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Institute
- Institut für Physik und Astronomie (26)
- Institut für Geowissenschaften (20)
- Institut für Biochemie und Biologie (18)
- Institut für Chemie (13)
- Hasso-Plattner-Institut für Digital Engineering GmbH (8)
- Institut für Umweltwissenschaften und Geographie (7)
- Department Psychologie (3)
- Institut für Mathematik (3)
- Department Linguistik (2)
- Department Sport- und Gesundheitswissenschaften (2)
In this thesis, I examine different A-bar movement dependencies in Igbo, a Benue-Congo language spoken in southern Nigeria. Movement dependencies are found in constructions where an element is moved to the left edge of the clause to express information-structural categories such as in questions, relativization and focus. I show that these constructions in Igbo are very uniform from a syntactic point of view. The constructions are built on two basic fronting operations: relativization and focus movement, and are biclausal. I further investigate several morphophonological effects that are found in these A-bar constructions. I propose that these effects are reflexes of movement that are triggered when an element is moved overtly in relativization or focus. This proposal helps to explain the tone patterns that have previously been assumed to be a property of relative clauses. The thesis adds to the growing body of tonal reflexes of A-bar movement reported for a few African languages. The thesis also provides an insight into the complementizer domain (C-domain) of Igbo.
Cardiac valves are essential for the continuous and unidirectional flow of blood throughout the body. During embryonic development, their formation is strictly connected to the mechanical forces exerted by blood flow. The endocardium that lines the interior of the heart is a specialized endothelial tissue and is highly sensitive to fluid shear stress. Endocardial cells harbor a signal transduction machinery required for the translation of these forces into biochemical signaling, which strongly impacts cardiac morphogenesis and physiology. To date, we lack a solid understanding on the mechanisms by which endocardial cells sense the dynamic mechanical stimuli and how they trigger different cellular responses. In the zebrafish embryo, endocardial cells at the atrioventricular canal respond to blood flow by rearranging from a monolayer to a double-layer, composed of a luminal cell population subjected to blood flow and an abluminal one that is not exposed to it. These early morphological changes lead to the formation of an immature valve leaflet. While previous studies mainly focused on genes that are positively regulated by shear stress, the mechanisms regulating cell behaviors and fates in cells that lack the stimulus of blood flow are largely unknown. One key discovery of my work is that the flow-sensitive Notch receptor and Krüppel-like factor (Klf) 2, one of the best characterized flow-regulated transcriptional factors, are activated by shear stress but that they function in two parallel signal transduction pathways. Each of these two pathways is essential for the rearrangement of atrioventricular cells into an immature double-layered valve leaflets. A second key discovery of my study is the finding that both Notch and Klf2 signaling negatively regulate the expression of the angiogenesis receptor Vegfr3/Flt4, which becomes restricted to abluminal endocardial cells of the valve leaflet. Within these cells, Flt4 downregulates the expressions of the cell adhesion proteins Alcam and VE-cadherin. A loss of Flt4 causes abluminal endocardial cells to ectopically express Notch, which is normally restricted to luminal cells, and impairs valve morphology. My study suggests that abluminal endocardial cells that do not experience mechanical stimuli loose Notch expression and this triggers expression of Flt4. In turn, Flt4 negatively regulates Notch on the abluminal side of the valve leaflet. These antagonistic signaling activities and fine-tuned gene regulatory mechanisms ultimately shape cardiac valve leaflets by inducing unique differences in the fates of endocardial cells.
The East Asian monsoons characterize the modern-day Asian climate, yet their geological history and driving mechanisms remain controversial. The southeasterly summer monsoon provides moisture, whereas the northwesterly winter monsoon sweeps up dust from the arid Asian interior to form the Chinese Loess Plateau. The onset of this loess accumulation, and therefore of the monsoons, was thought to be 8 million years ago (Ma). However, in recent years these loess records have been extended further back in time to the Eocene (56-34 Ma), a period characterized by significant changes in both the regional geography and global climate. Yet the extent to which these reconfigurations drive atmospheric circulation and whether the loess-like deposits are monsoonal remains debated. In this thesis, I study the terrestrial deposits of the Xining Basin previously identified as Eocene loess, to derive the paleoenvironmental evolution of the region and identify the geological processes that have shaped the Asian climate.
I review dust deposits in the geological record and conclude that these are commonly represented by a mix of both windblown and water-laid sediments, in contrast to the pure windblown material known as loess. Yet by using a combination of quartz surface morphologies, provenance characteristics and distinguishing grain-size distributions, windblown dust can be identified and quantified in a variety of settings. This has important implications for tracking aridification and dust-fluxes throughout the geological record.
Past reversals of Earth’s magnetic field are recorded in the deposits of the Xining Basin and I use these together with a dated volcanic ash layer to accurately constrain the age to the Eocene period. A combination of pollen assemblages, low dust abundances and other geochemical data indicates that the early Eocene was relatively humid suggesting an intensified summer monsoon due to the warmer greenhouse climate at this time. A subsequent shift from predominantly freshwater to salt lakes reflects a long-term aridification trend possibly driven by global cooling and the continuous uplift of the Tibetan Plateau. Superimposed on this aridification are wetter intervals reflected in more abundant lake deposits which correlate with highstands of the inland proto-Paratethys Sea. This sea covered the Eurasian continent and thereby provided additional moisture to the winter-time westerlies during the middle to late Eocene.
The long-term aridification culminated in an abrupt shift at 40 Ma reflected by the onset of windblown dust, an increase in steppe-desert pollen, the occurrence of high-latitude orbital cycles and northwesterly winds identified in deflated salt deposits. Together, these indicate the onset of a Siberian high atmospheric pressure system driving the East Asian winter monsoon as well as dust storms and was triggered by a major sea retreat from the Asian interior. These results therefore show that the proto-Paratethys Sea, though less well recognized than the Tibetan Plateau and global climate, has been a major driver in setting up the modern-day climate in Asia.
Largescale patterns of global land use change are very frequently accompanied by natural habitat loss. To assess the consequences of habitat loss for the remaining natural and semi-natural biotopes, inclusion of cumulative effects at the landscape level is required. The interdisciplinary concept of vulnerability constitutes an appropriate assessment framework at the landscape level, though with few examples of its application for ecological assessments. A comprehensive biotope vulnerability analysis allows identification of areas most affected by landscape change and at the same time with the lowest chances of regeneration.
To this end, a series of ecological indicators were reviewed and developed. They measured spatial attributes of individual biotopes as well as some ecological and conservation characteristics of the respective resident species community. The final vulnerability index combined seven largely independent indicators, which covered exposure, sensitivity and adaptive capacity of biotopes to landscape changes. Results for biotope vulnerability were provided at the regional level. This seems to be an appropriate extent with relevance for spatial planning and designing the distribution of nature reserves.
Using the vulnerability scores calculated for the German federal state of Brandenburg, hot spots and clusters within and across the distinguished types of biotopes were analysed. Biotope types with high dependence on water availability, as well as biotopes of the open landscape containing woody plants (e.g., orchard meadows) are particularly vulnerable to landscape changes. In contrast, the majority of forest biotopes appear to be less vulnerable. Despite the appeal of such generalised statements for some biotope types, the distribution of values suggests that conservation measures for the majority of biotopes should be designed specifically for individual sites. Taken together, size, shape and spatial context of individual biotopes often had a dominant influence on the vulnerability score.
The implementation of biotope vulnerability analysis at the regional level indicated that large biotope datasets can be evaluated with high level of detail using geoinformatics. Drawing on previous work in landscape spatial analysis, the reproducible approach relies on transparent calculations of quantitative and qualitative indicators. At the same time, it provides a synoptic overview and information on the individual biotopes. It is expected to be most useful for nature conservation in combination with an understanding of population, species, and community attributes known for specific sites. The biotope vulnerability analysis facilitates a foresighted assessment of different land uses, aiding in identifying options to slow habitat loss to sustainable levels. It can also be incorporated into planning of restoration measures, guiding efforts to remedy ecological damage. Restoration of any specific site could yield synergies with the conservation objectives of other sites, through enhancing the habitat network or buffering against future landscape change.
Biotope vulnerability analysis could be developed in line with other important ecological concepts, such as resilience and adaptability, further extending the broad thematic scope of the vulnerability concept. Vulnerability can increasingly serve as a common framework for the interdisciplinary research necessary to solve major societal challenges.
Even though the majority of individuals know that exercising is healthy, a high percentage struggle to achieve the recommended amount of exercise. The (social-cognitive) theories that are commonly applied to explain exercise motivation refer to the assumption that people base their decisions mainly on rational reasoning. However, behavior is not only bound to reflection. In recent years, the role of automaticity and affect for exercise motivation has been increasingly discussed. In this dissertation, central assumptions of the affective–reflective theory of physical inactivity and exercise (ART; Brand & Ekkekakis, 2018), an exercise-specific dual-process theory that emphasizes the role of a momentary automatic affective reaction for exercise-decisions, were examined. The central aim of this dissertation was to investigate exercisers and non-exercisers automatic affective reactions to exercise-related stimuli (i.e., type-1 process). In particular, the two components of the ART’s type-1 process, that are, automatic associations with exercise and the automatic affective valuation to exercise, were under study.
In the first publication (Schinkoeth & Antoniewicz, 2017), research on automatic (evaluative) associations with exercise was summarized and evaluated in a systematic review. The results indicated that automatic associations with exercise appeared to be relevant predictors for exercise behavior and other exercise-related variables, providing evidence for a central assumption of the ART’s type-1 process. Furthermore, indirect methods seem to be suitable to assess automatic associations. The aim of the second publication (Schinkoeth, Weymar, & Brand, 2019) was to approach the somato-affective core of the automatic valuation of exercise using analysis of reactivity in vagal HRV while viewing exercise-related pictures. Results revealed that differences in exercise volume could be regressed on HRV reactivity. In light of the ART, these findings were interpreted as evidence of an inter-individual affective reaction elicited at the thought of exercise and triggered by exercise-stimuli. In the third publication (Schinkoeth & Brand, 2019, subm.), it was sought to disentangle and relate to each other the ART’s type-1 process components—automatic associations and the affective valuation of exercise. Automatic associations to exercise were assessed with a recoding-free variant of an implicit association test (IAT). Analysis of HRV reactivity was applied to approach a somatic component of the affective valuation, and facial reactions in a facial expression (FE) task served as indicators of the automatic affective reaction’s valence. Exercise behavior was assessed via self-report. The measurement of the affective valuation’s valence with the FE task did not work well in this study. HRV reactivity was predicted by the IAT score and did also statistically predict exercise behavior. These results thus confirm and expand upon the results of publication two and provide empirical evidence for the type-1 process, as defined in the ART. This dissertation advances the field of exercise psychology concerning the influence of automaticity and affect on exercise motivation. Moreover, both methodical implications and theoretical extensions for the ART can be derived from the results.
Depending on the biochemical and biotechnical approach, the aim of this work was to understand the mechanism of protein-glucan interactions in regulation and control of starch degradation. Although starch degradation starts with the phosphorylation process, the mechanisms by which this process is controlling and adjusting starch degradation are not yet fully understood. Phosphorylation is a major process performed by the two dikinases enzymes α-glucan, water dikinase (GWD) and phosphoglucan water dikinase (PWD). GWD and PWD enzymes phosphorylate the starch granule surface; thereby stimulate starch degradation by hydrolytic enzymes. Despite these important roles for GWD and PWD, so far the biochemical processes by which these enzymes are able to regulate and adjust the rate of phosphate incorporation into starch during the degradation process haven‘t been understood. Recently, some proteins were found associated with the starch granule. Two of these proteins are named Early Starvation Protein 1 (ESV1) and its homologue Like-Early Starvation Protein 1 (LESV). It was supposed that both are involved in the control of starch degradation, but their function has not been clearly known until now. To understand how ESV1 and LESV-glucan interactions are regulated and affect the starch breakdown, it was analyzed the influence of ESV1 and LESV proteins on the phosphorylating enzyme GWD and PWD and hydrolysing enzymes ISA, BAM, and AMY. However, the analysis determined the location of LESV and ESV1 in the chloroplast stroma of Arabidopsis. Mass spectrometry data predicted ESV1and LESV proteins as a product of the At1g42430 and At3g55760 genes with a predicted mass of ~50 kDa and ~66 kDa, respectively. The ChloroP program predicted that ESV1 lacks the chloroplast transit peptide, but it predicted the first 56 amino acids N-terminal region as a chloroplast transit peptide for LESV. Usually, the transit peptide is processed during transport of the proteins into plastids. Given that this processing is critical, two forms of each ESV1 and LESV were generated and purified, a full-length form and a truncated form that lacks the transit peptide, namely, (ESV1and tESV1) and (LESV and tLESV), respectively. Both protein forms were included in the analysis assays, but only slight differences in glucan binding and protein action between ESV1 and tESV1 were observed, while no differences in the glucan binding and effect on the GWD and PWD action were observed between LESV and tLESV. The results revealed that the presence of the N-terminal is not massively altering the action of ESV1 or LESV. Therefore, it was only used the ESV1 and tLESV forms data to explain the function of both proteins.
However, the analysis of the results revealed that LESV and ESV1 proteins bind strongly at the starch granule surface. Furthermore, not all of both proteins were released after their incubation with starches after washing the granules with 2% [w/v] SDS indicates to their binding to the deeper layers of the granule surface. Supporting of this finding comes after the binding of both proteins to starches after removing the free glucans chains from the surface by the action of ISA and BAM. Although both proteins are capable of binding to the starch structure, only LESV showed binding to amylose, while in ESV1, binding was not observed. The alteration of glucan structures at the starch granule surface is essential for the incorporation of phosphate into starch granule while the phosphorylation of starch by GWD and PWD increased after removing the free glucan chains by ISA. Furthermore, PWD showed the possibility of starch phosphorylation without prephosphorylation by GWD.
