Filtern
Erscheinungsjahr
- 2018 (154) (entfernen)
Dokumenttyp
- Dissertation (154) (entfernen)
Sprache
- Englisch (154) (entfernen)
Schlagworte
- Fernerkundung (3)
- Magnetismus (3)
- climate change (3)
- magnetism (3)
- remote sensing (3)
- uncertainty (3)
- Angriffserkennung (2)
- Bakterien (2)
- Big Data (2)
- Biodiversität (2)
Institut
- Institut für Physik und Astronomie (28)
- Institut für Biochemie und Biologie (27)
- Institut für Chemie (24)
- Institut für Geowissenschaften (23)
- Extern (14)
- Hasso-Plattner-Institut für Digital Engineering GmbH (14)
- Wirtschaftswissenschaften (8)
- Department Psychologie (6)
- Department Linguistik (5)
- Institut für Ernährungswissenschaft (5)
- Sozialwissenschaften (5)
- Institut für Umweltwissenschaften und Geographie (3)
- Potsdam Institute for Climate Impact Research (PIK) e. V. (3)
- Institut für Informatik und Computational Science (2)
- Institut für Mathematik (2)
- Department Sport- und Gesundheitswissenschaften (1)
- Institut für Anglistik und Amerikanistik (1)
- Potsdam Research Institute for Multilingualism (PRIM) (1)
Be Creative, Now!
(2018)
Purpose – This thesis set out to explore, describe, and evaluate the reality behind the rhetoric of freedom and control in the context of creativity. The overarching subject is concerned with the relationship between creativity, freedom, and control, considering freedom is also seen as an element of control to manage creativity.
Design/methodology/approach – In-depth qualitative data gathered from at two innovative start-ups. Two ethnographic studies were conducted. The data are based on participatory observations, interviews, and secondary sources, each of which included a three months field study and a total of 41 interviews from both organizations.
Findings – The thesis provides explanations for the practice of freedom and the control of creativity within organizations and expands the existing theory of neo-normative control. The findings indicate that organizations use complex control systems that allow a high degree of freedom that paradoxically leads to more control. Freedom is a cover of control, which in turn leads to creativity. Covert control even results in the responsibility to be creative outside working hours.
Practical implications – Organizations, which rely on creativity might use the results of this thesis. Positive workplace control of creativity provides both freedom and structure for creative work. While freedom leads to organizational members being more motivated and committing themselves more strongly to their and the organization’s goals, and a specific structure also helps to provide the requirements for creativity.
Originality/value – The thesis provides an insight into an approach to workplace control, which has mostly neglected in creativity research and proposes a modified concept of neo-normative control. It serves to provide a further understanding of freedom for creativity and to challenge the liberal claims of new control forms.
The aim of this doctoral thesis was to establish a technique for the analysis of biomolecules with infrared matrix-assisted laser dispersion (IR-MALDI) ion mobility (IM) spectrometry. The main components of the work were the characterization of the IR-MALDI process, the development and characterization of different ion mobility spectrometers, the use of IR-MALDI-IM spectrometry as a robust, standalone spectrometer and the development of a collision cross-section estimation approach for peptides based on molecular dynamics and thermodynamic reweighting.
First, the IR-MALDI source was studied with atmospheric pressure ion mobility spectrometry and shadowgraphy. It consisted of a metal capillary, at the tip of which a self-renewing droplet of analyte solution was met by an IR laser beam. A relationship between peak shape, ion desolvation, diffusion and extraction pulse delay time (pulse delay) was established. First order desolvation kinetics were observed and related to peak broadening by diffusion, both influenced by the pulse delay. The transport mechanisms in IR-MALDI were then studied by relating different laser impact positions on the droplet surface to the corresponding ion mobility spectra. Two different transport mechanisms were determined: phase explosion due to the laser pulse and electrical transport due to delayed ion extraction. The velocity of the ions stemming from the phase explosion was then measured by ion mobility and shadowgraphy at different time scales and distances from the source capillary, showing an initially very high but rapidly decaying velocity. Finally, the anatomy of the dispersion plume was observed in detail with shadowgraphy and general conclusions over the process were drawn.
Understanding the IR-MALDI process enabled the optimization of the different IM spectrometers at atmospheric and reduced pressure (AP and RP, respectively). At reduced pressure, both an AP and an RP IR-MALDI source were used. The influence of the pulsed ion extraction parameters (pulse delay, width and amplitude) on peak shape, resolution and area was systematically studied in both AP and RP IM spectrometers and discussed in the context of the IR-MALDI process. Under RP conditions, the influence of the closing field and of the pressure was also examined for both AP and RP sources. For the AP ionization RP IM spectrometer, the influence of the inlet field (IF) in the source region was also examined. All of these studies led to the determination of the optimal analytical parameters as well as to a better understanding of the initial ion cloud anatomy.
The analytical performance of the spectrometer was then studied. Limits of detection (LOD) and linear ranges were determined under static and pulsed ion injection conditions and interpreted in the context of the IR-MALDI mechanism. Applications in the separation of simple mixtures were also illustrated, demonstrating good isomer separation capabilities and the advantages of singly charged peaks. The possibility to couple high performance liquid chromatography (HPLC) to IR-MALDI-IM spectrometry was also demonstrated. Finally, the reduced pressure spectrometer was used to study the effect of high reduced field strength on the mobility of polyatomic ions in polyatomic gases.
The last focus point was on the study of peptide ions. A dataset obtained with electrospray IM spectrometry was characterized and used for the calibration of a collision cross-section (CCS) determination method based on molecular dynamics (MD) simulations at high temperature. Instead of producing candidate structures which are evaluated one by one, this semi-automated method uses the simulation as a whole to determine a single average collision cross-section value by reweighting the CCS of a few representative structures. The method was compared to the intrinsic size parameter (ISP) method and to experimental results. Additional MD data obtained from the simulations was also used to further analyze the peptides and understand the experimental results, an advantage with regard to the ISP method. Finally, the CCS of peptide ions analyzed by IR-MALDI were also evaluated with both ISP and MD methods and the results compared to experiment, resulting in a first validation of the MD method. Thus, this thesis brings together the soft ionization technique that is IR-MALDI, which produces mostly singly charged peaks, with ion mobility spectrometry, which can distinguish between isomers, and a collision cross-section determination method which also provides structural information on the analyte at hand.
Previous studies on native language (L1) anaphor resolution have found that monolingual native speakers are sensitive to syntactic, pragmatic, and semantic constraints on pronouns and reflexive resolution. However, most studies have focused on English and other Germanic languages, and little is currently known about the online (i.e., real-time) processing of anaphors in languages with syntactically less restricted anaphors, such as Turkish. We also know relatively little about how 'non-standard' populations such as non-native (L2) speakers and heritage speakers (HSs) resolve anaphors.
This thesis investigates the interpretation and real-time processing of anaphors in German and in a typologically different and as yet understudied language, Turkish. It compares hypotheses about differences between native speakers' (L1ers) and L2 speakers' (L2ers) sentence processing, looking into differences in processing mechanisms as well as the possibility of cross-linguistic influence. To help fill the current research gap regarding HS sentence comprehension, it compares findings for this group with those for L2ers.
To investigate the representation and processing of anaphors in these three populations, I carried out a series of offline questionnaires and Visual-World eye-tracking experiments on the resolution of reflexives and pronouns in both German and Turkish. In the German experiments, native German speakers as well as L2ers of German were tested, while in the Turkish experiments, non-bilingual native Turkish speakers as well as HSs of Turkish with L2 German were tested. This allowed me to observe both cross-linguistic differences as well as population differences between monolinguals' and different types of bilinguals' resolution of anaphors.
Regarding the comprehension of Turkish anaphors by L1ers, contrary to what has been previously assumed, I found that Turkish has no reflexive that follows Condition A of Binding theory (Chomsky, 1981). Furthermore, I propose more general cross-linguistic differences between Turkish and German, in the form of a stronger reliance on pragmatic information in anaphor resolution overall in Turkish compared to German.
As for the processing differences between L1ers and L2ers of a language, I found evidence in support of hypotheses which propose that L2ers of German rely more strongly on non-syntactic information compared to L1ers (Clahsen & Felser, 2006, 2017; Cunnings, 2016, 2017) independent of a potential influence of their L1. HSs, on the other hand, showed a tendency to overemphasize interpretational contrasts between different Turkish anaphors compared to monolingual native speakers. However, lower-proficiency HSs were likely to merge different forms for simplified representation and processing. Overall, L2ers and HSs showed differences from monolingual native speakers both in their final interpretation of anaphors and during online processing. However, these differences were not parallel between the two types of bilingual and thus do not support a unified model of L2 and HS processing (cf. Montrul, 2012).
The findings of this thesis contribute to the field of anaphor resolution by providing data from a previously unexplored language, Turkish, as well as contributing to research on native and non-native processing differences. My results also illustrate the importance of considering individual differences in the acquisition process when studying bilingual language comprehension. Factors such as age of acquisition, language proficiency and the type of input a language learner receives may influence the processing mechanisms they develop and employ, both between and within different bilingual populations.
Systemic inflammation is a hallmark of cancer cachexia. Among tumor-host interactions, the white adipose tissue (WAT) is an important contributor to inflammation as it suffers morphological reorganization and lipolysis, releasing free fatty acids (FA), bioactive lipid mediators (LM) and pro-inflammatory cytokines, which accentuate the activation of pro-inflammatory signaling pathways and the recruitment of immune cells to the tissue. This project aimed to investigate which inflammatory factors are involved in the local adipose tissue inflammation and what is the influence of such factors upon enzymes involved in FA or LM metabolism in healthy individuals (Control), weight stable gastro-intestinal cancer patients (WSC) and cachectic cancer patients (CC). The results demonstrated that the inflammatory signature of systemic inflammation is different from local adipose tissue inflammation. The systemic inflammation of the cachectic cancer patients was characterized by higher levels of circulating saturated fatty acids (SFA), tumor-necrosis-factor-α (TNF-α), interleukins IL-6, IL-8 and CRP while levels of polyunsaturated fatty acids (PUFAs), especially n3-PUFAs, were lower in CC than in the other groups. In vitro and in adipose tissue explants, pro-inflammatory cytokines and SFAs were shown to increase the chemokines IL-8 and CXCL10 that were found to be augmented in adipose tissue inflammation in CC which was more profound in the visceral adipose tissue (VAT) than in subcutaneous adipose tissue (SAT). Systemic inflammation was negatively associated with the expression of PUFA synthesizing enzymes, though gene and protein expression did hardly differ between groups. The effects of inflammatory factors on enzymes in the whole tissue could have been masked by differentiated modulation of the diverse cell types in the same tissue. In vitro experiments showed that the expression of FA-modifying enzymes such as desaturases and elongases in adipocytes and macrophages was regulated into opposing directions by TNF-α, IL-6, LPS or palmitate. The higher plasma concentration of the pro-resolving LM resolvin D1 in CC cannot compensate the overall inflammatory status and the results indicate that inflammatory cytokines interfere with synthesis pathways of pro-resolving LM. In summary, the data revealed a complex inter-tissue and inter-cellular crosstalk mediated by pro-inflammatory cytokines and lipid compounds enhancing inflammation in cancer cachexia by feed-forward mechanisms.
Together with the gradual change of mean values, ongoing climate change is projected to increase frequency and amplitude of temperature and precipitation extremes in many regions of Europe. The impacts of such in most cases short term extraordinary climate situations on terrestrial ecosystems are a matter of central interest of recent climate change research, because it can not per se be assumed that known dependencies between climate variables and ecosystems are linearly scalable. So far, yet, there is a high demand for a method to quantify such impacts in terms of simultaneities of event time series.
In the course of this manuscript the new statistical approach of Event Coincidence Analysis (ECA) as well as it's R implementation is introduced, a methodology that allows assessing whether or not two types of event time series exhibit similar sequences of occurrences. Applications of the method are presented, analyzing climate impacts on different temporal and spacial scales: the impact of extraordinary expressions of various climatic variables on tree stem variations (subdaily and local scale), the impact of extreme temperature and precipitation events on the owering time of European shrub species (weekly and country scale), the impact of extreme temperature events on ecosystem health in terms of NDVI (weekly and continental scale) and the impact of El Niño and La Niña events on precipitation anomalies (seasonal and global scale).
