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In recent years, entire industries and their participants have been affected by disruptive technologies, resulting in dramatic market changes and challenges to firm’s business logic and thus their business models (BMs). Firms from mature industries are increasingly realizing that BMs that worked successfully for years have become insufficient to stay on track in today’s “move fast and break things” economy. Firms must scrutinize the core logic that informs how they do business, which means exploring novel ways to engage customers and get them to pay. This can lead to a complete renewal of existing BMs or innovating completely new BMs.
BMs have emerged as a popular object of research within the last decade. Despite the popularity of the BM, the theoretical and empirical foundation underlying the concept is still weak. In particular, the innovation process for BMs has been developed and implemented in firms, but understanding of the mechanisms behind it is still lacking. Business model innovation (BMI) is a complex and challenging management task that requires more than just novel ideas. Systematic studies to generate a better understanding of BMI and support incumbents with appropriate concepts to improve BMI development are in short supply. Further, there is a lack of knowledge about appropriate research practices for studying BMI and generating valid data sets in order to meet expectations in both practice and academia.
This paper-based dissertation aims to contribute to research practice in the field of BM and BMI and foster better understanding of the BM concept and BMI processes in incumbent firms from mature industries. The overall dissertation presents three main results. The first result is a new perspective, or the systems thinking view, on the BM and BMI. With the systems thinking view, the fuzzy BM concept is clearly structured and a BMI framework is proposed. The second result is a new research strategy for studying BMI. After analyzing current research practice in the areas of BMs and BMI, it is obvious that there is a need for better research on BMs and BMI in terms of accuracy, transparency, and practical orientation. Thus, the action case study approach combined with abductive methodology is proposed and proven in the research setting of this thesis. The third result stems from three action case studies in incumbent firms from mature industries employed to study how BMI occurs in practice. The new insights and knowledge gained from the action case studies help to explain BMI in such industries and increase understanding of the core of these processes.
By studying these issues, the articles complied in this thesis contribute conceptually and empirically to the recently consolidated but still increasing literature on the BM and BMI. The conclusions and implications made are intended to foster further research and improve managerial practices for achieving BMI in a dramatically changing business environment.
In this thesis we use integral-field spectroscopy to detect and understand of Lyman α (Lyα) emission from high-redshift galaxies.
Intrinsically the Lyα emission at λ = 1216 Å is the strongest recombination line from galaxies. It arises from the 2p → 1s transition in hydrogen. In star-forming galaxies the line is powered by ionisation of the interstellar gas by hot O- and B- stars. Galaxies with star-formation rates of 1 - 10 Msol/year are expected to have Lyα luminosities of 42 dex - 43 dex (erg/s), corresponding to fluxes ~ -17 dex - -18 dex (erg/s/cm²) at redshifts z~3, where Lyα is easily accessible with ground-based telescopes. However, star-forming galaxies do not show these expected Lyα fluxes. Primarily this is a consequence of the high-absorption cross-section of neutral hydrogen for Lyα photons σ ~ -14 dex (cm²). Therefore, in typical interstellar environments Lyα photons have to undergo a complex radiative transfer. The exact conditions under which Lyα photons can escape a galaxy are poorly understood.
Here we present results from three observational projects. In Chapter 2, we show integral field spectroscopic observations of 14 nearby star-forming galaxies in Balmer α radiation (Hα, λ = 6562.8 Å). These observations were obtained with the Potsdam Multi Aperture Spectrophotometer at the Calar-Alto 3.5m Telescope}. Hα directly traces the intrinsic Lyα radiation field. We present Hα velocity fields and velocity dispersion maps spatially registered onto Hubble Space Telescope Lyα and Hα images. From our observations, we conjecture a causal connection between spatially resolved Hα kinematics and Lyα photometry for individual galaxies. Statistically, we find that dispersion-dominated galaxies are more likely to emit Lyα photons than galaxies where ordered gas-motions dominate. This result indicates that turbulence in actively star-forming systems favours an escape of Lyα radiation.
Not only massive stars can power Lyα radiation, but also non-thermal emission from an accreting super-massive black hole in the galaxy centre. If a galaxy harbours such an active galactic nucleus, the rate of hydrogen-ionising photons can be more than 1000 times higher than that of a typical star-forming galaxy. This radiation can potentially ionise large regions well outside the main stellar body of galaxies. Therefore, it is expected that the neutral hydrogen from these circum-galactic regions shines fluorescently in Lyα. Circum-galactic gas plays a crucial role in galaxy formation. It may act as a reservoir for fuelling star formation, and it is also subject to feedback processes that expel galactic material. If Lyα emission from this circum-galactic medium (CGM) was detected, these important processes could be studied in-situ around high-z galaxies. In Chapter 3, we show observations of five radio-quiet quasars with PMAS to search for possible extended CGM emission in the Lyα line. However, in four of the five objects, we find no significant traces of this emission. In the fifth object, there is evidence for a weak and spatially quite compact Lyα excess at several kpc outside the nucleus. The faintness of these structures is consistent with the idea that radio-quiet quasars typically reside in dark matter haloes of modest masses. While we were not able to detect Lyα CGM emission, our upper limits provide constraints for the new generation of IFS instruments at 8--10m class telescopes.
The Multi Unit Spectroscopic Explorer (MUSE) at ESOs Very Large Telescopeis such an unique instrument. One of the main motivating drivers in its construction was the use as a survey instrument for Lyα emitting galaxies at high-z. Currently, we are conducting such a survey that will cover a total area of ~100 square arcminutes with 1 hour exposures for each 1 square arcminute MUSE pointing. As a first result from this survey we present in Chapter 5 a catalogue of 831 emission-line selected galaxies from a 22.2 square arcminute region in the Chandra Deep Field South. In order to construct the catalogue, we developed and implemented a novel source detection algorithm -- LSDCat -- based on matched filtering for line emission in 3D spectroscopic datasets (Chapter 4). Our catalogue contains 237 Lyα emitting galaxies in the redshift range 3 ≲ z ≲ 6. Only four of those previously had spectroscopic redshifts in the literature. We conclude this thesis with an outlook on the construction of a Lyα luminosity function based on this unique sample (Chapter 6).
This dissertation examines the impact of the type of referring expression on the acquisition of word order variation in German-speaking preschoolers. A puzzle in the area of language acquisition concerns the production-comprehension asymmetry for non-canonical sentences like "Den Affen fängt die Kuh." (“The monkey, the cow chases.”), that is, preschoolers usually have difficulties in accurately understanding non-canonical sentences approximately until age six (e.g., Dittmar et al., 2008) although they produce non-canonical sentences already around age three (e.g., Poeppel & Wexler, 1993; Weissenborn, 1990). This dissertation investigated the production and comprehension of non-canonical sentences to address this issue.
Three corpus analyses were conducted to investigate the impact of givenness, topic status and the type of referring expression on word order in the spontaneous speech of two- to four-year-olds and the child-directed speech produced by their mothers. The positioning of the direct object in ditransitive sentences was examined; in particular, sentences in which the direct object occurred before or after the indirect object in the sentence-medial positions and sentences in which it occurred in the sentence-initial position. The results reveal similar ordering patterns for children and adults. Word order variation was to a large extent predictable from the type of referring expression, especially with respect to the word order involving the sentence-medial positions. Information structure (e.g., topic status) had an additional impact only on word order variation that involved the sentence-initial position.
Two comprehension experiments were conducted to investigate whether the type of referring expression and topic status influences the comprehension of non-canonical transitive sentences in four- and five-year-olds. In the first experiment, the topic status of the one of the sentential arguments was established via a preceding context sentence, and in the second experiment, the type of referring expression for the sentential arguments was additionally manipulated by using either a full lexical noun phrase (NP) or a personal pronoun. The results demonstrate that children’s comprehension of non-canonical sentences improved when the topic argument was realized as a personal pronoun and this improvement was independent of the grammatical role of the arguments. However, children’s comprehension was not improved when the topic argument was realized as a lexical NP.
In sum, the results of both production and comprehension studies support the view that referring expressions may be seen as a sentence-level cue to word order and to the information status of the sentential arguments. The results highlight the important role of the type of referring expression on the acquisition of word order variation and indicate that the production-comprehension asymmetry is reduced when the type of referring expression is considered.
The cytoskeleton is an essential component of living cells. It is composed of different types of protein filaments that form complex, dynamically rearranging, and interconnected networks. The cytoskeleton serves a multitude of cellular functions which further depend on the cell context. In animal cells, the cytoskeleton prominently shapes the cell's mechanical properties and movement. In plant cells, in contrast, the presence of a rigid cell wall as well as their larger sizes highlight the role of the cytoskeleton in long-distance intracellular transport. As it provides the basis for cell growth and biomass production, cytoskeletal transport in plant cells is of direct environmental and economical relevance. However, while knowledge about the molecular details of the cytoskeletal transport is growing rapidly, the organizational principles that shape these processes on a whole-cell level remain elusive.
This thesis is devoted to the following question: How does the complex architecture of the plant cytoskeleton relate to its transport functionality? The answer requires a systems level perspective of plant cytoskeletal structure and transport. To this end, I combined state-of-the-art confocal microscopy, quantitative digital image analysis, and mathematically powerful, intuitively accessible graph-theoretical approaches.
This thesis summarizes five of my publications that shed light on the plant cytoskeleton as a transportation network: (1) I developed network-based frameworks for accurate, automated quantification of cytoskeletal structures, applicable in, e.g., genetic or chemical screens; (2) I showed that the actin cytoskeleton displays properties of efficient transport networks, hinting at its biological design principles; (3) Using multi-objective optimization, I demonstrated that different plant cell types sustain cytoskeletal networks with cell-type specific and near-optimal organization; (4) By investigating actual transport of organelles through the cell, I showed that properties of the actin cytoskeleton are predictive of organelle flow and provided quantitative evidence for a coordination of transport at a cellular level; (5) I devised a robust, optimization-based method to identify individual cytoskeletal filaments from a given network representation, allowing the investigation of single filament properties in the network context. The developed methods were made publicly available as open-source software tools.
Altogether, my findings and proposed frameworks provide quantitative, system-level insights into intracellular transport in living cells. Despite my focus on the plant cytoskeleton, the established combination of experimental and theoretical approaches is readily applicable to different organisms. Despite the necessity of detailed molecular studies, only a complementary, systemic perspective, as presented here, enables both understanding of cytoskeletal function in its evolutionary context as well as its future technological control and utilization.
It is "scientific folklore" coming from physical heuristics that solutions to the heat equation on a Riemannian manifold can be represented by a path integral. However, the problem with such path integrals is that they are notoriously ill-defined. One way to make them rigorous (which is often applied in physics) is finite-dimensional approximation, or time-slicing approximation: Given a fine partition of the time interval into small subintervals, one restricts the integration domain to paths that are geodesic on each subinterval of the partition. These finite-dimensional integrals are well-defined, and the (infinite-dimensional) path integral then is defined as the limit of these (suitably normalized) integrals, as the mesh of the partition tends to zero.
In this thesis, we show that indeed, solutions to the heat equation on a general compact Riemannian manifold with boundary are given by such time-slicing path integrals. Here we consider the heat equation for general Laplace type operators, acting on sections of a vector bundle. We also obtain similar results for the heat kernel, although in this case, one has to restrict to metrics satisfying a certain smoothness condition at the boundary. One of the most important manipulations one would like to do with path integrals is taking their asymptotic expansions; in the case of the heat kernel, this is the short time asymptotic expansion. In order to use time-slicing approximation here, one needs the approximation to be uniform in the time parameter. We show that this is possible by giving strong error estimates.
Finally, we apply these results to obtain short time asymptotic expansions of the heat kernel also in degenerate cases (i.e. at the cut locus). Furthermore, our results allow to relate the asymptotic expansion of the heat kernel to a formal asymptotic expansion of the infinite-dimensional path integral, which gives relations between geometric quantities on the manifold and on the loop space. In particular, we show that the lowest order term in the asymptotic expansion of the heat kernel is essentially given by the Fredholm determinant of the Hessian of the energy functional. We also investigate how this relates to the zeta-regularized determinant of the Jacobi operator along minimizing geodesics.
In this thesis, the two prototype catalysts Fe(CO)₅ and Cr(CO)₆ are investigated with time-resolved photoelectron spectroscopy at a high harmonic setup. In both of these metal carbonyls, a UV photon can induce the dissociation of one or more ligands of the complex. The mechanism of the dissociation has been debated over the last decades. The electronic dynamics of the first dissociation occur on the femtosecond timescale.
For the experiment, an existing high harmonic setup was moved to a new location, was extended, and characterized. The modified setup can induce dynamics in gas phase samples with photon energies of 1.55eV, 3.10eV, and 4.65eV. The valence electronic structure of the samples can be probed with photon energies between 20eV and 40eV. The temporal resolution is 111fs to 262fs, depending on the combination of the two photon energies.
The electronically excited intermediates of the two complexes, as well as of the reaction product Fe(CO)₄, could be observed with photoelectron spectroscopy in the gas phase for the first time. However, photoelectron spectroscopy gives access only to the final ionic states. Corresponding calculations to simulate these spectra are still in development. The peak energies and their evolution in time with respect to the initiation pump pulse have been determined, these peaks have been assigned based on literature data. The spectra of the two complexes show clear differences. The dynamics have been interpreted with the assumption that the motion of peaks in the spectra relates to the movement of the wave packet in the multidimensional energy landscape. The results largely confirm existing models for the reaction pathways. In both metal carbonyls, this pathway involves a direct excitation of the wave packet to a metal-to-ligand charge transfer state and the subsequent crossing to a dissociative ligand field state. The coupling of the electronic dynamics to the nuclear dynamics could explain the slower dissociation in Fe(CO)₅ as compared to Cr(CO)₆.
The goal of the presented work is to explore the interaction between gold nanorods (GNRs) and hyper-sound waves. For the generation of the hyper-sound I have used Azobenzene-containing polymer transducers. Multilayer polymer structures with well-defined thicknesses and smooth interfaces were built via layer-by-layer deposition. Anionic polyelectrolytes with Azobenzene side groups (PAzo) were alternated with cationic polymer PAH, for the creation of transducer films. PSS/PAH multilayer were built for spacer layers, which do not absorb in the visible light range. The properties of the PAzo/PAH film as a transducer are carefully characterized by static and transient optical spectroscopy. The optical and mechanical properties of the transducer are studied on the picosecond time scale. In particular the relative change of the refractive index of the photo-excited and expanded PAH/PAzo is Δn/n = - 2.6*10‐4. Calibration of the generated strain is performed by ultrafast X-ray diffraction calibrated the strain in a Mica substrate, into which the hyper-sound is transduced. By simulating the X-ray data with a linear-chain-model the strain in the transducer under the excitation is derived to be Δd/d ~ 5*10‐4.