Biochemical studies on protein-glucan interactions between LESV or ESV1 with different types of starch showed a potentially important mechanism of regulating and adjusting the phosphorylation process while the binding of LESV and ESV1 leads to altering the glucan structures of starches, hence, render the effect of the action of dikinases enzymes (GWD and PWD) more able to control the rate of starch degradation. Despite the presence of ESV1 which revealed an antagonistic effect on the PWD action as the PWD action was decreased without prephosphorylation by GWD and increased after prephosphorylation by GWD (Chapter 4), PWD showed a significant reduction in its action with or without prephosphorylation by GWD in the presence of ESV1 whether separately or together with LESV (Chapter 5). However, the presence of LESV and ESV1 together revealed the same effect compared to the effect of each one alone on the phosphorylation process, therefore it is difficult to distinguish the specific function between them. However, non-interactions were detected between LESV and ESV1 or between each of them with GWD and PWD or between GWD and PWD indicating the independent work for these proteins. It was also observed that the alteration of the starch structure by LESV and ESV1 plays a role in adjusting starch degradation rates not only by affecting the dikinases but also by affecting some of the hydrolysing enzymes since it was found that the presence of LESV and ESV1leads to the reduction of the action of BAM, but does not abolish it.
Ferruginous conditions were a prominent feature of the oceans throughout the Precambrian Eons and thus throughout much of Earth’s history. Organic matter mineralization and diagenesis within the ferruginous sediments that deposited from Earth’s early oceans likely played a key role in global biogeochemical cycling. Knowledge of organic matter mineralization in ferruginous sediments, however, remains almost entirely conceptual, as modern analogue environments are extremely rare and largely unstudied, to date. Lake Towuti on the island of Sulawesi, Indonesia is such an analogue environment and the purpose of this PhD project was to investigate the rates and pathways of organic matter mineralization in its ferruginous sediments.
Lake Towuti is the largest tectonic lake in Southeast Asia and is hosted in the mafic and ultramafic rocks of the East Sulawesi Ophiolite. It has a maximum water depth of 203 m and is weakly thermally stratified. A well-oygenated surface layer extends to 70 m depth, while waters below 130 m are persistently anoxic. Intensive weathering of the ultramafic catchment feeds the lake with large amounts of iron(oxy)hydroxides while the runoff contains only little sulfate, leading to sulfate-poor (< 20 µM) lake water and anoxic ferruginous conditions below 130 m. Such conditions are analogous to the ferruginous water columns that persisted throughout much of the Archean and Proterozoic eons. Short (< 35 cm) sediment cores were collected from different water depths corresponding to different bottom water redox conditions. Also, a drilling campaign of the International Continental Scientific Drilling Program (ICDP) retrieved a 114 m long sediment core dedicated for geomicrobiological investigations from a water depth of 153 m, well below the depth of oxygen penetration at the time of sampling. Samples collected from these sediment cores form the fundament of this thesis and were used to perform a suite of biogeochemical and microbiological analyses.
Geomirobiological investigations depend on uncontaminated samples. However, exploration of subsurface environments relies on drilling, which requires the use of a drilling fluid. Drilling fluid infiltration during drilling can not be avoided. Thus, in order to trace contamination of the sediment core and to identify uncontaminated samples for further analyses a simple and inexpensive technique for assessing contamination during drilling operations was developed and applied during the ICDP drilling campaign. This approach uses an aqeous fluorescent pigment dispersion commonly used in the paint industry as a particulate tracer. It has the same physical properties as conventionally used particulate tracers. However, the price is nearly four orders of magnitude lower solving the main problem of particulate tracer approaches. The approach requires only a minimum of equipment and allows for a rapid contamination assessment potentially even directly on site, while the senstitivity is in the range of already established approaches. Contaminated samples in the drill core were identified and not included for further geomicrobiological investigations.
Biogeochemical analyses of short sediment cores showed that Lake Towutis sediments are strongly depleted in electron acceptors commonly used in microbial organic matter mineralization (i.e. oxygen, nitrate, sulfate). Still, the sediments harbor high microbial cell densities, which are a function of redox conditions of Lake Towuti’s bottom water. In shallow water depths bottom water oxygenation leads to a higher input of labile organic matter and electron acceptors like sulfate and iron, which promotes a higher microbial abundance. Microbial analyses showed that a versatile microbial community with a potential to perform metabolisms related to iron and sulfate reduction, fermentation as well as methanogenesis inhabits Lake Towuti’s surface sediments.
Biogeochemical investigations of the upper 12 m of the 114 m sediment core showed that Lake Towuti’s sediment is extremely rich in iron with total concentrations up to 2500 µmol cm-3 (20 wt. %), which makes it the natural sedimentary environment with the highest total iron concentrations studied to date. In the complete or near absence of oxygen, nitrate and sulfate, organic matter mineralization in ferruginous sediments would be expected to proceed anaerobically via the energetically most favorable terminal electron acceptors available - in this case ferric iron. Astonishingly, however, methanogenesis is the dominant (>85 %) organic matter mineralization process in Lake Towuti’s sediment. Reactive ferric iron known to be available for microbial iron reduction is highly abundant throughout the upper 12 m and thus remained stable for at least 60.000 years. The produced methane is not oxidized anaerobically and diffuses out of the sediment into the water column. The proclivity towards methanogenesis, in these very iron-rich modern sediments, implies that methanogenesis may have played a more important role in organic matter mineralization thoughout the Precambrian than previously thought and thus could have been a key contributor to Earth’s early climate dynamics.
Over the whole sequence of the 114 m long sediment core siderites were identified and characterized using high-resolution microscopic and spectroscopic imaging together with microchemical and geochemical analyses. The data show early diagenetic growth of siderite crystals as a response to sedimentary organic matter mineralization. Microchemical zoning was identified in all siderite crystals. Siderite thus likely forms during diagenesis through growth on primary existing phases and the mineralogical and chemical features of these siderites are a function of changes in redox conditions of the pore water and sediment over time. Identification of microchemical zoning in ancient siderites deposited in the Precambrian may thus also be used to infer siderite growth histories in ancient sedimentary rocks including sedimentary iron formations.
Carbonates play a key role in the chemistry and dynamics of our planet. They are directly connected to the CO2 budget of our atmosphere and have a great impact on the deep carbon cycle. Moreover, recent studies have shown that carbonates are stable along the geothermal gradient down to Earth's lower mantle conditions, changing their crystal structure and related properties. Subducted carbonates may also react with silicates to form new phases. These reactions will redistribute elements, such as calcium (Ca), magnesium (Mg), iron (Fe) and carbon in the form of carbon dioxide (CO2), but also trace elements, that are carried by the carbonates. The trace elements of most interest are strontium (Sr) and rare earth elements (REE) which have been found to be important constituents in the composition of the primitive lower mantle and in mineral inclusions found in super-deep diamonds. However, the stability of carbonates in presence of mantle silicates at relevant temperatures is far from being well understood. Related to this, very little is known about distribution processes of trace elements between carbonates and mantle silicates. To shed light on these processes, we studied reactions between Sr- and REE-containing CaCO3 and Mg/Fe-bearing silicates of the system (Mg,Fe)2SiO4 - (Mg,Fe)SiO3 at high pressure and high temperature using synchrotron radiation based μ-X-ray diffraction (μ-XRD) and μ-X-ray fluorescence (μ-XRF) with μm-resolution in a laser-heated diamond anvil cell. X-ray diffraction is used to derive the structural changes of the phase reactions whereas X-ray fluorescence gives information on the chemical changes in the sample. In-situ experiments at high pressure and high temperature were performed at beamline P02.2 at PETRA III (Hamburg, Germany) and at beamline ID27 at ESRF (Grenoble, France). In addition to μ-XRD and μ-XRF, ex-situ measurements were made on the recovered sample material using transmission electron microscopy (TEM) and provided further insights into the reaction kinetics of carbonate-silicate reactions.
Our investigations show that CaCO3 is unstable in presence of mantle silicates above 1700 K and a reaction takes place in which magnesite plus CaSiO3-perovskite are formed. In addition, we observed that a high content of iron in the carbonate-silicate system favours dolomite formation during the reaction. The subduction of natural carbonates with significant amounts of Sr leads to a comprehensive investigation of the stability not only of CaCO3 phases in contact with mantle silicates but also of SrCO3 (and of Sr-bearing CaCO3). We found that SrCO3 reacts with (Mg,Fe)SiO3-perovskite to form magnesite and gained evidence for the formation of SrSiO3-perovskite.
To complement our study on the stability of SrCO3 at conditions of the Earth's lower mantle, we performed powder X-ray diffraction and single crystal X-ray diffraction experiments at ambient temperature and up to 49 GPa. We observed a transformation from SrCO3-I into a new high-pressure phase SrCO3-II at around 26 GPa with Pmmn crystal structure and a bulk modulus of 103(10) GPa. This information is essential to fully understand the phase behaviour and stability of carbonates in the Earth's lower mantle and to elucidate the possibility of introducing Sr into mantle silicates by carbonate-silicate reactions.
Simultaneous recording of μ-XRD and μ-XRF in the μm-range over the heated areas provides spatial information not only about phase reactions but also on the elemental redistribution during the reactions. A comparison of the spatial intensity distribution of the XRF signal before and after heating indicates a change in the elemental distribution of Sr and an increase in Sr-concentration was found around the newly formed SrSiO3-perovskite. With the help of additional TEM analyses on the quenched sample material the elemental redistribution was studied at a sub-micrometer scale. Contrary to expectations from combined μ-XRD and μ-XRF measurements, we found that La and Eu were not incorporated into the silicate phases, instead they tend to form either isolated oxide phases (e.g. Eu2O3, La2O3) or hydroxyl-bastnäsite (La(CO3)(OH)). In addition, we observed the transformation from (Mg,Fe)SiO3-perovskite to low-pressure clinoenstatite during pressure release. The monoclinic structure (P21/c) of this phase allows the incorporation of Ca as shown by additional EDX analyses and, to a minor extent, Sr too.
Based on our experiments, we can conclude that a detection of the trace elements in-situ at high pressure and high temperature remains challenging. However, our first findings imply that silicates may incorporate the trace elements provided by the carbonates and indicate that carbonates may have a major effect on the trace element contents of mantle phases.
The significant environmental and socioeconomic consequences of hydrometeorological extreme events, such as extreme rainfall, are constituted as a most important motivation for analyzing these events in the south-central Andes of NW Argentina. The steep topographic and climatic gradients and their interactions frequently lead to the formation of deep convective storms and consequently trigger extreme rainfall generation.
In this dissertation, I focus on identifying the dominant climatic variables and atmospheric conditions and their spatiotemporal variability leading to deep convection and extreme rainfall in the south-central Andes.
This dissertation first examines the significant contribution of temperature on atmospheric humidity (dew-point temperature, Td) and on convection (convective available potential energy, CAPE) for deep convective storms and hence, extreme rainfall along the topographic and climatic gradients. It was found that both climatic variables play an important role in extreme rainfall generation. However, their contributions differ depending on topographic and climatic sub-regions, as well as rainfall percentiles.
Second, this dissertation explores if (near real-time) the measurements conducted by the Global Navigation Satellite System (GNSS) on integrated water vapor (IWV) provide reliable data for explaining atmospheric humidity. I argue that GNSS-IWV, in conjunction with other atmospheric stability parameters such as CAPE, is able to decipher the extreme rainfall in the eastern central Andes. In my work, I rely on a multivariable regression analysis described by a theoretical relationship and fitting function analysis.
Third, this dissertation identifies the local impact of convection on extreme rainfall in the eastern Andes. Relying on a Principal Component Analysis (PCA) it was found that during the existence of moist and warm air, extreme rainfall is observed more often during local night hours. The analysis includes the mechanisms for this observation.
Exploring the atmospheric conditions and climatic variables leading to extreme rainfall is one of the main findings of this dissertation. The conditions and variables are a prerequisite for understanding the dynamics of extreme rainfall and predicting these events in the eastern Andes.
Cleft exhaustivity
(2020)
In this dissertation a series of experimental studies are presented which demonstrate that the exhaustive inference of focus-background it-clefts in English and their cross-linguistic counterparts in Akan, French, and German is neither robust nor systematic. The inter-speaker and cross-linguistic variability is accounted for with a discourse-pragmatic approach to cleft exhaustivity, in which -- following Pollard & Yasavul 2016 -- the exhaustive inference is derived from an interaction with another layer of meaning, namely, the existence presupposition encoded in clefts.
Completely water-based systems are of interest for the development of novel material for various reasons: On one hand, they provide benign environment for biological systems and on the other hand they facilitate effective molecular transport in a membrane-free environment. In order to investigate the general potential of aqueous two-phase systems (ATPSs) for biomaterials and compartmentalized systems, various solid particles were applied to stabilize all-aqueous emulsion droplets. The target ATPS to be investigated should be prepared via mixing of two aqueous solutions of water-soluble polymers, which turn biphasic when exceeding a critical polymer concentration. Hydrophilic polymers with a wide range of molar mass such as dextran/poly(ethylene glycol) (PEG) can therefore be applied. Solid particles adsorbed at the interfaces can be exceptionally efficient stabilizers forming so-called Pickering emulsions, and nanoparticles can bridge the correlation length of polymer solutions and are thereby the best option for water-in-water emulsions.
The first approach towards the investigation of ATPS was conducted with all aqueous dextran-PEG emulsions in the presence of poly(dopamine) particles (PDP) in Chapter 4. The water-in-water emulsions were formed with a PEG/dextran system via utilizing PDP as stabilizers. Studies of the formed emulsions were performed via laser scanning confocal microscope (CLSM), optical microscope (OM), cryo-scanning electron microscope (SEM) and tensiometry. The stable emulsions (at least 16 weeks) were demulsified easily via dilution or surfactant addition. Furthermore, the solid PDP at the water-water interface were crosslinked in order to inhibit demulsification of the Pickering emulsion. Transmission electron microscope (TEM) and scanning electron microscope (SEM) were used to visualize the morphology of PDP before and after crosslinking. PDP stabilized water-in-water emulsions were utilized in the following Chapter 5 to form supramolecular compartmentalized hydrogels. Here, hydrogels were prepared in pre-formed water-in-water emulsions and gelled via α-cyclodextrin-PEG (α-CD-PEG) inclusion complex formation. Studies of the formed complexes were performed via X-ray powder diffraction (XRD) and the mechanical properties of the hydrogels were measured with oscillatory shear rheology. In order to verify the compartmentalized state and its triggered decomposition, hydrogels and emulsions were assessed via OM, SEM and CLSM. The last chapter broadens the investigations from the previous two systems by utilizing various carbon nitrides (CN) as different stabilizers in ATPS. CN introduces another way to trigger demulsification, namely irradiation with visible light. Therefore, emulsification and demulsification with various triggers were probed. The investigated all aqueous multi-phase systems will act as model for future fabrication of biocompatible materials, cell micropatterning as well as separation of compartmentalized systems.
