters, DeDe, Michaud, & Reddy, 2007; Ferrill, Love, Walenski, & Shapiro, 2012; Hanne, Burchert, De Bleser, & Vasishth, 2015; Love, Swinney, Walenski, & Zurif, 2008). The main goal of this dissertation is to computationally investigate the processing sources of comprehension impairments in sentence processing in aphasia.
In this work, prominent theories of processing deficits coming from the aphasia literature are implemented within two cognitive models of sentence processing –the activation-based model (Lewis & Vasishth, 2005) and the direct-access model (McEl- ree, 2000)–. These models are two different expressions of the cue-based retrieval theory (Lewis, Vasishth, & Van Dyke, 2006), which posits that sentence processing is the result of a series of iterative retrievals from memory. These two models have been widely used to account for sentence processing in unimpaired populations in multiple languages and linguistic constructions, sometimes interchangeably (Parker, Shvarts- man, & Van Dyke, 2017). However, Nicenboim and Vasishth (2018) showed that when both models are implemented in the same framework and fitted to the same data, the models yield different results, because the models assume different data- generating processes. Specifically, the models hold different assumptions regarding the retrieval latencies. The second goal of this dissertation is to compare these two models of cue-based retrieval, using data from individuals with aphasia and control participants. We seek to answer the following question: Which retrieval mechanism is more likely to mediate sentence comprehension?
We model 4 subsets of existing data: Relative clauses in English and German; and control structures and pronoun resolution in German. The online data come from either self-paced listening experiments, or visual-world eye-tracking experiments. The offline data come from a complementary sentence-picture matching task performed at the end of the trial in both types of experiments. The two competing models of retrieval are implemented in the Bayesian framework, following Nicenboim and Vasishth (2018). In addition, we present a modified version of the direct-acess model that – we argue – is more suitable for individuals with aphasia.
This dissertation presents a systematic approach to implement and test verbally- stated theories of comprehension deficits in aphasia within cognitive models of sen- tence processing. The conclusions drawn from this work are that (a) the original direct-access model (as implemented here) cannot account for the full pattern of data from individuals with aphasia because it cannot account for slow misinterpretations; and (b) an activation-based model of retrieval can account for sentence comprehension deficits in individuals with aphasia by assuming a delay in syntactic structure building, and noise in the processing system. The overall pattern of results support an activation-based mechanism of memory retrieval, in which a combination of processing deficits, namely slow syntax and intermittent deficiencies, cause comprehension difficulties in individuals with aphasia.
Essays in labor economics
(2022)
This thesis offers insights into the process of workers decisions to invest into work-related training. Specifically, the role of personality traits and attitudes is analysed. The aim is to understand whether such traits contribute to an under-investment into training. Importantly, general and specific training are distinguished, where the worker’s productivity increases in many firms in the former and only in the current firm in the latter case. Additionally, this thesis contributes to the evaluation of the German minimum wage introduction in 2015, identifying causal effects on wages and working hours.
Chapters two to four focus on the work-related training decision. First, individuals with an internal locus of control see a direct link between their own actions and their labor market success, while external individuals connect their outcomes to fate, luck, and other people. Consequently, it can be expected that internal individuals expect higher returns to training and are, thus, more willing to participate. The results reflect this hypothesis with internal individuals being more likely to participate in general (but not specific) training. Second, training can be viewed either as a risky investment or as an insurance against negative labor income shocks. In both cases, risk attitudes are expected to play a role in the decision process. The data point towards risk seeking individuals being more likely to participate in general (but not specific) training, and thus, training being viewed on average as a risky investment. Third, job satisfaction influences behavioral decisions in the job context, where dissatisfied workers may react by neglecting their duties, improving the situation or quitting the job. In the first case, dissatisfied workers are expected to invest less in training, while the latter two reactions could lead to higher participation rates amongst dissatisfied workers. The results suggest that on average dissatisfied workers are less likely to invest into training than satisfied workers. However, closer inspections of quit intentions and different sources of dissatisfaction paint less clear pictures, pointing towards the complexity of the job satisfaction construct.
Chapters five and six evaluate the introduction of the minimum wage in Germany in 2015. First, in 2015 an increase in the growth of hourly wages can be identified as a causal effect of the minimum wage introduction. However, at the same time, a reduction in the weekly working hours results in an overall unchanged growth in monthly earnings. When considering the effects in 2016, the decrease in weekly working hours disappears, resulting in a significant increase in the growth of monthly earnings due to the minimum wage. Importantly, the analysis suggests that the increase in hourly wages was not sufficient to ensure all workers receiving the minimum wage. This points to non-compliance being an issue in the first years after the minimum wage introduction.
Vegetation change at high latitudes is one of the central issues nowadays with respect to ongoing climate changes and triggered potential feedback. At high latitude ecosystems, the expected changes include boreal treeline advance, compositional, phenological, physiological (plants), biomass (phytomass) and productivity changes. However, the rate and the extent of the changes under climate change are yet poorly understood and projections are necessary for effective adaptive strategies and forehanded minimisation of the possible negative feedbacks.
The vegetation itself and environmental conditions, which are playing a great role in its development and distribution are diverse throughout the Subarctic to the Arctic. Among the least investigated areas is central Chukotka in North-Eastern Siberia, Russia. Chukotka has mountainous terrain and a wide variety of vegetation types on the gradient from treeless tundra to northern taiga forests. The treeline there in contrast to subarctic North America and north-western and central Siberia is represented by a deciduous conifer, Larix cajanderi Mayr. The vegetation varies from prostrate lichen Dryas octopetala L. tundra to open graminoid (hummock and non-hummock) tundra to tall Pinus pumila (Pall.) Regel shrublands to sparse and dense larch forests.
Hence, this thesis presents investigations on recent compositional and above-ground biomass (AGB) changes, as well as potential future changes in AGB in central Chukotka. The aim is to assess how tundra-taiga vegetation develops under changing climate conditions particularly in Fareast Russia, central Chukotka. Therefore, three main research questions were considered:
1) What changes in vegetation composition have recently occurred in central Chukotka?
2) How have the above-ground biomass AGB rates and distribution changed in central Chukotka?
3) What are the spatial dynamics and rates of tree AGB change in the upcoming millennia in the northern tundra-taiga of central Chukotka?
Remote sensing provides information on the spatial and temporal variability of vegetation. I used Landsat satellite data together with field data (foliage projective cover and AGB) from two expeditions in 2016 and 2018 to Chukotka to upscale vegetation types and AGB for the study area. More specifically, I used Landsat spectral indices (Normalised Difference Vegetation Index (NDVI), Normalised Difference Water Index (NDWI) and Normalised Difference Snow Index (NDSI)) and constrained ordination (Redundancy analysis, RDA) for further k-means-based land-cover classification and general additive model (GAM)-based AGB maps for 2000/2001/2002 and 2016/2017. I also used Tandem-X DEM data for a topographical correction of the Landsat satellite data and to derive slope, aspect, and Topographical Wetness Index (TWI) data for forecasting AGB.
Firstly, in 2016, taxa-specific projective cover data were collected during a Russian-German expedition. I processed the field data and coupled them with Landsat spectral Indices in the RDA model that was used for k-means classification. I could establish four meaningful land-cover classes: (1) larch closed-canopy forest, (2) forest tundra and shrub tundra, (3) graminoid tundra and (4) prostrate herb tundra and barren areas, and accordingly, I produced the land cover maps for 2000/2001/2002 and 2016/20017. Changes in land-cover classes between the beginning of the century (2000/2001/2002) and the present time (2016/2017) were estimated and interpreted as recent compositional changes in central Chukotka. The transition from graminoid tundra to forest tundra and shrub tundra was interpreted as shrubification and amounts to a 20% area increase in the tundra-taiga zone and 40% area increase in the northern taiga. Major contributors of shrubification are alder, dwarf birch and some species of the heather family. Land-cover change from the forest tundra and shrub tundra class to the larch closed-canopy forest class is interpreted as tree infilling and is notable in the northern taiga. We find almost no land-cover changes in the present treeless tundra.
Secondly, total AGB state and change were investigated for the same areas. In addition to the total vegetation AGB, I provided estimations for the different taxa present at the field sites. As an outcome, AGB in the study region of central Chukotka ranged from 0 kg m-2 at barren areas to 16 kg m-2 in closed-canopy forests with the larch trees contributing the highest. A comparison of changes in AGB within the investigated period from 2000 to 2016 shows that the greatest changes (up to 1.25 kg m 2 yr 1) occurred in the northern taiga and in areas where land cover changed to larch closed-canopy forest. Our estimations indicate a general increase in total AGB throughout the investigated tundra-taiga and northern taiga, whereas the tundra showed no evidence of change in AGB within the 15 years from 2002 to 2017.