Additional to the investigation of the properties of the transducer itself, I have performed a series of experiments to study the penetration of the generated strain into various adjacent materials. By depositing the PAzo/PAH film onto a PAH/PSS structure with gold nanorods incorporated in it, I have shown that nanoscale impurities can be detected via the scattering of hyper-sound.
Prior to the investigation of complex structures containing GNRs and the transducer, I have performed several sets of experiments on GNRs deposited on a small buffer of PSS/PAH. The static and transient response of GNRs is investigated for different fluence of the pump beam and for different dielectric environments (GNRs covered by PSS/PAH).
A systematic analysis of sample architectures is performed in order to construct a sample with the desired effect of GNRs responding to the hyper-sound strain wave. The observed shift of a feature related to the longitudinal plasmon resonance in the transient reflection spectra is interpreted as the event of GNRs sensing the strain wave. We argue that the shift of the longitudinal plasmon resonance is caused by the viscoelastic deformation of the polymer around the nanoparticle. The deformation is induced by the out of plane difference in strain in the area directly under a particle and next to it. Simulations based on the linear chain model support this assumption. Experimentally this assumption is proven by investigating the same structure, with GNRs embedded in a PSS/PAH polymer layer.
The response of GNRs to the hyper-sound wave is also observed for the sample structure with GNRs embedded in PAzo/PAH films. The response of GNRs in this case is explained to be driven by the change of the refractive index of PAzo during the strain propagation.
Proteins are amphiphilic and adsorb at liquid interfaces. Therefore, they can be efficient stabilizers of foams and emulsions. β-lactoglobulin (BLG) is one of the most widely studied proteins due to its major industrial applications, in particular in food technology.
In the present work, the influence of different bulk concentration, solution pH and ionic strength on the dynamic and equilibrium pressures of BLG adsorbed layers at the solution/tetradecane (W/TD) interface has been investigated. Dynamic interfacial pressure (Π) and interfacial dilational elastic modulus (E’) of BLG solutions for various concentrations at three different pH values of 3, 5 and 7 at a fixed ionic strength of 10 mM and for a selected fixed concentration at three different ionic strengths of 1 mM, 10 mM and 100 mM are measured by Profile Analysis Tensiometer PAT-1 (SINTERFACE Technologies, Germany). A quantitative data analysis requires additional consideration of depletion due to BLG adsorption at the interface at low protein bulk concentrations. This fact makes experiments more efficient when oil drops are studied in the aqueous protein solutions rather than solution drops formed in oil. On the basis of obtained experimental data, concentration dependencies and the effect of solution pH on the protein surface activity was qualitatively analysed. In the presence of 10 mM buffer, we observed that generally the adsorbed amount is increasing with increasing BLG bulk concentration for all three pH values. The adsorption kinetics at pH 5 result in the highest Π values at any time of adsorption while it exhibits a less active behaviour at pH 3.
Since the experimental data have not been in a good agreement with the classical diffusion controlled model due to the conformational changes which occur when the protein molecules get in contact with the hydrophobic oil phase in order to adapt to the interfacial environment, a new theoretical model is proposed here. The adsorption kinetics data were analysed with the newly proposed model, which is the classical diffusion model but modified by assuming an additional change in the surface activity of BLG molecules when adsorbing at the interface. This effect can be expressed through the adsorption activity constant in the corresponding equation of state. The dilational visco-elasticity of the BLG adsorbed interfacial layers is determined from measured dynamic interfacial tensions during sinusoidal drop area variations. The interfacial tension responses to these harmonic drop oscillations are interpreted with the same thermodynamic model which is used for the corresponding adsorption isotherm.
At a selected BLG concentration of 2×10-6 mol/l, the influence of the ionic strength using different buffer concentration of 1, 10 and 100 mM on the interfacial pressure was studied. It is affected weakly at pH 5, whereas it has a strong impact by increasing buffer concentration at pH 3 and 7. In conclusion, the structure formation of BLG adsorbed layer in the early stage of adsorption at the W/TD interface is similar to those of the solution/air (W/A) surface. However, the equation of state at the W/TD interface provides an adsorption activity constant which is almost two orders of magnitude higher than that for the solution/air surface.
At the end of this work, a new experimental tool called Drop and Bubble Micro Manipulator DBMM (SINTERFACE Technologies, Germany) has been introduced to study the stability of protein covered bubbles against coalescence. Among the available protocols the lifetime between the moment of contact and coalescence of two contacting bubble is determined for different BLG concentrations. The adsorbed amount of BLG is determined as a function of time and concentration and correlates with the observed coalescence behaviour of the contacting bubbles.
In this thesis sentence processing was investigated using a psychophysiological measure known as pupillometry as well as Event-Related Potentials (ERP). The scope of the the- sis was broad, investigating the processing of several different movement constructions with native speakers of English and second language learners of English, as well as word order and case marking in German speaking adults and children. Pupillometry and ERP allowed us to test competing linguistic theories and use novel methodologies to investigate the processing of word order. In doing so we also aimed to establish pupillometry as an effective way to investigate the processing of word order thus broadening the methodological spectrum.
The relationship between climate and forest productivity is an intensively studied subject in forest science. This Thesis is embedded within the general framework of future forest growth under climate change and its implications for the ongoing forest conversion. My objective is to investigate the future forest productivity at different spatial scales (from a single specific forest stand to aggregated information across Germany) with focus on oak-pine forests in the federal state of Brandenburg. The overarching question is: how are the oak-pine forests affected by climate change described by a variety of climate scenarios. I answer this question by using a model based analysis of tree growth processes and responses to different climate scenarios with emphasis on drought events. In addition, a method is developed which considers climate change uncertainty of forest management planning.
As a first 'screening' of climate change impacts on forest productivity, I calculated the change in net primary production on the base of a large set of climate scenarios for different tree species and the total area of Germany. Temperature increases up to 3 K lead to positive effects on the net primary production of all selected tree species. But, in water-limited regions this positive net primary production trend is dependent on the length of drought periods which results in a larger uncertainty regarding future forest productivity. One of the regions with the highest uncertainty of net primary production development is the federal state of Brandenburg.
To enhance the understanding and ability of model based analysis of tree growth sensitivity to drought stress two water uptake approaches in pure pine and mixed oak-pine stands are contrasted. The first water uptake approach consists of an empirical function for root water uptake. The second approach is more mechanistic and calculates the differences of soil water potential along a soil-plant-atmosphere continuum. I assumed the total root resistance to vary at low, medium and high total root resistance levels. For validation purposes three data sets on different tree growth relevant time scales are used. Results show that, except the mechanistic water uptake approach with high total root resistance, all transpiration outputs exceeded observed values. On the other hand high transpiration led to a better match of observed soil water content. The strongest correlation between simulated and observed annual tree ring width occurred with the mechanistic water uptake approach and high total root resistance. The findings highlight the importance of severe drought as a main reason for small diameter increment, best supported by the mechanistic water uptake approach with high root resistance. However, if all aspects of the data sets are considered no approach can be judged superior to the other. I conclude that the uncertainty of future productivity of water-limited forest ecosystems under changing environmental conditions is linked to simulated root water uptake.
Finally my study aimed at the impacts of climate change combined with management scenarios on an oak-pine forest to evaluate growth, biomass and the amount of harvested timber. The pine and the oak trees are 104 and 9 years old respectively. Three different management scenarios with different thinning intensities and different climate scenarios are used to simulate the performance of management strategies which explicitly account for the risks associated with achieving three predefined objectives (maximum carbon storage, maximum harvested timber, intermediate). I found out that in most cases there is no general management strategy which fits best to different objectives. The analysis of variance in the growth related model outputs showed an increase of climate uncertainty with increasing climate warming. Interestingly, the increase of climate-induced uncertainty is much higher from 2 to 3 K than from 0 to 2 K.
Recently, due to an increasing demand on functionality and flexibility, beforehand isolated systems have become interconnected to gain powerful adaptive Systems of Systems (SoS) solutions with an overall robust, flexible and emergent behavior. The adaptive SoS comprises a variety of different system types ranging from small embedded to adaptive cyber-physical systems. On the one hand, each system is independent, follows a local strategy and optimizes its behavior to reach its goals. On the other hand, systems must cooperate with each other to enrich the overall functionality to jointly perform on the SoS level reaching global goals, which cannot be satisfied by one system alone. Due to difficulties of local and global behavior optimizations conflicts may arise between systems that have to be solved by the adaptive SoS.
This thesis proposes a modeling language that facilitates the description of an adaptive SoS by considering the adaptation capabilities in form of feedback loops as first class entities. Moreover, this thesis adopts the Models@runtime approach to integrate the available knowledge in the systems as runtime models into the modeled adaptation logic. Furthermore, the modeling language focuses on the description of system interactions within the adaptive SoS to reason about individual system functionality and how it emerges via collaborations to an overall joint SoS behavior. Therefore, the modeling language approach enables the specification of local adaptive system behavior, the integration of knowledge in form of runtime models and the joint interactions via collaboration to place the available adaptive behavior in an overall layered, adaptive SoS architecture.
Beside the modeling language, this thesis proposes analysis rules to investigate the modeled adaptive SoS, which enables the detection of architectural patterns as well as design flaws and pinpoints to possible system threats. Moreover, a simulation framework is presented, which allows the direct execution of the modeled SoS architecture. Therefore, the analysis rules and the simulation framework can be used to verify the interplay between systems as well as the modeled adaptation effects within the SoS. This thesis realizes the proposed concepts of the modeling language by mapping them to a state of the art standard from the automotive domain and thus, showing their applicability to actual systems. Finally, the modeling language approach is evaluated by remodeling up to date research scenarios from different domains, which demonstrates that the modeling language concepts are powerful enough to cope with a broad range of existing research problems.
In this thesis, a route to temperature-, pH-, solvent-, 1,2-diol-, and protein-responsive sensors made of biocompatible and low-fouling materials is established. These sensor devices are based on the sensitivemodulation of the visual band gap of a photonic crystal (PhC), which is induced by the selective binding of analytes, triggering a volume phase transition.
The PhCs introduced by this work show a high sensitivity not only for small biomolecules, but also for large analytes, such as glycopolymers or proteins. This enables the PhC to act as a sensor that detects analytes without the need of complex equipment.
Due to their periodical dielectric structure, PhCs prevent the propagation of specific wavelengths. A change of the periodicity parameters is thus indicated by a change in the reflected wavelengths. In the case explored, the PhC sensors are implemented as periodically structured responsive hydrogels in formof an inverse opal.
The stimuli-sensitive inverse opal hydrogels (IOHs) were prepared using a sacrificial opal template of monodispersed silica particles. First, monodisperse silica particles were assembled with a hexagonally packed structure via vertical deposition onto glass slides. The obtained silica crystals, also named colloidal crystals (CCs), exhibit structural color. Subsequently, the CCs templates were embedded in polymer matrix with low-fouling properties. The polymer matrices were composed of oligo(ethylene glycol) methacrylate derivatives (OEGMAs) that render the hydrogels thermoresponsive. Finally, the silica particles were etched, to produce highly porous hydrogel replicas of the CC. Importantly, the inner structure and thus the ability for light diffraction of the IOHs formed was maintained.
The IOH membrane was shown to have interconnected pores with a diameter as well as interconnections between the pores of several hundred nanometers. This enables not only the detection of small analytes, but also, the detection of even large analytes that can diffuse into the nanostructured IOH membrane. Various recognition unit – analyte model systems, such as benzoboroxole – 1,2-diols, biotin – avidin and mannose – concanavalin A, were studied by incorporating functional
comonomers of benzoboroxole, biotin and mannose into the copolymers. The incorporated recognition units specifically bind to certain low and highmolar mass biomolecules, namely to certain saccharides, catechols, glycopolymers or proteins.
Their specific binding strongly changes the overall hydrophilicity, thus modulating the swelling of the IOH matrices, and in consequence, drastically changes their internal periodicity. This swelling is amplified by the thermoresponsive properties of the polymer matrix. The shift of the interference band gap due to the specific molecular recognition is easily visible by the naked eye (up to 150 nm shifts). Moreover, preliminary trial were attempted to detect even larger entities. Therefore anti-bodies were immobilized on hydrogel platforms via polymer-analogous esterification. These platforms incorporate comonomers made of tri(ethylene glycol) methacrylate end-functionalized with a carboxylic acid. In these model systems, the bacteria analytes are too big to penetrate into the IOH membranes, but can only interact with their surfaces. The selected model bacteria, as Escherichia coli, show a specific affinity to anti-body-functionalized hydrogels. Surprisingly in the case functionalized IOHs, this study produced weak color shifts, possibly opening a path to detect directly living organism, which will need further investigations.
Widespread landscape changes are presently observed in the Arctic and are most likely to
accelerate in the future, in particular in permafrost regions which are sensitive to climate warming. To assess current and future developments, it is crucial to understand past
environmental dynamics in these landscapes. Causes and interactions of environmental variability can hardly be resolved by instrumental records covering modern time scales. However, long-term
environmental variability is recorded in paleoenvironmental archives. Lake sediments are important archives that allow reconstruction of local limnogeological processes as well as past environmental changes driven directly or indirectly by climate dynamics. This study aims at
reconstructing Late Quaternary permafrost and thermokarst dynamics in central-eastern Beringia,
the terrestrial land mass connecting Eurasia and North America during glacial sea-level low stands. In order to investigate development, processes and influence of thermokarst dynamics, several sediment cores from extant lakes and drained lake basins were analyzed to answer the
following research questions:
1. When did permafrost degradation and thermokarst lake development take place and what were enhancing and inhibiting environmental factors?
2. What are the dominant processes during thermokarst lake development and how are
they reflected in proxy records?
3. How did, and still do, thermokarst dynamics contribute to the inventory and properties of organic matter in sediments and the carbon cycle?
Methods applied in this study are based upon a multi-proxy approach combining
sedimentological, geochemical, geochronological, and micropaleontological analyses, as well as
analyses of stable isotopes and hydrochemistry of pore-water and ice. Modern field observations of water quality and basin morphometrics complete the environmental investigations.
The investigated sediment cores reveal permafrost degradation and thermokarst dynamics on different time scales. The analysis of a sediment core from GG basin on the northern Seward
Peninsula (Alaska) shows prevalent terrestrial accumulation of yedoma throughout the Early to
Mid Wisconsin with intermediate wet conditions at around 44.5 to 41.5 ka BP. This first wetland
development was terminated by the accumulation of a 1-meter-thick airfall tephra most likely originating from the South Killeak Maar eruption at 42 ka BP. A depositional hiatus between 22.5 and 0.23 ka BP may indicate thermokarst lake formation in the surrounding of the site which forms a yedoma upland till today. The thermokarst lake forming GG basin initiated 230 ± 30 cal a
BP and drained in Spring 2005 AD. Four years after drainage the lake talik was still unfrozen below 268 cm depth.