In the present study, we employ the angle-resolved photoemission spectroscopy (ARPES) technique to study the electronic structure of topological states of matter. In particular, the so-called topological crystalline insulators (TCIs) Pb1-xSnxSe and Pb1-xSnxTe, and the Mn-doped Z2 topological insulators (TIs) Bi2Te3 and Bi2Se3. The Z2 class of strong topological insulators is protected by time-reversal symmetry and is characterized by an odd number of metallic Dirac type surface states in the surface Brillouin zone. The topological crystalline insulators on the other hand are protected by the individual crystal symmetries and exhibit an even number of Dirac cones.
The topological properties of the lead tin chalcogenides topological crystalline insulators can be tuned by temperature and composition. Here, we demonstrate that Bi-doping of the Pb1-xSnxSe(111) epilayers induces a quantum phase transition from a topological crystalline insulator to a Z2 topological insulator. This occurs because Bi-doping lifts the fourfold valley degeneracy in the bulk. As a consequence a gap appears at ⌈¯, while the three Dirac cones at the M̅ points of the surface Brillouin zone remain intact. We interpret this new phase transition is caused by lattice distortion. Our findings extend the topological phase diagram enormously and make strong topological insulators switchable by distortions or electric field. In contrast, the bulk Bi doping of epitaxial Pb1-xSnxTe(111) films induces a giant Rashba splitting at the surface that can be tuned by the doping level. Tight binding calculations identify their origin as Fermi level pinning by trap states at the surface.
Magnetically doped topological insulators enable the quantum anomalous Hall effect (QAHE) which provide quantized edge states for lossless charge transport applications. The edge states are hosted by a magnetic energy gap at the Dirac point which has not been experimentally observed to date. Our low temperature ARPES studies unambiguously reveal the magnetic gap of Mn-doped Bi2Te3. Our analysis shows a five times larger gap size below the Tc than theoretically predicted. We assign this enhancement to a remarkable structure modification induced by Mn doping. Instead of a disordered impurity system, a self-organized alternating sequence of MnBi2Te4 septuple and Bi2Te3quintuple layers is formed. This enhances the wave-function overlap and gives rise to a large magnetic gap. Mn-doped Bi2Se3 forms similar heterostructure, but only a nonmagnetic gap is observed in this system. This correlates with the difference in magnetic anisotropy due to the much larger spin-orbit interaction in Bi2Te3 compared to Bi2Se3. These findings provide crucial insights for pushing lossless transport in topological insulators towards room-temperature applications.
The Andean Plateau (Altiplano-Puna Plateau) of the southern Central Andes is the second-highest orogenic plateau on our planet after Tibet. The Andean Plateau and its foreland exhibit a pronounced segmentation from north to south regarding the style and magnitude of deformation. In the Altiplano (northern segment), more than 300 km of tectonic shortening has been recorded, which started during the Eocene. A well-developed thin-skinned thrust wedge located at the eastern flank of the plateau (Subandes) indicates a simple-shear shortening mode. In contrast, the Puna (southern segment) records approximately half of the shortening of the Altiplano - and the shortening started later. The tectonic style in the Puna foreland switches to a thick-skinned mode, which is related to pure-shear shortening. In this study, carried out in the framework of the StRATEGy project, high-resolution 2D thermomechanical models were developed to systematically investigate controls of deformation patterns in the orogen-foreland pair. The 2D and 3D models were subsequently applied to study the evolution of foreland deformation and surface topography in the Altiplano-Puna Plateau. The models demonstrate that three principal factors control the foreland-deformation patterns: (i) strength differences in the upper lithosphere between the orogen and its foreland, rather than a strength difference in the entire lithosphere; (ii) gravitational potential energy of the orogen (GPE) controlled by crustal and lithospheric thicknesses, and (iii) the strength and thickness of foreland-basin sediments. The high-resolution 2D models are constrained by observations and successfully reproduce deformation structures and surface topography of different segments of the Altiplano-Puna plateau and its foreland. The developed 3D models confirm these results and suggest that a relatively high shortening rate in the Altiplano foreland (Subandean foreland fold-and-thrust belt) is due to simple-shear shortening facilitated by thick and mechanically weak sediments, a process which requires a much lower driving force than the pure-shear shortening deformation mode in the adjacent broken foreland of the Puna, where these thick sedimentary basin fills are absent. Lower shortening rate in the Puna foreland is likely accommodated in the forearc by the slab retreat.
Unlike today’s prevailing terrestrial features, the geologic past of Central Asia witnessed marine environments and conditions as well. A vast, shallow sea, known as proto-Paratethys, extended across Eurasia from the Mediterranean Tethys to the Tarim Basin in western China during Cretaceous to Paleogene times. This sea formed about 160 million years ago (during Jurassic times) when the waters of the Tethys Ocean flooded into Eurasia. It drastically retreated to the west and became isolated as the Paratethys during the Late Eocene-Oligocene (ca. 34 Ma).
Having well-constrained timing and paleogeography for the Cretaceous-Paleogene proto-Paratethys sea incursions in Central Asia is essential to properly understand and distinguish the controlling mechanisms and their link to Asian paleoenvironmental and paleoclimatic change. The Cretaceous-Paleogene tectonic evolution of the Pamir and Tibet and their far-field effects play a significant role on the sedimentological and structural evolution of the Central Asian basins and on the evolution of the proto-Paratethys sea fluctuations as well. Comparing the records of the sea incursions to the tectonic and eustatic events has paramount importance to reveal the controlling mechanisms behind the sea incursions. However, due to inaccuracies in the dating of rocks (mostly continental rocks and marine rocks with benthic microfossils providing low-resolution biostratigraphic constraints) and conflicting results, there has been no consensus on the timing of the sea incursions and interpretation of their records has been in question. Here, we present a new chronostratigraphic framework based on biostratigraphy and magnetostratigraphy as well as a detailed paleoenvironmental analysis for the Cretaceous and Paleogene proto-Paratethys Sea incursions in the Tajik and Tarim basins, in Central Asia. This enables us to identify the major drivers of marine fluctuations and their potential consequences on regional and global climate, particularly Asian aridification and the global carbon cycle perturbations such as the Paleocene-Eocene Thermal Maximum (PETM). To estimate the paleogeographic evolution of the proto-Paratethys Sea, the refined age constraints and detailed paleoenvironmental interpretations are combined with successive paleogeographic maps. Regional coastlines and depositional environments during the Cretaceous-Paleogene sea advances and retreats were drawn based on the results of this thesis and integrated with existing literature to generate new paleogeographic maps.
Before its final westward retreat in the Eocene, a total of six Cretaceous and Paleogene major sea incursions have been distinguished from the sedimentary records of the Tajik and Tarim basins in Central Asia. All have been studied and documented here.
We identify the presence of marine conditions already in the Early Cretaceous in the western Tajik Basin, followed by the Cenomanian (ca. 100 Ma) and Santonian (ca. 86 Ma) major marine incursions far into the eastern Tajik and Tarim basins separated by a Turonian-Coniacian (ca. 92-86 Ma) regression. Basin-wide tectonic subsidence analyses imply that the Early Cretaceous invasion of the sea into the Tajik Basin is related to increased Pamir tectonism (at ca. 130 – 90 Ma) in a retro-arc basin setting inferred to be linked to collision and subduction. This tectonic event mainly governed the Cenomanian (ca. 100 Ma) sea incursion in conjunction with a coeval global eustatic high resulting in the maximum geographic extent of the sea. The following Turonian-Coniacian (ca. 92-86 Ma) major regression, driven by eustasy, coincides with a sharp slowdown in tectonic subsidence related to a regime change in Pamir tectonism from compression to extension. The Santonian (ca. 86 Ma) major sea incursion was more likely controlled dominantly by eustasy as also evidenced by the coeval fluctuations in the west Siberian Basin. During the early Maastrichtian, the global Late Cretaceous cooling is inferred from the disappearance of mollusk-rich limestones and the dominance of bryozoan-rich and echinoderm-rich limestones in the Tajik Basin documenting the first evidence for the Late Cretaceous cooling event in Central Asia.
Following the last Cretaceous sea incursion, a major regional restriction event, marked by the exceptionally thick (≤ 400 m) shelf evaporites is assigned a Danian-Selandian age (ca. 63-59 Ma). This is followed by the largest recorded proto-Paratethys sea incursion with a transgression estimated as early Thanetian (ca. 59-57 Ma) and a regression within the Ypresian (ca. 53-52 Ma). The transgression of the next incursion is now constrained as early Lutetian (ca. 47-46 Ma), whereas its regression is constrained as late Lutetian (ca. 41 Ma) and is associated with a drastic increase in both tectonic subsidence and basin infilling. The age of the final and least pronounced sea incursion restricted to the westernmost margin of the Tarim Basin is assigned as Bartonian–Priabonian (ca. 39.7-36.7 Ma). We interpret the long-term westward retreat of the proto-Paratethys Sea starting at ca. 41 Ma to be associated with far-field tectonic effects of the Indo-Asia collision and Pamir/Tibetan plateau uplift. Short-term eustatic sea level transgressions are superimposed on this long-term regression and seem coeval with the transgression events in the other northern Peri-Tethyan sedimentary provinces for the 1st and 2nd Paleogene sea incursions. However, the last Paleogene sea incursion is interpreted as related to tectonism. The transgressive and regressive intervals of the proto-Paratethys Sea correlate well with the reported humid and arid phases, respectively in the Qaidam and Xining basins, thus demonstrating the role of the proto-Paratethys Sea as an important moisture source for the Asian interior and its regression as a contributor to Asian aridification.
We lastly study the mechanics, relative contribution and preservation efficiency of ancient epicontinental seas as carbon sinks with new and existing data, using organic rich (sapropel) deposits dated to the PETM from the extensive epicontinental proto-Paratethys and West Siberian seas. We estimate ca. 1390±230 Gt organic C burial, a substantial amount compared to previously estimated global total excess organic C burial (ca. 1700-2900 Gt) is focused in the proto-Paratethys and West Siberian seas alone. We also speculate that enhanced organic carbon burial later over much of the proto-Paratethys (and later Paratethys) basin (during the deposition of the Kuma Formation and Maikop series, repectively) may have majorly contributed to drawdown of atmospheric carbon dioxide before and during the EOT cooling and glaciation of Antarctica. For past periods with smaller epicontinental seas, the effectiveness of this negative carbon cycle feedback was arguably diminished, and the same likely applies to the present-day.
Im Jahre 1960 behauptete Yamabe folgende Aussage bewiesen zu haben: Auf jeder kompakten Riemannschen Mannigfaltigkeit (M,g) der Dimension n ≥ 3 existiert eine zu g konform äquivalente Metrik mit konstanter Skalarkrümmung. Diese Aussage ist äquivalent zur Existenz einer Lösung einer bestimmten semilinearen elliptischen Differentialgleichung, der Yamabe-Gleichung. 1968 fand Trudinger einen Fehler in seinem Beweis und infolgedessen beschäftigten sich viele Mathematiker mit diesem nach Yamabe benannten Yamabe-Problem. In den 80er Jahren konnte durch die Arbeiten von Trudinger, Aubin und Schoen gezeigt werden, dass diese Aussage tatsächlich zutrifft. Dadurch ergeben sich viele Vorteile, z.B. kann beim Analysieren von konform invarianten partiellen Differentialgleichungen auf kompakten Riemannschen Mannigfaltigkeiten die Skalarkrümmung als konstant vorausgesetzt werden.
Es stellt sich nun die Frage, ob die entsprechende Aussage auch auf Lorentz-Mannigfaltigkeiten gilt. Das Lorentz'sche Yamabe Problem lautet somit: Existiert zu einer gegebenen räumlich kompakten global-hyperbolischen Lorentz-Mannigfaltigkeit (M,g) eine zu g konform äquivalente Metrik mit konstanter Skalarkrümmung? Das Ziel dieser Arbeit ist es, dieses Problem zu untersuchen.
Bei der sich aus dieser Fragestellung ergebenden Yamabe-Gleichung handelt es sich um eine semilineare Wellengleichung, deren Lösung eine positive glatte Funktion ist und aus der sich der konforme Faktor ergibt. Um die für die Behandlung des Yamabe-Problems benötigten Grundlagen so allgemein wie möglich zu halten, wird im ersten Teil dieser Arbeit die lokale Existenztheorie für beliebige semilineare Wellengleichungen für Schnitte auf Vektorbündeln im Rahmen eines Cauchy-Problems entwickelt. Hierzu wird der Umkehrsatz für Banachräume angewendet, um mithilfe von bereits existierenden Existenzergebnissen zu linearen Wellengleichungen, Existenzaussagen zu semilinearen Wellengleichungen machen zu können. Es wird bewiesen, dass, falls die Nichtlinearität bestimmte Bedingungen erfüllt, eine fast zeitglobale Lösung des Cauchy-Problems für kleine Anfangsdaten sowie eine zeitlokale Lösung für beliebige Anfangsdaten existiert.
Der zweite Teil der Arbeit befasst sich mit der Yamabe-Gleichung auf global-hyperbolischen Lorentz-Mannigfaltigkeiten. Zuerst wird gezeigt, dass die Nichtlinearität der Yamabe-Gleichung die geforderten Bedingungen aus dem ersten Teil erfüllt, so dass, falls die Skalarkrümmung der gegebenen Metrik nahe an einer Konstanten liegt, kleine Anfangsdaten existieren, so dass die Yamabe-Gleichung eine fast zeitglobale Lösung besitzt. Mithilfe von Energieabschätzungen wird anschließend für 4-dimensionale global-hyperbolische Lorentz-Mannigfaltigkeiten gezeigt, dass unter der Annahme, dass die konstante Skalarkrümmung der konform äquivalenten Metrik nichtpositiv ist, eine zeitglobale Lösung der Yamabe-Gleichung existiert, die allerdings nicht notwendigerweise positiv ist. Außerdem wird gezeigt, dass, falls die H2-Norm der Skalarkrümmung bezüglich der gegebenen Metrik auf einem kompakten Zeitintervall auf eine bestimmte Weise beschränkt ist, die Lösung positiv auf diesem Zeitintervall ist. Hierbei wird ebenfalls angenommen, dass die konstante Skalarkrümmung der konform äquivalenten Metrik nichtpositiv ist. Falls zusätzlich hierzu gilt, dass die Skalarkrümmung bezüglich der gegebenen Metrik negativ ist und die Metrik gewisse Bedingungen erfüllt, dann ist die Lösung für alle Zeiten in einem kompakten Zeitintervall positiv, auf dem der Gradient der Skalarkrümmung auf eine bestimmte Weise beschränkt ist. In beiden Fällen folgt unter den angeführten Bedingungen die Existenz einer zeitglobalen positiven Lösung, falls M = I x Σ für ein beschränktes offenes Intervall I ist. Zum Schluss wird für M = R x Σ ein Beispiel für die Nichtexistenz einer globalen positiven Lösung angeführt.