In the third manuscript, potential future AGB changes were estimated based on the results of simulations of the individual-based spatially explicit vegetation model LAVESI using different climate scenarios, depending on Representative Concentration Pathways (RCPs) RCP 2.6, RCP 4.5 and RCP 8.5 with or without cooling after 2300 CE. LAVESI-based AGB was simulated for the current state until 3000 CE for the northern tundra-taiga study area for larch species because we expect the most notable changes to occur will be associated with forest expansion in the treeline ecotone. The spatial distribution and current state of tree AGB was validated against AGB field data, AGB extracted from Landsat satellite data and a high spatial resolution image with distinctive trees visible. The simulation results are indicating differences in tree AGB dynamics plot wise, depending on the distance to the current treeline. The simulated tree AGB dynamics are in concordance with fundamental ecological (emigrational and successional) processes: tree stand formation in simulated results starts with seed dispersion, tree stand establishment, tree stand densification and episodic thinning. Our results suggest mostly densification of existing tree stands in the study region within the current century in the study region and a lagged forest expansion (up to 39% of total area in the RCP 8.5) under all considered climate scenarios without cooling in different local areas depending on the closeness to the current treeline. In scenarios with cooling air temperature after 2300 CE, forests stopped expanding at 2300 CE (up to 10%, RCP 8.5) and then gradually retreated to their pre-21st century position. The average tree AGB rates of increase are the strongest in the first 300 years of the 21st century. The rates depend on the RCP scenario, where the highest are as expected under RCP 8.5.
Overall, this interdisciplinary thesis shows a successful integration of field data, satellite data and modelling for tracking recent and predicting future vegetation changes in mountainous subarctic regions. The obtained results are unique for the focus area in central Chukotka and overall, for mountainous high latitude ecosystems.
The key to reduce the energy required for specific transformations in a selective manner is the employment of a catalyst, a very small molecular platform that decides which type of energy to use. The field of photocatalysis exploits light energy to shape one type of molecules into others, more valuable and useful.
However, many challenges arise in this field, for example, catalysts employed usually are based on metal derivatives, which abundance is limited, they cannot be recycled and are expensive. Therefore, carbon nitrides materials are used in this work to expand horizons in the field of photocatalysis.
Carbon nitrides are organic materials, which can act as recyclable, cheap, non-toxic, heterogeneous photocatalysts. In this thesis, they have been exploited for the development of new catalytic methods, and shaped to develop new types of processes.
Indeed, they enabled the creation of a new photocatalytic synthetic strategy, the dichloromethylation of enones by dichloromethyl radical generated in situ from chloroform, a novel route for the making of building blocks to be used for the productions of active pharmaceutical compounds.
Then, the ductility of these materials allowed to shape carbon nitride into coating for lab vials, EPR capillaries, and a cell of a flow reactor showing the great potential of such flexible technology in photocatalysis.
Afterwards, their ability to store charges has been exploited in the reduction of organic substrates under dark conditions, gaining new insights regarding multisite proton coupled electron transfer processes.
Furthermore, the combination of carbon nitrides with flavins allowed the development of composite materials with improved photocatalytic activity in the CO2 photoreduction.
Concluding, carbon nitrides are a versatile class of photoactive materials, which may help to unveil further scientific discoveries and to develop a more sustainable future.
Traditional organizations are strongly encouraged by emerging digital customer behavior and digital competition to transform their businesses for the digital age. Incumbents are particularly exposed to the field of tension between maintaining and renewing their business model. Banking is one of the industries most affected by digitalization, with a large stream of digital innovations around Fintech. Most research contributions focus on digital innovations, such as Fintech, but there are only a few studies on the related challenges and perspectives of incumbent organizations, such as traditional banks. Against this background, this dissertation examines the specific causes, effects and solutions for traditional banks in digital transformation − an underrepresented research area so far.
The first part of the thesis examines how digitalization has changed the latent customer expectations in banking and studies the underlying technological drivers of evolving business-to-consumer (B2C) business models. Online consumer reviews are systematized to identify latent concepts of customer behavior and future decision paths as strategic digitalization effects. Furthermore, the service attribute preferences, the impact of influencing factors and the underlying customer segments are uncovered for checking accounts in a discrete choice experiment. The dissertation contributes here to customer behavior research in digital transformation, moving beyond the technology acceptance model. In addition, the dissertation systematizes value proposition types in the evolving discourse around smart products and services as key drivers of business models and market power in the platform economy.
The second part of the thesis focuses on the effects of digital transformation on the strategy development of financial service providers, which are classified along with their firm performance levels. Standard types are derived based on fuzzy-set qualitative comparative analysis (fsQCA), with facade digitalization as one typical standard type for low performing incumbent banks that lack a holistic strategic response to digital transformation. Based on this, the contradictory impact of digitalization measures on key business figures is examined for German savings banks, confirming that the shift towards digital customer interaction was not accompanied by new revenue models diminishing bank profitability. The dissertation further contributes to the discourse on digitalized work designs and the consequences for job perceptions in banking customer advisory. The threefold impact of the IT support perceived in customer interaction on the job satisfaction of customer advisors is disentangled.
In the third part of the dissertation, solutions are developed design-oriented for core action areas of digitalized business models, i.e., data and platforms. A consolidated taxonomy for data-driven business models and a future reference model for digital banking have been developed. The impact of the platform economy is demonstrated here using the example of the market entry by Bigtech. The role-based e3-value modeling is extended by meta-roles and role segments and linked to value co-creation mapping in VDML. In this way, the dissertation extends enterprise modeling research on platform ecosystems and value co-creation using the example of banking.
Public administrations confront fundamental challenges, including globalization, digitalization, and an eroding level of trust from society. By developing joint public service delivery with other stakeholders, public administrations can respond to these challenges. This increases the importance of inter-organizational governance—a development often referred to as New Public Governance, which to date has not been realized because public administrations focus on intra-organizational practices and follow the traditional “governmental chain.”
E-government initiatives, which can lead to high levels of interconnected public services, are currently perceived as insufficient to meet this goal. They are not designed holistically and merely affect the interactions of public and non-public stakeholders. A fundamental shift toward a joint public service delivery would require scrutiny of established processes, roles, and interactions between stakeholders.
Various scientists and practitioners within the public sector assume that the use of blockchain institutional technology could fundamentally change the relationship between public and non-public stakeholders. At first glance, inter-organizational, joint public service delivery could benefit from the use of blockchain. This dissertation aims to shed light on this widespread assumption. Hence, the objective of this dissertation is to substantiate the effect of blockchain on the relationship between public administrations and non-public stakeholders.
This objective is pursued by defining three major areas of interest. First, this dissertation strives to answer the question of whether or not blockchain is suited to enable New Public Governance and to identify instances where blockchain may not be the proper solution. The second area aims to understand empirically the status quo of existing blockchain implementations in the public sector and whether they comply with the major theoretical conclusions. The third area investigates the changing role of public administrations, as the blockchain ecosystem can significantly increase the number of stakeholders.
Corresponding research is conducted to provide insights into these areas, for example, combining theoretical concepts with empirical actualities, conducting interviews with subject matter experts and key stakeholders of leading blockchain implementations, and performing a comprehensive stakeholder analysis, followed by visualization of its results.
The results of this dissertation demonstrate that blockchain can support New Public Governance in many ways while having a minor impact on certain aspects (e.g., decentralized control), which account for this public service paradigm. Furthermore, the existing projects indicate changes to relationships between public administrations and non-public stakeholders, although not necessarily the fundamental shift proposed by New Public Governance. Lastly, the results suggest that power relations are shifting, including the decreasing influence of public administrations within the blockchain ecosystem. The results raise questions about the governance models and regulations required to support mature solutions and the further diffusion of blockchain for public service delivery.
Objective: The behaviors of endothelial cells or mesenchymal stem cells are remarkably influenced by the mechanical properties of their surrounding microenvironments. Here, electrospun fiber meshes containing various mechanical characteristics were developed from polyetheresterurethane (PEEU) copolymers. The goal of this study was to explore how fiber mesh stiffness affected endothelial cell shape, growth, migration, and angiogenic potential of endothelial cells. Furthermore, the effects of the E-modulus of fiber meshes on human adipose-derived stem cells (hADSCs) osteogenic potential was investigated.
Methods: Polyesteretherurethane (PEEU) polymers with various poly(p-dioxanone) (PPDO) to poly (ε-caprolactone) (PCL) weight percentages (40 wt.%, 50 wt.%, 60 wt.%, and 70 wt.%) were synthesized, termed PEEU40, PEEU50, PEEU60, and PEEU70, accordingly. The electrospinning method was used for the preparation of PEEU fiber meshes. The effects of PEEU fiber meshes with varying elasticities on the human umbilical vein endothelial cells (HUVECs) shape, growth, migration and angiogenic potential were characterized. To determine how the E-modulus of fiber meshes affects the osteogenic potential of hADSCs, the cellular and nuclear morphologies and osteogenic differentiation abilities were evaluated.
Results: With the increasing stiffness of PEEU fiber meshes, the aspect ratios of HUVECs cultivated on PEEU materials increased. HUVECs cultivated on high stiffness fiber meshes (4.5 ± 0.8 MPa) displayed a considerably greater proliferation rate and migratory velocity, in addition demonstrating increased tube formation capability, compared with those of the cells cultivated on lower stiffness fiber meshes (2.6 ± 0.8 MPa). Furthermore, in comparison to those cultivated on lower stiffness fiber meshes, hADSCs adhered to the highest stiffness fiber meshes PEEU70 had an elongated shape. The hADSCs grown on the softer PEEU40 fiber meshes showed a reduced nuclear aspect ratio (width to height) than those cultivated on the stiffer fiber meshes. Culturing hADSCs on stiffer fibers improved their osteogenic differentiation potential. Compared with cells cultured on PEEU40, osteocalcin expression and alkaline phosphatase (ALP) activity increased by 73 ± 10% and 43 ± 16%, respectively, in cells cultured on PEEU70.