The applications presented in this thesis refine already known relationships based on classical methods and also deliver substantial new findings to the scientific community: the widely known positive correlation between flowering time and temperature for example is confirmed to be valid for the tails of the distributions while the widely assumed positive dependency between stem diameter variation and temperature is shown to be not valid for very warm and very cold days. The larger scale investigations underline the sensitivity of anthrogenically shaped landscapes towards temperature extremes in Europe and provide a comprehensive global ENSO impact map for strong precipitation events.
Finally, by publishing the R implementation of the method, this thesis shall enable other researcher to further investigate on similar research questions by using Event Coincidence Analysis.
Answer Set Programming (ASP) is a declarative problem solving approach, combining a rich yet simple modeling language with high-performance solving capabilities. Although this has already resulted in various applications, certain aspects of such applications are more naturally modeled using variables over finite domains, for accounting for resources, fine timings, coordinates, or functions. Our goal is thus to extend ASP with constraints over integers while preserving its declarative nature. This allows for fast prototyping and elaboration tolerant problem descriptions of resource related applications. The resulting paradigm is called Constraint Answer Set Programming (CASP).
We present three different approaches for solving CASP problems. The first one, a lazy, modular approach combines an ASP solver with an external system for handling constraints. This approach has the advantage that two state of the art technologies work hand in hand to solve the problem, each concentrating on its part of the problem. The drawback is that inter-constraint dependencies cannot be communicated back to the ASP solver, impeding its learning algorithm. The second approach translates all constraints to ASP. Using the appropriate encoding techniques, this results in a very fast, monolithic system. Unfortunately, due to the large, explicit representation of constraints and variables, translation techniques are restricted to small and mid-sized domains. The third approach merges the lazy and the translational approach, combining the strength of both while removing their weaknesses. To this end, we enhance the dedicated learning techniques of an ASP solver with the inferences of the translating approach in a lazy way. That is, the important knowledge is only made explicit when needed.
By using state of the art techniques from neighboring fields, we provide ways to tackle real world, industrial size problems. By extending CASP to reactive solving, we open up new application areas such as online planning with continuous domains and durations.
The development of self-adaptive software requires the engineering of an adaptation engine that controls the underlying adaptable software by a feedback loop. State-of-the-art approaches prescribe the feedback loop in terms of numbers, how the activities (e.g., monitor, analyze, plan, and execute (MAPE)) and the knowledge are structured to a feedback loop, and the type of knowledge. Moreover, the feedback loop is usually hidden in the implementation or framework and therefore not visible in the architectural design. Additionally, an adaptation engine often employs runtime models that either represent the adaptable software or capture strategic knowledge such as reconfiguration strategies. State-of-the-art approaches do not systematically address the interplay of such runtime models, which would otherwise allow developers to freely design the entire feedback loop.
This thesis presents ExecUtable RuntimE MegAmodels (EUREMA), an integrated model-driven engineering (MDE) solution that rigorously uses models for engineering feedback loops. EUREMA provides a domain-specific modeling language to specify and an interpreter to execute feedback loops. The language allows developers to freely design a feedback loop concerning the activities and runtime models (knowledge) as well as the number of feedback loops. It further supports structuring the feedback loops in the adaptation engine that follows a layered architectural style. Thus, EUREMA makes the feedback loops explicit in the design and enables developers to reason about design decisions.
To address the interplay of runtime models, we propose the concept of a runtime megamodel, which is a runtime model that contains other runtime models as well as activities (e.g., MAPE) working on the contained models. This concept is the underlying principle of EUREMA. The resulting EUREMA (mega)models are kept alive at runtime and they are directly executed by the EUREMA interpreter to run the feedback loops. Interpretation provides the flexibility to dynamically adapt a feedback loop. In this context, EUREMA supports engineering self-adaptive software in which feedback loops run independently or in a coordinated fashion within the same layer as well as on top of each other in different layers of the adaptation engine. Moreover, we consider preliminary means to evolve self-adaptive software by providing a maintenance interface to the adaptation engine.
This thesis discusses in detail EUREMA by applying it to different scenarios such as single, multiple, and stacked feedback loops for self-repairing and self-optimizing the mRUBiS application. Moreover, it investigates the design and expressiveness of EUREMA, reports on experiments with a running system (mRUBiS) and with alternative solutions, and assesses EUREMA with respect to quality attributes such as performance and scalability.
The conducted evaluation provides evidence that EUREMA as an integrated and open MDE approach for engineering self-adaptive software seamlessly integrates the development and runtime environments using the same formalism to specify and execute feedback loops, supports the dynamic adaptation of feedback loops in layered architectures, and achieves an efficient execution of feedback loops by leveraging incrementality.
The sequencing of the human genome in the early 2000s led to an increased interest in cheap and fast sequencing technologies. This interest culminated in the advent of next generation sequencing (NGS). A number of different NGS platforms have arisen since then all promising to do the same thing, i.e. produce large amounts of genetic information for relatively low costs compared to more traditional methods such as Sanger sequencing. The capabilities of NGS meant that researchers were no longer bound to species for which a lot of previous work had already been done (e.g. model organisms and humans) enabling a shift in research towards more novel and diverse species of interest. This capability has greatly benefitted many fields within the biological sciences, one of which being the field of evolutionary biology. Researchers have begun to move away from the study of laboratory model organisms to wild, natural populations and species which has greatly expanded our knowledge of evolution. NGS boasts a number of benefits over more traditional sequencing approaches. The main benefit comes from the capability to generate information for drastically more loci for a fraction of the cost. This is hugely beneficial to the study of wild animals as, even when large numbers of individuals are unobtainable, the amount of data produced still allows for accurate, reliable population and species level results from a small selection of individuals.
The use of NGS to study species for which little to no previous research has been carried out on and the production of novel evolutionary information and reference datasets for the greater scientific community were the focuses of this thesis. Two studies in this thesis focused on producing novel mitochondrial genomes from shotgun sequencing data through iterative mapping, bypassing the need for a close relative to serve as a reference sequence. These mitochondrial genomes were then used to infer species level relationships through phylogenetic analyses. The first of these studies involved reconstructing a complete mitochondrial genome of the bat eared fox (Otocyon megalotis). Phylogenetic analyses of the mitochondrial genome confidently placed the bat eared fox as sister to the clade consisting of the raccoon dog and true foxes within the canidae family. The next study also involved reconstructing a mitochondrial genome but in this case from the extinct Macrauchenia of South America. As this study utilised ancient DNA, it involved a lot of parameter testing, quality controls and strict thresholds to obtain a near complete mitochondrial genome devoid of contamination known to plague ancient DNA studies. Phylogenetic analyses confidently placed Macrauchenia as sister to all living representatives of Perissodactyla with a divergence time of ~66 million years ago. The third and final study of this thesis involved de novo assemblies of both nuclear and mitochondrial genomes from brown and striped hyena and focussed on demographic, genetic diversity and population genomic analyses within the brown hyena. Previous studies of the brown hyena hinted at very low levels of genomic diversity and, perhaps due to this, were unable to find any notable population structure across its range. By incorporating a large number of genetic loci, in the form of complete nuclear genomes, population structure within the brown hyena was uncovered. On top of this, genomic diversity levels were compared to a number of other species. Results showed the brown hyena to have the lowest genomic diversity out of all species included in the study which was perhaps caused by a continuous and ongoing decline in effective population size that started about one million years ago and dramatically accelerated towards the end of the Pleistocene.
The studies within this thesis show the power NGS sequencing has and its utility within evolutionary biology. The most notable capabilities outlined in this thesis involve the study of species for which no reference data is available and in the production of large amounts of data, providing evolutionary answers at the species and population level that data produced using more traditional techniques simply could not.
Business process management is an acknowledged asset for running an organization in a productive and sustainable way. One of the most important aspects of business process management, occurring on a daily basis at all levels, is decision making. In recent years, a number of decision management frameworks have appeared in addition to existing business process management systems. More recently, Decision Model and Notation (DMN) was developed by the OMG consortium with the aim of complementing the widely used Business Process Model and Notation (BPMN). One of the reasons for the emergence of DMN is the increasing interest in the evolving paradigm known as the separation of concerns. This paradigm states that modeling decisions complementary to processes reduces process complexity by externalizing decision logic from process models and importing it into a dedicated decision model. Such an approach increases the agility of model design and execution. This provides organizations with the flexibility to adapt to the ever increasing rapid and dynamic changes in the business ecosystem. The research gap, identified by us, is that the separation of concerns, recommended by DMN, prescribes the externalization of the decision logic of process models in one or more separate decision models, but it does not specify this can be achieved.
The goal of this thesis is to overcome the presented gap by developing a framework for discovering decision models in a semi-automated way from information about existing process decision making. Thus, in this thesis we develop methodologies to extract decision models from: (1) control flow and data of process models that exist in enterprises; and (2) from event logs recorded by enterprise information systems, encapsulating day-to-day operations. Furthermore, we provide an extension of the methodologies to discover decision models from event logs enriched with fuzziness, a tool dealing with partial knowledge of the process execution information. All the proposed techniques are implemented and evaluated in case studies using real-life and synthetic process models and event logs. The evaluation of these case studies shows that the proposed methodologies provide valid and accurate output decision models that can serve as blueprints for executing decisions complementary to process models. Thus, these methodologies have applicability in the real world and they can be used, for example, for compliance checks, among other uses, which could improve the organization's decision making and hence it's overall performance.
Active and passive source data from two seismic experiments within the interdisciplinary project TIPTEQ (from The Incoming Plate to mega Thrust EarthQuake processes) were used to image and identify the structural and petrophysical properties (such as P- and S-velocities, Poisson's ratios, pore pressure, density and amount of fluids) within the Chilean seismogenic coupling zone at 38.25°S, where in 1960 the largest earthquake ever recorded (Mw 9.5) occurred. Two S-wave velocity models calculated using traveltime and noise tomography techniques were merged with an existing velocity model to obtain a 2D S-wave velocity model, which gathered the advantages of each individual model. In a following step, P- and S-reflectivity images of the subduction zone were obtained using different pre stack and post-stack depth migration techniques. Among them, the recent prestack line-drawing depth migration scheme yielded revealing results. Next, synthetic seismograms modelled using the reflectivity method allowed, through their input 1D synthetic P- and S-velocities, to infer the composition and rocks within the subduction zone. Finally, an image of the subduction zone is given, jointly interpreting the results from this work with results from other studies. The Chilean seismogenic coupling zone at 38.25°S shows a continental crust with highly reflective horizontal, as well as (steep) dipping events. Among them, the Lanalhue Fault Zone (LFZ), which is interpreted to be east-dipping, is imaged to very shallow depths. Some steep reflectors are observed for the first time, for example one near the coast, related to high seismicity and another one near the LFZ. Steep shallow reflectivity towards the volcanic arc could be related to a steep west-dipping reflector interpreted as fluids and/or melts, migrating upwards due to material recycling in the continental mantle wedge. The high resolution of the S-velocity model in the first kilometres allowed to identify several sedimentary basins, characterized by very low P- and S-velocities, high Poisson's ratios and possible steep reflectivity. Such high Poisson's ratios are also observed within the oceanic crust, which reaches the seismogenic zone hydrated due to bending-related faulting. It is interpreted to release water until reaching the coast and under the continental mantle wedge. In terms of seismic velocities, the inferred composition and rocks in the continental crust is in agreement with field geology observations at the surface along the proflle. Furthermore, there is no requirement to call on the existence of measurable amounts of present-day fluids above the plate interface in the continental crust of the Coastal Cordillera and the Central Valley in this part of the Chilean convergent margin. A large-scale anisotropy in the continental crust and upper mantle, previously proposed from magnetotelluric studies, is proposed from seismic velocities. However, quantitative studies on this topic in the continental crust of the Chilean seismogenic zone at 38.25°S do not exist to date.