Successfully completing any data science project demands careful consideration across its whole process. Although the focus is often put on later phases of the process, in practice, experts spend more time in earlier phases, preparing data, to make them consistent with the systems' requirements or to improve their models' accuracies. Duplicate detection is typically applied during the data cleaning phase, which is dedicated to removing data inconsistencies and improving the overall quality and usability of data. While data cleaning involves a plethora of approaches to perform specific operations, such as schema alignment and data normalization, the task of detecting and removing duplicate records is particularly challenging. Duplicates arise when multiple records representing the same entities exist in a database. Due to numerous reasons, spanning from simple typographical errors to different schemas and formats of integrated databases. Keeping a database free of duplicates is crucial for most use-cases, as their existence causes false negatives and false positives when matching queries against it. These two data quality issues have negative implications for tasks, such as hotel booking, where users may erroneously select a wrong hotel, or parcel delivery, where a parcel can get delivered to the wrong address. Identifying the variety of possible data issues to eliminate duplicates demands sophisticated approaches.
While research in duplicate detection is well-established and covers different aspects of both efficiency and effectiveness, our work in this thesis focuses on the latter. We propose novel approaches to improve data quality before duplicate detection takes place and apply the latter in datasets even when prior labeling is not available. Our experiments show that improving data quality upfront can increase duplicate classification results by up to 19%. To this end, we propose two novel pipelines that select and apply generic as well as address-specific data preparation steps with the purpose of maximizing the success of duplicate detection. Generic data preparation, such as the removal of special characters, can be applied to any relation with alphanumeric attributes. When applied, data preparation steps are selected only for attributes where there are positive effects on pair similarities, which indirectly affect classification, or on classification directly. Our work on addresses is twofold; first, we consider more domain-specific approaches to improve the quality of values, and, second, we experiment with known and modified versions of similarity measures to select the most appropriate per address attribute, e.g., city or country.
To facilitate duplicate detection in applications where gold standard annotations are not available and obtaining them is not possible or too expensive, we propose MDedup. MDedup is a novel, rule-based, and fully automatic duplicate detection approach that is based on matching dependencies. These dependencies can be used to detect duplicates and can be discovered using state-of-the-art algorithms efficiently and without any prior labeling. MDedup uses two pipelines to first train on datasets with known labels, learning to identify useful matching dependencies, and then be applied on unseen datasets, regardless of any existing gold standard. Finally, our work is accompanied by open source code to enable repeatability of our research results and application of our approaches to other datasets.
This work presents a new design for programming environments that promote the exploration of domain-specific software artifacts and the construction of graphical tools for such program comprehension tasks. In complex software projects, tool building is essential because domain- or task-specific tools can support decision making by representing concerns concisely with low cognitive effort. In contrast, generic tools can only support anticipated scenarios, which usually align with programming language concepts or well-known project domains.
However, the creation and modification of interactive tools is expensive because the glue that connects data to graphics is hard to find, change, and test. Even if valuable data is available in a common format and even if promising visualizations could be populated, programmers have to invest many resources to make changes in the programming environment. Consequently, only ideas of predictably high value will be implemented. In the non-graphical, command-line world, the situation looks different and inspiring: programmers can easily build their own tools as shell scripts by configuring and combining filter programs to process data.
We propose a new perspective on graphical tools and provide a concept to build and modify such tools with a focus on high quality, low effort, and continuous adaptability. That is, (1) we propose an object-oriented, data-driven, declarative scripting language that reduces the amount of and governs the effects of glue code for view-model specifications, and (2) we propose a scalable UI-design language that promotes short feedback loops in an interactive, graphical environment such as Morphic known from Self or Squeak/Smalltalk systems.
We implemented our concept as a tool building environment, which we call VIVIDE, on top of Squeak/Smalltalk and Morphic. We replaced existing code browsing and debugging tools to iterate within our solution more quickly. In several case studies with undergraduate and graduate students, we observed that VIVIDE can be applied to many domains such as live language development, source-code versioning, modular code browsing, and multi-language debugging. Then, we designed a controlled experiment to measure the effect on the time to build tools. Several pilot runs showed that training is crucial and, presumably, takes days or weeks, which implies a need for further research.
As a result, programmers as users can directly work with tangible representations of their software artifacts in the VIVIDE environment. Tool builders can write domain-specific scripts to populate views to approach comprehension tasks from different angles. Our novel perspective on graphical tools can inspire the creation of new trade-offs in modularity for both data providers and view designers.
Metal halide perovskites have merged as an attractive class of materials for photovoltaic applications due to their excellent optoelectronic properties. However, the long term stability is a roadblock for this class of material’s industrial pathway. Increasing evidence shows that intrinsic defects in perovskite promote material degradation. Consequently, understanding defect behaviours in perovskite materials is essential to further improve device stability and performance. This dissertation, hence, focuses on the topic of defect chemistry in halide perovskites.
The first part of the dissertation gives a brief overview of the defect properties in halide perovskite. Subsequently, the second part shows that doping methylammonium lead iodide with a small amount of alkaline earth metals (Sr and Mg) creates a higher quality, less defective material resulted in high open circuit voltages in both n-i-p and p-i-n architecture. It has been found that the mechanism of doping has two distinct regimes in which a low doping concentration enables the inclusion of the dopants into the lattice whereas higher doping concentrations lead to phase segregation. The material can be more n-doped in the low doping regime while being less n-doped in the high doping regime. The threshold of these two regimes is based on the atomic size of the dopants.
The next part of the dissertation examines the photo-induced degradation in methylammonium lead iodide. This degradation mechanism links closely to the formation and migration of ionic defects. After they are formed, these ionic defects can migrate, however, not freely depending on the defect concentration and their distribution. In fact, a highly concentrated defect region such as the grain boundaries can inhibit the migration of ionic defects. This has implications for material design as perovskite solar cells normally employ a polycrystalline thin-film which has a high density of grain boundary.
The final study presented in this PhD dissertation focuses on the stability of the state-of-the-art triple cation perovskite-based solar devices under external bias. Prolonged bias (more than three hours) is found to promote amorphization in halide perovskite. The amorphous phase is suspected to accumulate at the interfaces especially between the hole selective layer and perovskite. This amorphous phase inhibits the charge collection and severely affects the device performance. Nonetheless, the devices can recover after resting without bias in the dark. This amorphization is attributed to ionic defect migration most likely halides. This provides a new understanding of the potential degradation mechanisms in perovskite solar cells under operational conditions.
In recent years people have realised non-renewability of our modern society which relays on spending huge amounts of energy mostly produced from fosil fuels, such as oil and coal, and the shift towards more sustainable energy sources has started. However, sustainable sources of energy, such as wind-, solar- and hydro-energy, produce primarily electrical energy and can not just be poured in canister like many fosil fuels, creating necessity for rechragable batteries. However, modern Li-ion batteries are made from toxic heavy metals and sustainable alternatives are needed. Here we show that naturally abundant catecholic and guaiacyl groups can be utilised to replace heavy metals in Li-ion batteries.
Foremost vanillin, a naturally occurring food additive that can be sustainably synthesised from industrial biowaste, lignin, was utilised to synthesise materials that showed extraordinary performance as cathodes in Li-ion batteries. Furthermore, behaviour of catecholic and guiacyl groups in Li-ion system was compared, confirming usability of guiacayl containing biopolymers as cathodes in Li-ion batteries. Lastly, naturally occurring polyphenol, tannic acid, was incorporated in fully bioderived hybrid material that shows performance comparable to commercial Li-ion batteries and good stability.
This thesis presents an important advancement in understanding of biowaste derived cathode materials for Li-ion batteries. Further research should be conducted to better understand behaviour of guaiacyl groups during Li-ion battery cycling. Lastly, challenges of incorporation of lignin, an industrial biowaste, have to be addressed and lignin should be incorporated as a cathode material in Li-ion batteries.
Since the golden era of antibiotics natural products are of ever growing interest to both basic research and applied sciences as they are the main source of new bioactive compounds delivering lead structures for new pharmaceuticals with potent antibiotic, anti-inflammatory or anti-cancer activities. Alongside the technological advances in high-throughput genome sequencing and the better understanding of the general organization of those modular biosynthetic assembly lines of secondary metabolites, there was also a shift from wet-lab screening of active cell extracts towards algorithm-based in silico screening for new natural product biosynthesis gene clusters (BGCs). Although the increasing availability of full genome sequences revealed that such non-ribosomal peptide synthetases (NRPS), polyketide synthases (PKS) and ribosomally synthesized and post-translationally modified peptides (RiPPs) can be found in all three kingdoms of life, certain phyla like actinobacteria and cyanobacteria show a very high density of these secondary metabolite BGCs.
The facultative symbiotic, N2-fixing model organism N. punctiforme PCC73102 is a terrestrial type IV cyanobacterium that not only dedicates are very large fraction of its genome to secondary metabolite production but is also amenable to genetic modification. AntiSMASH analysis of the genome showed that there are sixteen potential secondary metabolite BGCs encoded in N. punctiforme, but until now there were only two compounds assigned to their respective BGC leaving the remaining fourteen orphan. This makes the organism a perfect subject for the establishment of a novel combinatorial genomic mining approach for the detection of new natural products.
In the course of this study a combinatorial approach of genomic mining, independent monitoring techniques and alteration of cultivation conditions lead to new insights in cyanobacterial natural product biosynthesis and ultimately to the description of a novel compound produced by N. punctiforme. With the generation and investigation of a reporter strain library consisting of CFP-producing transcriptional reporter mutants for every predicted secondary metabolite BGC of N. punctiforme, it could be shown that natural product expression is in fact not silent for all those BGCs where no compound can be detected. Instead several distinct expression patterns could be described highlighting that secondary metabolite production is under tight regulation and only a minor fraction of these BGCs is in fact silent under standard laboratory conditions. Furthermore, increasing light intensity and carbon dioxide availability and cultivating N. punctiforme to very high cell densities had a tremendous impact on the overall metabolic activity of the organism. Investigation of high density cultivated cell extracts ultimately lead to the detection of a so far undescribed set of microviridins with unusual extended peptide sequences named Microviridin N3 – N9. Both cultivation of the transcriptional reporter mutants as well as RTqPCR-based detection of secondary metabolite BGC transcription levels revealed that in fact 50% of N. punctiforme’s natural product BGCs are upregulated under high cell density conditions. In contrast to this very broad response, co-cultivation of N. punctiforme in chemical or physical contact with a N-deprived host plant (Blasia pusilla) lead to a very specific upregulation of two natural product BGCs, namely RIPP3 and RIPP4. Although this response could be confirmed by various independent monitoring techniques and heavy analytical efforts were spent, no compound could be assigned to either of these BGCs.
This study is the first in-depth systematic investigation of a cyanobacterial secondary metabolome by a combinatorial approach of genome mining and independent monitoring techniques that can serve as a new strategic approach to gain further insight into natural product synthesis of various organisms. Although there are single well described examples of secondary metabolites like the cell differentiation factor PatS in Anabaena sp. strain PCC 7120, the level and extent of regulation observed in this study is unprecedented and understanding of these mechanisms might be the key to streamline natural product discovery. However, the results of this study also highlight that induction of secondary metabolite BGCs is not the real challenge. Instead the new insights point towards analytical issues being a severe hurdle and finding reliable strategies to overcome these problems might as well drive natural product discovery.
Ein wesentlicher Grund für den fortdauernden wirtschaftlichen Rückstand Ostdeutschlands, im Vergleich zu Westdeutschland, liegt am geringeren Gewicht technologieintensiver Branchen und, damit zusammenhängend, an fehlenden regionalen Wachstumszentren („Clustern“). Die Économie des conventions (EC), ein wirtschaftswissenschaftliches und wirtschaftssoziologisches Paradigma, das in Frankreich in den 80er Jahren entstanden ist, ermöglicht die Analyse von Unternehmen und Märkten und wurde für die vorliegende Dissertation verwendet, um unterschiedliche „Qualitätskonventionen“ in einer vergleichenden Analyse in der west- und ostdeutschen Maschinenbaubranche zu identifizieren. Anhand von Studien des Instituts für Wirtschaftsforschung in Halle (IWH), der Baden-Württembergischen Landesregierung und des Verbandes des Deutschen Maschinen- und Anlagenbaus e. V. (VDMA) wurde das Feld auf fünf ostdeutsche und acht baden-württembergische Raumordungsregionen eingegrenzt und ein qualitativer Stichprobenplan entwickelt. Empirisch wurden 21 leitfadengestützte Experteninterviews mit Geschäftsführern der Maschinen- und Anlagenbaubranche durchgeführt, die mit der Qualitativen Inhaltsanalyse methodisch ausgewertet und dann mit Bezug zur EC zu Idealtypen verdichtet wurden.