Conclusion: The mechanical characteristics of the substrate are crucial in the modulation of cell behaviors. These findings indicate that adjusting the elasticity of fiber meshes might be a useful method for controlling the blood vessels development and regeneration. Furthermore, the mechanical characteristics of PEEU fiber meshes might be modified to control the osteogenic potential of hADSCs.
The present dissertation conducts empirical research on the relationship between urban life and its economic costs, especially for the environment. On the one hand, existing gaps in research on the influence of population density on air quality are closed and, on the other hand, innovative policy measures in the transport sector are examined that are intended to make metropolitan areas more sustainable. The focus is on air pollution, congestion and traffic accidents, which are important for general welfare issues and represent significant cost factors for urban life. They affect a significant proportion of the world's population. While 55% of the world's people already lived in cities in 2018, this share is expected to reach approximately 68% by 2050.
The four self-contained chapters of this thesis can be divided into two sections: Chapters 2 and 3 provide new causal insights into the complex interplay between urban structures and air pollution. Chapters 4 and 5 then examine policy measures to promote non-motorised transport and their influence on air quality as well as congestion and traffic accidents.
Distances affect economic decision-making in numerous situations. The time at which we make a decision about future consumption has an impact on our consumption behavior. The spatial distance to employer, school or university impacts the place where we live and vice versa. The emotional closeness to other individuals influences our willingness to give money to them. This cumulative thesis aims to enrich the literature on the role of distance for economic decision-making. Thereby, each of my research projects sheds light on the impact of one kind of distance for efficient decision-making.
Macrophages play an integral role for the innate immune system. It is critically important for basic research and therapeutic applications to find approaches to potentially modulate their function as the first line of defense. Transient genetic engineering via delivery of synthetic mRNA can serve for such purposes as a robust, reliable and safe technology to modulate macrophage functions. However, a major drawback particularly in the transfection of sensitive immune cells such as macrophages is the immunogenicity of exogenous IVT-mRNAs. Consequently, the direct modulation of human macrophage activity by mRNA-mediated genetic engineering was the aim of this work. The synthetic mRNA can instruct macrophages to synthesize specific target proteins, which can steer macrophage activity in a tailored fashion. Thus, the focus of this dissertation was to identify parameters triggering unwanted immune activation of macrophages, and to find approaches to minimize such effects. When comparing different carrier types as well as mRNA chemistries, the latter had unequivocally a more pronounced impact on activation of human macrophages and monocytes. Exploratory investigations revealed that the choice of nucleoside chemistry, particularly of modified uridine, plays a crucial role for IVT-mRNA-induced immune activation, in a dose-dependent fashion. Additionally, the contribution of the various 5’ cap structures tested was only minor. Moreover, to address the technical aspects of the delivery of multiple genes as often mandatory for advanced gene delivery studies, two different strategies of payload design were investigated, namely “bicistronic” delivery and “monocistronic” co-delivery. The side-by-side comparison of mRNA co-delivery via a bicistronic design (two genes, one mRNA) with a monocistronic design (two gene, two mRNAs) unexpectedly revealed that, despite the intrinsic equimolar nature of the bicistronic approach, it was outperformed by the monocistronic approach in terms of reliable co-expression when quantified on the single cell level. Overall, the incorporation of chemical modifications into IVT-mRNA by using respective building blocks, primarily with the aim to minimize immune activation as exemplified in this thesis, has the potential to facilitate the selection of the proper mRNA chemistry to address specific biological and clinical challenges. The technological aspects of gene delivery evaluated and validated by the quantitative methods allowed us to shed light on crucial process parameters and mRNA design criteria, required for reliable co-expression schemes of IVT-mRNA delivery.
The NAC transcription factor (TF) JUNGBRUNNEN1 (JUB1) is an important negative regulator of plant senescence, as well as of gibberellic acid (GA) and brassinosteroid (BR) biosynthesis in Arabidopsis thaliana. Overexpression of JUB1 promotes longevity and enhances tolerance to drought and other abiotic stresses. A similar role of JUB1 has been observed in other plant species, including tomato and banana. Our data show that JUB1 overexpressors (JUB1-OXs) accumulate higher levels of proline than WT plants under control conditions, during the onset of drought stress, and thereafter. We identified that overexpression of JUB1 induces key proline biosynthesis and suppresses key proline degradation genes. Furthermore, bZIP63, the transcription factor involved in proline metabolism, was identified as a novel downstream target of JUB1 by Yeast One-Hybrid (Y1H) analysis and Chromatin immunoprecipitation (ChIP). However, based on Electrophoretic Mobility Shift Assay (EMSA), direct binding of JUB1 to bZIP63 could not be confirmed. Our data indicate that JUB1-OX plants exhibit reduced stomatal conductance under control conditions. However, selective overexpression of JUB1 in guard cells did not improve drought stress tolerance in Arabidopsis. Moreover, the drought-tolerant phenotype of JUB1 overexpressors does not solely depend on the transcriptional control of the DREB2A gene. Thus, our data suggest that JUB1 confers tolerance to drought stress by regulating multiple components. Until today, none of the previous studies on JUB1´s regulatory network focused on identifying protein-protein interactions. We, therefore, performed a yeast two-hybrid screen (Y2H) which identified several protein interactors of JUB1, two of which are the calcium-binding proteins CaM1 and CaM4. Both proteins interact with JUB1 in the nucleus of Arabidopsis protoplasts. Moreover, JUB1 is expressed with CaM1 and CaM4 under the same conditions. Since CaM1.1 and CaM4.1 encode proteins with identical amino acid sequences, all further experiments were performed with constructs involving the CaM4 coding sequence. Our data show that JUB1 harbors multiple CaM-binding sites, which are localized in both the N-terminal and C-terminal regions of the protein. One of the CaM-binding sites, localized in the DNA-binding domain of JUB1, was identified as a functional CaM-binding site since its mutation strongly reduced the binding of CaM4 to JUB1. Furthermore, JUB1 transactivates expression of the stress-related gene DREB2A in mesophyll cells; this effect is significantly reduced when the calcium-binding protein CaM4 is expressed as well. Overexpression of both genes in Arabidopsis results in early senescence observed through lower chlorophyll content and an enhanced expression of senescence-associated genes (SAGs) when compared with single JUB1 overexpressors. Our data also show that JUB1 and CaM4 proteins interact in senescent leaves, which have increased Ca2+ levels when compared to young leaves. Collectively, our data indicate that JUB1 activity towards its downstream targets is fine-tuned by calcium-binding proteins during leaf senescence.
Carbohydrates are found in every living organism, where they are responsible for numerous, essential biological functions and processes. Synthetic polymers with pendant saccharides, called glycopolymers, mimic natural glycoconjugates in their special properties and functions. Employing such biomimetics furthers the understanding and controlling of biological processes. Hence, glycopolymers are valuable and interesting for applications in the medical and biological field. However, the synthesis of carbohydrate-based materials can be very challenging. In this thesis, the synthesis of biofunctional glycopolymers is presented, with the focus on aqueous-based, protecting group free and short synthesis routes to further advance in the field of glycopolymer synthesis.
A practical and versatile precursor for glycopolymers are glycosylamines. To maintain biofunctionality of the saccharides after their amination, regioselective functionalization was performed. This frequently performed synthesis was optimized for different sugars. The optimization was facilitated using a design of experiment (DoE) approach to enable a reduced number of necessary experiments and efficient procedure. Here, the utility of using DoE for optimizing the synthesis of glycosylamines is discussed.
The glycosylamines were converted to glycomonomers which were then polymerized to yield biofunctional glycopolymers. Here, the glycopolymers were aimed to be applicable as layer-by-layer (LbL) thin film coatings for drug delivery systems. To enable the LbL technique, complimentary glycopolymer electrolytes were synthesized by polymerization of the glycomonomers and subsequent modification or by post-polymerization modification. For drug delivery, liposomes were embedded into the glycopolymer coating as potential cargo carriers. The stability as well as the integrity of the glycopolymer layers and liposomes were investigated at physiological pH range.
Different glycopolymers were also synthesized to be applicable as anti-adhesion therapeutics by providing advanced architectures with multivalent presentations of saccharides, which can inhibit the binding of pathogene lectins. Here, the synthesis of glycopolymer hydrogel particles based on biocompatible poly(N-isopropylacrylamide) (NiPAm) was established using the free-radical precipitation polymerization technique. The influence of synthesis parameters on the sugar content in the gels and on the hydrogel morphology is discussed. The accessibility of the saccharides to model lectins and their enhanced, multivalent interaction were investigated.
At the end of this work, the synthesis strategies for the glycopolymers are generally discussed as well as their potential application in medicine.