Earth's climate varies continuously across space and time, but humankind has witnessed only a small snapshot of its entire history, and instrumentally documented it for a mere 200 years. Our knowledge of past climate changes is therefore almost exclusively based on indirect proxy data, i.e. on indicators which are sensitive to changes in climatic variables and stored in environmental archives. Extracting the data from these archives allows retrieval of the information from earlier times. Obtaining accurate proxy information is a key means to test model predictions of the past climate, and only after such validation can the models be used to reliably forecast future changes in our warming world. The polar ice sheets of Greenland and Antarctica are one major climate archive, which record information about local air temperatures by means of the isotopic composition of the water molecules embedded in the ice. However, this temperature proxy is, as any indirect climate data, not a perfect recorder of past climatic variations. Apart from local air temperatures, a multitude of other processes affect the mean and variability of the isotopic data, which hinders their direct interpretation in terms of climate variations. This applies especially to regions with little annual accumulation of snow, such as the Antarctic Plateau. While these areas in principle allow for the extraction of isotope records reaching far back in time, a strong corruption of the temperature signal originally encoded in the isotopic data of the snow is expected. This dissertation uses observational isotope data from Antarctica, focussing especially on the East Antarctic low-accumulation area around the Kohnen Station ice-core drilling site, together with statistical and physical methods, to improve our understanding of the spatial and temporal isotope variability across different scales, and thus to enhance the applicability of the proxy for estimating past temperature variability. The presented results lead to a quantitative explanation of the local-scale (1–500 m) spatial variability in the form of a statistical noise model, and reveal the main source of the temporal variability to be the mixture of a climatic seasonal cycle in temperature and the effect of diffusional smoothing acting on temporally uncorrelated noise. These findings put significant limits on the representativity of single isotope records in terms of local air temperature, and impact the interpretation of apparent cyclicalities in the records. Furthermore, to extend the analyses to larger scales, the timescale-dependency of observed Holocene isotope variability is studied. This offers a deeper understanding of the nature of the variations, and is crucial for unravelling the embedded true temperature variability over a wide range of timescales.
Microswimmers, i.e. swimmers of micron size experiencing low Reynolds numbers, have received a great deal of attention in the last years, since many applications are envisioned in medicine and bioremediation. A promising field is the one of magnetic swimmers, since magnetism is biocom-patible and could be used to direct or actuate the swimmers. This thesis studies two examples of magnetic microswimmers from a physics point of view.
The first system to be studied are magnetic cells, which can be magnetic biohybrids (a swimming cell coupled with a magnetic synthetic component) or magnetotactic bacteria (naturally occurring bacteria that produce an intracellular chain of magnetic crystals). A magnetic cell can passively interact with external magnetic fields, which can be used for direction. The aim of the thesis is to understand how magnetic cells couple this magnetic interaction to their swimming strategies, mainly how they combine it with chemotaxis (the ability to sense external gradient of chemical species and to bias their walk on these gradients). In particular, one open question addresses the advantage given by these magnetic interactions for the magnetotactic bacteria in a natural environment, such as porous sediments. In the thesis, a modified Active Brownian Particle model is used to perform simulations and to reproduce experimental data for different systems such as bacteria swimming in the bulk, in a capillary or in confined geometries. I will show that magnetic fields speed up chemotaxis under special conditions, depending on parameters such as their swimming strategy (run-and-tumble or run-and-reverse), aerotactic strategy (axial or polar), and magnetic fields (intensities and orientations), but it can also hinder bacterial chemotaxis depending on the system.
The second example of magnetic microswimmer are rigid magnetic propellers such as helices or random-shaped propellers. These propellers are actuated and directed by an external rotating magnetic field. One open question is how shape and magnetic properties influence the propeller behavior; the goal of this research field is to design the best propeller for a given situation. The aim of the thesis is to propose a simulation method to reproduce the behavior of experimentally-realized propellers and to determine their magnetic properties. The hydrodynamic simulations are based on the use of the mobility matrix. As main result, I propose a method to match the experimental data, while showing that not only shape but also the magnetic properties influence the propellers swimming characteristics.
This project was focused on exploring the phase behavior of poly(styrene)187000-block-poly(2-vinylpyridine)203000 (SV390) with high molecular weight (390 kg/mol) in thin films, in which the self-assembly of block copolymers (BCPs) was realized via thermo-solvent annealing. The advanced processing technique of solvent vapor treatment provides controlled and stable conditions.
In Chapter 3, the factors to influence the annealing process and the swelling behavior of homopolymers are presented and discussed. The swelling behavior of BCP in films is controlled by the temperature of the vapor and of the substrate, on one hand, and variation of the saturation of the solvent vapor atmosphere (different solvents), on the other hand. Additional factors like the geometry and material of the chamber, the type of flow inside the chamber etc. also influence the reproducibility and stability of the processing. The slightly selective solvent vapor of chloroform gives 10% more swelling of P2VP than PS in films with thickness of ~40 nm.
The tunable morphology in ultrathin films of high molecular weight BCP (SV390) was investigated in Chapter 4. First, the swelling behavior can be precisely tuned by temperature and/or vapor flow separately, which provided information for exploring the multiple-parameter-influenced segmental chain mobility of polymer films. The equilibrium state of SV390 in thin films influenced by temperature was realized at various temperatures with the same degree of swelling. Various methods including characterization with SFM, metallization and RIE were used to identify the morphology of films as porous half-layer with PS dots and P2VP matrix. The kinetic investigations demonstrate that on substrates with either weak or strong interaction the original morphology of the BCP with high molecular weight is changed very fast within 5 min, and the further annealing serves for annihilation of defects.
The morphological development of symmetric BCP in films with thickness increasing from half-layer to one-layer influenced by confinement factors of gradient film thicknesses and various surface properties of substrates was studied in Chapter 5. SV390 and SV99 films show bulk lamella-forming morphology after slightly selective solvent vapor (chloroform) treatment. SV99 films show cylinder-forming morphology under strongly selective solvent vapor (toluene) treatment since the asymmetric structure (caused by toluene uptake in PS blocks only) of SV99 block copolymer during annealing. Both kinds of morphology (lamella and cylinder) are influenced by the film thickness. The annealed morphology of SV390 and SV99 influenced by the combination of confined film and substrate property is similar to the morphology on flat silicon wafers. In this chapter the gradients in the film thickness and surface properties of the substrates with regard to their influence on the morphological development in thin BCP films are presented. Directed self-assembly (graphoepitaxy) of this SV390 was also investigated to compare with systematically reported SV99.
In Chapter 6 an approach to induced oriented microphase separation in thick block copolymer films via treatment with the oriented vapor flow using mini-extruder is envisaged to be an alternative to existing methodologies, e.g. via non-solvent-induced phase separation. The preliminary tests performed in this study confirm potential perspective of this method, which alters the structure through the bulk of the film (as revealed by SAXS measurements), but more detailed studies have to be conducted in order to optimize the preparation.
BACKGROUND: Physical activity involving high spinal load has been exposed to possess a crucial impact in the genesis of acute and chronic low back pain and disorder. Vigorous spinal loads are surmised in drop landings, for which strenuous bending loads were formerly evinced for the lower extremity structures. Thus far, clinical studies revealed that repetitive landing impacts can evoke benign structural adaptions or damage to the lumbar vertebrae. Though, causes for these observations are hitherto not conclusively evinced; since actual spinal load has to date not been experimentally documented. Moreover, it is yet undetermined how physiological activation of trunk musculature compensates for landing impact induced spinal loads, and to which extend trunk activity and spinal load are affected by landing demands and performer characteristics. AIMS of this study are 1. the localisation and quantification of spinal bending loads under various landing demands and 2. the identification of compensatory trunk muscular activity pattern, which potentially alleviate spinal load magnitudes. Three consecutive Hypotheses (H1 - H3) were hereto postulated: H1 posits that spinal bending loads in segregated motion planes can feasibly and reliably be evaluated from peak spine segmental angular accelerations. H2 furthermore assumes that vertical drop landings elicit highest spine bending load in sagittal flexion of the lumbar spine. Based on these verifications, a second study shall prove the successive hypothesis (H3) that diversified landing conditions, like performer’s landing familiarity and gender, as an implementation of an instantaneous follow-up task, affect the emerging lumbar spinal bending load. Herein it is moreover surmised that lumbar spinal bending loads under distinct landing conditions are predominantly modulated by herewith disparately deployed conditioned pre-activations of trunk muscles. METHODS: To test the above arrayed hypothesis, two successive studies were carried out. In STUDY 1, 17 subjects were repetitively assessed performing various drop landings (heigth: 15, 30, 45, 60cm; unilateral, bilateral, blindfolded, catching a ball) in a test-retest-design. Herein individual peak angular accelerations [αMAX] were derived from three-dimensional motion data of four trunk-segments (upper thoracic, lower thoracic, lumbar, pelvis). αMAX was herein assessed in flexion, lateral flexion, and rotation of each spinal joint, formed by two adjacent segments. Reliability of αMAX within and between test-days was evaluated by CV%, ICC 2.1, TRV%, and Bland & Altman Analysis (BIAS±LoA). Subsequently, peak flexion acceleration of the lumbo-pelvic joint [αFLEX[LS-PV]] was statistically compared to αMAX expressions of each other assessed spinal joint and motion plane (Mean ±SD, Independent Samples T-test). STUDY 2 deliberately assessed mere peak lumbo-pelvic flexion accelerations [αFLEX[LS-PV]] and electro-myographic trunk pre-activity prior to αFLEX[LS-PV] on 43 subjects performing varied landing tasks (height 45cm; with definite or indefinite predictability of a subsequent instant follow up jump). Subjects were contrasted with respect to their previous landing familiarity ( >1000 vs. <100 landings performed in the past 10 years) and gender. Differences of αFLEX[LS-PV] and muscular pre-activity between contrasted subject groups as between landing tasks were equally statistically tested by three-way mixed ANOVA with Post-hoc tests. Associations between αFLEX[LS-PV] and muscular pre-activity were factor-specifically assessed by Spearman’s rank order correlation coefficient (rS). Complementarily, muscular pre-activity was subdivided by landing phases [DROP, IMPACT] and discretely assessed for phase specific associations to αFLEX[LS-PV]. Each muscular activity was moreover pairwise compared between DROP and IMPACT (Mean ±SD, Dependent Samples T-test). RESULTS: αMAX was presented with overall high variability within test-days (CV =36%). Lowest intra-individual variability and highest reproducibility of αMAX between test-days was shown in flexion of the spine. αFLEX[LS-PV] showed largely consistent sig. higher magnitudes compared to αMAX presented in more cranial spinal joints and other motion planes. αFLEX[LS-PV] moreover gradually increased with escalations in landing heights. Landing unfamiliar subjects presented sig. higher αFLEX[LS-PV] in contrast to landing familiar ones (p=.016). M. Obliquus Int. with M. Transversus Abd. (66 ±32%MVC) and M. Erector Spinae (47 ±15%MVC) presented maredly highest activity in contrast to lowest activity of M. Rectus Abd. (10 ±4%MVC). Landing unfamiliar subjects showed compared to landing familiar ones sig. higher activity of M. Obliquus Ext. (17 ±8%MVC, 12 ±7%MVC, p= .044). M. Obliquus Ext. and its co-contraction ratio with M. Erector Spinae moreover exhibited low but sig. positive correlations to αFLEX[LS-PV] (rs=.39, rs=.31). Each trunk muscule distributed larger shares of its activity to DROP, whereas peak activations of most muscles emerged in the proportionally shorter IMPACT phase. Commonly increased muscular pre-activation particularly at IMPACT was found in landings with a contrived follow up jump and in female subjects, whereby αFLEX[LS-PV] was hereof only marginally affected. DISCUSSION: Highest spine segmental angular accelerations in drop landings emerge in sagittal flexion of the lumbar spine. The compensatory stabilisation of the spine appears to be preponderantly provided by a dorso-ventral co-contraction of M. Obliquus Int., M. Transversus Abd. and M. Erector Spinae. Elevated pre-activity of M. Obliquuis Ext. supposably characterises poor landing experience, which might engender increased bending loads to the lumbar spine. A pervasive large variability of spinal angular accelerations measured across all landing types, suggests a multifarious utilisation of diverse mechanisms compensating for spinal impacts in landing performances. A standardised assessment and valid evaluation of landing evoked lumbar bending loads is hereof largley confined. CONCLUSION: Drop landings elicit most strenuous lumbo-pelvic flexion accelerations, which can be appraised as representatives for high energetic bending loads to the spine. Such entail the highest risk to overload the spinal tissue, when landing demands exceed the individual’s landing skill. Previous landing experience and training appears to effectively improve muscular spine stabilisation pattern, diminishing spinal bending loads.
East Africa is a natural laboratory: Studying its unique geological and biological history can help us better inform our theories and models. Studying its present and future can help us protect its globally important biodiversity and ecosystem services. East African vegetation plays a central role in all these aspects, and this dissertation aims to quantify its dynamics through computer simulations.