Im Ost-West-Vergleich zeigte sich, dass für ostdeutsche Unternehmen eine Entwicklung hin zum Systemanbieter, die Projekte koordinieren (Netzwerkkonvention), um damit auf (internationalen) Märkten höhere Preise durchzusetzen (Marktkonvention), am vielversprechendsten ist. Damit einher geht der Aufbau und die Aufrechterhaltung von Netzwerken (Netzwerkkonvention), die Herausforderung besteht aber darin, auch mit Wettbewerbern (Marktkonvention) vertrauensvoll zusammen zu arbeiten. Des Weiteren zeigte sich, dass bei öffentlich geförderten Verbundprojekten („Clusterpolitik“) die Marktkonvention ebenfalls nicht dominant sein darf bzw. sie zumindest Kompromisse mit anderen Konventionen eingehen muss, damit diese Netzwerke nicht nach Ende der Förderperiode auseinander fallen. Diese Befunde decken sich mit Arbeiten aus der Wirtschaftsgeographie und verwandter Fächer, bei denen gezeigt wurde, dass erst ein Gebilde aus spezifischen regionale Institutionen technologisches Lernen ermöglicht bzw. dass insbesondere die gleichzeitige Ausprägung von Konkurrenz- und Kooperationsprinzipien („Coopetition“) auf der gleichen Wertschöpfungsstufe, es Unternehmen ermöglicht, neue wettbewerbsfähige Produkte auf den Markt zu bringen. Eine theoretisch fundierte Clusterpolitik sollte daher nicht nur Vernetzungsaktivitäten (Netzwerkkonvention), sondern auch den Wettbewerb (Marktkonvention) im Cluster mit fördern. Im Fazit wurden dann die Instrumente, die in der Literatur genannt werden, um vorhandene Clusterstrukturen weiter zu entwickeln, mit der rekonstruierten Typologie der Qualitätskonventionen verknüpft.
Methane is an important greenhouse gas contributing to global climate change. Natural environments and restored wetlands contribute a large proportion to the global methane budget. Methanogenic archaea (methanogens) and methane oxidizing bacteria (methanotrophs), the biogenic producers and consumers of methane, play key roles in the methane cycle in those environments. A large number of studies revealed the distribution, diversity and composition of these microorganisms in individual habitats. However, uncertainties exist in predicting the response and feedback of methane-cycling microorganisms to future climate changes and related environmental changes due to the limited spatial scales considered so far, and due to a poor recognition of the biogeography of these important microorganisms combining global and local scales.
With the aim of improving our understanding about whether and how methane-cycling microbial communities will be affected by a series of dynamic environmental factors in response to climate change, this PhD thesis investigates the biogeographic patterns of methane-cycling communities, and the driving factors which define these patterns at different spatial scales. At the global scale, a meta-analysis was performed by implementing 94 globally distributed public datasets together with environmental data from various natural environments including soils, lake sediments, estuaries, marine sediments, hydrothermal sediments and mud volcanos. In combination with a global biogeographic map of methanogenic archaea from multiple natural environments, this thesis revealed that biogeographic patterns of methanogens exist. The terrestrial habitats showed higher alpha diversities than marine environments. Methanoculleus and Methanosaeta (Methanothrix) are the most frequently detected taxa in marine habitats, while Methanoregula prevails in terrestrial habitats. Estuary ecosystems, the transition zones between marine and terrestrial/limnic ecosystems, have the highest methanogenic richness but comparably low methane emission rates. At the local scale, this study compared two rewetted fens with known high methane emissions in northeastern Germany, a coastal brackish fen (Hütelmoor) and a freshwater riparian fen (Polder Zarnekow). Consistent with different geochemical conditions and land-use history, the two rewetted fens exhibit dissimilar methanogenic and, especially, methanotrophic community compositions. The methanotrophic community was generally under-represented among the prokaryotic communities and both fens show similarly low ratios of methanotrophic to methanogenic abundances. Since few studies have characterized methane-cycling microorganisms in rewetted fens, this study provides first evidence that the rapid and well re-established methanogenic community in combination with the low and incomplete re-establishment of the methanotrophic community after rewetting contributes to elevated sustained methane fluxes following rewetting.
Finally, this thesis demonstrates that dispersal limitation only slightly regulates the biogeographic distribution patterns of methanogenic microorganisms in natural environments and restored wetlands. Instead, their existence, adaption and establishment are more associated with the selective pressures under different environmental conditions. Salinity, pH and temperature are identified as the most important factors in shaping microbial community structure at different spatial scales (global versus terrestrial environments). Predicted changes in climate, such as increasing temperature, changes in precipitation patterns and increasing frequency of flooding events, are likely to induce a series of environmental alterations, which will either directly or indirectly affect the driving environmental forces of methanogenic communities, leading to changes in their community composition and thus potentially also in methane emission patterns in the future.
Potato is the 4th most important food crop in the world. Especially in tropical and sub-tropical potato production, drought is a yield limiting factor. Potato is sensitive to water stress. Potato yield loss under water stress could be reduced by using tolerant varieties and adjusted agronomic practices. Direct selection for yield under water-stressed conditions requires long selection cycles. Thus, identification of markers for marker-assisted selection may speed up breeding. The objective of this thesis is to identify morphological markers for drought tolerance by continuously monitoring plant growth and canopy temperature with an automatic phenotyping system.
The phenotyping was performed in drought-stress experiments that were conducted in population A with 64 genotypes and population B with 21 genotypes in the screenhouse in 2015 and 2016 (population A) and in 2017 and 2018 (population B). Drought tolerance was quantified as deviation of the relative tuber starch yield from the experimental median (DRYM) and parent median (DRYMp). Relative tuber starch yield is starch yield under drought stress relative to the average starch yield of the respective cultivar under control conditions in the same experiment. The specific DRYM value was calculated based on the yield data of the same experiment or the global DRYM that was calculated from yield data derived from data combined over yeas of respective population or across multiple experiments including VALDIS and TROST experiments (2011-2016).
Analysis of variance found a significant effect of genotype on DRYM indicating that the tolerance variation required for marker identification was given in both populations.
Canopy growth was monitored continuously six times a day over five to ten weeks by a laser scanner system and yielded information on leaf area, plant height and leaf angle for population A and additionally on leaf inclination and light penetration depth for population B. Canopy temperature was measured 48 times a day over six to seven weeks by infrared thermometry in population B. From the continuous IRT surface temperature data set, the canopy temperature for each plant was selected by matching the time stamp of the IRT data with laser scanner data.
Mean, maximum, range and growth rate values were calculated from continuous laser scanner measurements of respective canopy parameters. Among the canopy parameters, the maximum and mean values in long-term stress conditions showed better correlation with DRYM values calculated in the same experiment than growth rate and diurnal range values. Therefore, drought tolerance index prediction was done from maximum and mean values of canopy parameters.
The tolerance index in specific experiment condition was linearly predicted by simple regression model from different single canopy parameters under long-term stress condition in population A (2016) and population B (2017 and 2018). Among the canopy parameters maximum light penetration depth (2017), mean leaf angle (2017, 2018, and 2016), mean leaf inclination or mean canopy temperature depression (2017 and 2018), maximum plant height (2017) were selected as tolerance predictors. However, no single parameters were sufficient to predict DRYM. Therefore, several independent parameters were integrated in a multiple regression model.
In multiple regression model, specific experiment DRYM values in population A was predicted from mean leaf angle (2016). In population B, specific tolerance could be predicted from maximum light penetration depth and mean leaf inclination (2017) and mean leaf inclination (2018) or mean canopy temperature depression and mean leaf angle (2018).
In data combined over season of population A, the multiple linear regression model selected maximum plant height and mean leaf angle as tolerance predictor. In Population B, mean leaf inclination was selected as tolerance predictor. However, in population A, the variation explained by the final model was too low.
Furthermore, the average tolerances respective to parent median (2011-2018) across FGH plants or all plants (FGH and field) were predicted from maximum plant height (population A) and maximum plant height and mean leaf inclination (population B). Altogether, canopy parameters could be used as markers for drought tolerance. Therefore, water stress breeding in potato could be speed up through using leaf inclination, light penetration depth, plant height and canopy temperature depression as markers for drought tolerance, especially in long-term stress conditions.
To investigate the reliability and stability of spherical harmonic models based on archeo/-paleomagnetic data, 2000 Geomagnetic models were calculated. All models are based on the same data set but with randomized uncertainties. Comparison of these models to the geomagnetic field model gufm1 showed that large scale magnetic field structures up to spherical harmonic degree 4 are stable throughout all models. Through a ranking of all models by comparing the dipole coefficients to gufm1 more realistic uncertainty estimates were derived than the authors of the data provide.
The derived uncertainty estimates were used in further modelling, which combines archeo/-paleomagnetic and historical data. The huge difference in data count, accuracy and coverage of these two very different data sources made it necessary to introduce a time dependent spatial damping, which was constructed to constrain the spatial complexity of the model. Finally 501 models were calculated by considering that each data point is a Gaussian random variable, whose mean is the original value and whose standard deviation is its uncertainty. The final model arhimag1k is calculated by taking the mean of the 501 sets of Gauss coefficients. arhimag1k fits different dependent and independent data sets well. It shows an early reverse flux patch at the core-mantle boundary between 1000 AD and 1200 AD at the location of the South Atlantic Anomaly today. Another interesting feature is a high latitude flux patch over Greenland between 1200 and 1400 AD. The dipole moment shows a constant behaviour between 1600 and 1840 AD.
In the second part of the thesis 4 new paleointensities from 4 different flows of the island Fogo, which is part of Cape Verde, are presented. The data is fitted well by arhimag1k with the exception of the value at 1663 of 28.3 microtesla, which is approximately 10 microtesla lower than the model suggest.
Seismic receiver arrays have variety of applications in seismology, particularly when the signal enhancement is a prerequisite to detect seismic events, and in situations where installing and maintaining sparse networks are impractical. This thesis has mainly focused on the development of a new approach for seismological source and receiver array design.The proposed approach deals with the array design task as an optimization problem. The criteria and prerequisite constraints in array design task are integrated in objective function definition and evaluation of a optimization process. Three cases are covered in this thesis: (1) a 2-D receiver array geometry optimization, (2) a 3-D source array optimization, and (3) an array application to monitor microseismic data, where the effect of different types of noise are evaluated.
A flexible receiver array design framework implements a customizable scenario modelling and optimization scheme by making use of synthetic seismograms. Using synthetic seismograms to evaluate array performance makes it possible to consider additional constraints, e.g. land ownership, site-specific noise levels or characteristics of the seismic sources under investigation. The use of synthetic array beamforming as an array design criteria is suggested. The framework is customized by designing a 2-D small scale receiver array to monitor earthquake swarm activity in northwest Bohemia/ Vogtland in central Europe. Two sub-functions are defined to verify the accuracy of horizontal slowness estimation; one to suppress aliasing effects due to possible secondary lobes of synthetic array beamforming calculated in horizontal slowness space, and the other to reduce the event's mislocation caused by miscalculation of the horizontal slowness vector. Subsequently, a weighting technique is applied to combine the sub-functions into one single scalar objective function to use in the optimization process.
The idea of optimal array is employed to design a 3-D source array, given a well-located catalog of events. The conditions to make source arrays are formulated in four objective functions and a weighted sum technique is used to combine them in one single scalar function. The criteria are: (1) accurate slowness vector estimation, (2) high waveform coherency, (3) low location error and (4) high energy of coda phases. The method is evaluated by two experiments, (1) a synthetic test using realistic synthetic seismograms, (2) using real seismograms, and for each case optimized SA elements are configured using the data from the Vogtland area.
The location of a possible scatterer in the velocity model, that makes the converted/reflected phases, e.g. sp-phases, is retrieved by a grid search method using the optimized SA. The accuracy of the approach and the obtained results demonstrated that the method is applicable to study the crustal structure and the location of crustal scatterers when the strong converted phases are observed in the data and a well-located catalog is available.
Small aperture arrays are employed in seismology for a variety of applications, ranging from pure event detection to monitor and study of microcosmic activities. The monitoring of microseismicity during temporary human activities is often difficult, as the signal-to-noise ratio is very low and noise is strongly increased during the operation. The combination of small aperture seismic arrays with shallow borehole sensors offers a solution. We tested this monitoring approach at two different sites, (1) accompanying a fracking experiment in sedimentary shale at 4~km depth, and (2) above a gas field under depletion. Arrays recordings are compared with recordings available from shallow borehole sensors and examples of detection and location performance of the array are given. The effect of different types of noise at array and borehole stations are compared and discussed.
In dieser Arbeit wurden Nano-Elektroden-Arrays zur Einzel-Objekt-Immobilisierung mittels Dielektrophorese verwendet. Hierbei wurden fluoreszenzmarkierte Nano-Sphären als Modellsystem untersucht und die gewonnenen Ergebnisse auf biologische Proben übertragen. Die Untersuchungen in Kombination mit verschiedenen Elektrodenlayouts führten zu einer deterministischen Vereinzelung der Nano-Sphären ab einem festen Größenverhältnis zwischen Nano-Sphäre und Durchmesser der Elektrodenspitzen. An den Proteinen BSA und R-PE konnte eine dielektrophoretische Immobilisierung ebenfalls demonstriert und R-PE Moleküle zur Vereinzelung gebracht werden. Hierfür war neben einem optimierten Elektrodenlayout, das durch Feldsimulationen den Feldgradienten betreffend gesucht wurde, eine Optimierung der Feldparameter, insbesondere von Spannung und Frequenz, erforderlich.
Neben der Dielektrophorese erfolgten auch Beobachtungen anderer Effekte des elektrischen Feldes, wie z.B. Elektrolyse an Nano-Elektroden und Strömungen über dem Elektroden-Array, hervorgerufen durch Joulesche Wärme und AC-elektroosmotischen Fluss. Zudem konnte Dielektrophorese an Silberpartikeln beobachtet werden und mittels Fluoreszenz-, Atom-Kraft-, Raster-Elektronen-Mikroskopie und energiedispersiver Röntgenspektroskopie untersucht werden. Schließlich wurden die verwendeten Objektive und Kameras auf ihre Lichtempfindlichkeit hin analysiert, so dass die Vereinzelung von Biomolekülen an Nano-Elektroden nachweisbar war.
Festzuhalten bleibt also, dass die Vereinzelung von Nano-Objekten und Biomolekülen an Nano-Elektroden-Arrays gelungen ist. Durch den parallelen Ansatz erlaubt dies, Aussagen über das Verhalten von Einzelmolekülen mit guter Statistik zu treffen.