Deep geological repositories represent a promising solution for the final disposal of nuclear waste. Due to its low permeability, high sorption capacity and self-sealing potential, Opalinus Clay (OPA) is considered a suitable host rock formation for the long-term storage of nuclear waste in Switzerland and Germany. However, the clay formation is characterized by compositional and structural variabilities including the occurrence of carbonate- and quartz-rich layers, pronounced bedding planes as well as tectonic elements such as pre-existing fault zones and fractures, suggesting heterogeneous rock mass properties.
Characterizing the heterogeneity of host rock properties is therefore essential for safety predictions of future repositories. This includes a detailed understanding of the mechanical and hydraulic properties, deformation behavior and the underlying deformation processes for an improved assessment of the sealing integrity and long-term safety of a deep repository in OPA. Against this background, this thesis presents the results of deformation experiments performed on intact and artificially fractured specimens of the quartz-rich, sandy and clay-rich, shaly facies of OPA. The experiments focus on the influence of mineralogical composition on the deformation behavior as well as the reactivation and sealing properties of pre-existing faults and fractures at different boundary conditions (e.g., pressure, temperature, strain rate).
The anisotropic mechanical properties of the sandy facies of OPA are presented in the first section, which were determined from triaxial deformation experiments using dried and resaturated samples loaded at 0°, 45° and 90° to the bedding plane orientation. A Paterson-type deformation apparatus was used that allowed to investigate how the deformation behavior is influenced by the variation of confining pressure (50 – 100 MPa), temperature (25 – 200 °C), and strain rate (1 × 10-3 – 5 × 10-6 s-1). Constant strain rate experiments revealed brittle to semi-brittle deformation behavior of the sandy facies at the applied conditions. Deformation behavior showed a strong dependence on confining pressure, degree of water saturation as well as bedding orientation, whereas the variation of temperature and strain rate had no significant effect on deformation. Furthermore, the sandy facies displays higher strength and stiffness compared to the clay-rich shaly facies deformed at similar conditions by Nüesch (1991). From the obtained results it can be concluded that cataclastic mechanisms dominate the short-term deformation behavior of dried samples from both facies up to elevated pressure (<200 MPa) and temperature (<200 °C) conditions.
The second part presents triaxial deformation tests that were performed to investigate how structural discontinuities affect the deformation behavior of OPA and how the reactivation of preexisting faults is influenced by mineral composition and confining pressure. To this end, dried cylindrical samples of the sandy and shaly facies of OPA were used, which contained a saw-cut fracture oriented at 30° to the long axis. After hydrostatic pre-compaction at 50 MPa, constant strain rate deformation tests were performed at confining pressures of 5, 20 or 35 MPa. With increasing confinement, a gradual transition from brittle, highly localized fault slip including a stress drop at fault reactivation to semi-brittle deformation behavior, characterized by increasing delocalization and non-linear strain hardening without dynamic fault reactivation, can be observed. Brittle localization was limited by the confining pressure at which the fault strength exceeded the matrix yield strength, above which strain partitioning between localized fault slip and distributed matrix deformation occurred. The sandy facies displayed a slightly higher friction coefficient (≈0.48) compared to the shaly facies (≈0.4). In addition, slide-hold-slide tests were conducted, revealing negative or negligible frictional strengthening, which suggests stable creep and long-term weakness of faults in both facies of OPA. The conducted experiments demonstrate that dilatant brittle fault reactivation in OPA may be favored at high overconsolidation ratios and shallow depths, increasing the risk of seismic hazard and the creation of fluid pathways.
The final section illustrates how the sealing capacity of fractures in OPA is affected by mineral composition. Triaxial flow-through experiments using Argon-gas were performed with dried samples from the sandy and shaly facies of OPA containing a roughened, artificial fracture. Slate, graywacke, quartzite, natural fault gouge, and granite samples were also tested to highlight the influence of normal stress, mineralogy and diagenesis on the sustainability of fracture transmissivity. With increasing normal stress, a non-linear decrease of fracture transmissivity can be observed that resulted in a permanent reduction of transmissivity after stress release. The transmissivity of rocks with a high portion of strong minerals (e.g., quartz) and high unconfined compressive strength was less sensitive to stress changes. In accordance with this, the sandy facies of OPA displayed a higher initial transmissivity that was less sensitive to stress changes compared to the shaly facies. However, transmissivity of rigid slate was less sensitive to stress changes than the sandy facies of OPA, although the slate is characterized by a higher phyllosilicate content. This demonstrates that in addition to mineral composition, other factors such as the degree of metamorphism, cementation and consolidation have to be considered when evaluating the sealing capacity of phyllosilicate-rich rocks.
The results of this thesis highlighted the role of confining pressure on the failure behavior of intact and artificially fractured OPA. Although the quartz-rich sandy facies may be considered as being more favorable for underground constructions due to its higher shear strength and stiffness than the shaly facies, the results indicate that when fractures develop in the sandy facies, they are more conductive and remain more permeable compared to fractures in the clay-dominated shaly facies at a given stress. The results may provide the basis for constitutive models to predict the integrity and evolution of a future repository. Clearly, the influence of composition and consolidation, e.g., by geological burial and uplift, on the mechanical sealing behavior of OPA highlights the need for a detailed site-specific material characterization for a future repository.
Variation in traits permeates and affects all levels of biological organisation, from within individuals to between species. Yet, intraspecific trait variation (ITV) is not sufficiently represented in many ecological theories. Instead, species averages are often assumed. Especially ITV in behaviour has only recently attracted more attention as its pervasiveness and magnitude became evident. The surge in interest in ITV in behaviour was accompanied by a methodological and technological leap in the field of movement ecology. Many aspects of behaviour become visible via movement, allowing us to observe inter-individual differences in fundamental processes such as foraging, mate searching, predation or migration. ITV in movement behaviour may result from within-individual variability and consistent, repeatable among-individual differences. Yet, questions on why such among-individual differences occur in the first place and how they are integrated with life-history have remained open. Furthermore, consequences of ITV, especially of among-individual differences in movement behaviour, on populations and species communities are not sufficiently understood. In my thesis, I approach timely questions on the sources and consequences of ITV, particularly, in movement behaviour. After outlining fundamental concepts and the current state of knowledge, I approach these questions by using agent-based models to integrate concepts from behavioural and movement ecology and to develop novel perspectives.
Modern coexistence theory is a central pillar of community ecology, yet, insufficiently considers ITV in behaviour. In chapter 2, I model a competitive two-species system of ground-dwelling, central-place foragers to investigate the consequences of among-individual differences in movement behaviour on species coexistence. I show that the simulated among-individual differences, which matched with empirical data, reduce fitness differences betweem species, i.e. provide an equalising coexistence mechanism. Furthermore, I explain this result mechanistically and, thus, resolve an apparent ambiguity of the consequences of ITV on species coexistence described in previous studies.
In chapter 3, I turn the focus to sources of among-individual differences in movement behaviour and their potential integration with life-history. The pace-of-life syndrome (POLS) theory predicts that the covariation between among-individual differences in behaviour and life-history is mediated by a trade-off between early and late reproduction. This theory has generated attention but is also currently scrutinised. In chapter 3, I present a model which supports a recent conceptual development that suggests fluctuating density-dependent selection as a cause of the POLS. Yet, I also identified processes that may alter the association between movement behaviour and life-history across levels of biological organization.
ITV can buffer populations, i.e. reduce their extinction risk. For instance, among-individual differences can mediate portfolio effects or increase evolvability and, thereby, facilitate rapid evolution which can alleviate extinction risk. In chapter 4, I review ITV, environmental heterogeneity, and density-dependent processes which constitute local buffer mechanisms. In the light of habitat isolation, which reduces connectivity between populations, local buffer mechanisms may become more relevant compared to dispersal-related regional buffer mechanisms. In this chapter, I argue that capacities, latencies, and interactions of local buffer mechanisms should motivate more process-based and holistic integration of local buffer mechanisms in theoretical and empirical studies.
Recent perspectives propose to apply principles from movement and community ecology to study filamentous fungi. It is an open question whether and how the arrangement and geometry of microstructures select for certain movement traits, and, thus, facilitate coexistence-stabilising niche partitioning. As a coauthor of chapter 5, I developed an agent-based model of hyphal tips navigating in soil-like microstructures along a gradient of soil porosity. By measuring network properties, we identified changes in the optimal movement behaviours along the gradient. Our findings suggest that the soil architecture facilitates niche partitioning.
The core chapters are framed by a general introduction and discussion. In the general introduction, I outline fundamental concepts of movement ecology and describe theory and open questions on sources and consequences of ITV in movement behaviour. In the general discussion, I consolidate the findings of the core chapters and critically discuss their respective value and, if applicable, their impact. Furthermore, I emphasise promising avenues for further research.
Infectious diseases are an increasing threat to biodiversity and human health. Therefore, developing a general understanding of the drivers shaping host-pathogen dynamics is of key importance in both ecological and epidemiological research. Disease dynamics are driven by a variety of interacting processes such as individual host behaviour, spatiotemporal resource availability or pathogen traits like virulence and transmission. External drivers such as global change may modify the system conditions and, thus, the disease dynamics. Despite their importance, many of these drivers are often simplified and aggregated in epidemiological models and the interactions among multiple drivers are neglected.