A permafrost core from Mama Rhonda basin on the northern Seward Peninsula preserved a
full lacustrine record including several lake phases. The first lake generation developed at 11.8 cal ka BP during the Lateglacial-Early Holocene transition; its old basin (Grandma Rhonda) is still partially preserved at the southern margin of the study basin. Around 9.0 cal ka BP a shallow and more dynamic thermokarst lake developed with actively eroding shorelines and potentially intermediate shallow water or wetland phases (Mama Rhonda). Mama Rhonda lake drainage at 1.1 cal ka BP was followed by gradual accumulation of terrestrial peat and top-down refreezing of the lake talik. A significant lower organic carbon content was measured in Grandma Rhonda deposits (mean TOC of 2.5 wt%) than in Mama Rhonda deposits (mean TOC of 7.9 wt%) highlighting the impact of thermokarst dynamics on biogeochemical cycling in different lake generations by thawing and mobilization of organic carbon into the lake system.
Proximal and distal sediment cores from Peatball Lake on the Arctic Coastal Plain of Alaska revealed young thermokarst dynamics since about 1,400 years along a depositional gradient based on reconstructions from shoreline expansion rates and absolute dating results. After its initiation as a remnant pond of a previous drained lake basin, a rapidly deepening lake with increasing oxygenation of the water column is evident from laminated sediments, and higher Fe/Ti and Fe/S ratios in the sediment. The sediment record archived characterizing shifts in depositional regimes and sediment sources from upland deposits and re-deposited sediments from drained thaw lake basins depending on the gradually changing shoreline configuration. These changes are evident from alternating organic inputs into the lake system which highlights the potential for thermokarst lakes to recycle old carbon from degrading permafrost deposits of its catchment.
The lake sediment record from Herschel Island in the Yukon (Canada) covers the full Holocene period. After its initiation as a thermokarst lake at 11.7 cal ka BP and intense thermokarst activity until 10.0 cal ka BP, the steady sedimentation was interrupted by a depositional hiatus at 1.6 cal ka BP which likely resulted from lake drainage or allochthonous slumping due to collapsing shore lines. The specific setting of the lake on a push moraine composed of marine deposits is reflected in the sedimentary record. Freshening of the maturing lake is indicated by decreasing electrical conductivity in pore-water. Alternation of marine to freshwater ostracods and foraminifera confirms decreasing salinity as well but also reflects episodical re-deposition of allochthonous marine sediments.
Based on permafrost and lacustrine sediment records, this thesis shows examples of the Late Quaternary evolution of typical Arctic permafrost landscapes in central-eastern Beringia and the complex interaction of local disturbance processes, regional environmental dynamics and global climate patterns. This study confirms that thermokarst lakes are important agents of organic matter recycling in complex and continuously changing landscapes.
In complement to the well-established zwitterionic monomers 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (“SPE”) and 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (“SPP”), the closely related sulfobetaine monomers were synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar mass were characterized with respect to their solubility in water, deuterated water, and aqueous salt solutions. These poly(sulfobetaine)s show thermoresponsive behavior in water, exhibiting upper critical solution temperatures (UCST). Phase transition temperatures depend notably on the molar mass and polymer concentration, and are much higher in D2O than in H2O. Also, the phase transition temperatures are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed structure of the zwitterionic side chain, on the other hand. For the polymers with the same zwitterionic side chain, it is found that methacrylamide-based poly(sulfobetaine)s exhibit higher UCST-type transition temperatures than their methacrylate analogs. The extension of the distance between polymerizable unit and zwitterionic groups from 2 to 3 methylene units decreases the UCST-type transition temperatures. Poly(sulfobetaine)s derived from aliphatic esters show higher UCST-type transition temperatures than their analogs featuring cyclic ammonium cations. The UCST-type transition temperatures increase markedly with spacer length separating the cationic and anionic moieties from 3 to 4 methylene units. Thus, apparently small variations of their chemical structure strongly affect the phase behavior of the polyzwitterions in specific aqueous environments.
Water-soluble block copolymers were prepared from the zwitterionic monomers and the non-ionic monomer N-isopropylmethacrylamide (“NIPMAM”) by the RAFT polymerization. Such block copolymers with two hydrophilic blocks exhibit twofold thermoresponsive behavior in water. The poly(sulfobetaine) block shows an UCST, whereas the poly(NIPMAM) block exhibits a lower critical solution temperature (LCST). This constellation induces a structure inversion of the solvophobic aggregate, called “schizophrenic micelle”. Depending on the relative positions of the two different phase transitions, the block copolymer passes through a molecularly dissolved or an insoluble intermediate regime, which can be modulated by the polymer concentration or by the addition of salt. Whereas, at low temperature, the poly(sulfobetaine) block forms polar aggregates that are kept in solution by the poly(NIPMAM) block, at high temperature, the poly(NIPMAM) block forms hydrophobic aggregates that are kept in solution by the poly(sulfobetaine) block. Thus, aggregates can be prepared in water, which switch reversibly their “inside” to the “outside”, and vice versa.
This cumulative dissertation contains four self-contained articles which are related to EU regional policy and its structural funds as the overall research topic. In particular, the thesis addresses the question if EU regional policy interventions can at all be scientifically justified and legitimated on theoretical and empirical grounds from an economics point of view. The first two articles of the thesis (“The EU structural funds as a means to hamper migration” and “Internal migration and EU regional policy transfer payments: a panel data analysis for 28 EU member countries”) enter into one particular aspect of the debate regarding the justification and legitimisation of EU regional policy. They theoretically and empirically analyse as to whether regional policy or the market force of the free flow of labour (migration) in the internal European market is the better instrument to improve and harmonise the living and working conditions of EU citizens. Based on neoclassical market failure theory, the first paper argues that the structural funds of the EU are inhibiting internal migration, which is one of the key measures in achieving convergence among the nations in the single European market. It becomes clear that European regional policy aiming at economic growth and cohesion among the member states cannot be justified and legitimated if the structural funds hamper instead of promote migration. The second paper, however, shows that the empirical evidence on the migration and regional policy nexus is not unambiguous, i.e. different empirical investigations show that EU structural funds hamper and promote EU internal migration. Hence, the question of the scientific justification and legitimisation of EU regional policy cannot be readily and unambiguously answered on empirical grounds. This finding is unsatisfying but is in line with previous theoretical and empirical literature. That is why, I take a step back and reconsider the theoretical beginnings of the thesis, which took for granted neoclassical market failure theory as the starting point for the positive explanation as well as the normative justification and legitimisation of EU regional policy. The third article of the thesis (“EU regional policy: theoretical foundations and policy conclusions revisited”) deals with the theoretical explanation and legitimisation of EU regional policy as well as the policy recommendations given to EU regional policymakers deduced from neoclassical market failure theory. The article elucidates that neoclassical market failure is a normative concept, which justifies and legitimates EU regional policy based on a political and thus subjective goal or value-judgement. It can neither be used, therefore, to give a scientifically positive explanation of the structural funds nor to obtain objective and practically applicable policy instruments. Given this critique of neoclassical market failure theory, the third paper consequently calls into question the widely prevalent explanation and justification of EU regional policy given in static neoclassical equilibrium economics. It argues that an evolutionary non-equilibrium economics perspective on EU regional policy is much more appropriate to provide a realistic understanding of one of the largest policies conducted by the EU. However, this does neither mean that evolutionary economic theory can be unreservedly seen as the panacea to positively explain EU regional policy nor to derive objective policy instruments for EU regional policymakers. This issue is discussed in the fourth article of the thesis (“Market failure vs. system failure as a rationale for economic policy? A critique from an evolutionary perspective”). This article reconsiders the explanation of economic policy from an evolutionary economics perspective. It contrasts the neoclassical equilibrium notions of market and government failure with the dominant evolutionary neo-Schumpeterian and Austrian-Hayekian perceptions. Based on this comparison, the paper criticises the fact that neoclassical failure reasoning still prevails in non-equilibrium evolutionary economics when economic policy issues are examined. This is surprising, since proponents of evolutionary economics usually view their approach as incompatible with its neoclassical counterpart. The paper therefore argues that in order to prevent the otherwise fruitful and more realistic evolutionary approach from undermining its own criticism of neoclassical economics and to create a consistent as well as objective evolutionary policy framework, it is necessary to eliminate the equilibrium spirit. Taken together, the main finding of this thesis is that European regional policy and its structural funds can neither theoretically nor empirically be justified and legitimated from an economics point of view. Moreover, the thesis finds that the prevalent positive and instrumental explanation of EU regional policy given in the literature needs to be reconsidered, because these theories can neither scientifically explain the emergence and development of this policy nor are they appropriate to derive objective and scientific policy instruments for EU regional policymakers.
The cell interior is a highly packed environment in which biological macromolecules evolve and function. This crowded media has effects in many biological processes such as protein-protein binding, gene regulation, and protein folding. Thus, biochemical reactions that take place in such crowded conditions differ from diluted test tube conditions, and a considerable effort has been invested in order to understand such differences.
In this work, we combine different computationally tools to disentangle the effects of molecular crowding on biochemical processes. First, we propose a lattice model to study the implications of molecular crowding on enzymatic reactions. We provide a detailed picture of how crowding affects binding and unbinding events and how the separate effects of crowding on binding equilibrium act together. Then, we implement a lattice model to study the effects of molecular crowding on facilitated diffusion. We find that obstacles on the DNA impair facilitated diffusion. However, the extent of this effect depends on how dynamic obstacles are on the DNA. For the scenario in which crowders are only present in the bulk solution, we find that at some conditions presence of crowding agents can enhance specific-DNA binding. Finally, we make use of structure-based techniques to look at the impact of the presence of crowders on the folding a protein. We find that polymeric crowders have stronger effects on protein stability than spherical crowders. The strength of this effect increases as the polymeric crowders become longer. The methods we propose here are general and can also be applied to more complicated systems.
It is the intention of this study to contribute to further rethinking and innovating in the Microcredit business which stands at a turning point – after around 40 years of practice it is endangered to fail as a tool for economic development and to become a doubtful finance product with a random scope instead. So far, a positive impact of Microfinance on the improvement of the lives of the poor could not be confirmed. Over-indebtment of borrowers due to the pre-dominance of consumption Microcredits has become a widespread problem. Furthermore, a rising number of abusive and commercially excessive practices have been reported.
In fact, the Microfinance sector appears to suffer from a major underlying deficit: there does not exist a coherent and transparent understanding of its meaning and objectives so that Microfinance providers worldwide follow their own approaches of Microfinance which tend to differ considerably from each other.
In this sense the study aims at consolidating the multi-faced and very often confusingly different Microcredit profiles that exist nowadays. Subsequently, in this study, the Microfinance spectrum will be narrowed to one clear-cut objective, in fact away from the mere monetary business transactions to poor people it has gradually been reduced to back towards a tool for economic development as originally envisaged by its pioneers.
Hence, the fundamental research question of this study is whether, and under which conditions, Microfinance may attain a positive economic impact leading to an improvement of the living of the poor.
The study is structured in five parts: the three main parts (II.-IV.) are surrounded by an introduction (I.) and conclusion (V.). In part II., the Microfinance sector is analysed critically aiming to identify the challenges persisting as well as their root causes. In the third part, a change to the macroeconomic perspective is undertaken in oder to learn about the potential and requirements of small-scale finance to enhance economic development, particularly within the economic context of less developed countries. By consolidating the insights gained in part IV., the elements of a new concept of Microfinance with the objecitve to achieve economic development of its borrowers are elaborated.
Microfinance is a rather sensitive business the great fundamental idea of which is easily corruptible and, additionally, the recipients of which are predestined victims of abuse due to their limited knowledge in finance. It therefore needs to be practiced responsibly, but also according to clear cut definitions of its meaning and objectives all institutions active in the sector should be devoted to comply with. This is especially relevant as the demand for Microfinance services is expected to rise further within the years coming. For example, the recent refugee migration movement towards Europe entails a vast potential for Microfinance to enable these people to make a new start into economic life. This goes to show that Microfinance may no longer mainly be associated with a less developed economic context, but that it will gain importance as a financial instrument in the developed economies, too.
This publications-based thesis summarizes my contribution to the scientific field of ultrafast structural dynamics. It consists of 16 publications, about the generation, detection and coupling of coherent gigahertz longitudinal acoustic phonons, also called hypersonic waves. To generate such high frequency phonons, femtosecond near infrared laser pulses were used to heat nanostructures composed of perovskite oxides on an ultrashort timescale. As a consequence the heated regions of such a nanostructure expand and a high frequency acoustic phonon pulse is generated. To detect such coherent acoustic sound pulses I use ultrafast variants of optical Brillouin and x-ray scattering. Here an incident optical or x-ray photon is scattered by the excited sound wave in the sample. The scattered light intensity measures the occupation of the phonon modes.
The central part of this work is the investigation of coherent high amplitude phonon wave packets which can behave nonlinearly, quite similar to shallow water waves which show a steepening of wave fronts or solitons well known as tsunamis. Due to the high amplitude of the acoustic wave packets in the solid, the acoustic properties can change significantly in the vicinity of the sound pulse. This may lead to a shape change of the pulse. I have observed by time-resolved Brillouin scattering, that a single cycle hypersound pulse shows a wavefront steepening. I excited hypersound pulses with strain amplitudes until 1% which I have calibrated by ultrafast x-ray diffraction (UXRD).
On the basis of this first experiment we developed the idea of the nonlinear mixing of narrowband phonon wave packets which we call "nonlinear phononics" in analogy with the nonlinear optics, which summarizes a kaleidoscope of surprising optical phenomena showing up at very high electric fields. Such phenomena are for instance Second Harmonic Generation, four-wave-mixing or solitons. But in case of excited coherent phonons the wave packets have usually very broad spectra which make it nearly impossible to look at elementary scattering processes between phonons with certain momentum and energy.
For that purpose I tested different techniques to excite narrowband phonon wave packets which mainly consist of phonons with a certain momentum and frequency. To this end epitaxially grown metal films on a dielectric substrate were excited with a train of laser pulses. These excitation pulses drive the metal film to oscillate with the frequency given by their inverse temporal displacement and send a hypersonic wave of this frequency into the substrate. The monochromaticity of these wave packets was proven by ultrafast optical Brillouin and x-ray scattering.