Computer models help us recreate past settings, forecast into the future or conduct simulation experiments that we cannot otherwise perform in the field. But before all that, one needs to test their performance. The outputs that the model produced using the present day-inputs, agreed well with present-day observations of East African vegetation. Next, I simulated past vegetation for which we have fossil pollen data to compare. With computer models, we can fill the gaps of knowledge between sites where we have fossil pollen data from, and create a more complete picture of the past. Good level of agreement between model and pollen data where they overlapped in space further validated our model performance.
Once the model was tested and validated for the region, it became possible to probe one of the long standing questions regarding East African vegetation: How did East Africa lose its tropical forests? The present-day vegetation in the tropics is mainly characterized by continuous forests worldwide except in tropical East Africa, where forests only occur as patches. In a series of simulation experiments, I was able to show under which conditions these forest patches could have been connected and fragmented in the past. This study showed the sensitivity of East African vegetation to climate change and variability such as those expected under future climate change.
El Niño Southern Oscillation (ENSO) events that result from the fluctuations in temperature between the ocean and atmosphere, bring further variability to East African climate and are predicted to increase in intensity in the future. But climate models are still not good at capturing the pattens of these events. In a study where I quantified the influence of ENSO events on East African vegetation, I showed how different the future vegetation could be from what we currently predict with these climate models that lack accurate ENSO contribution. Consideration of these discrepancies is important for our future global carbon budget calculations and management decisions.
Ferroic materials have attracted a lot of attention over the years due to their wide range of applications in sensors, actuators, and memory devices. Their technological applications originate from their unique properties such as ferroelectricity and piezoelectricity. In order to optimize these materials, it is necessary to understand the coupling between their nanoscale structure and transient response, which are related to the atomic structure of the unit cell.
In this thesis, synchrotron X-ray diffraction is used to investigate the structure of ferroelectric thin film capacitors during application of a periodic electric field. Combining electrical measurements with time-resolved X-ray diffraction on a working device allows for visualization of the interplay between charge flow and structural motion. This constitutes the core of this work. The first part of this thesis discusses the electrical and structural dynamics of a ferroelectric Pt/Pb(Zr0.2,Ti0.8)O3/SrRuO3 heterostructure during charging, discharging, and polarization reversal. After polarization reversal a non-linear piezoelectric response develops on a much longer time scale than the RC time constant of the device. The reversal process is inhomogeneous and induces a transient disordered domain state. The structural dynamics under sub-coercive field conditions show that this disordered domain state can be remanent and can be erased with an appropriate voltage pulse sequence. The frequency-dependent dynamic characterization of a Pb(Zr0.52,Ti0.48)O3 layer, at the morphotropic phase boundary, shows that at high frequency, the limited domain wall velocity causes a phase lag between the applied field and both the structural and electrical responses. An external modification of the RC time constant of the measurement delays the switching current and widens the electromechanical hysteresis loop while achieving a higher compressive piezoelectric strain within the crystal.
In the second part of this thesis, time-resolved reciprocal space maps of multiferroic BiFeO3 thin films were measured to identify the domain structure and investigate the development of an inhomogeneous piezoelectric response during the polarization reversal. The presence of 109° domains is evidenced by the splitting of the Bragg peak.
The last part of this work investigates the effect of an optically excited ultrafast strain or heat pulse propagating through a ferroelectric BaTiO3 layer, where we observed an additional current response due to the laser pulse excitation of the metallic bottom electrode of the heterostructure.
In this thesis, we discuss the characterization of orthogroups by so-called disjunctions of identities. The orthogroups are a subclass of the class of completely regular semigroups, a generalization of the concept of a group. Thus there is for all elements of an orthogroup some kind of an inverse element such that both elements commute. Based on a fundamental result by A.H. Clifford, every completely regular semigroup is a semilattice of completely simple semigroups. This allows the description the gross structure of such semigroup. In particular every orthogroup is a semilattice of rectangular groups which are isomorphic to direct products of rectangular bands and groups. Semilattices of rectangular groups coming from various classes are characterized using the concept of an alternative variety, a generalization of the classical idea of a variety by Birkhoff.
After starting with some fundamental definitions and results concerning semigroups, we introduce the concept of disjunctions of identities and summarize some necessary properties. In particular we present some disjunction of identities which is sufficient for a semigroup for being completely regular. Furthermore we derive from this identity some statements concerning Rees matrix semigroups, a possible representation of completely simple semigroups. A main result of this thesis is the general description of disjunctions of identities such that a completely regular semigroup satisfying the described identity is a semilattice of left groups (right groups / groups). In this case the completely regular semigroup is an orthogroup. Furthermore we define various classes of rectangular groups such that there is an exponent taken from a set of pairwise coprime positive integers. An important result is the characterization of the class of all semilattices of particular rectangular groups (taken from the classes defined before) using a set-theoretic minimal set of disjunctions of identities. Additionally we investigate semilattices of groups (so-called Clifford semigroups). For this purpose we consider abelian groups of particular exponents and prove some well-known results from the theory of Clifford semigroups in an alternative way applying the concept of disjunctions of identities. As a practical application of the results concerning semilattices of left zero semigroups and right zero semigroups we identify a particular transformation semigroup. For more detailed information about the product of two arbitrary elements of a semilattice of semigroups we introduce the concept of strong semilattices of semigroups. It is well-known that a semilattice of groups is a strong semilattice of groups. So we can characterize a strong semilattice of groups of particular pairwise coprime exponents by disjunctions of identities. Additionally we describe the class of all strong semilattices of left zero semigroups and right zero semigroups with the help of such kind of identity, and we relate this statement to the theory of normal bands. A possible extension of the already described semilattices of rectangular groups can be achieved by an auxiliary total order (in terms of chains of semigroups). To this end we present a corresponding characterization due to disjunctions of identities which is obviously minimal. A list of open questions which have arisen during the research for this thesis, but left crude, is attached.
Synthesis of artificial building blocks for sortase-mediated ligation and their enzymatic linkage
(2018)
The enzyme Sortase A catalyzes the formation of a peptide bond between the recognition sequence LPXTG and an oligoglycine. While manifold ligations between proteins and various biomolecules, proteins and small synthetic molecules as well as proteins and surfaces have been reported, the aim of this thesis was to investigate the sortase-catalyzed linkage between artificial building blocks. Hence, this could pave the way for the use of sortase A for tasks from a chemical point of view and maybe even materials science.
For the proof of concept, the studied systems were kept as simple as possible at first by choosing easily accessible silica NPs and commercially available polymers. These building blocks were functionalized with peptide motifs for sortase-mediated ligation. Silica nanoparticles were synthesized with diameters of 60 and 200 nm and surface modified with C=C functionalities. Then, peptides bearing a terminal cysteine were covalently linked by means of a thiol-ene reaction. 60 nm SiO2 NPs were functionalized with pentaglycines, while peptides with LPETG motif were linked to 200 nm silica particles. Polyethyleneglycol (PEG) and poly(N isopropylacrylamide) (PNIPAM) were likewise functionalized with peptides by thiol-ene reaction between cysteine residues and C=C units in the polymer end groups. Hence, G5-PEG and PNIPAM-LPETG conjugates were obtained. With this set of building blocks, NP–polymer hybrids, NP–NP, and polymer–polymer structures were generated by sortase-mediated ligation and the product formation shown by transmission electron microscopy, MALDI-ToF mass spectrometry and dynamic light scatting, among others. Thus, the linkage of these artificial building blocks by the enzyme sortase A could be demonstrated.
However, when using commercially available polymers, the purification of the polymer–peptide conjugates was impossible and resulted in a mixture containing unmodified polymer. Therefore, strategies were developed for the own synthesis of pure peptide-polymer and polymer-peptide conjugates as building blocks for sortase-mediated ligation. The designed routes are based on preparing polymer blocks via RAFT polymerization from CTAs that are attached to N- or C-terminus, respectively, of a peptide. GG-PNIPAM was synthesized through attachment of a suitable RAFT CTA to Fmoc-GG in an esterification reaction, followed by polymerization of NIPAM and cleavage of the Fmoc protection group. Furthermore, several peptides were synthesized by solid-phase peptide synthesis. The linkage of a RAFT CTA (or
polymerization initiator) to the N-terminus of a peptide can be conducted in an automated fashion as last step in a peptide synthesizer. The synthesis of such a conjugate couldn’t be realized in the time frame of this thesis, but many promising strategies exist to continue this strategy using different coupling reagents. Such polymer building blocks can be used to synthesize protein-polymer conjugates catalyzed by sortase A and the approach can be carried on to the synthesis of block copolymers by using polymer blocks with peptide motifs on both ends.
Although the proof of concept demonstrated in this thesis only shows examples that can be also synthesized by exclusively chemical techniques, a toolbox of such building blocks will enable the future formation of new materials and pave the way for the application of enzymes in materials science. In addition to nanoparticle systems and block copolymers, this also includes combination with protein-based building blocks to form hybrid materials. Hence, sortase could become an enzymatic tool that complements established chemical linking technologies and provides specific peptide motifs that are orthogonal to all existing chemical functional groups.
Spectroscopy at the limit
(2018)
Thematic role assignment and word order preferences in the child language acquisition of Tagalog
(2018)
A critical task in daily communications is identifying who did what to whom in an utterance, or assigning the thematic roles agent and patient in a sentence. This dissertation is concerned with Tagalog-speaking children’s use of word order and morphosyntactic markers for thematic role assignment. It aims to explain children’s difficulties in interpreting sentences with a non-canonical order of arguments (i.e., patient-before-agent) by testing the predictions of the following accounts: the frequency account (Demuth, 1989), the Competition model (MacWhinney & Bates, 1989), and the incremental processing account (Trueswell & Gleitman, 2004). Moreover, the experiments in this dissertation test the influence of a word order strategy in a language like Tagalog, where the thematic roles are always unambiguous in a sentence, due to its verb-initial order and its voice-marking system. In Tagalog’s voice-marking system, the inflection on the verb indicates the thematic role of the noun marked by 'ang.' First, the possible basis for a word order strategy in Tagalog was established using a sentence completion experiment given to adults and 5- and 7-year-old children (Chapter 2) and a child-directed speech corpus analysis (Chapter 3). In general, adults and children showed an agent-before-patient preference, although adults’ preference was also affected by sentence voice. Children’s comprehension was then examined through a self-paced listening and picture verification task (Chapter 3) and an eye-tracking and picture selection task (Chapter 4), where word order (agent-initial or patient-initial) and voice (agent voice or patient voice) were manipulated. Offline (i.e., accuracy) and online (i.e., listening times, looks to the target) measures revealed that 5- and 7-year-old Tagalog-speaking children had a bias to interpret the first noun as the agent. Additionally, the use of word order and morphosyntactic markers was found to be modulated by voice. In the agent voice, children relied more on a word order strategy; while in the patient voice, they relied on the morphosyntactic markers. These results are only partially explained by the accounts being tested in this dissertation. Instead, the findings support computational accounts of incremental word prediction and learning such as Chang, Dell, & Bock’s (2006) model.
Future magnetic recording industry needs a high-density data storage technology. However, switching the magnetization of small bits requires high magnetic fields that cause excessive heat dissipation. Therefore, controlling magnetism without applying external magnetic field is an important research topic for potential applications in data storage devices with low power consumption. Among the different approaches being investigated, two of them stand out, namely i) all-optical helicity dependent switching (AO-HDS) and ii) ferroelectric control of magnetism. This thesis aims to contribute towards a better understanding of the physical processes behinds these effects as well as reporting new and exciting possibility for the optical and/or electric control of magnetic properties. Hence, the thesis contains two differentiated chapters of results; the first devoted to AO-HDS on TbFe alloys and the second to the electric field control of magnetism in an archetypal Fe/BaTiO3 system.
In the first part, the scalability of the AO-HDS to small laser spot-sizes of few microns in the ferrimagnetic TbFe alloy is investigated by spatially resolving the magnetic contrast with photo-emission electron microscopy (PEEM) and X-ray magnetic circular dichroism (XMCD). The results show that the AO-HDS is a local effect within the laser spot size that occurs in the ring-shaped region in the vicinity of thermal demagnetization. Within the ring region, the helicity dependent switching occurs via thermally activated domain wall motion. Further, the thesis reports on a novel effect of thickness dependent inversion of the switching orientation. It addresses some of the important questions like the role of laser heating and the microscopic mechanism driving AO-HDS.