In my thesis, I investigate disease dynamics using a mechanistic approach that includes both bottom-up effects - from landscape dynamics to individual movement behaviour - as well as top-down effects - from pathogen virulence on host density and contact rates. To this end, I extended an established spatially explicit individual-based model that simulates epidemiological and ecological processes stochastically, to incorporate a dynamic resource landscape that can be shifted away from the timing of host population-dynamics (chapter 2). I also added the evolution of pathogen virulence along a theoretical virulence-transmission trade-off (chapter 3). In chapter 2, I focus on bottom-up effects, specifically how a temporal shift of resource availability away from the timing of biological events of host-species - as expected under global change - scales up to host-pathogen interactions and disease dynamics. My results show that the formation of temporary disease hotspots in combination with directed individual movement acted as key drivers for pathogen persistence even under highly unfavourable conditions for the host. Even with drivers like global change further increasing the likelihood of unfavourable interactions between host species and their environment, pathogens can continue to persist with heir hosts. In chapter 3, I demonstrate that the top-down effect caused by pathogen-associated mortality on its host population can be mitigated by selection for lower virulent pathogen strains when host densities are reduced through mismatches between seasonal resource availability and host life-history events. I chapter 4, I combined parts of both theoretical models into a new model that includes individual host movement decisions and the evolution of pathogenic virulence to simulate pathogen outbreaks in realistic landscapes. I was able to match simulated patterns of pathogen spread to observed patterns from long-term outbreak data of classical swine fever in wild boar in Northern Germany. The observed disease course was best explained by a simulated high virulent strain, whereas sampling schemes and vaccination campaigns could explain differences in the age-distribution of infected hosts. My model helps to understand and disentangle how the combination of individual decision making and evolution of virulence can act as important drivers of pathogen spread and persistence.
As I show across the chapters of this thesis, the interplay of both bottom-up and top-down processes is a key driver of disease dynamics in spatially structured host populations, as they ultimately shape host densities and contact rates among moving individuals. My findings are an important step towards a paradigm shift in disease ecology away from simplified assumptions towards the inclusion of mechanisms, such as complex multi-trophic interactions, and their feedbacks on pathogen spread and disease persistence. The mechanisms presented here should be at the core of realistic predictive and preventive epidemiological models.
This thesis deals with the synthesis of protein and composite protein-mineral microcapsules by the application of high-intensity ultrasound at the oil-water interface. While one system is stabilized by BSA molecules, the other system is stabilized by different nanoparticles modified with BSA. A comprehensive study of all synthesis stages as well as of resulting capsules were carried out and a plausible explanation of the capsule formation mechanism was proposed. During the formation of BSA microcapsules, the protein molecules adsorb firstly at the O/W interface and unfold there forming an interfacial network stabilized by hydrophobic interactions and hydrogen bonds between neighboring molecules. Simultaneously, the ultrasonic treatment causes the cross-linking of the BSA molecules via the formation of intermolecular disulfide bonds. In this thesis, the experimental evidences of ultrasonically induced cross-linking of the BSA in the shells of protein-based microcapsules are demonstrated. Therefore, the concept proposed many years ago by Suslick and co-workers is confirmed by experimental evidences for the first time. Moreover, a consistent mechanism for the formation of intermolecular disulfide bonds in capsule shells is proposed that is based on the redistribution of thiol and disulfide groups in BSA under the action of high-energy ultrasound. The formation of composite protein-mineral microcapsules loaded with three different oils and shells composed of nanoparticles was also successful. The nature of the loaded oil and the type of nanoparticles in the shell, had influence on size and shape of the microcapsules. The examination of the composite capsule revealed that the BSA molecules adsorbed on the nanoparticles surface in the capsule shell are not cross-linked by intermolecular disulfide bonds. Instead, a Pickering emulsion formation takes place. The surface modification of composite microcapsules through both pre-modification of main components and also the post-modification of the surface of ready composite microcapsules was successfully demonstrated. Additionally, the mechanical properties of protein and composite protein-mineral microcapsules were compared. The results showed that the protein microcapsules are more resistant to elastic deformation.
This thesis is analyzing multiple coordination challenges which arise with the digital transformation of public administration in federal systems, illustrated by four case studies in Germany. I make various observations within a multi-level system and provide an in-depth analysis. Theoretical explanations from both federalism research and neo-institutionalism are utilized to explain the findings of the empirical driven work. The four articles evince a holistic picture of the German case and elucidate its role as a digital government laggard. Their foci range from macro, over meso to micro level of public administration, differentiating between the governance and the tool dimension of digital government.
The first article shows how multi-level negotiations lead to expensive but eventually satisfying solutions for the involved actors, creating a subtle balance between centralization and decentralization. The second article identifies legal, technical, and organizational barriers for cross-organizational service provision, highlighting the importance of inter-organizational and inter-disciplinary exchange and both a common language and trust. Institutional change and its effects on the micro level, on citizens and the employees in local one-stop shops, mark the focus of the third article, bridging the gap between reforms and the administrative reality on the local level. The fourth article looks at the citizens’ perspective on digital government reforms, their expectations, use and satisfaction. In this vein, this thesis provides a detailed account of the importance of understanding the digital divide and therefore the necessity of reaching out to different recipients of digital government reforms. I draw conclusions from the factors identified as causes for Germany’s shortcomings for other federal systems where feasible and derive reform potential therefrom. This allows to gain a new perspective on digital government and its coordination challenges in federal contexts.
Stimuli-promoted in situ formation of hydrogels with thiol/thioester containing peptide precursors
(2022)
Hydrogels are potential synthetic ECM-like substitutes since they provide functional and structural similarities compared to soft tissues. They can be prepared by crosslinking of macromolecules or by polymerizing suitable precursors. The crosslinks are not necessarily covalent bonds, but could also be formed by physical interactions such as π-π interactions, hydrophobic interactions, or H-bonding. On demand in situ forming hydrogels have garnered increased interest especially for biomedical applications over preformed gels due to the relative ease of in vivo delivery and filling of cavities. The thiol-Michael addition reaction provides a straightforward and robust strategy for in situ gel formation with its fast reaction kinetics and ability to proceed under physiological conditions. The incorporation of a trigger function into a crosslinking system becomes even more interesting since gelling can be controlled with stimulus of choice. The use of small molar mass crosslinker precursors with active groups orthogonal to thiol-Michael reaction type electrophile provides the opportunity to implement an on-demand in situ crosslinking without compromising the fast reaction kinetics.
It was postulated that short peptide sequences due to the broad range structural-function relations available with the different constituent amino acids, can be exploited for the realisation of stimuli-promoted in situ covalent crosslinking and gelation applications. The advantages of this system over conventional polymer-polymer hydrogel systems are the ability tune and predict material property at the molecular level.
The main aim of this work was to develop a simplified and biologically-friendly stimuli-promoted in situ crosslinking and hydrogelation system using peptide mimetics as latent crosslinkers. The approach aims at using a single thiodepsipeptide sequence to achieve separate pH- and enzyme-promoted gelation systems with little modification to the thiodepsipeptide sequence. The realization of this aim required the completion of three milestones.
In the first place, after deciding on the thiol-Michael reaction as an effective in situ crosslinking strategy, a thiodepsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) with expected propensity towards pH-dependent thiol-thioester exchange (TTE) activation, was proposed as a suitable crosslinker precursor for pH-promoted gelation system. Prior to the synthesis of the proposed peptide-mimetic, knowledge of the thiol-Michael reactivity of the would-be activated thiol moiety SH-Leu, which is internally embedded in the thiodepsipeptide was required. In line with pKa requirements for a successful TTE, the reactivity of a more acidic thiol, SH-Phe was also investigated to aid the selection of the best thiol to be incorporated in the thioester bearing peptide based crosslinker precursor. Using ‘pseudo’ 2D-NMR investigations, it was found that only reactions involving SH-Leu yielded the expected thiol-Michael product, an observation that was attributed to the steric hindrance of the bulkier nature of SH-Phe. The fast reaction rates and complete acrylate/maleimide conversion obtained with SH-Leu at pH 7.2 and higher aided the direct elimination of SH-Phe as a potential thiol for the synthesis of the peptide mimetic.
Based on the initial studies, for the pH-promoted gelation system, the proposed Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH was kept unmodified. The subtle difference in pKa values between SH-Leu (thioester thiol) and the terminal cysteamine thiol from theoretical conditions should be enough to effect a ‘pseudo’ intramolecular TTE. In polar protic solvents and under basic aqueous conditions, TDP successfully undergoes a ‘pseudo’ intramolecular TTE reaction to yield an α,ω-dithiol tripeptide, HSLeu-Leu-Gly-NEtSH. The pH dependence of thiolate ion generation by the cysteamine thiol aided the incorporation of the needed stimulus (pH) for the overall success of TTE (activation step) – thiol-Michael addition (crosslinking) strategy.