Using the excitation of such narrowband phonon wave packets I was able to observe the Second Harmonic Generation (SHG) of coherent phonons as a first example of nonlinear wave mixing of nanometric phonon wave packets.
Among the bloom-forming and potentially harmful cyanobacteria, the genus Microcystis represents a most diverse taxon, on the genomic as well as on morphological and secondary metabolite levels. Microcystis communities are composed of a variety of diversified strains. The focus of this study lies on potential interactions between Microcystis representatives and the roles of secondary metabolites in these interaction processes.
The role of secondary metabolites functioning as signaling molecules in the investigated interactions is demonstrated exemplary for the prevalent hepatotoxin microcystin. The extracellular and intracellular roles of microcystin are tested in microarray-based transcriptomic approaches. While an extracellular effect of microcystin on Microcystis transcription is confirmed and connected to a specific gene cluster of another secondary metabolite in this study, the intracellularly occurring microcystin is related with several pathways of the primary metabolism. A clear correlation of a microcystin knockout and the SigE-mediated regulation of carbon metabolism is found. According to the acquired transcriptional data, a model is proposed that postulates the regulating effect of microcystin on transcriptional regulators such as the alternative sigma factor SigE, which in return captures an essential role in sugar catabolism and redox-state regulation.
For the purpose of simulating community conditions as found in the field, Microcystis colonies are isolated from the eutrophic lakes near Potsdam, Germany and established as stably growing under laboratory conditions. In co-habitation simulations, the recently isolated field strain FS2 is shown to specifically induce nearly immediate aggregation reactions in the axenic lab strain Microcystis aeruginosa PCC 7806. In transcriptional studies via microarrays, the induced expression program in PCC 7806 after aggregation induction is shown to involve the reorganization of cell envelope structures, a highly altered nutrient uptake balance and the reorientation of the aggregating cells to a heterotrophic carbon utilization, e.g. via glycolysis. These transcriptional changes are discussed as mechanisms of niche adaptation and acclimation in order to prevent competition for resources.
Understanding the role of natural climate variability under the pressure of human induced changes of climate and landscapes, is crucial to improve future projections and adaption strategies. This doctoral thesis aims to reconstruct Holocene climate and environmental changes in NE Germany based on annually laminated lake sediments. The work contributes to the ICLEA project (Integrated CLimate and Landscape Evolution Analyses). ICLEA intends to compare multiple high-resolution proxy records with independent chronologies from the N central European lowlands, in order to disentangle the impact of climate change and human land use on landscape development during the Lateglacial and Holocene. In this respect, two study sites in NE Germany are investigated in this doctoral project, Lake Tiefer See and palaeolake Wukenfurche. While both sediment records are studied with a combination of high-resolution sediment microfacies and geochemical analyses (e.g. µ-XRF, carbon geochemistry and stable isotopes), detailed proxy understanding mainly focused on the continuous 7.7 m long sediment core from Lake Tiefer See covering the last ~6000 years. Three main objectives are pursued at Lake Tiefer See: (1) to perform a reliable and independent chronology, (2) to establish microfacies and geochemical proxies as indicators for climate and environmental changes, and (3) to trace the effects of climate variability and human activity on sediment deposition.
Addressing the first aim, a reliable chronology of Lake Tiefer See is compiled by using a multiple-dating concept. Varve counting and tephra findings form the chronological framework for the last ~6000 years. The good agreement with independent radiocarbon dates of terrestrial plant remains verifies the robustness of the age model. The resulting reliable and independent chronology of Lake Tiefer See and, additionally, the identification of nine tephras provide a valuable base for detailed comparison and synchronization of the Lake Tiefer See data set with other climate records. The sediment profile of Lake Tiefer See exhibits striking alternations between well-varved and non-varved sediment intervals. The combination of microfacies, geochemical and microfossil (i.e. Cladocera and diatom) analyses indicates that these changes of varve preservation are caused by variations of lake circulation in Lake Tiefer See. An exception is the well-varved sediment deposited since AD 1924, which is mainly influenced by human-induced lake eutrophication. Well-varved intervals before the 20th century are considered to reflect phases of reduced lake circulation and, consequently, stronger anoxic conditions. Instead, non-varved intervals indicate increased lake circulation in Lake Tiefer See, leading to more oxygenated conditions at the lake ground. Furthermore, lake circulation is not only influencing sediment deposition, but also geochemical processes in the lake. As, for example, the proxy meaning of δ13COM varies in time in response to changes of the oxygen regime in the lake hypolinion. During reduced lake circulation and stronger anoxic conditions δ13COM is influenced by microbial carbon cycling. In contrast, organic matter degradation controls δ13COM during phases of intensified lake circulation and more oxygenated conditions. The varve preservation indicates an increasing trend of lake circulation at Lake Tiefer See after ~4000 cal a BP. This trend is superimposed by decadal to centennial scale variability of lake circulation intensity. Comparison to other records in Central Europe suggests that the long-term trend is probably related to gradual changes in Northern Hemisphere orbital forcing, which induced colder and windier conditions in Central Europe and, therefore, reinforced lake circulation. Decadal to centennial scale periods of increased lake circulation coincide with settlement phases at Lake Tiefer See, as inferred from pollen data of the same sediment record. Deforestation reduced the wind shelter of the lake, which probably increased the sensitivity of lake circulation to wind stress. However, results of this thesis also suggest that several of these phases of increased lake circulation are additionally reinforced by climate changes. A first indication is provided by the comparison to the Baltic Sea record, which shows striking correspondence between major non-varved intervals at Lake Tiefer See and bioturbated sediments in the Baltic Sea. Furthermore, a preliminary comparison to the ICLEA study site Lake Czechowskie (N central Poland) shows a coincidence of at least three phases of increased lake circulation in both lakes, which concur with periods of known climate changes (2.8 ka event, ’Migration Period’ and ’Little Ice Age’). These results suggest an additional over-regional climate forcing also on short term increased of lake circulation in Lake Tiefer See.
In summary, the results of this thesis suggest that lake circulation at Lake Tiefer See is driven by a combination of long-term and short-term climate changes as well as of anthropogenic deforestation phases. Furthermore, the lake circulation drives geochemical cycles in the lake affecting the meaning of proxy data. Therefore, the work presented here expands the knowledge of climate and environmental variability in NE Germany. Furthermore, the integration of the Lake Tiefer See multi-proxy record in a regional comparison with another ICLEA side, Lake Czechowskie, enabled to better decipher climate changes and human impact on the lake system. These first results suggest a huge potential for further detailed regional comparisons to better understand palaeoclimate dynamics in N central Europe.
Gene expression describes the process of making functional gene products (e.g. proteins or special RNAs) from instructions encoded in the genetic information (e.g. DNA). This process is heavily regulated, allowing cells to produce the appropriate gene products necessary for cell survival, adapting production as necessary for different cell environments. Gene expression is subject to regulation at several levels, including transcription, mRNA degradation, translation and protein degradation. When intact, this system maintains cell homeostasis, keeping the cell alive and adaptable to different environments. Malfunction in the system can result in disease states and cell death. In this dissertation, we explore several aspects of gene expression control by analyzing data from biological experiments. Most of the work following uses a common mathematical model framework based on Markov chain models to test hypotheses, predict system dynamics or elucidate network topology. Our work lies in the intersection between mathematics and biology and showcases the power of statistical data analysis and math modeling for validation and discovery of biological phenomena.
Over the last decades, the world’s population has been growing at a faster rate, resulting in increased urbanisation, especially in developing countries. More than half of the global population currently lives in urbanised areas with an increasing tendency. The growth of cities results in a significant loss of vegetation cover, soil compaction and sealing of the soil surface which in turn results in high surface runoff during high-intensity storms and causes the problem of accelerated soil water erosion on streets and building grounds. Accelerated soil water erosion is a serious environmental problem in cities as it gives rise to the contamination of aquatic bodies, reduction of ground water recharge and increase in land degradation, and also results in damages to urban infrastructures, including drainage systems, houses and roads. Understanding the problem of water erosion in urban settings is essential for the sustainable planning and management of cities prone to water erosion. However, in spite of the vast existence of scientific literature on water erosion in rural regions, a concrete understanding of the underlying dynamics of urban erosion still remains inadequate for the urban dryland environments.
This study aimed at assessing water erosion and the associated socio-environmental determinants in a typical dryland urban area and used the city of Windhoek, Namibia, as a case study. The study used a multidisciplinary approach to assess the problem of water erosion. This included an in depth literature review on current research approaches and challenges of urban erosion, a field survey method for the quantification of the spatial extent of urban erosion in the dryland city of Windhoek, and face to face interviews by using semi-structured questionnaires to analyse the perceptions of stakeholders on urban erosion.
The review revealed that around 64% of the literatures reviewed were conducted in the developed world, and very few researches were carried out in regions with extreme climate, including dryland regions. Furthermore, the applied methods for erosion quantification and monitoring are not inclusive of urban typical features and they are not specific for urban areas. The reviewed literature also lacked aspects aimed at addressing the issues of climate change and policies regarding erosion in cities. In a field study, the spatial extent and severity of an urban dryland city, Windhoek, was quantified and the results show that nearly 56% of the city is affected by water erosion showing signs of accelerated erosion in the form of rills and gullies, which occurred mainly in the underdeveloped, informal and semi-formal areas of the city. Factors influencing the extent of erosion in Windhoek included vegetation cover and type, socio-urban factors and to a lesser extent slope estimates. A comparison of an interpolated field survey erosion map with a conventional erosion assessment tool (the Universal Soil Loss Equation) depicted a large deviation in spatial patterns, which underlines the inappropriateness of traditional non-urban erosion tools to urban settings and emphasises the need to develop new erosion assessment and management methods for urban environments. It was concluded that measures for controlling water erosion in the city need to be site-specific as the extent of erosion varied largely across the city.
The study also analysed the perceptions and understanding of stakeholders of urban water erosion in Windhoek, by interviewing 41 stakeholders using semi-structured questionnaires. The analysis addressed their understanding of water erosion dynamics, their perceptions with regards to the causes and the seriousness of erosion damages, and their attitudes towards the responsibilities for urban erosion. The results indicated that there is less awareness of the process as a phenomenon, instead there is more awareness of erosion damages and the factors contributing to the damages. About 69% of the stakeholders considered erosion damages to be ranging from moderate to very serious. However, there were notable disparities between the private householders and public authority groups. The study further found that the stakeholders have no clear understanding of their responsibilities towards the management of the control measures and payment for the damages. The private householders and local authority sectors pointed fingers at each other for the responsibilities for erosion damage payments and for putting up prevention measures. The reluctance to take responsibility could create a predicament for areas affected, specifically in the informal settlements where land management is not carried out by the local authority and land is not owned by the occupants.
The study concluded that in order to combat urban erosion, it is crucial to understand diverse dynamics aggravating the process of urbanisation from different scales. Accordingly, the study suggests that there is an urgent need for the development of urban-specific approaches that aim at: (a) incorporating the diverse socio-economic-environmental aspects influencing erosion, (b) scientifically improving natural cycles that influence water storages and nutrients for plants in urbanised dryland areas in order to increase the amount of vegetation cover, (c) making use of high resolution satellite images to improve the adopted methods for assessing urban erosion, (d) developing water erosion policies, and (e) continuously monitoring the impact of erosion and the influencing processes from local, national and international levels.
A majority of studies documented a reduced ankle muscle activity, particularly of the peroneus longus muscle (PL), in patients with functional ankle instability (FI). It is considered valid that foot orthoses as well as sensorimotor training have a positive effect on ankle muscle activity in healthy individuals and those with lower limb overuse injuries or flat arched feet (reduced reaction time by sensorimotor exercises; increased ankle muscle amplitude by orthoses use). However, the acute- and long-term influence of foot orthoses on ankle muscle activity in individuals with FI is unknown.
AIMS: The present thesis addressed (1a) acute- and (1b) long-term effects of foot orthoses compared to sensorimotor training on ankle muscle activity in patients with FI. (2) Further, it was investigated if the orthosis intervention group demonstrate higher ankle muscle activity by additional short-term use of a measurement in-shoe orthosis (compared to short-term use of “shoe only”) after intervention. (3) As prerequisite, it was evaluated if ankle muscle activity can be tested reliably and (4) if this differs between healthy individuals and those with FI.
METHODS: Three intervention groups (orthosis group [OG], sensorimotor training group [SMTG], control group [CG]), consisting of both, healthy individuals and those with FI, underwent one longitudinal investigation (randomised controlled trial). Throughout 6 weeks of intervention, OG wore an in-shoe orthosis with a specific “PL stimulation module”, whereas SMTG conducted home-based exercises. CG served to measure test-retest reliability of ankle muscle activity (PL, M. tibialis anterior [TA] and M. gastrocnemius medialis [GM]). Pre- and post-intervention, ankle muscle activity (EMG amplitude) was recorded during “normal” unperturbed (NW) and perturbed walking (PW) on a split-belt treadmill (stimulus 200 ms post initial heel contact [IC]) as well as during side cutting (SC), each while wearing “shoes only” and additional measurement in-shoe orthoses (randomized order). Normalized RMS values (100% MVC, mean±SD) were calculated pre- (100-50 ms) and post (200-400 ms) - IC.
RESULTS: (3) Test-retest reliability showed a high range of values in healthy individuals and those with FI. (4) Compared to healthy individuals, patients with FI demonstrated lower PL pre-activity during SC, however higher PL pre-activity for NW and PW. (1a) Acute orthoses use did not influence ankle muscle activity. (1b) For most conditions, sensorimotor training was more effective in individuals with FI than long-term orthotic intervention (increased: PL and GM pre-activity and TA reflex-activity for NW, PL pre-activity and TA, PL and GM reflex-activity for SC, PL reflex-activity for PW). However, prolonged orthoses use was more beneficial in terms of an increase in GM pre-activity during SC. For some conditions, long-term orthoses intervention was as effective as sensorimotor training for individuals with FI (increased: PL pre-activity for PW, TA pre-activity for SC, PL and GM reflex-activity for NW). Prolonged orthoses use was also advantageous in healthy individuals (increased: PL and GM pre-activity for NW and PW, PL pre-activity for SC, TA and PL reflex-activity for NW, PL and GM reflex-activity for PW). (2) The orthosis intervention group did not present higher ankle muscle activity by the additional short-term use of a measurement in-shoe orthosis at re-test after intervention.