As one of the most-produced commodity polymers, polypropylene draws considerable scientific and commercial interest as an electret material. In the present thesis, the influence of the surface chemical modification and crystalline reconstruction on the electret properties of the polypropylene thin films will be discussed. The chemical treatment with orthophosphoric acid can significantly improve the surface charge stability of the polypropylene electrets by introducing phosphorus- and oxygen-containing structures onto the modified surface. The thermally stimulated discharge measurement and charge profiling by means of piezoelectrically generated pressure steps are used to investigate the electret behaviour. It is concluded that deep traps of limited number density are created during the treatment with inorganic chemicals. Hence, the improvement dramatically decreases when the surface-charge density is substantially higher than ±1.2×10^(-3) C·m^(-2). The newly formed traps also show a higher trapping energy for negative charges. The energetic distributions of the traps in the non-treated and chemically treated samples offer an insight regarding the surface and foreign-chemical dominance on the charge storage and transport in the polypropylene electrets.
Additionally, different electret properties are observed on the polypropylene films with the spherulitic and transcrystalline structures. It indicates the dependence of the charge storage and transport on the crystallite and molecular orientations in the crystalline phase. In general, a more diverse crystalline growth in the spherulitic samples can result in a more complex energetic trap distribution, in comparison to that in a transcrystalline polypropylene. The double-layer transcrystalline polypropylene film with a crystalline interface in the middle can be obtained by crystallising the film in contact with rough moulding surfaces on both sides. A layer of heterocharges appears on each side of the interface in the double-layer transcrystalline polypropylene electrets after the thermal poling. However, there is no charge captured within the transcrystalline layers. The phenomenon reveals the importance of the crystalline interface in terms of creating traps with the higher activation energy in polypropylene. The present studies highlight the fact that even slight variations in the polypropylene film may lead to dramatic differences in its electret properties.
Near-Earth space represents a significant scientific and technological challenge. Particularly at magnetic low-latitudes, the horizontal magnetic field geometry at the dip equator and its closed field-lines support the existence of a distinct electric current system, abrupt electric field variations and the development of plasma irregularities. Of particular interest are small-scale irregularities associated with equatorial plasma depletions (EPDs). They are responsible for the disruption of trans-ionospheric radio waves used for navigation, communication, and Earth observation. The fast increase of satellite missions makes it imperative to study the near-Earth space, especially the phenomena known to harm space technology or disrupt their signals. EPDs correspond to the large-scale structure (i.e., tens to hundreds of kilometers) of topside F region irregularities commonly known as Spread F. They are observed as depleted-plasma density channels aligned with the ambient magnetic field in the post-sunset low-latitude ionosphere. Although the climatological variability of their occurrence in terms of season, longitude, local time and solar flux is well-known, their day to day variability is not. The sparse observations from ground-based instruments like radars and the few simultaneous measurements of ionospheric parameters by space-based instruments have left gaps in the knowledge of EPDs essential to comprehend their variability.
In this dissertation, I profited from the unique observations of the ESA’s Swarm constellation mission launched in November 2013 to tackle three issues that revealed novel and significant results on the current knowledge of EPDs. I used Swarm’s measurements of the electron density, magnetic, and electric fields to answer, (1.) what is the direction of propagation of the electromagnetic energy associated with EPDs?, (2.) what are the spatial and temporal characteristics of the electric currents (field-aligned and diamagnetic currents) related to EPDs, i.e., seasonal/geographical, and local time dependencies?, and (3.) under what conditions does the balance between magnetic and plasma pressure across EPDs occur?
The results indicate that: (1.) The electromagnetic energy associated with EPDs presents a preference for interhemispheric flows; that is, the related Poynting flux directs from one magnetic hemisphere to the other and varies with longitude and season. (2.) The field-aligned currents at the edges of EPDs are interhemispheric. They generally close in the hemisphere with the highest Pedersen conductance. Such hemispherical preference presents a seasonal/longitudinal dependence. The diamagnetic currents increase or decrease the magnetic pressure inside EPDs. These two effects rely on variations of the plasma temperature inside the EPDs that depend on longitude and local time. (3.) EPDs present lower or higher plasma pressure than the ambient. For low-pressure EPDs the plasma pressure gradients are mostly dominated by variations of the plasma density so that variations of the temperature are negligible. High-pressure EPDs suggest significant temperature variations with magnitudes of approximately twice the ambient. Since their occurrence is more frequent in the vicinity of the South Atlantic magnetic anomaly, such high temperatures are suggested to be due to particle precipitation.
In a broader context, this dissertation shows how dedicated satellite missions with high-resolution capabilities improve the specification of the low-latitude ionospheric electrodynamics and expand knowledge on EPDs which is valuable for current and future communication, navigation, and Earth-observing missions. The contributions of this investigation represent several ’firsts’ in the study of EPDs: (1.) The first observational evidence of interhemispheric electromagnetic energy flux and field-aligned currents. (2.) The first spatial and temporal characterization of EPDs based on their associated field-aligned and diamagnetic currents. (3.) The first evidence of high plasma pressure in regions of depleted plasma density in the ionosphere. These findings provide new insights that promise to advance our current knowledge of not only EPDs but the low-latitude post-sunset ionosphere environment.
Die Gesundheitswirtschaft in Deutschland steht vor zahlreichen Veränderungen in ihrem Umfeld. Dabei mangelt es der Krankenhauslandschaft an ärztlichem Personal. Es fehlt insbesondere an Arztstunden bei zugleich steigendem Bedarf an medizinischen Leistungen. Der demografische Wandel, Abwanderung ins Ausland (z. B. in die Schweiz) und Extrapolationen wie Feminisierung des Arztberufs und der Wertewandel respektive Generationenforschung begünstigen diese
Entwicklung. Zudem wird der Arbeitsplatz Krankenhaus zunehmend als unattraktiv von zukünftigen Arbeitnehmerkohorten angesehen. Nachwuchsärzte entscheiden sich bereits im Studium vermehrt gegen die kurative Medizin beziehungsweise gegen eine medizinisch-klinische Tätigkeit. Ein virulentes Beschaffungsproblem zeichnet sich ab, das es zu lösen gilt.
Das Forschungsziel ist die Entwicklung eines ganzheitlichen strategischen Lösungsansatzes mit marktorientierter Akzentuierung für den Arbeitgeber Krankenhaus. Dabei wird das Krankenhaus als wissens- und kompetenzintensive Dienstleistungsorganisation definiert. Employer Branding stellt den Bezugsrahmen eines marktorientierten Personalmanagements dar. Ein forschungstheoretischer Unterbau wird durch strategische Managementansätze integriert. Employer Branding schlägt die Brücke vom Market-based View zum Competence-based View und ist Markenmanagement im Kontext des strategischen Personalmanagements. In der vorliegenden Arbeit wird ein holistischer Bezugsrahmen vorgestellt, der die Wirkungszusammenhänge respektive Employer Branding darstellt. Das Herzstück ist die Employer Value Proposition, die auf der Markenidentität der Organisation basiert. Ziel des Employer Branding Ansatzes ist es, unter anderem eine präferenzerzeugende Wirkung im Prozess der Arbeitsplatzwahl sicherzustellen.
Die Zielrichtung und die Erkenntnis-Interessen erfordern einen breit angelegten Forschungsansatz, der qualitative und quantitative Methoden kombiniert. Ziel der leitfadengesteuerten Tiefeninterviews (exploratives Studiendesign) ist es, bestehende und noch zu entwickelnde Kompetenzstärken der Krankenhausorganisationen zu identifizieren. Bei der Stichprobe handelt es sich um ein „Typical Case Sampling“ (N=12). Defizitäre Befunde, welche Werte und Attraktivitätsfaktoren bei angehenden Ärzten ausgeprägt sind, werden bestätigt. In der Krankenhauslandschaft wird eine fragmentarische und reaktive Herangehensweise identifiziert, die die erfolgreiche Rekrutierung von qualifiziertem Krankenhauspersonal erschwert.
Durch die qualitative Marktforschung werden Anforderungen des Marktes – also zukünftiges, ärztliches Krankenhauspersonal – auf faktorenanalytischer Basis analysiert. Die Stichprobe (N=475) ist isomorph. Dabei wird der Prozess der Einstellungsbildung in das neobehavioristische Erklärungsmodell des Käuferverhaltens eingeordnet. Die Vereinbarkeit von Beruf, Karriere und Familie sowie die betriebliche Kinderbetreuung werden als Schlüsselkomponenten erkannt.
Wichtigste Arbeitswerte in Bezug auf einen attraktiven Arbeitgeber sind Verlässlichkeit, Verantwortung und Respekt. Diese Komponenten haben kommunikativen Nutzen und Differenzierungskraft. Schließlich bewerten Bewerber ein Krankenhaus positiver im Prozess der Arbeitsplatzwahl, je mehr die Werte des potentiellen Arbeitnehmers mit dem Werteprofil der Person übereinstimmen (Person-Organisation Fit).
Krankenhausorganisationen, die den Employer Branding Ansatz implementieren und als Chance zur Definition ihrer Stärken, ihrer Vorzüge und ihres Leistungsangebots als Arbeitgeber annehmen, rüsten sich für das verstärkte Werben um Jungmediziner. Schließlich setzt Employer Branding als marktorientierter Strategieansatz intern und extern Kräfte frei, die Differenzierungsvorteile gegenüber anderen Arbeitgebern bringen. Dabei hat Employer Branding positive Auswirkungen auf den Human Ressource-Bereich entlang der Wertschöpfungskette und mindert das gesamtwirtschaftliche Problem.
Im Rahmen der vom Bundesministerium für Bildung und -forschung geförderten Forschungsinitiative „BonaRes – Boden als nachhaltige Ressource der Bioökonomie“ soll sich das Teilprojekt „I4S – integrated system for site-specific soil fertility management“ der Entwicklung eines integrierten Systems zum ortsspezifischen Management der Bodenfruchtbarkeit widmen. Hierfür ist eine Messplattform zur Bestimmung relevanter Bodeneigenschaften und der quantitativen Analyse ausgewählter Makro- und Mikronährstoffe geplant. In der ersten Phase dieses Projekts liegt das Hauptaugenmerk auf der Kalibrierung und Validierung der verschiedenen Sensoren auf die Matrix Boden, der Probennahme auf dem Acker und der Planung sowie dem Aufbau der Messplattform. Auf dieser Plattform sollen in der zweiten Phase des Projektes die verschiedenen Bodensensoren installiert, sowie Modelle und Entscheidungsalgorithmen zur Steuerung der Düngung und dementsprechend Verbesserung der Bodenfunktionen erstellt werden.
Ziel der vorliegenden Arbeit ist die Grundlagenuntersuchung und Entwicklung einer robusten Online-Analyse mittels Energie-dispersiver Röntgenfluoreszenzspektroskopie (EDRFA) zur Quantifizierung ausgewählter Makro- und Mikronährstoffe in Böden für eine kostengünstige und flächendeckende Kartierung von Ackerflächen. Für die Entwicklung eines Online-Verfahrens wurde ein dem Stand der Technik entsprechender Röntgenfluoreszenzmesskopf in Betrieb genommen und die dazugehörigen Geräteparameter auf die Matrix Boden optimiert. Die Bestimmung der analytischen Qualitäts-merkmale wie Präzision und Nachweisgrenzen fand für eine Auswahl an Nährelementen von Aluminium bis Zink statt. Um eine möglichst Matrix-angepasste Kalibrierung zu erhalten, wurde sowohl mit zertifizierten Referenzmaterialien (CRM), als auch mit Ackerböden kalibriert. Da einer der größten Nachteile der Röntgenfluoreszenzanalyse die Beeinflussung durch Matrixeffekte ist, wurde neben der klassischen univariaten Datenauswertung auch die chemometrische multivariate Methode der Partial Least Squares Regression (PLSR) eingesetzt. Die PLSR bietet dabei den Vorteil, Matrixeffekte auszugleichen, wodurch robustere Kalibriermodelle erhalten werden können. Zusätzlich wurde eine Hauptkomponentenanalyse (PCA) durchgeführt, um Gemeinsamkeiten und Ausreißer innerhalb des Probensets zu identifizieren. Es zeigte sich, dass eine Klassifizierung der Böden anhand ihrer Textur Sand, Schluff, Lehm und Ton möglich ist.
Aufbauend auf den Ergebnissen idealer Bodenproben (zu Tabletten gepresste luftgetrocknete Proben mit Korngrößen < 0,5 mm) wurde im Verlauf dieser Arbeit die Probenvorbereitung immer weiter reduziert und der Einfluss verschiedener Kenngrößen untersucht. Diese Einflussfaktoren können die Dichte und die Homogenität der Probe, sowie Korngrößeneffekte und die Feuchtigkeit sein. Anhand des RMSE (Wurzel der mittleren Fehlerquadratsumme) und unter Berücksichtigung der Residuen werden die jeweils erstellten Kalibriermodelle miteinander verglichen. Um die Güte der Modelle zu bewerten, wurden diese mit einem Testset validiert. Hierfür standen 662 Bodenproben von 15 verschiedenen Standorten in Deutschland zur Verfügung. Da die Ergebnisse an gepressten Tabletten für die Elemente Al, Si, K, Ca, Ti, Mn, Fe und Zn den Anforderungen für eine spätere Online-Analyse entsprechen, wurden im weiteren Verlauf dieser Arbeit Kalibriermodelle mit losen Bodenproben erstellt. Auch hier konnten gute Ergebnisse durch ausreichende Nachweisgrenzen und eine niedrige gemittelte Messabweichung bei der Vorhersage unbekannter Testproben erzielt werden. Es zeigte sich, dass die Vorhersagefähigkeit mit der multivariaten PLSR besser ist als mit der univariaten Datenauswertung, insbesondere für die Elemente Mn und Zn.
Der untersuchte Einfluss der Feuchtigkeit und der Korngrößen auf die Quantifizierung der Elementgehalte war vor allem bei leichteren Elementen deutlich zu sehen. Es konnte schließlich eine multivariate Kalibrierung unter Berücksichtigung dieser Faktoren für die Elemente Al bis Zn erstellt werden, so dass ein Einsatz an Böden auf dem Acker möglich sein sollte. Eine höhere Messunsicherheit muss dabei einkalkuliert werden. Für eine spätere Probennahme auf dem Feld wurde zudem der Unterschied zwischen statischen und dynamischen Messungen betrachtet, wobei sich zeigte, dass beide Varianten genutzt werden können. Zum Abschluss wurde der hier eingesetzte Sensor mit einem kommerziell erhältlichen Hand-Gerät auf sein Quantifizierungspotential hin verglichen. Der Sensor weist anhand seiner Ergebnisse ein großes Potential als Online-Sensor für die Messplattform auf. Die Ergebnisse unter Laborbedingungen zeigen, dass eine robuste Analyse Ackerböden unter Berücksichtigung der Einflussfaktoren möglich ist.