Secondly, with potential biomedical applications in focus, the susceptibility of TDP, like other thioesters, to intermolecular TTE reaction was probed with a group of thiols of varying thiol pKa values, since biological milieu characteristically contain peptide/protein thiols. L-cysteine, which is a biologically relevant thiol, and a small molecular weight thiol, methylthioglycolate both with relatively similar thiol pKa, values, led to an increase concentration of the dithiol crosslinker when reacted with TDP. In the presence of acidic thiols (p-NTP and 4MBA), a decrease in the dithiol concentration was observed, an observation that can be attributed to the inability of the TTE tetrahedral intermediate to dissociate into exchange products and is in line with pKa requirements for successful TTE reaction. These results additionally makes TDP more attractive and the potentially the first crosslinker precursor for applications in biologically relevant media.
Finally, the ability of TDP to promote pH-sensitive in situ gel formation was probed with maleimide functionalized 4-arm polyethylene glycol polymers in tris-buffered media of varying pHs. When a 1:1 thiol: maleimide molar ratio was used, TDP-PEG4MAL hydrogels formed within 3, 12 and 24 hours at pH values of 8.5, 8.0 and 7.5 respectively. However, gelation times of 3, 5 and 30 mins were observed for the same pH trend when the thiol: maleimide molar was increased to 2:1.
A direct correlation of thiol content with G’ of the gels at each pH could also be drawn by comparing gels with thiol: maleimide ratios of 1:1 to those with 2:1 thiol: maleimide mole ratios. This is supported by the fact that the storage modulus (G') is linearly dependent on the crosslinking density of the polymer. The values of initial G′ for all gels ranged between (200 – 5000 Pa), which falls in the range of elasticities of certain tissue microenvironments for example brain tissue 200 – 1000 Pa and adipose tissue (2500 – 3500 Pa).
Knowledge so far gained from the study on the ability to design and tune the exchange reaction of thioester containing peptide mimetic will give those working in the field further insight into the development of new sequences tailored towards specific applications.
TTE substrate design using peptide mimetic as presented in this work has revealed interesting new insights considering the state-of-the-art. Using the results obtained as reference, the strategy provides a possibility to extend the concept to the controlled delivery of active molecules needed for other robust and high yielding crosslinking reactions for biomedical applications. Application for this sequentially coupled functional system could be seen e.g. in the treatment of inflamed tissues associated with urinary tract like bladder infections for which pH levels above 7 were reported. By the inclusion of cell adhesion peptide motifs, the hydrogel network formed at this pH could act as a new support layer for the healing of damage epithelium as shown in interfacial gel formation experiments using TDP and PEG4MAL droplets.
The versatility of the thiodepsipeptide sequence, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-(TDPo) was extended for the design and synthesis of a MMP-sensitive 4-arm PEG-TDPo conjugate. The purported cleavage of TDPo at the Gly-SLeu bond yields active thiol units for subsequent reaction of orthogonal Michael acceptor moieties. One of the advantages of stimuli-promoted in situ crosslinking systems using short peptides should be the ease of design of required peptide molecules due to the predictability of peptide functions their sequence structure. Consequently the functionalisation of a 4-arm PEG core with the collagenase active TDPo sequence yielded an MMP-sensitive 4-arm thiodepsipeptide-PEG conjugate (PEG4TDPo) substrate.
Cleavage studies using thiol flourometric assay in the presence of MMPs -2 and -9 confirmed the susceptibility of PEG4TDPo towards these enzymes. The resulting time-dependent increase in fluorescence intensity in the presence of thiol assay signifies the successful cleavage of TDPo at the Gly-SLeu bond as expected. It was observed that the cleavage studies with thiol flourometric assay introduces a sigmoid non-Michaelis-Menten type kinetic profile, hence making it difficult to accurately determine the enzyme cycling parameters, kcat and KM .
Gelation studies with PEG4MAL at 10 % wt. concentrations revealed faster gelation with MMP-2 than MMP-9 with 28 and 40 min gelation times respectively. Possible contributions by hydrolytic cleavage of PEG4TDPo has resulted in the gelation of PEG4MAL blank samples but only after 60 minutes of reaction. From theoretical considerations, the simultaneous gelation reaction would be expected to more negatively impact the enzymatic than hydrolytic cleavage. The exact contributions from hydrolytic cleavage of PEG4TDPo would however require additional studies.
In summary this new and simplified in situ crosslinking system using peptide-based crosslinker precursors with tuneable properties exhibited in situ crosslinking gelation kinetics on similar levels with already active dithiols reported. The advantageous on-demand functionality associated with its pH-sensitivity and physiological compatibility makes it a strong candidate worth further research as biomedical applications in general and on-demand material synthesis is concerned.
Results from MMP-promoted gelation system unveils a simple but unexplored approach for in situ synthesis of covalently crosslinked soft materials, that could lead to the development of an alternative pathway in addressing cancer metastasis by making use of MMP overexpression as a trigger. This goal has so far not being reach with MMP inhibitors despite the extensive work this regard.
The availability of commercial 3D printers and matching 3D design software has allowed a wide range of users to create physical prototypes – as long as these objects are not larger than hand size. However, when attempting to create larger, "human-scale" objects, such as furniture, not only are these machines too small, but also the commonly used 3D design software is not equipped to design with forces in mind — since forces increase disproportionately with scale.
In this thesis, we present a series of end-to-end fabrication software systems that support users in creating human-scale objects. They achieve this by providing three main functions that regular "small-scale" 3D printing software does not offer: (1) subdivision of the object into small printable components combined with ready-made objects, (2) editing based on predefined elements sturdy enough for larger scale, i.e., trusses, and (3) functionality for analyzing, detecting, and fixing structural weaknesses. The presented software systems also assist the fabrication process based on either 3D printing or steel welding technology.
The presented systems focus on three levels of engineering challenges: (1) fabricating static load-bearing objects, (2) creating mechanisms that involve motion, such as kinematic installations, and finally (3) designing mechanisms with dynamic repetitive movement where power and energy play an important role.
We demonstrate and verify the versatility of our systems by building and testing human-scale prototypes, ranging from furniture pieces, pavilions, to animatronic installations and playground equipment. We have also shared our system with schools, fablabs, and fabrication enthusiasts, who have successfully created human-scale objects that can withstand with human-scale forces.
Growth differentiation factor 15 (GDF15) is a stress-induced cytokine secreted into the circulation by a number of tissues under different pathological conditions such as cardiovascular disease, cancer or mitochondrial dysfunction, among others. While GDF15 signaling through its recently identified hindbrain-specific receptor GDNF family receptor alpha-like (GFRAL) has been proposed to be involved in the metabolic stress response, its endocrine role under chronic stress conditions is still poorly understood. Mitochondrial dysfunction is characterized by the impairment of oxidative phosphorylation (OXPHOS), leading to inefficient functioning of mitochondria and consequently, to mitochondrial stress. Importantly, mitochondrial dysfunction is among the pathologies to most robustly induce GDF15 as a cytokine in the circulation.
The overall aim of this thesis was to elucidate the role of the GDF15-GFRAL pathway under mitochondrial stress conditions. For this purpose, a mouse model of skeletal muscle-specific mitochondrial stress achieved by ectopic expression of uncoupling protein 1 (UCP1), the HSA-Ucp1-transgenic (TG) mouse, was employed. As a consequence of mitochondrial stress, TG mice display a metabolic remodeling consisting of a lean phenotype, an improved glucose metabolism, an increased metabolic flexibility and a metabolic activation of white adipose tissue.
Making use of TG mice crossed with whole body Gdf15-knockout (GdKO) and Gfral-knockout (GfKO) mouse models, this thesis demonstrates that skeletal muscle mitochondrial stress induces the integrated stress response (ISR) and GDF15 in skeletal muscle, which is released into the circulation as a myokine (muscle-induced cytokine) in a circadian manner. Further, this work identifies GDF15-GFRAL signaling to be responsible for the systemic metabolic remodeling elicited by mitochondrial stress in TG mice. Moreover, this study reveals a daytime-restricted anorexia induced by the GDF15-GFRAL axis under muscle mitochondrial stress, which is, mechanistically, mediated through the induction of hypothalamic corticotropin releasing hormone (CRH). Finally, this work elucidates a so far unknown physiological outcome of the GDF15-GFRAL pathway: the induction of anxiety-like behavior.
In conclusion, this study uncovers a muscle-brain crosstalk under skeletal muscle mitochondrial stress conditions through the induction of GDF15 as a myokine that signals through the hindbrain-specific GFRAL receptor to elicit a stress response leading to metabolic remodeling and modulation of ingestive- and anxiety-like behavior.
The ongoing climate change is altering the living conditions for many organisms on this planet at an unprecedented pace. Hence, it is crucial for the survival of species to adapt to these changing conditions. In this dissertation Silene vulgaris is used as a model organism to understand the adaption strategies of widely distributed plant species to the current climate change. Especially plant species that possess a wide geographic range are expected to have a high phenotypic plasticity or to show genetic differentiation in response to the different climate conditions they grow in. However, they are often underrepresented in research.
In the greenhouse experiment presented in this thesis, I examined the phenotypic responses and plasticity in S. vulgaris to estimate its’ adaptation potential. Seeds from 25 wild European populations were collected along a latitudinal gradient and grown in a greenhouse under three different precipitation (65 mm, 75 mm, 90 mm) and two different temperature regimes (18°C, 21°C) that resembled a possible climate change scenario for central Europe. Afterwards different biomass and fecundity-related plant traits were measured.