CONCLUSION: High variations of reproducibility reflect physiological variability in muscle activity during gait and therefore deemed acceptable. The main findings confirm the presence of sensorimotor long-term effects of specific foot orthoses in healthy individuals (primary preventive effect) and those with FI (therapeutic effect). Neuromuscular compensatory feedback- as well as anticipatory feedforward adaptation mechanism to prolonged orthoses use, specifically of the PL muscle, underpins the key role of PL in providing essential dynamic ankle joint stability. Due to its advantages over sensorimotor training (positive subjective feedback in terms of comfort, time-and-cost-effectiveness), long-term foot orthoses use can be recommended as an applicable therapy alternative in the treatment of FI. Long-term effect of foot orthoses in a population with FI must be validated in a larger sample size with longer follow-up periods to substantiate the generalizability of the existing outcomes.
Over the past decades, rapid and constant advances have motivated GNSS technology to approach the ability to monitor transient ground motions with mm to cm accuracy in real-time. As a result, the potential of using real-time GNSS for natural hazards prediction and early warning has been exploited intensively in recent years, e.g., landslides and volcanic eruptions monitoring. Of particular note, compared with traditional seismic instruments, GNSS does not saturate or tilt in terms of co-seismic displacement retrieving, which makes it especially valuable for earthquake and earthquake induced tsunami early warning. In this thesis, we focus on the application of real-time GNSS to fast seismic source inversion and tsunami early warning.
Firstly, we present a new approach to get precise co-seismic displacements using cost effective single-frequency receivers. As is well known, with regard to high precision positioning, the main obstacle for single-frequency GPS receiver is ionospheric delay. Considering that over a few minutes, the change of ionospheric delay is almost linear, we constructed a linear model for each satellite to predict ionospheric delay. The effectiveness of this method has been validated by an out-door experiment and 2011 Tohoku event, which confirms feasibility of using dense GPS networks for geo-hazard early warning at an affordable cost.
Secondly, we extended temporal point positioning from GPS-only to GPS/GLONASS and assessed the potential benefits of multi-GNSS for co-seismic displacement determination. Out-door experiments reveal that when observations are conducted in an adversary environment, adding a couple of GLONASS satellites could provide more reliable results. The case study of 2015 Illapel Mw 8.3 earthquake shows that the biases between co-seismic displacements derived from GPS-only and GPS/GLONASS vary from station to station, and could be up to 2 cm in horizontal direction and almost 3 cm in vertical direction. Furthermore, slips inverted from GPS/GLONASS co-seismic displacements using a layered crust structure on a curved plane are shallower and larger for the Illapel event.
Thirdly, we tested different inversion tools and discussed the uncertainties of using real-time GNSS for tsunami early warning. To be exact, centroid moment tensor inversion, uniform slip inversion using a single Okada fault and distributed slip inversion in layered crust on a curved plane were conducted using co-seismic displacements recorded during 2014 Pisagua earthquake. While the inversion results give similar magnitude and the rupture center, there are significant differences in depth, strike, dip and rake angles, which lead to different tsunami propagation scenarios. Even though, resulting tsunami forecasting along the Chilean coast is close to each other for all three models.
Finally, based on the fact that the positioning performance of BDS is now equivalent to GPS in Asia-Pacific area and Manila subduction zone has been identified as a zone of potential tsunami hazard, we suggested a conceptual BDS/GPS network for tsunami early warning in South China Sea. Numerical simulations with two earthquakes (Mw 8.0 and Mw 7.5) and induced tsunamis demonstrate the viability of this network. In addition, the advantage of BDS/GPS over a single GNSS system by source inversion grows with decreasing earthquake magnitudes.
Geospatial data has become a natural part of a growing number of information systems and services in the economy, society, and people's personal lives. In particular, virtual 3D city and landscape models constitute valuable information sources within a wide variety of applications such as urban planning, navigation, tourist information, and disaster management. Today, these models are often visualized in detail to provide realistic imagery. However, a photorealistic rendering does not automatically lead to high image quality, with respect to an effective information transfer, which requires important or prioritized information to be interactively highlighted in a context-dependent manner.
Approaches in non-photorealistic renderings particularly consider a user's task and camera perspective when attempting optimal expression, recognition, and communication of important or prioritized information. However, the design and implementation of non-photorealistic rendering techniques for 3D geospatial data pose a number of challenges, especially when inherently complex geometry, appearance, and thematic data must be processed interactively. Hence, a promising technical foundation is established by the programmable and parallel computing architecture of graphics processing units.
This thesis proposes non-photorealistic rendering techniques that enable both the computation and selection of the abstraction level of 3D geospatial model contents according to user interaction and dynamically changing thematic information. To achieve this goal, the techniques integrate with hardware-accelerated rendering pipelines using shader technologies of graphics processing units for real-time image synthesis. The techniques employ principles of artistic rendering, cartographic generalization, and 3D semiotics—unlike photorealistic rendering—to synthesize illustrative renditions of geospatial feature type entities such as water surfaces, buildings, and infrastructure networks. In addition, this thesis contributes a generic system that enables to integrate different graphic styles—photorealistic and non-photorealistic—and provide their seamless transition according to user tasks, camera view, and image resolution.
Evaluations of the proposed techniques have demonstrated their significance to the field of geospatial information visualization including topics such as spatial perception, cognition, and mapping. In addition, the applications in illustrative and focus+context visualization have reflected their potential impact on optimizing the information transfer regarding factors such as cognitive load, integration of non-realistic information, visualization of uncertainty, and visualization on small displays.
The ever-increasing fat content in Western diet, combined with decreased levels of physical activity, greatly enhance the incidence of metabolic-related diseases. Cancer cachexia (CC) and Metabolic syndrome (MetS) are both multifactorial highly complex metabolism related syndromes, whose etiology is not fully understood, as the mechanisms underlying their development are not completely unveiled. Nevertheless, despite being considered “opposite sides”, MetS and CC share several common issues such as insulin resistance and low-grade inflammation. In these scenarios, tissue macrophages act as key players, due to their capacity to produce and release inflammatory mediators. One of the main features of MetS is hyperinsulinemia, which is generally associated with an attempt of the β-cell to compensate for diminished insulin sensitivity (insulin resistance). There is growing evidence that hyperinsulinemia per se may contribute to the development of insulin resistance, through the establishment of low grade inflammation in insulin responsive tissues, especially in the liver (as insulin is secreted by the pancreas into the portal circulation). The hypothesis of the present study was that insulin may itself provoke an inflammatory response culminating in diminished hepatic insulin sensitivity. To address this premise, firstly, human cell line U937 differentiated macrophages were exposed to insulin, LPS and PGE2. In these cells, insulin significantly augmented the gene expression of the pro-inflammatory mediators IL-1β, IL-8, CCL2, Oncostatin M (OSM) and microsomal prostaglandin E2 synthase (mPGES1), and of the anti-inflammatory mediator IL-10. Moreover, the synergism between insulin and LPS enhanced the induction provoked by LPS in IL-1β, IL-8, IL-6, CCL2 and TNF-α gene. When combined with PGE2, insulin enhanced the induction provoked by PGE2 in IL-1β, mPGES1 and COX2, and attenuated the inhibition induced by PGE2 in CCL2 and TNF-α gene expression contributing to an enhanced inflammatory response by both mechanisms. Supernatants of insulin-treated U937 macrophages reduced the insulin-dependent induction of glucokinase in hepatocytes by 50%. Cytokines contained in the supernatant of insulin-treated U937 macrophages also activated hepatocytes ERK1/2, resulting in inhibitory serine phosphorylation of the insulin receptor substrate. Additionally, the transcription factor STAT3 was activated by phosphorylation resulting in the induction of SOCS3, which is capable of interrupting the insulin receptor signal chain. MicroRNAs, non-coding RNAs linked to protein expression regulation, nowadays recognized as active players in the generation of several inflammatory disorders such as cancer and type II diabetes are also of interest. Considering that in cancer cachexia, patients are highly affected by insulin resistance and inflammation, control, non-cachectic and cachectic cancer patients were selected and the respective circulating levels of pro-inflammatory mediators and microRNA-21-5p, a posttranscriptional regulator of STAT3 expression, assessed and correlated. Cachectic patients circulating cytokines IL-6 and IL-8 levels were significantly higher than those of non-cachectic and controls, and the expression of microRNA-21-5p was significantly lower. Additionally, microRNA-21-5p reduced expression correlated negatively with IL-6 plasma levels. These results indicate that hyperinsulinemia per se might contribute to the low grade inflammation prevailing in MetS patients and thereby promote the development
of insulin resistance particularly in the liver. Diminished MicroRNA-21-5p expression may enhance inflammation and STAT3 expression in cachectic patients, contributing to the development of insulin resistance.
Change points in time series are perceived as heterogeneities in the statistical or dynamical characteristics of the observations. Unraveling such transitions yields essential information for the understanding of the observed system’s intrinsic evolution and potential external influences. A precise detection of multiple changes is therefore of great importance for various research disciplines, such as environmental sciences, bioinformatics and economics. The primary purpose of the detection approach introduced in this thesis is the investigation of transitions underlying direct or indirect climate observations. In order to develop a diagnostic approach capable to capture such a variety of natural processes, the generic statistical features in terms of central tendency and dispersion are employed in the light of Bayesian inversion. In contrast to established Bayesian approaches to multiple changes, the generic approach proposed in this thesis is not formulated in the framework of specialized partition models of high dimensionality requiring prior specification, but as a robust kernel-based approach of low dimensionality employing least informative prior distributions.
First of all, a local Bayesian inversion approach is developed to robustly infer on the location and the generic patterns of a single transition. The analysis of synthetic time series comprising changes of different observational evidence, data loss and outliers validates the performance, consistency and sensitivity of the inference algorithm. To systematically investigate time series for multiple changes, the Bayesian inversion is extended to a kernel-based inference approach. By introducing basic kernel measures, the weighted kernel inference results are composed into a proxy probability to a posterior distribution of multiple transitions. The detection approach is applied to environmental time series from the Nile river in Aswan and the weather station Tuscaloosa, Alabama comprising documented changes. The method’s performance confirms the approach as a powerful diagnostic tool to decipher multiple changes underlying direct climate observations.
Finally, the kernel-based Bayesian inference approach is used to investigate a set of complex terrigenous dust records interpreted as climate indicators of the African region of the Plio-Pleistocene period. A detailed inference unravels multiple transitions underlying the indirect climate observations, that are interpreted as conjoint changes. The identified conjoint changes coincide with established global climate events. In particular, the two-step transition associated to the establishment of the modern Walker-Circulation contributes to the current discussion about the influence of paleoclimate changes on the environmental conditions in tropical and subtropical Africa at around two million years ago.
This doctoral thesis seeks to elaborate how Wittgenstein’s very sparse writings on ethics and ethical thought, together with his later work on the more general problem of normativity and his approach to philosophical problems as a whole, can be applied to contemporary meta-ethical debates about the nature of moral thought and language and the sources of moral obligation. I begin with a discussion of Wittgenstein’s early “Lecture on Ethics”, distinguishing the thesis of a strict fact/value dichotomy that Wittgenstein defends there from the related thesis that all ethical discourse is essentially and intentionally nonsensical, an attempt to go beyond the limits of sense. The first chapter discusses and defends Wittgenstein’s argument that moral valuation always goes beyond any ascertaining of fact; the second chapter seeks to draw out the valuable insights from Wittgenstein’s (early) insistence that value discourse is nonsensical while also arguing that this thesis is ultimately untenable and also incompatible with later Wittgensteinian understanding of language. On the basis of this discussion I then take up the writings of the American philosopher Cora Diamond, who has worked out an ethical approach in a very closely Wittgensteinian spirit, and show how this approach shares many of the valuable insights of the moral expressivism and constructivism of contemporary authors such as Blackburn and Korsgaard while suggesting a way to avoid some of the problems and limitations of their approaches. Subsequently I turn to a criticism of the attempts by Lovibond and McDowell to enlist Wittgenstein in the support for a non-naturalist moral realism. A concluding chapter treats the ways that a broadly Wittgensteinian conception expands the subject of metaethics itself by questioning the primacy of discursive argument in moral thought and of moral propositions as the basic units of moral belief.
Light-triggered release of bioactive compounds from HA/PLL multilayer films for stimulation of cells
(2016)
The concept of targeting cells and tissues by controlled delivery of molecules is essential in the field of biomedicine. The layer-by-layer (LbL) technology for the fabrication of polymer multilayer films is widely implemented as a powerful tool to assemble tailor-made materials for controlled drug delivery. The LbL films can as well be engineered to act as mimics of the natural cellular microenvironment. Thus, due to the myriad possibilities such as controlled cellular adhesion and drug delivery offered by LbL films, it becomes easily achievable to direct the fate of cells by growing them on the films.
The aim of this work was to develop an approach for non-invasive and precise control of the presentation of bioactive molecules to cells. The strategy is based on employment of the LbL films, which function as support for cells and at the same time as reservoirs for bioactive molecules to be released in a controlled manner. UV light is used to trigger the release of the stored ATP with high spatio-temporal resolution. Both physico-chemical (competitive intermolecular interactions in the film) and biological aspects (cellular response and viability) are addressed in this study.
Biopolymers hyaluronic acid (HA) and poly-L-lysine (PLL) were chosen as the building blocks for the LbL film assembly. Poor cellular adhesion to native HA/PLL films as well as significant degradation by cells within a few days were shown. However, coating the films with gold nanoparticles not only improved cellular adhesion and protected the films from degradation, but also formed a size-exclusion barrier with adjustable cut-off in the size range of a few tens of kDa.
The films were shown to have high reservoir capacity for small charged molecules (reaching mM levels in the film). Furthermore, they were able to release the stored molecules in a sustained manner. The loading and release are explained by a mechanism based on interactions between charges of the stored molecules and uncompensated charges of the biopolymers in the film. Charge balance and polymer dynamics in the film play the pivotal role.
Finally, the concept of light-triggered release from the films has been proven using caged ATP loaded into the films from which ATP was released on demand. ATP induces a fast cellular response, i.e. increase in intracellular [Ca2+], which was monitored in real-time. Limitations of the cellular stimulation by the proposed approach are highlighted by studying the stimulation as a function of irradiation parameters (time, distance, light power). Moreover, caging molecules bind to the film stronger than ATP does, which opens new perspectives for the use of the most diverse chemical compounds as caging molecules.
Employment of HA/PLL films as a nouvelle support for cellular growth and hosting of bioactive molecules, along with the possibility to stimulate individual cells using focused light renders this approach highly efficient and unique in terms of precision and spatio-temporal resolution among those previously described. With its high potential, the concept presented herein provides the foundation for the design of new intelligent materials for single cell studies, with the focus on tissue engineering, diagnostics, and other cell-based applications.