Die Praktische Fahrerlaubnisprüfung dient der Erfassung und Beurteilung der Fahrkompe-tenz von Fahrerlaubnisbewerbern. Die aus dieser Prüfung gewonnenen Rückschlüsse auf das Niveau der Fahrkompetenz sollen insbesondere auch der Weiterentwicklung des Bewerbers dienen. Bisher erhalten Bewerber nur bei nicht bestandener Praktischer Fahrerlaubnisprü-fung eine Auflistung der wichtigsten Fehler, die zum Nichtbestehen geführt haben. Für ein zielgerichtetes Weiterlernen ist es aber notwendig, dass die Ergebnisse der Leistungserfas-sung und der Leistungsbewertung gemäß prüfungsdidaktischer Grundsätze pädagogisch an-spruchsvoll an alle Fahranfänger (unabhängig vom Prüfungsergebnis) zurückgemeldet wer-den.
Das Ziel der vorliegenden Arbeit besteht darin, die Gestaltungsgrundlagen und einen Umset-zungsvorschlag für ein kompetenzbezogenes und lernförderliches Rückmeldesystem für die Praktische Fahrerlaubnisprüfung zu erarbeiten. Dieses Rückmeldesystem soll in der Praxis erprobt werden. Darüber hinaus sollen anhand einer Bewerberbefragung zur Nutzerzufrie-denheit Erkenntnisse für die Weiterentwicklung gewonnen werden. Der Entwicklungs- und Erprobungsprozess des optimierten Rückmeldesystems lässt sich in drei Projektphasen auf-teilen:
1. Im Zuge der Optimierungsarbeiten zur Praktischen Fahrerlaubnisprüfung wurde in der ersten Projektphase ein neues Rückmeldesystem erarbeitet, das aus einem kompetenz-bezogenen mündlichen Auswertungsgespräch und einer ergänzenden schriftlichen Rückmeldung einschließlich weiterführender Lernhinweise für alle Bewerber besteht. Dieses Rückmeldesystem soll einerseits die Fahranfänger dabei unterstützen, die Leis-tungsbewertung inhaltlich besser zu verstehen sowie ein zielgerichtetes Weiterlernen ermöglichen. Andererseits soll es die Bewerber dazu motivieren, die festgestellten Kompetenzdefizite weiter zu bearbeiten, und dadurch Lernzuwachs fördern.
2. Das Rückmeldesystem wurde in der zweiten Projektphase in verschiedenen Modell-
regionen Deutschlands anhand von ca. 9.000 realen Praktischen Fahrerlaubnisprüfun-gen erprobt. Die Fahrerlaubnisbewerber, die in den Modellregionen an einer optimier-ten Praktischen Fahrerlaubnisprüfung teilgenommen und somit eine schriftliche Rückmeldung gemäß der optimierten Vorgaben bzw. einen individuellen Zugangscode zum Downloadbereich erhalten haben, wurden zu einer Befragung eingeladen. Dabei wurden vor allem Aspekte der Akzeptanz und der Lernwirksamkeit aus Sicht der Be-werber erfasst. Ziel war es, die Qualität der verkehrspädagogischen Gestaltung des Rückmeldesystems und seinen Nutzen zu untersuchen, um die erprobte Rückmeldung weiterzuentwickeln. Für die Bewerberbefragung wurde eine Onlinebefragung mit ei-nem standardisierten Fragebogen durchgeführt.
3. Die Erprobungs- und Befragungsergebnisse dienten in der dritten Projektphase der Ableitung von Schlussfolgerungen für die Weiterentwicklung des Rückmeldesystems. Die vorliegenden Ergebnisse der Felderprobung deuten darauf hin, dass die Bereitstel-lung einer schriftlichen, ausführlichen Rückmeldung zu den Prüfungsleistungen der Praktischen Fahrerlaubnisprüfungen insgesamt als nützlich und gewinnbringend ange-sehen wird. Allerdings wurde auch deutlich, dass bezüglich der Umsetzung noch Op-timierungspotenzial besteht. Im Anschluss an die Erprobung wurde die schriftliche Rückmeldung daher – ausgehend von den Nutzererfahrungen während der Felderpro-bung – umfassend überarbeitet und eine revidierte Version vorgelegt.
Als Ergebnis der Arbeit liegt ein in mehreren Schritten entwickeltes, empirisch fundiertes und erprobtes Rückmeldesystem vor, das eine differenzierte Kompetenzrückmeldung er-möglicht. Die umfassende Rückmeldung bietet künftig einerseits eine verbesserte Ausgangs-lage für eine ggf. anschließende Wiederholungsprüfung und andererseits ist es dem Bewer-ber anhand der aufgezeigten Stärken und Schwächen auch nach einer bestandenen Prüfung möglich, diese Rückmeldung für das weitere Lernen zu nutzen.
Die vorliegende Untersuchung analysierte den direkten Zusammenhang eines berufsbezogenen Angebots Sozialer Gruppenarbeit mit dem Ergebnis beruflicher Wiedereingliederung bei Rehabilitandinnen und Rehabilitanden in besonderen beruflichen Problemlagen. Sie wurde von der Deutschen Rentenversicherung Bund als Forschungsprojekt vom 01.01.2013 bis 31.12. 2015 gefördert und an der Professur für Rehabilitationswissenschaften der Universität Potsdam realisiert.
Die Forschungsfrage lautete: Kann eine intensive sozialarbeiterische Gruppenintervention im Rahmen der stationären medizinischen Rehabilitation soweit auf die Stärkung sozialer Kompetenzen und die Soziale Unterstützung von Rehabilitandinnen und Rehabilitanden einwirken, dass sich dadurch langfristige Verbesserungen hinsichtlich der beruflichen Wiedereingliederung im Vergleich zur konventionellen Behandlung ergeben?
Die Studie gliederte sich in eine qualitative und eine quantitative Erhebung mit einer zwischenliegenden Intervention. Eingeschlossen waren 352 Patientinnen und Patienten im Alter zwischen 18 und 65 Jahren mit kardiovaskulären Diagnosen, deren Krankheitsbilder häufig von komplexen Problemlagen begleitet sind, verbunden mit einer schlechten sozialmedizinischen Prognose.
Die Evaluation der Gruppenintervention erfolgte in einem clusterrandomisierten kontrollierten Studiendesign, um einen empirischen Nachweis darüber zu erbringen, inwieweit die Intervention gegenüber der regulären sozialarbeiterischen Behandlung höhere Effekte erzielen kann. Die Interventionsgruppen nahmen am Gruppenprogramm teil, die Kontrollgruppen erhielten die reguläre sozialarbeiterische Behandlung.
Im Ergebnis konnte mit dieser Stichprobe kein Nachweis zur Verbesserung der beruflichen Wiedereingliederung, der gesundheitsbezogenen Arbeitsfähigkeit, der Lebensqualität sowie der Sozialen Unterstützung durch die Teilnahme am sozialarbeiterischen Gruppenprogramm erbracht werden. Die Return-To-Work-Rate betrug 43,7 %, ein Viertel der Untersuchungsgruppe befand sich nach einem Jahr in Arbeitslosigkeit. Die durchgeführte Gruppenintervention ist dem konventionellen Setting Sozialer Arbeit als gleichwertig anzusehen.
Schlussfolgernd wurde auf eine sozialarbeiterische Unterstützung der beruflichen Wiedereingliederung über einen längeren Zeitraum nach einer kardiovaskulären Erkrankung verwiesen, insbesondere durch wohnortnahe Angebote zu einem späteren Zeitpunkt bei stabilerer Gesundheit. Aus den Erhebungen ließen sich mögliche Erfolge bei engerer Kooperation zwischen dem Fachbereich der Sozialen Arbeit und der Psychologie ableiten. Ebenfalls gab es Hinweise auf die einflussreiche Rolle der Angehörigen, die durch Einbindung in die Soziale Beratung unterstützend auf den Wiedereingliederungsprozess wirken könnten. Die Passgenauigkeit der untersuchten sozialarbeiterischen Gruppeninterventionen ist durch eine gezielte Soziale Diagnostik zu verbessern.
In den letzten Jahrzehnten ist die Nachfrage nach kostengünstigen und flächendeckenden Kartierungsmöglichkeiten im Hinblick auf eine ertragssteigernde und umweltfreundlichere Bewirtschaftung von landwirtschaftlichen Nutzflächen stark gestiegen. Hierfür eignen sich spektroskopische Methoden wie die Röntgenfluoreszenzanalyse (RFA), Raman- und Gammaspektroskopie sowie die laserinduzierte Plasmaspektroskopie (LIBS). In Abhängigkeit von der Funktionsweise der jeweiligen Methoden werden Informationen zu verschiedensten Bodeneigenschaften wie Nährelementgehalt, Textur und pH-Wert erhalten.
Ziel dieser Arbeit ist die Entwicklung eines Online-LIBS-Verfahrens zur Nährelementbestimmmung und Kartierung von Ackerflächen. Die LIBS ist eine schnelle und simultane Multielementanalyse bei der durch das Fokussieren eines hochenergetischen Laserpulses Probenmaterial von der Probenoberfläche ablatiert wird und in ein Plasma überführt wird. Beim Abkühlen des Plasmas wird Strahlung emittiert, welche Rückschlüsse über die elementare Zusammensetzung der Probe gibt. Diese Arbeit ist im Teilprojekt I4S (Intelligenz für Böden) im Forschungsprogramm BonaRes (Boden als nachhaltige Ressource für die Bioökonomie) des Bundesministerium für Bildung und Forschung (BMBF) entstanden. Es wurden insgesamt 651 Bodenproben von verschiedenen Test-Agrarflächen unterschiedlichster Standorte Deutschlands gemessen, ausgewertet und zu Validierungszwecken mit entsprechender Referenzanalytik wie die Optische Emissionsspektroskopie mittels induktiv gekoppeltem Plasma (ICP-OES) und die wellenlängendispersive Röntgenfluoreszenzanalyse (WDRFA) charakterisiert.
Für die Quantifizierung wurden zunächst die Messparameter des LIBS-Systems auf die Bodenmatrix optimiert und für die Elemente geeignete Linien ausgewählt sowie deren Nachweisgrenzen bestimmt. Es hat sich gezeigt, dass eine absolute Quantifizierung basierend auf einem univariaten Ansatz aufgrund der starken Matrixeffekte und der schlechten Reproduzierbarkeit des Plasmas nur eingeschränkt möglich ist. Bei Verwendung eines multivariaten Ansatz wie der Partial Least Squares Regression (PLSR) für die Kalibrierung konnten für die Nährelemente im Vergleich zur univariaten Variante Analyseergebnisse mit höherer Güte und geringeren Messunsicherheiten ermittelt werden. Die Untersuchungen haben gezeigt, dass das multivariate Modell weiter verbessert werden kann, indem mit einer Vielzahl von gut analysierten Böden verschiedener Standorte, Bodenarten und einem breiten Gehaltsbereich kalibriert wird. Mithilfe der Hauptkomponentenanalyse (PCA) wurde eine Klassifizierung der Böden nach der Textur realisiert. Weiterhin wurde auch eine Kalibrierung mit losem Bodenmaterial erstellt. Trotz der Signalabnahme konnten für die verschiedenen Nährelemente Kalibriergeraden mit ausreichender, analytischer Güte erstellt werden.
Für den Einsatz auf dem Acker wurde außerdem der Einfluss von Korngröße und Feuchtigkeit auf das LIBS-Signal untersucht. Die unterschiedlichen Korngrößen haben nur einen geringen Einfluss auf das LIBS-Signal und das Kalibriermodell lässt sich durch entsprechende Proben leicht anpassen. Dagegen ist der Einfluss der Feuchtigkeit deutlich stärker und hängt stark von der Bodenart ab, sodass für jede Bodenart ein separates Kalibriermodell für verschiedene Feuchtigkeitsgehalte erstellt werden muss. Mithilfe der PCA kann der Feuchtigkeitsgehalt im Boden grob abgeschätzt werden und die entsprechende Kalibrierung ausgewählt werden.
Diese Arbeit liefert essentielle Informationen für eine Echtzeit-Analyse von Nährelementen auf dem Acker mittels LIBS und leistet einen wichtigen Beitrag zu einer fortschrittlichen und zukunftsfähigen Nutzung von Ackerflächen.
Die Entwicklung nachhaltiger Bewirtschaftungs- und Produktionsmethoden ist eine der zentralen Fragestellungen der modernen Agrarwirtschaft. Die vorliegende Arbeit beschäftigt sich mit zwei Forschungsthemen, die das Konzept Nachhaltigkeit beinhalten. In beiden Fällen werden analytische Grundlagen für die Entwicklung entsprechender landwirtschaftlicher Arbeitsmethoden gelegt.
Das erste Thema ist an den sogenannten Präzisionsackerbau angelehnt. Bei diesem wird die Bearbeitung von Agrarflächen ortsabhängig ausgeführt. Das heißt, die Ausbringung von Saatgut, Dünger, Bewässerung usw. richtet sich nach den Eigenschaften des jeweiligen Standortes und wird nicht pauschal gleichmäßig über ein ganzes Feld verteilt. Voraussetzung hierfür ist eine genaue Kenntnis der Bodeneigenschaften. In der vorliegenden Arbeit sollten diese Parameter mittels der analytischen Technik der Laser-induzierten Breakdown Spektroskopie (LIBS), die eine Form der Elementaranalyse darstellt, bestimmt werden. Bei den hier gesuchten Bodeneigenschaften handelte es sich um die Gehalte von Nährstoffen sowie einige sekundäre Parameter wie den Humusanteil, den pH-Wert und den pflanzenverfügbaren Anteil einzelner Nährstoffe. Diese Eigenschaften wurden durch etablierte Referenzanalysen bestimmt. Darauf aufbauend wurden die Messergebnissen der LIBS-Untersuchungen durch verschiedene Methoden der sogenannten multivariaten Datenanalyse (MVA) ausgewertet. Daraus sollten Modelle zur Vorhersage der Bodenparameter in zukünftigen LIBS-Messungen erarbeitet werden. Die Ergebnisse dieser Arbeit zeigten, dass mit der Kombination von LIBS und MVA sämtliche Bodenparameter erfolgreich vorhergesagt werden konnten. Dies beinhaltete sowohl die tatsächlich messbaren Elemente als auch die sekundären Eigenschaften, welche durch die MVA mit den Elementgehalten in Zusammenhang gebracht wurden.