The treatments significantly influenced the plants but did not reveal a latitudinal difference in response to climate treatments for most plant traits. The number of flowers per individual however, showed a stronger plasticity in northern European populations (e.g., Swedish populations) where numbers decreased more drastically with increased temperature and decreased precipitation.
To gain an even deeper understanding of the adaptation of S. vulgaris to climate change it is also important to reveal the underlying phylogeny of the sampled populations. Therefore, I analysed their population genetic structure through whole genome sequencing via ddRAD.
The sequencing revealed three major genetic clusters in the S. vulgaris populations sampled in Europe: one cluster comprised Southern European populations, one cluster Western European populations and another cluster contained central European populations. A following analysis of experimental trait responses among the clusters to the climate-change scenario showed that the genetic clusters significantly differed in biomass-related traits and in the days to flowering. However, half of the traits showed parallel response patterns to the experimental climate-change scenario.
In addition to the potential geographic and genetic adaptation differences to climate change this dissertation also deals with the response differences between the sexes in S. vulgaris. As a gynodioecious species populations of S. vulgaris consist of female and hermaphrodite
individuals and the sexes can differ in their morphological traits which is known as sexual dimorphism. As climate change is becoming an important factor influencing plant morphology it remains unclear if and how different sexes may respond in sexually dimorphic species. To examine this question the sex of each individual plant was determined during the greenhouse experiment and the measured plant traits were analysed accordingly. In general, hermaphrodites had a higher number of flowers but a lower number of leaves than females. With regards to the climate change treatment, I found that hermaphrodites showed a milder negative response to higher temperatures in the number of flowers produced and in specific leaf area (SLA) compared to females.
Synthesis – The significant treatment response in Silene vulgaris, independent of population origin in most traits suggests a high degree of universal phenotypic plasticity. Also, the three European intraspecific genetic lineages detected showed comparable parallel response patterns in half of the traits suggesting considerable phenotypic plasticity. Hence, plasticity might represent a possible adaptation strategy of this widely distributed species during ongoing and future climatic changes. The results on sexual dimorphism show that females and hermaphrodites are differing mainly in their number of flowers and females are affected more strongly by the experimental climate-change scenario. These results provide a solid knowledge basis on the sexual dimorphism in S. vulgaris under climate change, but further research is needed to determine the long-term impact on the breeding system for the species.
In summary this dissertation provides a comprehensive insight into the adaptation mechanisms and consequences of a widely distributed and gynodioecious plant species and leverages our understanding of the impact of anthropogenic climate change on plants.
The importance of carbohydrate structures is enormous due to their ubiquitousness in our lives. The development of so-called glycomaterials is the result of this tremendous significance. These are not exclusively used for research into fundamental biological processes, but also, among other things, as inhibitors of pathogens or as drug delivery systems. This work describes the development of glycomaterials involving the synthesis of glycoderivatives, -monomers and -polymers. Glycosylamines were synthesized as precursors in a single synthesis step under microwave irradiation to significantly shorten the usual reaction time. Derivatization at the anomeric position was carried out according to the methods developed by Kochetkov and Likhorshetov, which do not require the introduction of protecting groups. Aminated saccharide structures formed the basis for the synthesis of glycomonomers in β-configuration by methacrylation. In order to obtain α-Man-based monomers for interactions with certain α-Man-binding lectins, a monomer synthesis by Staudinger ligation was developed in this work, which also does not require protective groups. Modification of the primary hydroxyl group of a saccharide was accomplished by enzyme-catalyzed synthesis. Ribose-containing cytidine was transesterified using the lipase Novozym 435 and microwave irradiation. The resulting monomer synthesis was optimized by varying the reaction partners. To create an amide bond instead of an ester bond, protected cytidine was modified by oxidation followed by amide coupling to form the monomer. This synthetic route was also used to isolate the monomer from its counterpart guanosine. After obtaining the nucleoside-based monomers, they were block copolymerized using the RAFT method. Pre-synthesized pHPMA served as macroCTA to yield cytidine- or guanosine-containing block copolymer. These isolated block copolymers were then investigated for their self-assembly behavior using UV-Vis, DLS and SEM to serve as a potential thermoresponsive drug delivery system.
The increasing demand for energy in the current technological era and the recent political decisions about giving up on nuclear energy diverted humanity to focus on alternative environmentally friendly energy sources like solar energy. Although silicon solar cells are the product of a matured technology, the search for highly efficient and easily applicable materials is still ongoing. These properties made the efficiency of halide perovskites comparable with silicon solar cells for single junctions within a decade of research. However, the downside of halide perovskites are poor stability and lead toxicity for the most stable ones.
On the other hand, chalcogenide perovskites are one of the most promising absorber materials for the photovoltaic market, due to their elemental abundance and chemical stability against moisture and oxygen. In the search of the ultimate solar absorber material, combining the good optoelectronic properties of halide perovskites with the stability of chalcogenides could be the promising candidate.
Thus, this work investigates new techniques for the synthesis and design of these novel chalcogenide perovskites, that contain transition metals as cations, e.g., BaZrS3, BaHfS3, EuZrS3, EuHfS3 and SrHfS3. There are two stages in the deposition techniques of this study: In the first stage, the binary compounds are deposited via a solution processing method. In the second stage, the deposited materials are annealed in a chalcogenide atmosphere to form the perovskite structure by using solid-state reactions.
The research also focuses on the optimization of a generalized recipe for a molecular ink to deposit precursors of chalcogenide perovskites with different binaries. The implementation of the precursor sulfurization resulted in either binaries without perovskite formation or distorted perovskite structures, whereas some of these materials are reported in the literature as they are more favorable in the needle-like non-perovskite configuration.
Lastly, there are two categories for the evaluation of the produced materials: The first category is about the determination of the physical properties of the deposited layer, e.g., crystal structure, secondary phase formation, impurities, etc. For the second category, optoelectronic properties are measured and compared to an ideal absorber layer, e.g., band gap, conductivity, surface photovoltage, etc.
Global heat adaptation among urban populations and its evolution under different climate futures
(2022)
Heat and increasing ambient temperatures under climate change represent a serious threat to human health in cities. Heat exposure has been studied extensively at a global scale. Studies comparing a defined temperature threshold with the future daytime temperature during a certain period of time, had concluded an increase in threat to human health. Such findings however do not explicitly account for possible changes in future human heat adaptation and might even overestimate heat exposure. Thus, heat adaptation and its development is still unclear. Human heat adaptation refers to the local temperature to which populations are adjusted to. It can be inferred from the lowest point of the U- or V-shaped heat-mortality relationship (HMR), the Minimum Mortality Temperature (MMT). While epidemiological studies inform on the MMT at the city scale for case studies, a general model applicable at the global scale to infer on temporal change in MMTs had not yet been realised. The conventional approach depends on data availability, their robustness, and on the access to daily mortality records at the city scale. Thorough analysis however must account for future changes in the MMT as heat adaptation happens partially passively. Human heat adaptation consists of two aspects: (1) the intensity of the heat hazard that is still tolerated by human populations, meaning the heat burden they can bear and (2) the wealth-induced technological, social and behavioural measures that can be employed to avoid heat exposure. The objective of this thesis is to investigate and quantify human heat adaptation among urban populations at a global scale under the current climate and to project future adaptation under climate change until the end of the century. To date, this has not yet been accomplished. The evaluation of global heat adaptation among urban populations and its evolution under climate change comprises three levels of analysis. First, using the example of Germany, the MMT is calculated at the city level by applying the conventional method. Second, this thesis compiles a data pool of 400 urban MMTs to develop and train a new model capable of estimating MMTs on the basis of physical and socio-economic city characteristics using multivariate non-linear multivariate regression. The MMT is successfully described as a function of the current climate, the topography and the socio-economic standard, independently of daily mortality data for cities around the world. The city-specific MMT estimates represents a measure of human heat adaptation among the urban population. In a final third analysis, the model to derive human heat adaptation was adjusted to be driven by projected climate and socio-economic variables for the future. This allowed for estimation of the MMT and its change for 3 820 cities worldwide for different combinations of climate trajectories and socio-economic pathways until 2100. The knowledge on the evolution of heat adaptation in the future is a novelty as mostly heat exposure and its future development had been researched. In this work, changes in heat adaptation and exposure were analysed jointly. A wide range of possible health-related outcomes up to 2100 was the result, of which two scenarios with the highest socio-economic developments but opposing strong warming levels were highlighted for comparison. Strong economic growth based upon fossil fuel exploitation is associated with a high gain in heat adaptation, but may not be able to compensate for the associated negative health effects due to increased heat exposure in 30% to 40% of the cities investigated caused by severe climate change. A slightly less strong, but sustainable growth brings moderate gains in heat adaptation but a lower heat exposure and exposure reductions in 80% to 84% of the cities in terms of frequency (number of days exceeding the MMT) and intensity (magnitude of the MMT exceedance) due to a milder global warming. Choosing a 2 ° C compatible development by 2100 would therefore lower the risk of heat-related mortality at the end of the century. In summary, this thesis makes diverse and multidisciplinary contributions to a deeper understanding of human adaptation to heat under the current and the future climate. It is one of the first studies to carry out a systematic and statistical analysis of urban characteristics which are useful as MMT drivers to establish a generalised model of human heat adaptation, applicable at the global level. A broad range of possible heat-related health options for various future scenarios was shown for the first time. This work is of relevance for the assessment of heat-health impacts in regions where mortality data are not accessible or missing. The results are useful for health care planning at the meso- and macro-level and to urban- and climate change adaptation planning. Lastly, beyond having met the posed objective, this thesis advances research towards a global future impact assessment of heat on human health by providing an alternative method of MMT estimation, that is spatially and temporally flexible in its application.