The Milky Way is only one out of billions of galaxies in the universe. However, it is a special galaxy because it allows to explore the main mechanisms involved in its evolution and formation history by unpicking the system star-by-star. Especially, the chemical fingerprints of its stars provide clues and evidence of past events in the Galaxy’s lifetime. These information help not only to decipher the current structure and building blocks of the Milky Way, but to learn more about the general formation process of galaxies.
In the past decade a multitude of stellar spectroscopic Galactic surveys have scanned millions of stars far beyond the rim of the solar neighbourhood. The obtained spectroscopic information provide unprecedented insights to the chemo-dynamics of the Milky Way. In addition analytic models and numerical simulations of the Milky Way provide necessary descriptions and predictions suited for comparison with observations in order to decode the physical properties that underlie the complex system of the Galaxy.
In the thesis various approaches are taken to connect modern theoretical modelling of galaxy formation and evolution with observations from Galactic stellar surveys. With its focus on the chemo-kinematics of the Galactic disk this work aims to determine new observational constraints on the formation of the Milky Way providing also proper comparisons with two different models. These are the population synthesis model TRILEGAL based on analytical distribution functions, which aims to simulate the number and distribution of stars in the Milky Way and its different components, and a hybrid model (MCM) that combines an N-body simulation of a Milky Way like galaxy in the cosmological framework with a semi-analytic chemical evolution model for the Milky Way. The major observational data sets in use come from two surveys, namely the “Radial Velocity Experiment” (RAVE) and the “Sloan Extension for Galactic Understanding and Exploration” (SEGUE).
In the first approach the chemo-kinematic properties of the thin and thick disk of the Galaxy as traced by a selection of about 20000 SEGUE G-dwarf stars are directly compared to the predictions by the MCM model. As a necessary condition for this, SEGUE's selection function and its survey volume are evaluated in detail to correct the spectroscopic observations for their survey specific selection biases. Also, based on a Bayesian method spectro-photometric distances with uncertainties below 15% are computed for the selection of SEGUE G-dwarfs that are studied up to a distance of 3 kpc from the Sun.
For the second approach two synthetic versions of the SEGUE survey are generated based on the above models. The obtained synthetic stellar catalogues are then used to create mock samples best resembling the compiled sample of observed SEGUE G-dwarfs. Generally, mock samples are not only ideal to compare predictions from various models. They also allow validation of the models' quality and improvement as with this work could be especially achieved for TRILEGAL. While TRILEGAL reproduces the statistical properties of the thin and thick disk as seen in the observations, the MCM model has shown to be more suitable in reproducing many chemo-kinematic correlations as revealed by the SEGUE stars. However, evidence has been found that the MCM model may be missing a stellar component with the properties of the thick disk that the observations clearly show. While the SEGUE stars do indicate a thin-thick dichotomy of the stellar Galactic disk in agreement with other spectroscopic stellar studies, no sign for a distinct metal-poor disk is seen in the MCM model.
Usually stellar spectroscopic surveys are limited to a certain volume around the Sun covering different regions of the Galaxy’s disk. This often prevents to obtain a global view on the chemo-dynamics of the Galactic disk. Hence, a suitable combination of stellar samples from independent surveys is not only useful for the verification of results but it also helps to complete the picture of the Milky Way. Therefore, the thesis closes with a comparison of the SEGUE G-dwarfs and a sample of RAVE giants. The comparison reveals that the chemo-kinematic relations agree in disk regions where the samples of both surveys show a similar number of stars. For those parts of the survey volumes where one of the surveys lacks statistics they beautifully complement each other. This demonstrates that the comparison of theoretical models on the one side, and the combined observational data gathered by multiple surveys on the other side, are key ingredients to understand and disentangle the structure and formation history of the Milky Way.
Proteins are natural polypeptides produced by cells; they can be found in both animals and plants, and possess a variety of functions. One of these functions is to provide structural support to the surrounding cells and tissues. For example, collagen (which is found in skin, cartilage, tendons and bones) and keratin (which is found in hair and nails) are structural proteins. When a tissue is damaged, however, the supporting matrix formed by structural proteins cannot always spontaneously regenerate. Tailor-made synthetic polypeptides can be used to help heal and restore tissue formation.
Synthetic polypeptides are typically synthesized by the so-called ring opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCA). Such synthetic polypeptides are generally non-sequence-controlled and thus less complex than proteins. As such, synthetic polypeptides are rarely as efficient as proteins in their ability to self-assemble and form hierarchical or structural supramolecular assemblies in water, and thus, often require rational designing. In this doctoral work, two types of amino acids, γ-benzyl-L/D-glutamate (BLG / BDG) and allylglycine (AG), were selected to synthesize a series of (co)polypeptides of different compositions and molar masses.
A new and versatile synthetic route to prepare polypeptides was developed, and its mechanism and kinetics were investigated. The polypeptide properties were thoroughly studied and new materials were developed from them. In particular, these polypeptides were able to aggregate (or self-assemble) in solution into microscopic fibres, very similar to those formed by collagen. By doing so, they formed robust physical networks and organogels which could be processed into high water-content, pH-responsive hydrogels. Particles with highly regular and chiral spiral morphologies were also obtained by emulsifying these polypeptides. Such polypeptides and the materials derived from them are, therefore, promising candidates for biomedical applications.
Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called “hot spots”, have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information.
Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA
(dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules.
In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that
single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami
substrates very well, which enables the monitoring of structural alterations by AFM imaging.
In this way, it is shown that graphene encapsulation significantly increases the structural
stability of bare DNA origami substrates towards mechanical force and prolonged exposure
to deionized water.
Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a
40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits
several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice.
Although SLG can significantly influence the SERS substrate in the aforementioned ways, all
those effects are strongly related to the extent of contact with the underlying AuNP dimer.
Ionothermal carbon materials
(2016)
Alternative concepts for energy storage and conversion have to be developed, optimized and employed to fulfill the dream of a fossil-independent energy economy. Porous carbon materials play a major role in many energy-related devices. Among different characteristics, distinct porosity features, e.g., specific surface area (SSA), total pore volume (TPV), and the pore size distribution (PSD), are important to maximize the performance in the final device. In order to approach the aim to synthesize carbon materials with tailor-made porosity in a sustainable fashion, the present thesis focused on biomass-derived precursors employing and developing the ionothermal carbonization.
During the ionothermal carbonization, a salt melt simultaneously serves as solvent and porogen. Typically, eutectic mixtures containing zinc chloride are employed as salt phase. The first topic of the present thesis addressed the possibility to precisely tailor the porosity of ionothermal carbon materials by an experimentally simple variation of the molar composition of the binary salt mixture. The developed pore tuning tool allowed the synthesis of glucose derived carbon materials with predictable SSAs in the range of ~ 900 to ~ 2100 m2 g-1. Moreover, the nucleobase adenine was employed as precursor introducing nitrogen functionalities in the final material. Thereby, the chemical properties of the carbon materials are varied leading to new application fields. Nitrogen doped carbons (NDCs) are able to catalyze the oxygen reduction reaction (ORR) which takes place on the cathodic site of a fuel cell. The herein developed porosity tailoring allowed the synthesis of adenine derived NDCs with outstanding SSAs of up to 2900 m2 g-1 and very large TPV of 5.19 cm3 g-1. Furthermore, the influence of the porosity on the ORR could be directly investigated enabling the precise optimization of the porosity characteristics of NDCs for this application. The second topic addressed the development of a new method to investigate the not-yet unraveled mechanism of the oxygen reduction reaction using a rotating disc electrode setup. The focus was put on noble-metal free catalysts. The results showed that the reaction pathway of the investigated catalysts is pH-dependent indicating different active species at different pH-values. The third topic addressed the expansion of the used salts for the ionothermal approach towards hydrated calcium and magnesium chloride. It was shown that hydrated salt phases allowed the introduction of a secondary templating effect which was connected to the coexistence of liquid and solid salt phases. The method enabled the synthesis of fibrous NDCs with SSAs of up to 2780 m2 g-1 and very large TPV of 3.86 cm3 g-1. Moreover, the concept of active site implementation by a facile low-temperature metalation employing the obtained NDCs as solid ligands could be shown for the first time in the context of ORR.
Overall, the thesis may pave the way towards highly porous carbon with tailor-made porosity materials prepared by an inexpensive and sustainable pathway, which can be applied in energy related field thereby supporting the needed expansion of the renewable energy sector.
In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes.
The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer.
The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts.
En route towards advanced catalyst materials for the electrocatalytic water splitting reaction
(2016)
The thesis on hand deals with the development of new types of catalysts based on pristine metals and ceramic materials and their application as catalysts for the electrocatalytic water splitting reaction. In order to breathe life into this technology, cost-efficient, stable and efficient catalysts are imploringly desired. In this manner, the preparation of Mn-, N-, S-, P-, and C-containing nickel materials has been investigated together with the theoretical and electrochemical elucidation of their activity towards the hydrogen (and oxygen) evolution reaction. The Sabatier principle has been used as the principal guideline towards successful tuning of catalytic sites. Furthermore, two pathways have been chosen to ameliorate the electrocatalytic performance, namely, the direct improvement of intrinsic properties through appropriate material selection and secondly the increase of surface area of the catalytic material with an increased amount of active sites. In this manner, bringing materials with optimized hydrogen adsorption free energy onto high surface area support, catalytic performances approaching the golden standards of noble metals were feasible. Despite varying applied synthesis strategies (wet chemistry in organic solvents, ionothermal reaction, gas phase reaction), one goal has been systematically pursued: to understand the driving mechanism of the growth. Moreover, deeper understanding of inherent properties and kinetic parameters of the catalytic materials has been gained.
Eye movements serve as a window into ongoing visual-cognitive processes and can thus be used to investigate how people perceive real-world scenes. A key issue for understanding eye-movement control during scene viewing is the roles of central and peripheral vision, which process information differently and are therefore specialized for different tasks (object identification and peripheral target selection respectively). Yet, rather little is known about the contributions of central and peripheral processing to gaze control and how they are coordinated within a fixation during scene viewing. Additionally, the factors determining fixation durations have long been neglected, as scene perception research has mainly been focused on the factors determining fixation locations. The present thesis aimed at increasing the knowledge on how central and peripheral vision contribute to spatial and, in particular, to temporal aspects of eye-movement control during scene viewing. In a series of five experiments, we varied processing difficulty in the central or the peripheral visual field by attenuating selective parts of the spatial-frequency spectrum within these regions. Furthermore, we developed a computational model on how foveal and peripheral processing might be coordinated for the control of fixation duration. The thesis provides three main findings. First, the experiments indicate that increasing processing demands in central or peripheral vision do not necessarily prolong fixation durations; instead, stimulus-independent timing is adapted when processing becomes too difficult. Second, peripheral vision seems to play a prominent role in the control of fixation durations, a notion also implemented in the computational model. The model assumes that foveal and peripheral processing proceed largely in parallel and independently during fixation, but can interact to modulate fixation duration. Thus, we propose that the variation in fixation durations can in part be accounted for by the interaction between central and peripheral processing. Third, the experiments indicate that saccadic behavior largely adapts to processing demands, with a bias of avoiding spatial-frequency filtered scene regions as saccade targets. We demonstrate that the observed saccade amplitude patterns reflect corresponding modulations of visual attention. The present work highlights the individual contributions and the interplay of central and peripheral vision for gaze control during scene viewing, particularly for the control of fixation duration. Our results entail new implications for computational models and for experimental research on scene perception.
The aim of this thesis was the elucidation of different ionization methods (resonance-enhanced multiphoton ionization – REMPI, electrospray ionization – ESI, atmospheric pressure chemical ionization – APCI) in ion mobility (IM) spectrometry. In order to gain a better understanding of the ionization processes, several spectroscopic, mass spectrometric and theoretical methods were also used. Another focus was the development of experimental techniques, including a high resolution spectrograph and various combinations of IM and mass spectrometry.
The novel high resolution 2D spectrograph facilitates spectroscopic resolutions in the range of commercial echelle spectrographs. The lowest full width at half maximum of a peak achieved was 25 pm. The 2D spectrograph is based on the wavelength separation of light by the combination of a prism and a grating in one dimension, and an etalon in the second dimension. This instrument was successfully employed for the acquisition of Raman and laser-induced breakdown spectra.
Different spectroscopic methods (light scattering and fluorescence spectroscopy) permitting a spatial as well as spectral resolution, were used to investigate the release of ions in the electrospray. The investigation is based on the 50 nm shift of the fluorescence band of rhodamine 6G ions of during the transfer from the electrospray droplets to the gas phase.
A newly developed ionization chamber operating at reduced pressure (0.5 mbar) was coupled to a time-of-flight mass spectrometer. After REMPI of H2S, an ionization chemistry analogous to H2O was observed with this instrument. Besides H2S+ and its fragments, H3S+ and protonated analyte ions could be observed as a result of proton-transfer reactions.
For the elucidation of the peaks in IM spectra, a combination of IM spectrometer and linear quadrupole ion trap mass spectrometer was developed. The instrument can be equipped with various ionization sources (ESI, REMPI, APCI) and was used for the characterization of the peptide bradykinin and the neuroleptic promazine.
The ionization of explosive compounds in an APCI source based on soft x-radiation was investigated in a newly developed ionization chamber attached to the ion trap mass spectrometer. The major primary and secondary reactions could be characterized and explosive compound ions could be identified and assigned to the peaks in IM spectra. The assignment is based on the comparison of experimentally determined and calculated IM. The methods of calculation currently available exhibit large deviations, especially in the case of anions. Therefore, on the basis of an assessment of available methods, a novel hybrid method was developed and characterized.
Foam fractionation of surfactant and protein solutions is a process dedicated to separate surface active molecules from each other due to their differences in surface activities. The process is based on forming bubbles in a certain mixed solution followed by detachment and rising of bubbles through a certain volume of this solution, and consequently on the formation of a foam layer on top of the solution column. Therefore, systematic analysis of this whole process comprises of at first investigations dedicated to the formation and growth of single bubbles in solutions, which is equivalent to the main principles of the well-known bubble pressure tensiometry. The second stage of the fractionation process includes the detachment of a single bubble from a pore or capillary tip and its rising in a respective aqueous solution. The third and final stage of the process is the formation and stabilization of the foam created by these bubbles, which contains the adsorption layers formed at the growing bubble surface, carried up and gets modified during the bubble rising and finally ends up as part of the foam layer.