The second part of the thesis focuses on the electric field control of magnetism in an artificial multiferroic heterostructure. The sample consists of an Fe wedge with thickness varying between 0:5 nm and 3 nm, deposited on top of a ferroelectric and ferroelastic BaTiO3 [001]-oriented single crystal substrate. Here, the magnetic contrast is imaged via PEEM and XMCD as a function of out-of-plane voltage. The results show the evidence of the electric field control of superparamagnetism mediated by a ferroelastic modification of the magnetic anisotropy. The changes in the magnetoelastic anisotropy drive the transition from the superparamagnetic to superferromagnetic state at localized sample positions.
Various ways of preparing enantiomerically pure 2-amino[6]helicene derivatives were explored. Ni(0) mediated cyclotrimerization of enantiopure triynes provided (M)- and (P)-7,8-bis(p-tolyl)hexahelicene-2-amine in >99% ee as well as its benzoderivative in >99% ee. The stereocontrol was found to be inefficient for a 2- aminobenzo[6]helicene congener with an embedded five-membered ring. Helically chiral imidazolium salts bearing one or two helicene moieties have been synthesized and applied in enantioselective [2+2+2] cyclotrimerization catalyzed by an in situ formed Ni(0)-NHC complex. The synthesis of the first helically chiral Pd- and Ru-NHC complexes and their application in enantioselective catalysis was demonstrated. The latter shows promising results in enantioselective olefin metathesis reactions. A mechanistic proposal for asymmetric ring closing metathesis is provided.
Eta Carinae
(2018)
The exceptional binary star Eta Carinae has been fascinating scientists and the people in the Southern hemisphere alike for hundreds of years. It survived an enormous outbreak, comparable to a supernova energy-wise, and for a short period became the brightest star of the night sky. From observations from the radio regime to X-rays the system's characteristics and its emission in photon energies up to ~ 50 keV are well studied today. The binary is composed of two massive stars of ~ 30 and ~ 100 solar masses. Either star drives a strong stellar wind that continuously carries away a fraction of its mass. The collision of these winds leads to a shock on each side of the encounter. In the wind-wind-collision region plasma gets heated when it is overrun by the shocks. Part of the emission seen in X-rays can be attributed to this plasma. Above ~ 50 keV the emission is no longer of thermal origin: the required plasma temperature exceeds the available mechanical energy input of the stellar winds. In contrast to its observational history in thermal energies observational evidence of Eta Carinae's non-thermal emission has only recently built up. In high-energy gamma-rays Eta Carinae is the only binary of its kind that has been detected unambiguously. Its energy spectrum reaches up to ~ hundred GeV, a regime where satellite-based gamma-ray experiments run out of statistics. Ground-based gamma-ray experiments have the advantage of large photon collection areas. H.E.S.S. is the only gamma-ray experiment located in the Southern hemisphere and thus able to observe Eta Carinae in this energy range. H.E.S.S. measures gamma-rays via electromagnetic showers of particles that very-high-energy gamma-rays initiate in the atmosphere. The main challenge in observations of Eta Carinae with H.E.S.S. is the UV emission of the Carina nebula that leads to a background that is up to 10 times stronger than usual for H.E.S.S. This thesis presents the first detection of a colliding-wind binary in very-high-energy gamma-rays and documents the studies that led to it. The differential gamma-ray energy spectrum of Eta Carinae is measured up to 700 GeV. A hadronic and leptonic origin of the gamma-ray emission is discussed and based on the comparison of cooling times a hadronic scenario is favoured.
Movement and navigation are essential for many organisms during some parts of their lives. This is also true for bacteria, which can move along surfaces and swim though liquid environments. They are able to sense their environment, and move towards environmental cues in a directed fashion.
These abilities enable microbial lifecyles in biofilms, improved food uptake, host infection, and many more. In this thesis we study aspects of the swimming movement - or motility - of the soil bacterium (P. putida). Like most bacteria, P. putida swims by rotating its helical flagella, but their arrangement differs from the main model organism in bacterial motility research: (E. coli). P. putida is known for its intriguing motility strategy, where fast and slow episodes can occur after each other. Up until now, it was not known how these two speeds can be produced, and what advantages they might confer to this bacterium.
Normally the flagella, the main component of thrust generation in bacteria, are not observable by ordinary light microscopy. In order to elucidate this behavior, we therefore used a fluorescent staining technique on a mutant strain of this species to specifically label the flagella, while leaving the cell body only faintly stained. This allowed us to image the flagella of the swimming bacteria with high spacial and temporal resolution with a customized high speed fluorescence microscopy setup. Our observations show that P. putida can swim in three different modes. First, It can swim with the flagella pushing the cell body, which is the main mode of swimming motility previously known from other bacteria. Second, it can swim with the flagella pulling the cell body, which was thought not to be possible in situations with multiple flagella. Lastly, it can wrap its flagellar bundle around the cell body, which results in a speed wich is slower by a factor of two. In this mode, the flagella are in a different physical conformation with a larger radius so the cell body can fit inside. These three swimming modes explain the previous observation of two speeds, as well as the non strict alternation of the different speeds.
Because most bacterial swimming in nature does not occur in smoothly walled glass enclosures under a microscope, we used an artificial, microfluidic, structured system of obstacles to study the motion of our model organism in a structured environment. Bacteria were observed in microchannels with cylindrical obstacles of different sizes and with different distances with video microscopy and cell tracking. We analyzed turning angles, run times, and run length, which we compared to a minimal model for movement in structured geometries. Our findings show that hydrodynamic interactions with the walls lead to a guiding of the bacteria along obstacles. When comparing the observed behavior with the statics of a particle that is deflected with every obstacle contact, we find that cells run for longer distances than that model.
Navigation in chemical gradients is one of the main applications of motility in bacteria. We studied the swimming response of P. putida cells to chemical stimuli (chemotaxis) of the common food preservative sodium benzoate. Using a microfluidic gradient generation device, we created gradients of varying strength, and observed the motion of cells with a video microscope and subsequent cell tracking. Analysis of different motility parameters like run lengths and times, shows that P. putida employs the classical chemotaxis strategy of E. coli: runs up the gradient are biased to be longer than those down the gradient. Using the two different run speeds we observed due to the different swimming modes, we classify runs into `fast' and `slow' modes with a Gaussian mixture model (GMM). We find no evidence that P. putida's uses its swimming modes to perform chemotaxis.
In most studies of bacterial motility, cell tracking is used to gather trajectories of individual swimming cells. These trajectories then have to be decomposed into run sections and tumble sections. Several algorithms have been developed to this end, but most require manual tuning of a number of parameters, or extensive measurements with chemotaxis mutant strains. Together with our collaborators, we developed a novel motility analysis scheme, based on generalized Kramers-Moyal-coefficients. From the underlying stochastic model, many parameters like run length etc., can be inferred by an optimization procedure without the need for explicit run and tumble classification. The method can, however, be extended to a fully fledged tumble classifier. Using this method, we analyze E. coli chemotaxis measurements in an aspartate analog, and find evidence for a chemotactic bias in the tumble angles.
The scientific drilling campaign PALEOVAN was conducted in the summer of 2010 and was part of the international continental drilling programme (ICDP). The main goal of the campaign was the recovery of a sensitive climate archive in the East of Anatolia. Lacustrine deposits underneath the lake floor of ‘Lake Van’ constitute this archive. The drilled core material was recovered from two locations: the Ahlat Ridge and the Northern Basin. A composite core was constructed from cored material of seven parallel boreholes at the Ahlat Ridge and covers an almost complete lacustrine history of Lake Van. The composite record offered sensitive climate proxies such as variations of total organic carbon, K/Ca ratios, or a relative abundance of arboreal pollen. These proxies revealed patterns that are similar to climate proxy variations from Greenland ice cores. Climate variations in Greenland ice cores have been dated by modelling the timing of orbital forces to affect the climate. Volatiles from melted ice aliquots are often taken as high-resolution proxies and provide a base for fitting the according temporal models.
The ICDP PALEOVAN scientific team fitted proxy data from the lacustrine drilling record to ice core data and constructed an age model. Embedded volcaniclastic layers had to be dated radiometrically in order to provide independent age constraints to the climate-stratigraphic age model. Solving this task by an application of the 40Ar/39Ar method was the main objective of this thesis. Earlier efforts to apply the 40Ar/39Ar dating resulted in inaccuracies that could not be explained satisfactorily.
The absence of K-rich feldspars in suitable tephra layers implied that feldspar crystals needed to be 500 μm in size minimum, in order to apply single-crystal 40Ar/39Ar dating. Some of the samples did not contain any of these grain sizes or only very few crystals of that size. In order to overcome this problem this study applied a combined single-crystal and multi-crystal approach with different crystal fractions from the same sample. The preferred method of a stepwise heating analysis of an aliquot of feldspar crystals has been applied to three samples. The Na-rich crystals and their young geological age required 20 mg of inclusion-free, non-corroded feldspars. Small sample volumes (usually 25 % aliquots of 5 cm3 of sample material – a spoon full of tephra) and the widespread presence of melt-inclusion led to the application of combined single- and multigrain total fusion analyses. 40Ar/39Ar analyses on single crystals have the advantage of being able to monitor the presence of excess 40Ar and detrital or xenocrystic contamination in the samples. Multigrain analyses may hide the effects from these obstacles. The results from the multigrain analyses are therefore discussed with respect to the findings from the respective cogenetic single crystal ages. Some of the samples in this study were dated by 40Ar/39Ar on feldspars on multigrain separates and (if available) in combination with only a few single crystals. 40Ar/39Ar ages from two of the samples deviated statistically from the age model. All other samples resulted in identical ages. The deviations displayed older ages than those obtained from the age model. t-Tests compared radiometric ages with available age control points from various proxies and from the relative paleointensity of the earth magnetic field within a stratigraphic range of ± 10 m. Concordant age control points from different relative chronometers indicated that deviations are a result of erroneous 40Ar/39Ar ages. The thesis argues two potential reasons for these ages: (1) the irregular appearance of 40Ar from rare melt- and fluid- inclusions and (2) the contamination of the samples with older crystals due to a rapid combination of assimilation and ejection.
Another aliquot of feldspar crystals that underwent separation for the application of 40Ar/39Ar dating was investigated for geochemical inhomogeneities. Magmatic zoning is ubiquitous in the volcaniclastic feldspar crystals. Four different types of magmatic zoning were detected. The zoning types are compositional zoning (C-type zoning), pseudo-oscillatory zoning of trace ele- ment concentrations (PO-type zoning), chaotic and patchy zoning of major and trace element concentrations (R-type zoning) and concentric zoning of trace elements (CC-type zoning). Sam- ples that deviated in 40Ar/39Ar ages showed C-type zoning, R-type zoning or a mix of different types of zoning (C-type and PO-type). Feldspars showing PO-type zoning typically represent the smallest grain size fractions in the samples. The constant major element compositions of these crystals are interpreted to represent the latest stages in the compositional evolution of feldspars in a peralkaline melt. PO-type crystals contain less melt- inclusions than other zoning types and are rarely corroded. This thesis concludes that feldspars that show PO-type zoning are most promising chronometers for the 40Ar/39Ar method, if samples provide mixed zoning types of Quaternary anorthoclase feldspars.
Five samples were dated by applying the 40Ar/39Ar method to volcanic glass. High fractions of atmospheric Ar (typically > 98%) significantly hampered the precision of the 40Ar/39Ar ages and resulted in rough age estimates that widely overlap the age model. Ar isotopes indicated that the glasses bore a chorine-rich Ar-end member. The chlorine-derived 38Ar indicated chlorine-rich fluid-inclusions or the hydration of the volcanic glass shards. This indication strengthened the evidence that irregularly distributed melt-inclusions and thus irregular distributed excess 40Ar influenced the problematic feldspar 40Ar/39Ar ages. Whether a connection between a corrected initial 40Ar/36Ar ratio from glasses to the 40Ar/36Ar ratios from pore waters exists remains unclear.
This thesis offers another age model, which is similarly based on the interpolation of the temporal tie points from geophysical and climate-stratigraphic data. The model used a PCHIP- interpolation (piecewise cubic hermite interpolating polynomial) whereas the older age model used a spline-interpolation. Samples that match in ages from 40Ar/39Ar dating of feldspars with the earlier published age model were additionally assigned with an age from the PCHIP- interpolation. These modelled ages allowed a recalculation of the Alder Creek sanidine mineral standard. The climate-stratigraphic calibration of an 40Ar/39Ar mineral standard proved that the age versus depth interpolations from PAELOVAN drilling cores were accurate, and that the applied chronometers recorded the temporal evolution of Lake Van synchronously.