The estimation of financial losses is an integral part of flood risk assessment. The application of existing flood loss models on locations or events different from the ones used to train the models has led to low performance, showing that characteristics of the flood damaging process have not been sufficiently well represented yet. To improve flood loss model transferability, I explore various model structures aiming at incorporating different (inland water) flood types and pathways. That is based on a large survey dataset of approximately 6000 flood-affected households which addresses several aspects of the flood event, not only the hazard characteristics but also information on the affected building, socioeconomic factors, the household's preparedness level, early warning, and impacts. Moreover, the dataset reports the coincidence of different flood pathways. Whilst flood types are a classification of flood events reflecting their generating process (e.g. fluvial, pluvial), flood pathways represent the route the water takes to reach the receptors (e.g. buildings). In this work, the following flood pathways are considered: levee breaches, river floods, surface water floods, and groundwater floods.
The coincidence of several hazard processes at the same time and place characterises a compound event. In fact, many flood events develop through several pathways, such as the ones addressed in the survey dataset used. Earlier loss models, although developed with one or multiple predictor variables, commonly use loss data from a single flood event which is attributed to a single flood type, disregarding specific flood pathways or the coincidence of multiple pathways. This gap is addressed by this thesis through the following research questions: 1. In which aspects do flood pathways of the same (compound inland) flood event differ? 2. How much do factors which contribute to the overall flood loss in a building differ in various settings, specifically across different flood pathways? 3. How well can Bayesian loss models learn from different settings? 4. Do compound, that is, coinciding flood pathways result in higher losses than a single pathway, and what does the outcome imply for future loss modelling?
Statistical analysis has found that households affected by different flood pathways also show, in general, differing characteristics of the affected building, preparedness, and early warning, besides the hazard characteristics. Forecasting and early warning capabilities and the preparedness of the population are dominated by the general flood type, but characteristics of the hazard at the object-level, the impacts, and the recovery are more related to specific flood pathways, indicating that risk communication and loss models could benefit from the inclusion of flood-pathway-specific information.
For the development of the loss model, several potentially relevant predictors are analysed: water depth, duration, velocity, contamination, early warning lead time, perceived knowledge about self-protection, warning information, warning source, gap between warning and action, emergency measures, implementation of property-level precautionary measures (PLPMs), perceived efficacy of PLPMs, previous flood experience, awareness of flood risk, ownership, building type, number of flats, building quality, building value, house/flat area, building area, cellar, age, household size, number of children, number of elderly residents, income class, socioeconomic status, and insurance against floods. After a variable selection, descriptors of the hazard, building, and preparedness were deemed significant, namely: water depth, contamination, duration, velocity, building area, building quality, cellar, PLPMs, perceived efficacy of PLPMs, emergency measures, insurance, and previous flood experience. The inclusion of the indicators of preparedness is relevant, as they are rarely involved in loss datasets and in loss modelling, although previous studies have shown their potential in reducing losses. In addition, the linear model fit indicates that the explanatory factors are, in several cases, differently relevant across flood pathways.
Next, Bayesian multilevel models were trained, which intrinsically incorporate uncertainties and allow for partial pooling (i.e. different groups of data, such as households affected by different flood pathways, can learn from each other), increasing the statistical power of the model. A new variable selection was performed for this new model approach, reducing the number of predictors from twelve to seven variables but keeping factors of the hazard, building, and preparedness, namely: water depth, contamination, duration, building area, PLPMs, insurance, and previous flood experience. The new model was trained not only across flood pathways but also across regions of Germany, divided according to general socioeconomic factors and insurance policies, and across flood events. The distinction across regions and flood events did not improve loss modelling and led to a large overlap of regression coefficients, with no clear trend or pattern. The distinction of flood pathways showed credibly distinct regression coefficients, leading to a better understanding of flood loss modelling and indicating one potential reason why model transferability has been challenging.
Finally, new model structures were trained to include the possibility of compound inland floods (i.e. when multiple flood pathways coincide on the same affected asset). The dataset does not allow for verifying in which sequence the flood pathway waves occurred and predictor variables reflect only their mixed or combined outcome. Thus, two Bayesian models were trained: 1. a multi-membership model, a structure which learns the regression coefficients for multiple flood pathways at the same time, and 2. a multilevel model wherein the combination of coinciding flood pathways makes individual categories. The multi-membership model resulted in credibly different coefficients across flood pathways but did not improve model performance in comparison to the model assuming only a single dominant flood pathway. The model with combined categories signals an increase in impacts after compound floods, but due to the uncertainty in model coefficients and estimates, it is not possible to ascertain such an increase as credible. That is, with the current level of uncertainty in differentiating the flood pathways, the loss estimates are not credibly distinct from individual flood pathways.
To overcome the challenges faced, non-linear or mixed models could be explored in the future. Interactions, moderation, and mediation effects, as well as non-linear effects, should also be further studied. Loss data collection should regularly include preparedness indicators, and either data collection or hydraulic modelling should focus on the distinction of coinciding flood pathways, which could inform loss models and further improve estimates. Flood pathways show distinct (financial) impacts, and their inclusion in loss modelling proves relevant, for it helps in clarifying the different contribution of influencing factors to the final loss, improving understanding of the damaging process, and indicating future lines of research.
Data profiling is the extraction of metadata from relational databases. An important class of metadata are multi-column dependencies. They come associated with two computational tasks. The detection problem is to decide whether a dependency of a given type and size holds in a database. The discovery problem instead asks to enumerate all valid dependencies of that type. We investigate the two problems for three types of dependencies: unique column combinations (UCCs), functional dependencies (FDs), and inclusion dependencies (INDs).
We first treat the parameterized complexity of the detection variants. We prove that the detection of UCCs and FDs, respectively, is W[2]-complete when parameterized by the size of the dependency. The detection of INDs is shown to be one of the first natural W[3]-complete problems. We further settle the enumeration complexity of the three discovery problems by presenting parsimonious equivalences with well-known enumeration problems. Namely, the discovery of UCCs is equivalent to the famous transversal hypergraph problem of enumerating the hitting sets of a hypergraph. The discovery of FDs is equivalent to the simultaneous enumeration of the hitting sets of multiple input hypergraphs. Finally, the discovery of INDs is shown to be equivalent to enumerating the satisfying assignments of antimonotone, 3-normalized Boolean formulas.
In the remainder of the thesis, we design and analyze discovery algorithms for unique column combinations. Since this is as hard as the general transversal hypergraph problem, it is an open question whether the UCCs of a database can be computed in output-polynomial time in the worst case. For the analysis, we therefore focus on instances that are structurally close to databases in practice, most notably, inputs that have small solutions. The equivalence between UCCs and hitting sets transfers the computational hardness, but also allows us to apply ideas from hypergraph theory to data profiling. We devise an discovery algorithm that runs in polynomial space on arbitrary inputs and achieves polynomial delay whenever the maximum size of any minimal UCC is bounded. Central to our approach is the extension problem for minimal hitting sets, that is, to decide for
a set of vertices whether they are contained in any minimal solution. We prove that this is yet another problem that is complete for the complexity class W[3], when parameterized by the size of the set that is to be extended. We also give several conditional lower bounds under popular hardness conjectures such as the Strong Exponential Time Hypothesis (SETH). The lower bounds suggest that the running time of our algorithm for the extension problem is close to optimal.
We further conduct an empirical analysis of our discovery algorithm on real-world databases to confirm that the hitting set perspective on data profiling has merits also in practice. We show that the resulting enumeration times undercut their theoretical worst-case bounds on practical data, and that the memory consumption of our method is much smaller than that of previous solutions. During the analysis we make two observations about the connection between databases and their corresponding hypergraphs. On the one hand, the hypergraph representations containing all relevant information are usually significantly smaller than the original inputs. On the other hand, obtaining those hypergraphs is the actual bottleneck of any practical application. The latter often takes much longer than enumerating the solutions, which is in stark contrast to the fact that the preprocessing is guaranteed to be polynomial while the enumeration may take exponential time.
To make the first observation rigorous, we introduce a maximum-entropy model for non-uniform random hypergraphs and prove that their expected number of minimal hyperedges undergoes a phase transition with respect to the total number of edges. The result also explains why larger databases may have smaller hypergraphs. Motivated by the second observation, we present a new kind of UCC discovery algorithm called Hitting Set Enumeration with Partial Information and Validation (HPIValid). It utilizes the fast enumeration times in practice in order to speed up the computation of the corresponding hypergraph. This way, we sidestep the bottleneck while maintaining the advantages of the hitting set perspective. An exhaustive empirical evaluation shows that HPIValid outperforms the current state of the art in UCC discovery. It is capable of processing databases that were previously out of reach for data profiling.