Bubble pressure tensiometry and bubble profile analysis tensiometry experiments were performed with protein solutions at different bulk concentrations, solution pH and ionic strength in order to describe the process of accumulation of protein and surfactant molecules at the bubble surface. The results obtained from the two complementary methods allow understanding the mechanism of adsorption, which is mainly governed by the diffusional transport of the adsorbing protein molecules to the bubble surface. This mechanism is the same as generally discussed for surfactant molecules. However, interesting peculiarities have been observed for protein adsorption kinetics at sufficiently short adsorption times. First of all, at short adsorption times the surface tension remains constant for a while before it decreases as expected due to the adsorption of proteins at the surface. This time interval is called induction time and it becomes shorter with increasing protein bulk concentration. Moreover, under special conditions, the surface tension does not stay constant but even increases over a certain period of time. This so-called negative surface pressure was observed for BCS and BLG and discussed for the first time in terms of changes in the surface conformation of the adsorbing protein molecules. Usually, a negative surface pressure would correspond to a negative adsorption, which is of course impossible for the studied protein solutions. The phenomenon, which amounts to some mN/m, was rather explained by simultaneous changes in the molar area required by the adsorbed proteins and the non-ideality of entropy of the interfacial layer. It is a transient phenomenon and exists only under dynamic conditions.
The experiments dedicated to the local velocity of rising air bubbles in solutions were performed in a broad range of BLG concentration, pH and ionic strength. Additionally, rising bubble experiments were done for surfactant solutions in order to validate the functionality of the instrument. It turns out that the velocity of a rising bubble is much more sensitive to adsorbing molecules than classical dynamic surface tension measurements. At very low BLG or surfactant concentrations, for example, the measured local velocity profile of an air bubble is changing dramatically in time scales of seconds while dynamic surface tensions still do not show any measurable changes at this time scale. The solution’s pH and ionic strength are important parameters that govern the measured rising velocity for protein solutions. A general theoretical description of rising bubbles in surfactant and protein solutions is not available at present due to the complex situation of the adsorption process at a bubble surface in a liquid flow field with simultaneous Marangoni effects. However, instead of modelling the complete velocity profile, new theoretical work has been started to evaluate the maximum values in the profile as characteristic parameter for dynamic adsorption layers at the bubble surface more quantitatively.
The studies with protein-surfactant mixtures demonstrate in an impressive way that the complexes formed by the two compounds change the surface activity as compared to the original native protein molecules and therefore lead to a completely different retardation behavior of rising bubbles. Changes in the velocity profile can be interpreted qualitatively in terms of increased or decreased surface activity of the formed protein-surfactant complexes. It was also observed that the pH and ionic strength of a protein solution have strong effects on the surface activity of the protein molecules, which however, could be different on the rising bubble velocity and the equilibrium adsorption isotherms. These differences are not fully understood yet but give rise to discussions about the structure of protein adsorption layer under dynamic conditions or in the equilibrium state.
The third main stage of the discussed process of fractionation is the formation and characterization of protein foams from BLG solutions at different pH and ionic strength. Of course a minimum BLG concentration is required to form foams. This minimum protein concentration is a function again of solution pH and ionic strength, i.e. of the surface activity of the protein molecules. Although at the isoelectric point, at about pH 5 for BLG, the hydrophobicity and hence the surface activity should be the highest, the concentration and ionic strength effects on the rising velocity profile as well as on the foamability and foam stability do not show a maximum. This is another remarkable argument for the fact that the interfacial structure and behavior of BLG layers under dynamic conditions and at equilibrium are rather different. These differences are probably caused by the time required for BLG molecules to adapt respective conformations once they are adsorbed at the surface.
All bubble studies described in this work refer to stages of the foam fractionation process. Experiments with different systems, mainly surfactant and protein solutions, were performed in order to form foams and finally recover a solution representing the foamed material. As foam consists to a large extent of foam lamella – two adsorption layers with a liquid core – the concentration in a foamate taken from foaming experiments should be enriched in the stabilizing molecules. For determining the concentration of the foamate, again the very sensitive bubble rising velocity profile method was applied, which works for any type of surface active materials. This also includes technical surfactants or protein isolates for which an accurate composition is unknown.
We do magnetohydrodynamic (MHD) simulations of local box models of turbulent Interstellar Medium (ISM) and analyse the process of amplification and saturation of mean magnetic fields with methods of mean field dynamo theory. It is shown that the process of saturation of mean fields can be partially described by the prolonged diffusion time scales in presence of the dynamically significant magnetic fields. However, the outward wind also plays an essential role in the saturation in higher SN rate case. Algebraic expressions for the back reaction of the magnetic field onto the turbulent transport coefficients are derived, which allow a complete description of the nonlinear dynamo. We also present the effects of dynamically significant mean fields on the ISM configuration and pressure distribution. We further add the cosmic ray component in the simulations and investigate the kinematic growth of mean fields with a dynamo perspective.
Exhaustivity
(2016)
The dissertation proposes an answer to the question of how to model exhaustive inferences and what the meaning of the linguistic material that triggers these inferences is. In particular, it deals with the semantics of exclusive particles, clefts, and progressive aspect in Ga, an under-researched language spoken in Ghana. Based on new data coming from the author’s original fieldwork in Accra, the thesis points to a previously unattested variation in the semantics of exclusives in a cross-linguistic perspective, analyzes the connections between exhaustive interpretation triggered by clefts and the aspectual interpretation of the sentence, and identifies a cross-categorial definite determiner. By that it sheds new light on several exhaustivity-related phenomena in both the nominal and the verbal domain and shows that both domains are closely connected.
Dietary approaches contribute to the prevention and treatment of type 2 diabetes. High protein diets were shown to exert beneficial as well as adverse effects on metabolism. However, it is unclear whether the protein origin plays a role in these effects. The LeguAN study investigated in detail the effects of two high protein diets, either from plant or animal origin, in type 2 diabetic patients. Both diets contained 30 EN% protein, 40 EN% carbohydrates, and 30 EN% fat. Fiber content, glycemic index, and composition of dietary fats were similar in both diets. In comparison to previous dietary habits, the fat content was exchanged for protein, while the carbohydrate intake was not modified. Overall, both high protein diets led to improvements of glycemic control, insulin sensitivity, liver fat, and cardiovascular risk markers without remarkable differences between the protein types.
Fasting glucose together with indices of insulin resistance were ameliorated by both interventions to varying extents but without significant differences between protein types. The decline of HbA1c was more pronounced in the plant protein group, whereby the improvement of insulin sensitivity in the animal protein group. The high protein intake had only slight influence on postprandial metabolism seen for free fatty acids and indices of insulin secretion, sensitivity and degradation. Except for GIP release, ingestion of animal and plant meals did not provoke differential metabolic and hormonal responses despite diverse circulating amino acid levels.
The animal protein diets led to a selective increase of fat-free mass and decrease of total fat mass, which was not significantly different from the plant protein diet. Moreover, the high protein diets potently decreased liver fat content by 42% on average which was linked to significantly diminished lipogenesis, free fatty acids flux and lipolysis in adipose tissue. Moderate decline of circulating liver enzymes was induced by both interventions. The liver fat reduction was associated with improved glucose homeostasis and insulin sensitivity which underlines the protective effect of the diets.
Blood lipid profile improved in all subjects and was probably related to the lower fat intake. Reductions in uric acid and markers of inflammation further argued for metabolic benefits of both high protein diets. Systolic and diastolic blood pressure declined only in the PP group pointing a possible role of arginine.
Kidney function was not altered by high protein consumption over 6 weeks. The rapid decrease of serum creatinine in the PP group was noteworthy and should be further investigated. Protein type did not seem to play a role but long-term studies are warranted to fully elucidate safety of high protein regimen.
Varying the source of dietary proteins did not affect the mTOR pathway in adipose tissue and blood cells under neither acute nor chronic settings. Enhancement of whole-body insulin sensitivity suggested also no alteration of mTOR and no impairment of insulin sensitivity in skeletal muscle.
A remarkable outcome was the extensive reduction of FGF21, critical regulator of metabolic processes, by approximately 50% independently of protein type. Whether hepatic ER-stress, ammonia flux or rather macronutrient preferences is behind this paradoxical finding remains to be investigated in detail.
Unlike initial expectations and previous reports plant protein based diet had no clear advantage over animal proteins. The pronounced beneficial effect of animal protein on insulin homeostasis despite high BCAA and methionine intake was certainly unexpected assuming more complex metabolic adaptations occurring upon prolonged consumption. In addition, the reduced fat intake may have also contributed to the overall improvements in both groups.
Taking into account the above observed study results, a short-term diet containing 30 EN% protein (either from plant or animal origin), 40 EN% carbohydrates, and 30 EN% fat with lower SFA amount leads to metabolic improvements in diabetic patients, regardless of protein source.
This work reports about new high-resolution imaging and spectroscopic observations of solar type III radio bursts at low radio frequencies in the range from 30 to 80 MHz. Solar type III radio bursts are understood as result of the beam-plasma interaction of electron beams in the corona. The Sun provides a unique opportunity to study these plasma processes of an active star. Its activity appears in eruptive events like flares, coronal mass ejections and radio bursts which are all accompanied by enhanced radio emission. Therefore solar radio emission carries important information about plasma processes associated with the Sun’s activity. Moreover, the Sun’s atmosphere is a unique plasma laboratory with plasma processes under conditions not found in terrestrial laboratories. Because of the Sun’s proximity to Earth, it can be studied in greater detail than any other star but new knowledge about the Sun can be transfer to them. This “solar stellar connection” is important for the understanding of processes on other stars.
The novel radio interferometer LOFAR provides imaging and spectroscopic capabilities to study these processes at low frequencies. Here it was used for solar observations.
LOFAR, the characteristics of its solar data and the processing and analysis of the latter with the Solar Imaging Pipeline and Solar Data Center are described. The Solar Imaging Pipeline is the central software that allows using LOFAR for solar observations. So its development was necessary for the analysis of solar LOFAR data and realized here. Moreover a new density model with heat conduction and Alfvén waves was developed that provides the distance of radio bursts to the Sun from dynamic radio spectra.
Its application to the dynamic spectrum of a type III burst observed on March 16, 2016 by LOFAR shows a nonuniform radial propagation velocity of the radio emission. The analysis of an imaging observation of type III bursts on June 23, 2012 resolves a burst as bright, compact region localized in the corona propagating in radial direction along magnetic field lines with an average velocity of 0.23c. A nonuniform propagation velocity is revealed. A new beam model is presented that explains the nonuniform motion of the radio source as a propagation effect of an electron ensemble with a spread velocity distribution and rules out a monoenergetic electron distribution. The coronal electron number density is derived in the region from 1.5 to 2.5 R☉ and fitted with the newly developed density model. It determines the plasma density for the interplanetary space between Sun and Earth. The values correspond to a 1.25- and 5-fold Newkirk model for harmonic and fundamental emission, respectively. In comparison to data from other radio instruments the LOFAR data shows a high sensitivity and resolution in space, time and frequency.
The new results from LOFAR’s high resolution imaging spectroscopy are consistent with current theories of solar type III radio bursts and demonstrate its capability to track fast moving radio sources in the corona. LOFAR solar data is found to be a valuable source for solar radio physics and opens a new window for studying plasma processes associated with highly energetic electrons in the solar corona.
Complex networks are ubiquitous in nature and society. They appear in vastly different domains, for instance as social networks, biological interactions or communication networks. Yet in spite of their different origins, these networks share many structural characteristics. For instance, their degree distribution typically follows a power law. This means that the fraction of vertices of degree k is proportional to k^(−β) for some constant β; making these networks highly inhomogeneous. Furthermore, they also typically have high clustering, meaning that links between two nodes are more likely to appear if they have a neighbor in common.
To mathematically study the behavior of such networks, they are often modeled as random graphs. Many of the popular models like inhomogeneous random graphs or Preferential Attachment excel at producing a power law degree distribution. Clustering, on the other hand, is in these models either not present or artificially enforced.
Hyperbolic random graphs bridge this gap by assuming an underlying geometry to the graph: Each vertex is assigned coordinates in the hyperbolic plane, and two vertices are connected if they are nearby. Clustering then emerges as a natural consequence: Two nodes joined by an edge are close by and therefore have many neighbors in common. On the other hand, the exponential expansion of space in the hyperbolic plane naturally produces a power law degree sequence. Due to the hyperbolic geometry, however, rigorous mathematical treatment of this model can quickly become mathematically challenging.
In this thesis, we improve upon the understanding of hyperbolic random graphs by studying its structural and algorithmical properties. Our main contribution is threefold. First, we analyze the emergence of cliques in this model. We find that whenever the power law exponent β is 2 < β < 3, there exists a clique of polynomial size in n. On the other hand, for β >= 3, the size of the largest clique is logarithmic; which severely contrasts previous models with a constant size clique in this case. We also provide efficient algorithms for finding cliques if the hyperbolic node coordinates are known. Second, we analyze the diameter, i. e., the longest shortest path in the graph. We find
that it is of order O(polylog(n)) if 2 < β < 3 and O(logn) if β > 3. To complement
these findings, we also show that the diameter is of order at least Ω(logn). Third, we provide an algorithm for embedding a real-world graph into the hyperbolic plane using only its graph structure. To ensure good quality of the embedding, we perform extensive computational experiments on generated hyperbolic random graphs. Further, as a proof of concept, we embed the Amazon product recommendation network and observe that products from the same category are mapped close together.
In the past decades, development cooperation (DC) led by conventional bi- and multilateral donors has been joined by a large number of small, private or public-private donors. This pluralism of actors raises questions as to whether or not these new donors are able to implement projects more or less effectively than their conventional counterparts. In contrast to their predecessors, the new donors have committed themselves to be more pragmatic, innovative and flexible in their development cooperation measures. However, they are also criticized for weakening the function of local civil society and have the reputation of being an intransparent and often controversial alternative to public services. With additional financial resources and their new approach to development, the new donors have been described in the literature as playing a controversial role in transforming development cooperation. This dissertation compares the effectiveness of initiatives by new and conventional donors with regard to the provision of public goods and services to the poor in the water and sanitation sector in India.
India is an emerging country but it is experiencing high poverty rates and poor water supply in predominantly rural areas. It lends itself for analyzing this research theme as it is currently being confronted by a large number of actors and approaches that aim to find solutions for these challenges .
In the theoretical framework of this dissertation, four governance configurations are derived from the interaction of varying actor types with regard to hierarchical and non-hierarchical steering of their interactions. These four governance configurations differ in decision-making responsibilities, accountability and delegation of tasks or direction of information flow. The assumption on actor relationships and steering is supplemented by possible alternative explanations in the empirical investigation, such as resource availability, the inheritance of structures and institutions from previous projects in a project context, gaining acceptance through beneficiaries (local legitimacy) as a door opener, and asymmetries of power in the project context.