Petrochemical discrimination of the sampled volcaniclastic material is also given in this thesis. 41 from 57 sampled volcaniclastic layers indicate Nemrut as their provenance. Criteria that served for the provenance assignment are provided and reviewed critically. Detailed correlations of selected PALEOVAN volcaniclastics to onshore samples that were described in detail by earlier studies are also discussed. The sampled volcaniclastics dominantly have a thickness of < 40 cm and have been ejected by small to medium sized eruptions. Onshore deposits from these types of eruptions are potentially eroded due to predominant strong winds on Nemrut and Süphan slopes. An exact correlation with the data presented here is therefore equivocal or not possible at all.
Deviating feldspar 40Ar/39Ar ages can possibly be explained by inherited 40Ar from feldspar xenocrysts contaminating the samples. In order to test this hypothesis diffusion couples of Ba were investigated in compositionally zoned feldspar crystals. The diffusive behaviour of Ba in feldspar is known, and gradients in the changing concentrations allowed for the calculation of the duration of the crystal’s magmatic development since the formation of the zoning interface. Durations were compared with degassing scenarios that model the Ar-loss during assimilation and subsequent ejection of the xenocrystals. Diffusive equilibration of the contrasting Ba concentrations is assumed to generate maximum durations as the gradient could have been developed in several growth and heating stages. The modelling does not show any indication of an involvement of inherited 40Ar in any of the deviating samples. However, the analytical set-up represents the lower limit of the required spatial resolution. Therefore, it cannot be excluded that the degassing modelling relies on a significant overestimation of the maximum duration of the magmatic history. Nevertheless, the modelling of xenocrystal degassing evidences that the irregular incorporation of excess 40Ar by melt- and fluid inclusions represents the most critical problem that needs to be overcome in dating volcaniclastic feldspars from the PALEOVAN drill cores. This thesis provides the complete background in generating and presenting 40Ar/39Ar ages that are compared to age data from a climate-stratigraphic model. Deviations are identified statistically and then discussed in order to find explanations from the age model and/or from 40Ar/39Ar geochronology. Most of the PALEOVAN stratigraphy provides several chronometers that have been proven for their synchronicity. Lacustrine deposits from Lake Van represent a key archive for reconstructing climate evolution in the eastern Mediterranean and in the Near East. The PALEOVAN record offers a climate-stratigraphic age model with a remarkable accuracy and resolution.
In this dissertation the lattice and the magnetic recovery dynamics of the two heavy rare-earth metals Dy and Gd after femtosecond photoexcitation are described. For the investigations, thin films of Dy and Gd were measured at low temperatures in the antiferromagnetic phase of Dy and close to room temperature in the ferromagnetic phase of Gd. Two different optical pump-x-ray probe techniques were employed: Ultrafast x-ray diffraction with hard x-rays (UXRD) yields the structural response of heavy rare-earth metals and resonant soft (elastic) x-ray diffraction (RSXD), which allows measuring directly changes in the helical antiferromagnetic order of Dy. The combination of both techniques enables to study the complex interaction between the magnetic and the phononic subsystems.
Microbiota analyses of patients suffering from various diseases suggest a beneficial role of Akkermansia muciniphila in the maintenance of health, whereas several studies in animal models of intestinal inflammation report that this organism may aggravate inflammation. Therefore, it is important to clarify under which circumstances A. muciniphila exerts negative effects in the intestine of its host.
The previously reported observation that A. muciniphila aggravates acute intestinal inflammation in the Salmonella enterica serovar Typhimurium infection mouse model colonized with a simplified human intestinal microbiota was investigated in this study. To unravel the underlying mechanism that led to the observed phenomenon, the time course of events following the infection was analyzed. In mice colonized with a simplified human intestinal microbiota, Salmonella infection induced clear signs of intestinal inflammation three days post infection. The inflammatory response was similar in mice colonized with A. muciniphila before Salmonella infection. These observations were independent of the time when colonization with the simplified human intestinal microbiota occurred, right after birth or only after weaning, and contradict the previous report.
To find out whether A. muciniphila influences the development of chronic intestinal inflammation in a genetically predisposed host, mono-associated interleukin-10-deficient (Il10-/-) mice, Il10-/- mice dual-associated with A. muciniphila and colitogenic Escherichia coli NC101, as well as Il10-/- mice associated with A. muciniphila and a simplified human intestinal microbiota were compared to the respective mice without A. muciniphila. The data clearly show that in these gnotobiotic Il10-/- mice, A. muciniphila neither induces intestinal inflammation itself nor modulates it after induction by a colitogenic bacterium or by a simplified human intestinal microbiota.
The experiments lead to the conclusion that the promotion of intestinal inflammation is not an intrinsic feature of this bacterium. The results of this study encourage the proposed use of A. muciniphila for the prevention or treatment of metabolic disorders.
Systems biology aims at investigating biological systems in its entirety by gathering and analyzing large-scale data sets about the underlying components. Computational systems biology approaches use these large-scale data sets to create models at different scales and cellular levels. In addition, it is concerned with generating and testing hypotheses about biological processes. However, such approaches are inevitably leading to computational challenges due to the high dimensionality of the data and the differences in the dimension of data from different cellular layers.
This thesis focuses on the investigation and development of computational approaches to analyze metabolite profiles in the context of cellular networks. This leads to determining what aspects of the network functionality are reflected in the metabolite levels. With these methods at hand, this thesis aims to answer three questions: (1) how observability of biological systems is manifested in metabolite profiles and if it can be used for phenotypical comparisons; (2) how to identify couplings of reaction rates from metabolic profiles alone; and (3) which regulatory mechanism that affect metabolite levels can be distinguished by integrating transcriptomics and metabolomics read-outs.
I showed that sensor metabolites, identified by an approach from observability theory, are more correlated to each other than non-sensors. The greater correlations between sensor metabolites were detected both with publicly available metabolite profiles and synthetic data simulated from a medium-scale kinetic model. I demonstrated through robustness analysis that correlation was due to the position of the sensor metabolites in the network and persisted irrespectively of the experimental conditions. Sensor metabolites are therefore potential candidates for phenotypical comparisons between conditions through targeted metabolic analysis.
Furthermore, I demonstrated that the coupling of metabolic reaction rates can be investigated from a purely data-driven perspective, assuming that metabolic reactions can be described by mass action kinetics. Employing metabolite profiles from domesticated and wild wheat and tomato species, I showed that the process of domestication is associated with a loss of regulatory control on the level of reaction rate coupling. I also found that the same metabolic pathways in Arabidopsis thaliana and Escherichia coli exhibit differences in the number of reaction rate couplings.
I designed a novel method for the identification and categorization of transcriptional effects on metabolism by combining data on gene expression and metabolite levels. The approach determines the partial correlation of metabolites with control by the principal components of the transcript levels. The principle components contain the majority of the transcriptomic information allowing to partial out the effect of the transcriptional layer from the metabolite profiles. Depending whether the correlation between metabolites persists upon controlling for the effect of the transcriptional layer, the approach allows us to group metabolite pairs into being associated due to post-transcriptional or transcriptional regulation, respectively. I showed that the classification of metabolite pairs into those that are associated due to transcriptional or post-transcriptional regulation are in agreement with existing literature and findings from a Bayesian inference approach.
The approaches developed, implemented, and investigated in this thesis open novel ways to jointly study metabolomics and transcriptomics data as well as to place metabolic profiles in the network context. The results from these approaches have the potential to provide further insights into the regulatory machinery in a biological system.
Physical computing covers the design and realization of interactive objects and installations and allows learners to develop concrete, tangible products of the real world, which arise from their imagination. This can be used in computer science education to provide learners with interesting and motivating access to the different topic areas of the subject in constructionist and creative learning environments. However, if at all, physical computing has so far mostly been taught in afternoon clubs or other extracurricular settings. Thus, for the majority of students so far there are no opportunities to design and create their own interactive objects in regular school lessons.
Despite its increasing popularity also for schools, the topic has not yet been clearly and sufficiently characterized in the context of computer science education. The aim of this doctoral thesis therefore is to clarify physical computing from the perspective of computer science education and to adequately prepare the topic both content-wise and methodologically for secondary school teaching. For this purpose, teaching examples, activities, materials and guidelines for classroom use are developed, implemented and evaluated in schools.
In the theoretical part of the thesis, first the topic is examined from a technical point of view. A structured literature analysis shows that basic concepts used in physical computing can be derived from embedded systems, which are the core of a large field of different application areas and disciplines. Typical methods of physical computing in professional settings are analyzed and, from an educational perspective, elements suitable for computer science teaching in secondary schools are extracted, e. g. tinkering and prototyping. The investigation and classification of suitable tools for school teaching show that microcontrollers and mini computers, often with extensions that greatly facilitate the handling of additional components, are particularly attractive tools for secondary education. Considering the perspectives of science, teachers, students and society, in addition to general design principles, exemplary teaching approaches for school education and suitable learning materials are developed and the design, production and evaluation of a physical computing construction kit suitable for teaching is described.
In the practical part of this thesis, with “My Interactive Garden”, an exemplary approach to integrate physical computing in computer science teaching is tested and evaluated in different courses and refined based on the findings in a design-based research approach. In a series of workshops on physical computing, which is based on a concept for constructionist professional development that is developed specifically for this purpose, teachers are empowered and encouraged to develop and conduct physical computing lessons suitable for their particular classroom settings. Based on their in-class experiences, a process model of physical computing teaching is derived. Interviews with those teachers illustrate that benefits of physical computing, including the tangibility of crafted objects and creativity in the classroom, outweigh possible drawbacks like longer preparation times, technical difficulties or difficult assessment. Hurdles in the classroom are identified and possible solutions discussed.
Empirical investigations in the different settings reveal that “My Interactive Garden” and physical computing in general have a positive impact, among others, on learner motivation, fun and interest in class and perceived competencies.
Finally, the results from all evaluations are combined to evaluate the design principles for physical computing teaching and to provide a perspective on the development of decision-making aids for physical computing activities in school education.
In the present work, we use symbolic regression for automated modeling of dynamical systems. Symbolic regression is a powerful and general method suitable for data-driven identification of mathematical expressions. In particular, the structure and parameters of those expressions are identified simultaneously.
We consider two main variants of symbolic regression: sparse regression-based and genetic programming-based symbolic regression. Both are applied to identification, prediction and control of dynamical systems.
We introduce a new methodology for the data-driven identification of nonlinear dynamics for systems undergoing abrupt changes. Building on a sparse regression algorithm derived earlier, the model after the change is defined as a minimum update with respect to a reference model of the system identified prior to the change. The technique is successfully exemplified on the chaotic Lorenz system and the van der Pol oscillator. Issues such as computational complexity, robustness against noise and requirements with respect to data volume are investigated.
We show how symbolic regression can be used for time series prediction. Again, issues such as robustness against noise and convergence rate are investigated us- ing the harmonic oscillator as a toy problem. In combination with embedding, we demonstrate the prediction of a propagating front in coupled FitzHugh-Nagumo oscillators. Additionally, we show how we can enhance numerical weather predictions to commercially forecast power production of green energy power plants.
We employ symbolic regression for synchronization control in coupled van der Pol oscillators. Different coupling topologies are investigated. We address issues such as plausibility and stability of the control laws found. The toolkit has been made open source and is used in turbulence control applications.
Genetic programming based symbolic regression is very versatile and can be adapted to many optimization problems. The heuristic-based algorithm allows for cost efficient optimization of complex tasks.
We emphasize the ability of symbolic regression to yield white-box models. In contrast to black-box models, such models are accessible and interpretable which allows the usage of established tool chains.
Biological invasions are the dispersal and following establishment of species outside their native habitat. Due to globalisation, connectivity of regions and climate changes the number of invasive species and their successful establishment is rising. The impact of these species is mostly negative, can induce community and habitat alterations, and is one main cause for biodiversity loss. This impact is particularly high and less researched in aquatic systems and microbial organisms and despite the high impact, the knowledge about overall mechanisms and specific factors affecting invasions are not fully understood. In general, the characteristics of the habitat, native community and invader determine the invasiveness.
In this thesis, I aimed to provide a better understanding of aquatic invasions focusing on the invader and its traits and identity. This thesis used a set of 12 strains of the invasive cyanobacterium <i>Cylindrospermopsis raciborskii</i> to examine the effect and impact of the invaders’ identity and genetic diversity. Further, the effect of timing on the invasion potential and success was determined, because aquatic systems in particular undergo seasonal fluctuations.
Most studies revealed a higher invasion success with increasing genetic diversity. Here, the increase of the genetic diversity, by either strain richness or phylogenetic dissimilarity, is not firstly driving the invasion, but the strain-identity. The high variability among the strains in traits important for invasions led to the highly varying strain-specific invasion success. This success was most dependent on nitrogen uptake and efficient resource use. The lower invasion success into communities comprising further N-fixing species indicates <i>C. raciborskii</i> can use this advantage only without the presence of competitive species. The relief of grazing pressure, which is suggested to be more important in aquatic invasions, was only promoting the invasion when unselective and larger consumers were present. High abundances of unselective consumers hampered the invasion success.
This indicates a more complex and temporal interplay of competitive and consumptive resistance mechanisms during the invasion process. Further, the fluctuation abundance and presence of competitors (= primary producers) and consumers (= zooplankton) in lakes can open certain ‘invasion windows’.
Remarkably, the composition of the resident community was also strain-specific affected and altered, independent of a high or low invasion success. Prior, this was only documented on the species level. Further, investigations on the population of invasive strains can reveal more about the invasion patterns and how multiple strain invasions change resident communities.
The present dissertation emphasises the importance of invader-addition experiments with a community context and the importance of the strain-level for microbial invasions and in general, e.g. for community assemblies and the outcome of experiments. The strain-specific community changes, also after days, may explain some sudden changes in communities, which have not been explained yet. This and further knowledge may also facilitate earlier and less cost-intensive management to step in, because these species are rarely tracked until they reach a high abundance or bloom, because of their small size.
Concluded for <i>C. raciborskii</i>, it shows that this species is no ‘generalistic’ invader and its invasion success depends more on the competitor presence than grazing pressure. This may explain its, still unknown, invasion pattern, as <i>C. raciborskii</i> is not found in all lakes of a region.
In the thesis there are constructed new quantizations for pseudo-differential boundary value problems (BVPs) on manifolds with edge. The shape of operators comes from Boutet de Monvel’s calculus which exists on smooth manifolds with boundary. The singular case, here with edge and boundary, is much more complicated. The present approach simplifies the operator-valued symbolic structures by using suitable Mellin quantizations on infinite stretched model cones of wedges with boundary. The Mellin symbols themselves are, modulo smoothing ones, with asymptotics, holomorphic in the complex Mellin covariable. One of the main results is the construction of parametrices of elliptic elements in the corresponding operator algebra, including elliptic edge conditions.
Basaltic fissure eruptions, such as on Hawai'i or on Iceland, are thought to be driven by the lateral propagation of feeder dikes and graben subsidence. Associated solid earth processes, such as deformation and structural development, are well studied by means of geophysical and geodetic technologies. The eruptions themselves, lava fountaining and venting dynamics, in turn, have been much less investigated due to hazardous access, local dimension, fast processes, and resulting poor data availability.
This thesis provides a detailed quantitative understanding of the shape and dynamics of lava fountains and the morphological changes at their respective eruption sites. For this purpose, I apply image processing techniques, including drones and fixed installed cameras, to the sequence of frames of video records from two well-known fissure eruptions in Hawai'i and Iceland. This way I extract the dimensions of multiple lava fountains, visible in all frames. By putting these results together and considering the acquisition times of the frames I quantify the variations in height, width and eruption velocity of the lava fountains. Then I analyse these time-series in both time and frequency domains and investigate the similarities and correlations between adjacent lava fountains. Following this procedure, I am able to link the dynamics of the individual lava fountains to physical parameters of the magma transport in the feeder dyke of the fountains.
The first case study in this thesis focuses on the March 2011 Pu'u'O'o eruption, Hawai'i, where a continuous pulsating behaviour at all eight lava fountains has been observed. The lava fountains, even those from different parts of the fissure that are closely connected, show a similar frequency content and eruption behaviour. The regular pattern in the heights of lava fountain suggests a controlling process within the magma feeder system like a hydraulic connection in the underlying dyke, affecting or even controlling the pulsating behaviour.
The second case study addresses the 2014-2015 Holuhraun fissure eruption, Iceland. In this case, the feeder dyke is highlighted by the surface expressions of graben-like structures and fault systems. At the eruption site, the activity decreases from a continuous line of fire of ~60 vents to a limited number of lava fountains. This can be explained by preferred upwards magma movements through vertical structures of the pre-eruptive morphology. Seismic tremors during the eruption reveal vent opening at the surface and/or pressure changes in the feeder dyke. The evolving topography of the cinder cones during the eruption interacts with the lava fountain behaviour. Local variations in the lava fountain height and width are controlled by the conduit diameter, the depth of the lava pond and the shape of the crater. Modelling of the fountain heights shows that long-term eruption behaviour is controlled mainly by pressure changes in the feeder dyke.
This research consists of six chapters with four papers, including two first author and two co-author papers. It establishes a new method to analyse lava fountain dynamics by video monitoring. The comparison with the seismicity, geomorphologic and structural expressions of fissure eruptions shows a complex relationship between focussed flow through dykes, the morphology of the cinder cones, and the lava fountain dynamics at the vents of a fissure eruption.
The topic of this thesis is the experimental investigation of evaporating thin films on planar solid substrates and the enrichment, the crystal growth and Marangoni flows near the three phase line in the case of partially wetting mixtures of volatile and non volatile liquids. In short, it deals with the properties of planar liquid films and with those of thin liquid sections near the three phase contact line. In both cases the liquid looses continuously one component by evaporation. One topic is the rupture behavior of ultra-thin films of binary mixtures of a volatile solvent and a nonvolatile solute. It is studied how the thickness at which the film ruptures is related to the solute crystallization at the liquid/ substrate interface as soon as the solute reaches supersaturation. A universal relation between the rupture thickness and the saturation behaviour is presented. The second research subject are individual nanoparticles embedded in molecularly thin films at planar substrates. It is found that the nanoparticles cause an unexpectedly large film surface distortion (meniscus). This distortion can be measured quantitatively by conventional reflective microscopy although the nanoparticles are much smaller than the Rayleigh diffraction limit. Investigations with binary mixtures of volatile solvents and non-volatile solutes (polymers) aim at a better understanding/prediction of the final solute coverage, the timeresolved film thinning, the time-resolved solvent evaporation, and the evolution of the solute concentration within the thinning film. A quantiative theoretical description of the experimental findings is derived. Experiments of completely miscible binary mixtures of volatile liquids, which individually form continuous planar films show unexpectedly that films of mixtures are not necessarily continuous and planar. Rather, they may form surface
undulations or even rupture. This is explained with surface Marangoni flows. A new method for the exceptionally fast fabrication (mm/min) of ultralong aligned diphenylalanin single crystals via dip casting is presented. It is shown how the specific evaporation conditions at the three phase line can be used for a controlled peptide crystal growth process. It is further demonstrated how the confinement inside a smalll capillary affects the peptide crystallization and how this can be understood (and used).
Synthesis, assembly and thermo-responsivity of polymer-functionalized magnetic cobalt nanoparticles
(2018)
This thesis mainly covers the synthesis, surface modification, magnetic-field-induced assembly and thermo-responsive functionalization of superparamagnetic Co NPs initially stabilized by hydrophobic small molecules oleic acid (OA) and trioctylphosphine oxide (TOPO), as well as the synthesis of both superparamagnetic and ferromagnetic Co NPs by using end-functionalized-polystyrene as stabilizer.
Co NPs, due to their excellent magnetic and catalytic properties, have great potential application in various fields, such as ferrofluids, catalysis, and magnetic resonance imaging (MRI). Superparamagnetic Co NPs are especially interesting, since they exhibit zero coercivity. They get magnetized in an external magnetic field and reach their saturation magnetization rapidly, but no magnetic moment remains after removal of the applied magnetic field. Therefore, they do not agglomerate in the body when they are used in biomedical applications. Normally, decomposition of metallic precursors at high temperature is one of the most important methods in preparation of monodisperse magnetic NPs, providing tunability in size and shape. Hydrophobic ligands like OA, TOPO and oleylamine are often used to both control the growth of NPs and protect them from agglomeration. The as-prepared magnetic NPs can be used in biological applications as long as they are transferred into water. Moreover, their supercrystal assemblies have the potential for high density data storage and electronic devices. In addition to small molecules, polymers can also be used as surfactants for the synthesis of ferromagnetic and superparamagnetic NPs by changing the reaction conditions. Therefore, chapter 2 gives an overview on the basic concept of synthesis, surface modification and self-assembly of magnetic nanoparticles. Various examples were used to illustrate the recent work.
The hydrophobic Co NPs synthesized with small molecules as surfactants limit their biological applications, which require a hydrophilic or aqueous environment. Surface modification (e.g., ligand exchange) is a general idea for either phase transition or surface-functionalization. Therefore, in chapter 3, a ligand exchange process was conducted to functionalize the surface of Co NPs. PNIPAM is one of the most popular smart polymers and its lower critical solution temperature (LCST) is around 32 °C, with a reversible change in the conformation structure between hydrophobic and hydrophilic. The novel nanocomposites of superparamagnetic Co NPs and thermo-responsive PNIPAM are of great interest. Thus, well-defined superparamagnetic Co NPs were firstly synthesized through the thermolysis of cobalt carbonyl by using OA and TOPO as surfactants. A functional ATRP initiator, containing an amine (as anchoring group) and a 2-bromopropionate group (SI-ATRP initiator), was used to replace the original ligands. This process is rapid and facial for efficient surface functionalization and afterwards the Co NPs can be dispersed into polar solvent DMF without aggregation. FT-IR spectroscopy showed that the TOPO was completely replaced, but a small amount of OA remained on the surface. A TGA measurement allowed the calculation of the grafting density of the initiator as around 3.2 initiator/nm2. Then, the surface-initiated ATRP was conducted for the polymerization of NIPAM on the surface of Co NPs and rendered the nanocomposites water-dispersible. A temperature-dependent dynamic light scattering study showed the aggregation behavior of PNIPAM-coated Co NPs upon heating and this process was proven to be reversible. The combination of superparamagnetic and thermo-responsive properties in these hybrid nanoparticles is promising for future applications e.g. in biomedicine.
In chapter 4, the magnetic-field-induced assembly of superparamagnetic cobalt nanoparticles both on solid substrates and at liquid-air interface was investigated. OA- and TOPO-coated Co NPs were synthesized via the thermolysis of cobalt carbonyl and dispersed into either hexane or toluene. The Co NP dispersion was dropped onto substrates (e.g., TEM grid, silicon wafer) and at liquid-air (water-air or ethylene glycol-air) interface. Due to the attractive dipolar interaction, 1-D chains formed in the presence of an external magnetic field. It is known that the concentration and the strength of the magnetic field can affect the assembly behavior of superparamagnetic Co NPs. Therefore, the influence of these two parameters on the morphology of the assemblies was studied. The formed 1-D chains were shorter and flexible at either lower concentration of the Co NP dispersion or lower strength of the external magnetic field due to thermal fluctuation. However, by increasing either the concentration of the NP dispersion or the strength of the applied magnetic field, these chains became longer, thicker and straighter. The reason could be that a high concentration led to a high fraction of short dipolar chains, and their interaction resulted in longer and thicker chains under applied magnetic field. On the other hand, when the magnetic field increased, the induced moments of the magnetic nanoparticles became larger, which dominated over the thermal fluctuation. Thus, the formed short chains connected to each other and grew in length. Thicker chains were also observed through chain-chain interaction. Furthermore, the induced moments of the NPs tended to direct into one direction with increased magnetic field, thus the chains were straighter. In comparison between the assembly on substrates, at water-air interface and at ethylene glycol-air interface, the assembly of Co NPs in hexane dispersion at ethylene glycol-air interface showed the most regular and homogeneous chain structures due to the better spreading of the dispersion on ethylene glycol subphase than on water subphase and substrates. The magnetic-field-induced assembly of superparamagnetic nanoparticles could provide a powerful approach for applications in data storage and electronic devices.