Case study evidence from seven projects reveals that the actors' relationship is important for successful project delivery. Additionally, the results show that there is a systematic difference between conventional and new donors. Projects led by conventional donors were consistently more successful, due to an actor relationship that placed the responsibility in the hands of the recipient actors and benefited from the trust and reputation of a long-term cooperation. The trust and reputation of conventional donors always went along with a back-up from federal level and trickled down as reputation also at local level implementation. Furthermore, charismatic leaders, as well as the acquired structures and institutions of predecessor projects, also proved to be a positive influencing factor for successful project implementation.
Despite the mixed results of the seven case studies, central recommendations for action can be derived for the various actors involved in development cooperation. For example, new donors could fulfill a supplementary function with conventional donors by developing innovative project approaches through pilot studies and then implementing them as a supplement to the projects of conventional donors on the ground. In return, conventional donors would have to make room the new donors by integrating their approaches into already programs in order to promote donor harmonization. It is also important to identify and occupy niches for activities and to promote harmonization among donors on state and federal sides.
The empirical results demonstrate the need for a harmonization strategy of different donor types in order to prevent duplication, over-experimentation and the failure of development programs. A transformation to successful and sustainable development cooperation can only be achieved through more coordination processes and national self-responsibility.
Solar-like stars maintain their magnetic fields thanks to a dynamo mechanism. The Babcock-Leighton dynamo is one possible dynamo that has the particularity to require magnetic flux tubes. Magnetic flux tubes are assumed to form at the bottom of the convective zone and rise buoyantly to the surface. A delayed dynamo model has been suggested, where the delay accounts for the rise time of the magnetic flux tubes; a time, that has been ignored by former studies.
The present thesis aims to study the applicability of the flux tube/Babcock-Leighton dynamo to other stars. To do so, we attempt to constrain the rise time of magnetic flux tubes thanks to the first fully compressible MHD simulations of rising magnetic flux tubes in stratified rotating spherical shells.
Such simulations are limited to an unrealistic parameter space, therefore, a scaling relation is required to scale the results to realistic physical regimes. We extended earlier works on 2D scaling relations and derived a general scaling law valid for both 2D and 3D. We then carried out two large series of numerical experiments and verified that the scaling law we have derived indeed applies to the fully non-linear case. It allowed us to extract a constraint for the rise time of magnetic flux tubes that is valid for any solar-like star. We finally introduced this constraint to a delayed dynamo model.
By carrying out simulations of a mean-field, delayed, flux tube/Babcock-Leighton dynamo, we were able to identify a new dynamo regime resulting from the delay. This regime requires delays about an entire cycle and exhibits subequipartition magnetic activity. Revealing this new regime shows that even for long delays the flux tube/Babcock-Leighton dynamo can still deliver non-decaying solutions and remains a good candidate for a wide range of solar-like stars.
Precision horticulture encompasses site- or tree-specific management in fruit plantations. Of decisive importance is spatially resolved data (this means data from each tree) from the production site, since it may enable customized and, therefore, resource-efficient production measures.
The present thesis involves an examination of the apparent electrical conductivity of the soil (ECa), the plant water status spatially measured by means of the crop water stress index (CWSI), and the fruit quality (e.g. fruit size) for Prunus domestica L. (plums) and Citrus x aurantium, Syn. Citrus paradisi (grapefruit). The goals of the present work were i) characterization of the 3D distribution of the apparent electrical conductivity of the soil and variability of the plant’s water status; ii) investigation of the interaction between ECa, CWSI, and fruit quality; and iii) an approach for delineating management zones with respect to managing trees individually.
To that end, the main investigations took place in the plum orchard. This plantation got a slope of 3° grade on Pleistocene and post-Pleistocene substrates in a semi-humid climate (Potsdam, Germany) and encloses an area of 0.37 ha with 156 trees of the cultivar ˈTophit Plusˈ on a Wavit rootstock. The plantation was laid in 2009 with annual and biannual trees spaced 4 m distance along the irrigation system and 5 m between the rows. The trees were watered three times a week with a drip irrigation system positioned 50 cm above ground level providing 1.6 l per tree per event. With the help of geoelectric measurements, the apparent electrical conductivity of the upper soil (0.25 m) was measured for each tree with an electrode spacing of 0.5 m (4-point light hp). In this manner, the plantation was spatially charted with respect to the soil’s ECa. Additionally, tomography measurements were performed for 3D mapping of the soil ECa and spot checks of drilled cores with a profile of up to 1 m. The vegetative, generative, and fruit quality data were collected for each tree. The instantaneous plant water status was comprehensively determined in spot checks with the established Scholander method for water potential analysis (Scholander pressure bomb) as well as thermal imaging. An infrared camera was used for the thermal imaging (ThermaCam SC 500), mounted on a tractor 3.3 m above ground level. The thermal images (320 x 240 px) of the canopy surface were taken with an aperture of 45° and a geometric resolution of 8.54 x 6.41 mm. With the aid of the canopy temperature readings from the thermal images, cross-checked with manual temperature measurements of a dry and a wet reference leaf, the crop water stress index (CWSI) was calculated. Adjustments in CWSI for measurements in a semi-humid climate were developed, whereas the collection of reference temperatures was automatically collected from thermal images.
The bonitur data were transformed with the help of a variance stabilization process into a normal distribution. The statistical analyses as well as the automatic evaluation routine were performed with several scripts in MATLAB® (R2010b and R2016a) and a free program (spatialtoolbox). The hot spot analysis served to check whether an observed pattern is statistically significant. The method was evaluated with an established k-mean analysis. To test the hot-spot analysis by comparison, data from a grapefruit plantation (Adana, Turkey) was collected, including soil ECa, trunk circumference, and yield data. The plantation had 179 trees on a soil of type Xerofkuvent with clay and clay-loamy texture. The examination of the interaction between the critical values from the soil and plant water status information and the vegetative and generative plant growth variables was performed with the application from ANOVA.
The study indicates that the variability of the soil and plant information in fruit production is high, even considering small orchards. It was further indicated that the spatial patterns found in the soil ECa stayed constant through the years (r = 0.88 in 2011-2012 and r = 0.71 in 2012-2013). It was also demonstrated that CWSI determination may also be possible in semi-humid climate. A correlation (r = - 0.65, p < 0.0001) with the established method of leaf water potential analysis was found. The interaction between the ECa from various depths and the plant variables produced a highly significant connection with the topsoil in which the irrigation system was to be found. A correlation between yield and ECatopsoil of r = 0.52 was determined. By using the hot-spot analysis, extreme values in the spatial data could be determined. These extremes served to divide the zones (cold-spot, random, hot-spot). The random zone showed the highest correlation to the plant variables.
In summary it may be said that the cumulative water use efficiency (WUEc) was enhanced with high crop load. While the CWSI had no effect on fruit quality, the interaction of CWSI and WUEc even outweighed the impact of soil ECa on fruit quality in the production system with irrigation. In the plum orchard, irrigation was relevant for obtaining high quality produce even in the semi-humid climate.
Discourse production is crucial for communicative success and is in the core of aphasia assessment and treatment. Coherence differentiates discourse from a series of utterances/sentences; it is internal unity and connectedness, and, as such, perhaps the most inherent property of discourse. It is unclear whether people with aphasia, who experience various language production difficulties, preserve the ability to produce coherent discourse. A more general question of how coherence is established and represented linguistically has been addressed in the literature, yet remains unanswered. This dissertation presents an investigation of discourse production in aphasia and the linguistic mechanisms of establishing coherence.
The Earth’s shallow subsurface with sedimentary cover acts as a waveguide to any incoming wavefield. Within the framework of my thesis, I focused on the characterization of this shallow subsurface within tens to few hundreds of meters of sediment cover. I imaged the seismic 1D shear wave velocity (and possibly the 1D compressional wave velocity). This information is not only required for any seismic risk assessment, geotechnical engineering or microzonation activities, but also for exploration and global seismology where site effects are often neglected in seismic waveform modeling.
First, the conventional frequency-wavenumber (f - k) technique is used to derive the dispersion characteristic of the propagating surface waves recorded using distinct arrays of seismometers in 1D and 2D configurations. Further, the cross-correlation technique is applied to seismic array data to estimate the Green’s function between receivers pairs combination assuming one is the source and the other the receiver. With the consideration of a 1D media, the estimated cross-correlation Green’s functions are sorted with interstation distance in a virtual 1D active seismic experiment. The f - k technique is then used to estimate the dispersion curves. This integrated analysis is important for the interpretation of a large bandwidth of the phase velocity dispersion curves and therefore improving the resolution of the estimated 1D Vs profile.
Second, the new theoretical approach based on the Diffuse Field Assumption (DFA) is used for the interpretation of the observed microtremors H/V spectral ratio. The theory is further extended in this research work to include not only the interpretation of the H/V measured at the surface, but also the H/V measured at depths and in marine environments. A modeling and inversion of synthetic H/V spectral ratio curves on simple predefined geological structures shows an almost perfect recovery of the model parameters (mainly Vs and to a lesser extent Vp). These results are obtained after information from a receiver at depth has been considered in the inversion.
Finally, the Rayleigh wave phase velocity information, estimated from array data, and the H/V(z, f) spectral ratio, estimated from a single station data, are combined and inverted for the velocity profile information. Obtained results indicate an improved depth resolution in comparison to estimations using the phase velocity dispersion curves only. The overall estimated sediment thickness is comparable to estimations obtained by inverting the full micortremor H/V spectral ratio.
Personal fabrication tools, such as 3D printers, are on the way of enabling a future in which non-technical users will be able to create custom objects. However, while the hardware is there, the current interaction model behind existing design tools is not suitable for non-technical users. Today, 3D printers are operated by fabricating the object in one go, which tends to take overnight due to the slow 3D printing technology. Consequently, the current interaction model requires users to think carefully before printing as every mistake may imply another overnight print. Planning every step ahead, however, is not feasible for non-technical users as they lack the experience to reason about the consequences of their design decisions.
In this dissertation, we propose changing the interaction model around personal fabrication tools to better serve this user group. We draw inspiration from personal computing and argue that the evolution of personal fabrication may resemble the evolution of personal computing: Computing started with machines that executed a program in one go before returning the result to the user. By decreasing the interaction unit to single requests, turn-taking systems such as the command line evolved, which provided users with feedback after every input. Finally, with the introduction of direct-manipulation interfaces, users continuously interacted with a program receiving feedback about every action in real-time. In this dissertation, we explore whether these interaction concepts can be applied to personal fabrication as well.
We start with fabricating an object in one go and investigate how to tighten the feedback-cycle on an object-level: We contribute a method called low-fidelity fabrication, which saves up to 90% fabrication time by creating objects as fast low-fidelity previews, which are sufficient to evaluate key design aspects. Depending on what is currently being tested, we propose different conversions that enable users to focus on different parts: faBrickator allows for a modular design in the early stages of prototyping; when users move on WirePrint allows quickly testing an object's shape, while Platener allows testing an object's technical function. We present an interactive editor for each technique and explain the underlying conversion algorithms.
By interacting on smaller units, such as a single element of an object, we explore what it means to transition from systems that fabricate objects in one go to turn-taking systems. We start with a 2D system called constructable: Users draw with a laser pointer onto the workpiece inside a laser cutter. The drawing is captured with an overhead camera. As soon as the the user finishes drawing an element, such as a line, the constructable system beautifies the path and cuts it--resulting in physical output after every editing step. We extend constructable towards 3D editing by developing a novel laser-cutting technique for 3D objects called LaserOrigami that works by heating up the workpiece with the defocused laser until the material becomes compliant and bends down under gravity. While constructable and LaserOrigami allow for fast physical feedback, the interaction is still best described as turn-taking since it consists of two discrete steps: users first create an input and afterwards the system provides physical output.
By decreasing the interaction unit even further to a single feature, we can achieve real-time physical feedback: Input by the user and output by the fabrication device are so tightly coupled that no visible lag exists. This allows us to explore what it means to transition from turn-taking interfaces, which only allow exploring one option at a time, to direct manipulation interfaces with real-time physical feedback, which allow users to explore the entire space of options continuously with a single interaction. We present a system called FormFab, which allows for such direct control. FormFab is based on the same principle as LaserOrigami: It uses a workpiece that when warmed up becomes compliant and can be reshaped. However, FormFab achieves the reshaping not based on gravity, but through a pneumatic system that users can control interactively. As users interact, they see the shape change in real-time.
We conclude this dissertation by extrapolating the current evolution into a future in which large numbers of people use the new technology to create objects. We see two additional challenges on the horizon: sustainability and intellectual property. We investigate sustainability by demonstrating how to print less and instead patch physical objects. We explore questions around intellectual property with a system called Scotty that transfers objects without creating duplicates, thereby preserving the designer's copyright.
This thesis is focused on the study and the exact simulation of two classes of real-valued Brownian diffusions: multi-skew Brownian motions with constant drift and Brownian diffusions whose drift admits a finite number of jumps.
The skew Brownian motion was introduced in the sixties by Itô and McKean, who constructed it from the reflected Brownian motion, flipping its excursions from the origin with a given probability. Such a process behaves as the original one except at the point 0, which plays the role of a semipermeable barrier. More generally, a skew diffusion with several semipermeable barriers, called multi-skew diffusion, is a diffusion everywhere except when it reaches one of the barriers, where it is partially reflected with a probability depending on that particular barrier. Clearly, a multi-skew diffusion can be characterized either as solution of a stochastic differential equation involving weighted local times (these terms providing the semi-permeability) or by its infinitesimal generator as Markov process.
In this thesis we first obtain a contour integral representation for the transition semigroup of the multiskew Brownian motion with constant drift, based on a fine analysis of its complex properties. Thanks to this representation we write explicitly the transition densities of the two-skew Brownian motion with constant drift as an infinite series involving, in particular, Gaussian functions and their tails.
Then we propose a new useful application of a generalization of the known rejection sampling method. Recall that this basic algorithm allows to sample from a density as soon as one finds an - easy to sample - instrumental density verifying that the ratio between the goal and the instrumental densities is a bounded function. The generalized rejection sampling method allows to sample exactly from densities for which indeed only an approximation is known. The originality of the algorithm lies in the fact that one finally samples directly from the law without any approximation, except the machine's.
As an application, we sample from the transition density of the two-skew Brownian motion with or without constant drift. The instrumental density is the transition density of the Brownian motion with constant drift, and we provide an useful uniform bound for the ratio of the densities. We also present numerical simulations to study the efficiency of the algorithm.
The second aim of this thesis is to develop an exact simulation algorithm for a Brownian diffusion whose drift admits several jumps. In the literature, so far only the case of a continuous drift (resp. of a drift with one finite jump) was treated. The theoretical method we give allows to deal with any finite number of discontinuities. Then we focus on the case of two jumps, using the transition densities of the two-skew Brownian motion obtained before. Various examples are presented and the efficiency of our approach is discussed.