Chapter 5 presented the synthesis of superparamagnetic and ferromagnetic cobalt nanoparticles through a dual-stage thermolysis of cobalt carbonyl (Co2(CO)8) by using polystyrene as surfactant. The amine end-functionalized polystyrene surfactants with different molecular weight were prepared via atom transfer radical polymerization technique. The molecular weight determination of polystyrene was conducted by gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry techniques. The results showed that, when the molecular weight distribution is low (Mw/Mn < 1.2), the measurement by GPC and MALDI-ToF MS provided nearly similar results. For example, the molecular weight of 10600 Da was obtained by MALDI-ToF MS, while GPC gave 10500 g/mol (Mw/Mn = 1.17). However, if the polymer is poly distributed, MALDI-ToF MS cannot provide an accurate value. This was exemplified for a polymer with a molecular weight of 3130 Da measured by MALDI-TOF MS, while GPC showed 2300 g/mol (Mw/Mn = 1.38). The size, size distribution and magnetic properties of the hybrid particles were different by changing either the molecular weight or concentration of the polymer surfactants. The analysis from TEM characterization showed that the size of cobalt nanoparticles stabilized with polystyrene of lower molecular weight (Mn = 2300 g/mol) varied from 12–22 nm, while the size with middle (Mn = 4500 g/mol) and higher molecular weight (Mn = 10500 g/mol) of polystyrene-coated cobalt nanoparticles showed little change. Magnetic measurements exhibited that the small cobalt particles (12 nm) were superparamagnetic, while larger particles (21 nm) were ferromagnetic and assembled into 1-D chains. The grafting density calculated from thermogravimetric analysis showed that a higher grafting density of polystyrene was obtained with lower molecular weight (Mn = 2300 g/mol) than those with higher molecular weight (Mn = 10500 g/mol). Due to the larger steric hindrance, polystyrene with higher molecular weight cannot form a dense shell on the surface of the nanoparticles, which resulted in a lower grafting density. Wide angle X-ray scattering measurements revealed the epsilon cobalt crystalline phases of both superparamagnetic Co NPs coated with polystyrene (Mn = 2300 g/mol) and ferromagnetic Co NPs coated with polystyrene (Mn = 10500 g/mol). Furthermore, a stability study showed that PS-Co NPs prepared with higher polymer concentration and polymer molecular weight exhibited a better stability.
Over the last decades mechanisms of recognition of morphologically complex words have been extensively examined in order to determine whether all word forms are stored and retrieved from the mental lexicon as wholes or whether they are decomposed into their morphological constituents such as stems and affixes. Most of the research in this domain focusses on English. Several factors have been argued to affect morphological processing including, for instance, morphological structure of a word (e.g., existence of allomorphic stem alternations) and its linguistic nature (e.g., whether it is a derived word or an inflected word form). It is not clear, however, whether processing accounts based on experimental evidence from English would hold for other languages. Furthermore, there is evidence that processing mechanisms may differ across various populations including children, adult native speakers and language learners. Recent studies claim that processing mechanisms could also differ between older and younger adults (Clahsen & Reifegerste, 2017; Reifegerste, Meyer, & Zwitserlood, 2017).
The present thesis examined how properties of the morphological structure, types of linguistic operations involved (i.e., the linguistic contrast between inflection and derivation) and characteristics of the particular population such as older adults (e.g., potential effects of ageing as a result of the cognitive decline or greater experience and exposure of older adults) affect initial, supposedly automatic stages of morphological processing in Russian and German. To this end, a series of masked priming experiments was conducted.
In experiments on Russian, the processing of derived -ost’ nouns (e.g., glupost’ ‘stupidity’) and of inflected forms with and without allomorphic stem alternations in 1P.Sg.Pr. (e.g., igraju – igrat’ ‘to play’ vs. košu – kosit’ ‘to mow’) was examined. The first experiment on German examined and directly compared processing of derived -ung nouns (e.g., Gründung ‘foundation’) and inflected -t past participles (e.g., gegründet ‘founded’), whereas the second one investigated the processing of regular and irregular plural forms (-s forms such as Autos ‘cars’ and -er forms such as Kinder ‘children’, respectively).
The experiments on both languages have shown robust and comparable facilitation effects for derived words and regularly inflected forms without stem changes (-t participles in German, forms of -aj verbs in Russian). Observed morphological priming effects could be clearly distinguished from purely semantic or orthographic relatedness between words. At the same time, we found a contrast between forms with and without allomorphic stem alternations in Russian and regular and irregular forms in German, with significantly more priming for unmarked stems (relative to alternated ones) and significantly more priming for regular (compared) word forms. These findings indicate the relevance of morphological properties of a word for initial stages of processing, contrary to claims made in the literature holding that priming effects are determined by surface form and meaning overlap only. Instead, our findings are more consistent with approaches positing a contrast between combinatorial, rule-based and lexically-stored forms (Clahsen, Sonnenstuhl, & Blevins, 2003).
The doctoral dissertation also addressed the role of ageing and age-related cognitive changes on morphological processing. The results obtained on this research issue are twofold. On the one hand, the data demonstrate effects of ageing on general measures of language performance, i.e., overall longer reaction times and/or higher accuracy rates in older than younger individuals. These findings replicate results from previous studies, which have been linked to the general slowing of processing speed at older age and to the larger vocabularies of older adults. One the other hand, we found that more specific aspects of language processing appear to be largely intact in older adults as revealed by largely similar morphological priming effects for older and younger adults. These latter results indicate that initial stages of morphological processing investigated here by means of the masked priming paradigm persist in older age. One caveat should, however, be noted. Achieving the same performance as a younger individual in a behavioral task may not necessarily mean that the same neural processes are involved. Older people may have to recruit a wider brain network than younger individuals, for example. To address this and related possibilities, future studies should examine older people’s neural representations and mechanisms involved in morphological processing.
Holocene climate variability is generally characterized by low frequency changes than compared to the last glaciations including the Lateglacial. However, there is vast evidence for decadal to centennial scale oscillations and millennial scale climate trends, which are within and beyond a human lifetime perception, respectively. Within the Baltic realm, a transitional zone between oceanic and continental climate influence, the impact of Holocene and Lateglacial climate and environmental change is currently partly understood. This is mainly attributed to the scarcity of well-dated and high-resolution sediment records and to the lacking continuity of already investigated archives.
The aim of this doctoral thesis is to reconstruct Holocene and Late Glacial climate variability on local to (over)regional scales based on varved (annually laminated) sediments from Lake Czechowskie down to annual resolution. This project was carried out within the Virtual Institute for Integrated Climate and Landscape Evolution Analyses (ICLEA) and funded by the Helmholtz Association and the Helmholtz Climate Initiative REKLIM (Regional Climate Change). ICLEA intended to gain a better understanding of climate variability and landscape evolution processes in the Northern Central European lowlands since the last deglaciation. REKLIM Topic 8 “Abrupt climate change derived from proxy data” aims at identifying spatiotemporal patterns of climate variability between e.g. higher and lower latitudes. The main aim of this thesis was (i) to establish a robust chronology based on a multiple dating approach for Lake Czechowskie covering the Late Glacial and Holocene and for the Trzechowskie palaeolake for the Lateglacial, respectively, (ii) to reconstruct past climatic and environmental conditions on centennial to multi-millennial time scales and (iii) to distinguish between local to regional different sediments responses to climate change.
Addressing the first aim, the Lake Czechowskie chronology has been established by a multiple dating approach comprising information from varve counting, tephrochronology, AMS 14C dating of terrestrial plant remains, biostratigraphy and 137Cs activity concentration measurements. Those independent age constraints covering the Lateglacial and the entire Holocene and have been further implemented in a Bayesian age model by using OxCal v.4.2. Thus, even within non-varved sediment intervals, robust chronological information has been used for absolute age determination. The identification of five cryptotephras, of which three are used as unambiguous isochrones, is furthermore a significant improvement of the Czechowskie chronology and currently unique for the Holocene within Poland. The first findings of coexisting early Holocene Hässeldalen and Askja-S cryptotephras within a varved sequence even allowed differential dating between both volcanic ashes and stimulated the discussion of revising the absolute ages of the Askja-S tephra.
The Trzechowskie palaeolake chronology has been established by a multiple dating approach comprising varve counting, tephrochronology, AMS 14C dating of terrestrial plant remains and biostratigraphy, covers the Lateglacial period (Allerød and Younger Dryas) and has been implemented in OxCal v.4.2. Those age constraints allowed regional correlation to other high-resolution climate archives and identifying leads and lags of proxy responses at the onset of the Younger Dryas.
The second aim has been accomplished by detailed micro-facies and geochemical analyses of the Czechowskie sediments for the entire Holocene. Thus, especially micro-facies changes had been linked to enhanced productivity at Lake Czechowskie. Most prominent changes have been recorded at 7.3, 6.5, 4.3 and 2.8 varve kyrs BP and are linked to a stepwise increasing influence of Atlantic air masses. Especially, the mid-Holocene change, which had been widely reported from palaeohydrological records in low latitudes, has been identified and linked to large scale reorganization of atmospheric circulation patterns. Thus, especially long-term changes of climatic and environmental boundary conditions are widely recorded by the Czechowskie sediments. The pronounced response to (multi)millennial scale changes is further corroborated by the lack of clear sediment responses to early Holocene centennial scale climate oscillations (e.g. the Preboreal Oscillation).
However, decadal scale changes at Lake Czechowskie during the most recent period (last 140 years) have been investigated in a lake comparison study. To fulfill the third aim of the doctoral thesis, three lakes in close vicinity to each other have been investigated in order to better distinguish how local, site-specific parameters, may superimpose regional climate driven changes. All lakes haven been unambiguously linked by the Askja AD1875 cryptotephra and independent varve chronologies. As a result, climate warming has only been recorded by sedimentation changes at the smallest and best sheltered lake (Głęboczek), whereas the largest lake (Czechowskie) and the shallowest lake (Jelonek) showed attenuated and less clear sediment responses, respectively. The different responses have been linked to morphological lake characteristics (lake size and depth, catchment area). This study highlights the potential of high-resolution lake comparison for robust proxy based climate reconstructions.
In summary, the doctoral thesis presents a high-resolution sediment record with an underlying age model, which is prerequisite for unprecedented age control down to annual resolution. Sediment proxy based climate reconstructions demonstrate the importance of the Czechowskie sediments for better understanding climate variability in the southern Baltic realm. Case studies showed the clear response on millennial time scale, while decadal scale fluctuations are either less well expressed or superimposed by local, site-specific parameters. The identification of volcanic ash layers is not only used for unambiguous isochrones, those are key tie lines for local to supra regional archive synchronization and establish the Lake Czechowskie as a key climate archive.
Plants are unable to move away from unwanted environments and therefore have to locally adapt to changing conditions. Arabidopsis thaliana (Arabidopsis), a model organism in plant biology, has been able to rapidly colonize a wide spectrum of environments with different biotic and abiotic challenges. In recent years, natural variation in Arabidopsis has shown to be an excellent resource to study genes underlying adaptive traits and hybridization’s impact on natural diversity. Studies on Arabidopsis hybrids have provided information on the genetic basis of hybrid incompatibilities and heterosis, as well as inheritance patterns in hybrids. However, previous studies have focused mainly on global accessions and yet much remains to be known about variation happening within a local growth habitat. In my PhD, I investigated the impact of heterozygosity at a local collection site of Arabidopsis and its role in local adaptation. I focused on two different projects, both including hybrids among Arabidopsis individuals collected around Tübingen in Southern Germany. The first project sought to understand the impact of hybridization on metabolism and growth within a local Arabidopsis collection site. For this, the inheritance patterns in primary and secondary metabolism, together with rosette size of full diallel crosses among seven parents originating from Southern Germany were analyzed. In comparison to primary metabolites, compounds from secondary metabolism were more variable and showed pronounced non-additive inheritance patterns. In addition, defense metabolites, mainly glucosinolates, displayed the highest degree of variation from the midparent values and were positively correlated with a proxy for plant size.
In the second project, the role of ACCELERATED CELL DEATH 6 (ACD6) in the defense response pathway of Arabidopsis necrotic hybrids was further characterized. Allelic interactions of ACD6 have been previously linked to hybrid necrosis, both among global and local Arabidopsis accessions. Hence, I characterized the early metabolic and ionic changes induced by ACD6, together with marker gene expression assays of physiological responses linked to its activation. An upregulation of simple sugars and metabolites linked to non-enzymatic antioxidants and the TCA cycle were detected, together with putrescine and acids linked to abiotic stress responses. Senescence was found to be induced earlier in necrotic hybrids and cytoplasmic calcium signaling was unaffected in response to temperature. In parallel, GFP-tagged constructs of ACD6 were developed.
This work therefore gave novel insights on the role of heterozygosity in natural variation and adaptation and expanded our current knowledge on the physiological and molecular responses associated with ACD6 activation.