Das zweite Thema beschäftigt sich mit der Vermeidung von Verlusten durch Schädlingsbefall bei der Getreidelagerung. Hier sollten mittels der Ionenmobilitätsspektrometrie (IMS) Schimmelpilzkontaminationen detektiert werden. Dabei wurde nach den flüchtigen Stoffwechselprodukten der Pilze gesucht. Die durch Referenzmessungen mit Massenspektrometern identifizierten Substanzen konnten durch IMS im Gasvolumen über den Proben, dem sogenannten Headspace, nachgewiesen werden. Dabei wurde nicht nur die Anwesenheit einer Kontamination festgestellt, sondern diese auch charakterisiert. Die freigesetzten Substanzen bildeten spezifische Muster, anhand derer die Pilze identifiziert werden konnten. Hier wurden sowohl verschiedene Gattungen als auch einzelne Arten unterschieden. Die Messungen fanden auf verschiedenen Nährböden statt um den Einfluss dieser auf die Stoffwechselprodukte zu beobachten. Auch die sekundären Stoffwechselprodukte der Schimmelpilze, die Mykotoxine, konnten durch IMS detektiert werden.
Beide in dieser Arbeit vorgestellten Forschungsthemen konnten erfolgreich abgeschlossen werden. Sowohl LIBS als auch IMS erwiesen sich für den Nachweis der jeweiligen Analyten als geeignet, und der Einsatz moderner computergestützter Auswertemethoden ermöglichte die genaue Charakterisierung der gesuchten Parameter. Beide Techniken können in Form von mobilen Geräten verwendet werden und zeichnen sich durch eine schnelle und sichere Analyse aus. In Kombination mit entsprechenden Modellen der MVA sind damit alle Voraussetzungen für Vor-Ort-Untersuchungen und damit für den Einsatz in der Landwirtschaft erfüllt.
In nature, bacteria are found to reside in multicellular communities encased in self-produced extracellular matrices. Indeed, biofilms are the default lifestyle of the bacteria which cause persistent infections in humans. The biofilm assembly protects bacterial cells from desiccation and limits the effectiveness of antimicrobial treatments. A myriad of biomolecules in the extracellular matrix, including proteins, exopolysaccharides, lipids, extracellular DNA and other, form a dense and viscoelastic three dimensional network. Many studies emphasized that a destabilization of the mechanical integrity of biofilm architectures potentially eliminates the protective shield and renders bacteria more susceptible to the immune system and antibiotics. Pantoea stewartii is a plant pathogen which infects monocotyledons such as maize and sweet corn. These bacteria produce dense biofilms in the xylem of infected plants which cause wilting of plants and crops. Stewartan is an exopolysaccharide which is produced by Pantoea stewartii and secreted as the major component to the extracellular matrix. It consists of heptasaccharide repeating units with a high degree of polymerization (2-4 MDa). In this work, the physicochemical properties of stewartan were investigated to understand the contributions of this exopolysaccharide to the mechanical integrity and cohesiveness of Pantoea stewartii biofilms. Therefore, a coarse-grained model of stewartan was developed with computational techniques to obtain a model for its three dimensional structural features. Here, coarse-grained molecular dynamic simulations revealed that the exopolysaccharide forms a hydrogel in which the exopolysaccharide chains arrange into a three dimensional mesh-like network. Simulations at different concentrations were used to investigate the influence of the water content on the network formation. Stewartan was further purified from 72 h grown Pantoea stewartii biofilms and the diffusion of bacteriophage and differently-sized nanoparticles (which ranged from 1.1 to 193 nm diameter) was analyzed in reconstituted stewartan solutions. Fluorescence correlation spectroscopy and single-particle tracking revealed that the stewartan network impeded the mobility of a set of differently-sized fluorescent particles in a size-dependent manner. Diffusion of these particles became more anomalous, as characterized by fitting the diffusion data to an anomalous diffusion model, with increasing stewartan concentrations. Further bulk and microrheological experiments were used to analyze the transitions in stewartan fluid behavior and stewartan chain entanglements were described. Moreover, it was noticed, that a small fraction of bacteriophage particles was trapped in small-sized pores deviating from classical random walks which highlighted the structural heterogeneity of the stewartan network. Additionally, the mobility of fluorescent particles
also depended on the charge of the stewartan exopolysaccharide and a model of a molecular sieve for the stewartan network was proposed. The here reported structural features of the stewartan polymers were used to provide a detailed description of the mechanical properties of typically glycan-based biofilms such as the one from Pantoea stewartii.
In addition, the mechanical properties of the biofilm architecture are permanently sensed by the embedded bacteria and enzymatic modifications of the extracellular matrix take place to address environmental cues. Hence, in this work the influence of enzymatic degradation of the stewartan exopolysaccharides on the overall exopolysaccharide network structure was analyzed to describe relevant physiological processes in Pantoea stewartii biofilms. Here, the stewartan hydrolysis kinetics of the tailspike protein from the ΦEa1h bacteriophage, which is naturally found to infect Pantoea stewartii cells, was compared to WceF. The latter protein is expressed from the Pantoea stewartii stewartan biosynthesis gene cluster wce I-III. The degradation of stewartan by the ΦEa1h tailspike protein was shown to be much faster than the hydrolysis kinetics of WceF, although both enzymes cleaved the β D GalIII(1→3)-α-D-GalI glycosidic linkage from the stewartan backbone. Oligosaccharide fragments which were produced during the stewartan cleavage, were analyzed in size-exclusion chromatography and capillary electrophoresis. Bioinformatic studies and the analysis of a WceF crystal structure revealed a remarkably high structural similarity of both proteins thus unveiling WceF as a bacterial tailspike-like protein. As a consequence, WceF might play a role in stewartan chain length control in Pantoea stewartii biofilms.
Understanding how organisms adapt to their local environment is a major focus of evolutionary biology. Local adaptation occurs when the forces of divergent natural selection are strong enough compared to the action of other evolutionary forces. An improved understanding of the genetic basis of local adaptation can inform about the evolutionary processes in populations and is of major importance because of its relevance to altered selection pressures due to climate change. So far, most insights have been gained by studying model organisms, but our understanding about the genetic basis of local adaptation in wild populations of species with little genomic resources is still limited.
With the work presented in this thesis I therefore set out to provide insights into the genetic basis of local adaptation in populations of two voles species: the common vole (Microtus arvalis) and the bank vole (Myodes glareolus). Both voles species are small mammals, they have a high evolutionary potential compared to their dispersal capabilities and are thus likely to show genetic responses to local conditions, moreover, they have a wide distribution in which they experience a broad range of different environmental conditions, this makes them an ideal species to study local adaptation.
The first study focused on producing a novel mitochondrial genome to facilitate further research in M. arvalis. To this end, I generated the first mitochondrial genome of M. arvalis using shotgun sequencing and an iterative mapping approach. This was subsequently used in a phylogenetic analysis that produced novel insights into the phylogenetic relationships of the Arvicolinae.
The following two studies then focused on the genetic basis of local adaptation using ddRAD-sequencing data and genome scan methods. The first of these involved sequencing the genomic DNA of individuals from three low-altitude and three high-altitude M. arvalis study sites in the Swiss Alps. High-altitude environments with their low temperatures and low levels of oxygen (hypoxia) pose considerable challenges for small mammals. With their small body size and proportional large body surface they have to sustain high rates of aerobic metabolism to support thermogenesis and locomotion, which can be restricted with only limited levels of oxygen available. To generate insights into high-altitude adaptation I identified a large number of single nucleotide polymorphisms (SNPs). These data were first used to identify high levels of differentiation between study sites and a clear pattern of population structure, in line with a signal of isolation by distance. Using genome scan methods, I then identified signals of selection associated with differences in altitude in genes with functions related to oxygen transport into tissue and genes related to aerobic metabolic pathways. This indicates that hypoxia is an important selection pressure driving local adaptation at high altitude in M. arvalis. A number of these genes were linked with high-altitude adaptation in other species before, which lead to the suggestion that high-altitude populations of several species have evolved in a similar manner as a response to the unique conditions at high altitude
The next study also involved the genetic basis of local adaptation, here I provided insights into climate-related adaptation in M. glareolus across its European distribution. Climate is an important environmental factor affecting the physiology of all organisms. In this study I identified a large number of SNPs in individuals from twelve M. glareolus populations distributed across Europe. I used these, to first establish that populations are highly differentiated and found a strong pattern of population structure with signal of isolation by distance. I then employed genome scan methods to identify candidate loci showing signals of selection associated with climate, with a particular emphasis on polygenic loci. A multivariate analysis was used to determine that temperature was the most important climate variable responsible for adaptive genetic variation among all variables tested. By using novel methods and genome annotation of related species I identified the function of genes of candidate loci. This showed that genes under selection have functions related to energy homeostasis and immune processes. Suggesting that M. glareolus populations have evolved in response to local temperature and specific local pathogenic selection pressures.
The studies presented in this thesis provide evidence for the genetic basis of local adaptation in two vole species across different environmental gradients, suggesting that the identified genes are involved in local adaptation. This demonstrates that with the help of novel methods the study of wild populations, which often have little genomic resources available, can provide unique insights into evolutionary processes.
Die Fehlerkorrektur in der Codierungstheorie beschäftigt sich mit der Erkennung und Behebung von Fehlern bei der Übertragung und auch Sicherung von Nachrichten.
Hierbei wird die Nachricht durch zusätzliche Informationen in ein Codewort kodiert.
Diese Kodierungsverfahren besitzen verschiedene Ansprüche, wie zum Beispiel die maximale Anzahl der zu korrigierenden Fehler und die Geschwindigkeit der Korrektur.
Ein gängiges Codierungsverfahren ist der BCH-Code, welches industriell für bis zu vier Fehler korrigiere Codes Verwendung findet. Ein Nachteil dieser Codes ist die technische Durchlaufzeit für die Berechnung der Fehlerstellen mit zunehmender Codelänge.
Die Dissertation stellt ein neues Codierungsverfahren vor, bei dem durch spezielle Anordnung kleinere Codelängen eines BCH-Codes ein langer Code erzeugt wird. Diese Anordnung geschieht über einen weiteren speziellen Code, einem LDPC-Code, welcher für eine schneller Fehlererkennung konzipiert ist.
Hierfür wird ein neues Konstruktionsverfahren vorgestellt, welches einen Code für einen beliebige Länge mit vorgebbaren beliebigen Anzahl der zu korrigierenden Fehler vorgibt. Das vorgestellte Konstruktionsverfahren erzeugt zusätzlich zum schnellen Verfahren der Fehlererkennung auch eine leicht und schnelle Ableitung eines Verfahrens zu Kodierung der Nachricht zum Codewort. Dies ist in der Literatur für die LDPC-Codes bis zum jetzigen Zeitpunkt einmalig.
Durch die Konstruktion eines LDPC-Codes wird ein Verfahren vorgestellt wie dies mit einem BCH-Code kombiniert wird, wodurch eine Anordnung des BCH-Codes in Blöcken erzeugt wird. Neben der allgemeinen Beschreibung dieses Codes, wird ein konkreter Code für eine 2-Bitfehlerkorrektur beschrieben. Diese besteht aus zwei Teilen, welche in verschiedene Varianten beschrieben und verglichen werden. Für bestimmte Längen des BCH-Codes wird ein Problem bei der Korrektur aufgezeigt, welche einer algebraischen Regel folgt.
Der BCH-Code wird sehr allgemein beschrieben, doch existiert durch bestimmte Voraussetzungen ein BCH-Code im engerem Sinne, welcher den Standard vorgibt. Dieser BCH-Code im engerem Sinne wird in dieser Dissertation modifiziert, so dass das algebraische Problem bei der 2-Bitfehler Korrektur bei der Kombination mit dem LDPC-Code nicht mehr existiert. Es wird gezeigt, dass nach der Modifikation der neue Code weiterhin ein BCH-Code im allgemeinen Sinne ist, welcher 2-Bitfehler korrigieren und 3-Bitfehler erkennen kann. Bei der technischen Umsetzung der Fehlerkorrektur wird des Weiteren gezeigt, dass die Durchlaufzeiten des modifizierten Codes im Vergleich zum BCH-Code schneller ist und weiteres Potential für Verbesserungen besitzt.
Im letzten Kapitel wird gezeigt, dass sich dieser modifizierte Code mit beliebiger Länge eignet für die Kombination mit dem LDPC-Code, wodurch dieses Verfahren nicht nur umfänglicher in der Länge zu nutzen ist, sondern auch durch die schnellere Dekodierung auch weitere Vorteile gegenüber einem BCH-Code im engerem Sinne besitzt.
With his September 2015 speech “Breaking the tragedy of the horizon”, the President of the Central Bank of England, Mark Carney, put climate change on the agenda of financial market regulators. Until then, climate change had been framed mainly as a problem of negative externalities leading to long-term economic costs, which resulted in countries trying to keep the short-term costs of climate action to a minimum. Carney argued that climate change, as well as climate policy, can also lead to short-term financial risks, potentially causing strong adjustments in asset prices. Analysing the effect of a sustainability transition on the financial sector challenges traditional economic and financial analysis and requires a much deeper understanding of the interrelations between climate policy and financial markets.
This dissertation thus investigates the implications of climate policy for financial markets as well as the role of financial markets in a transition to a sustainable economy. The approach combines insights from macroeconomic and financial risk analysis. Following an introduction and classification in Chapter 1, Chapter 2 shows a macroeconomic analysis that combines ambitious climate targets (negative externality) with technological innovation (positive externality), adaptive expectations and an investment program, resulting in overall positive macroeconomic outcomes. The analysis also reveals the limitations of climate economic models in their representation of financial markets. Therefore, the subsequent part of this dissertation is concerned with the link between climate policies and financial markets. In Chapter 3, an empirical analysis of stock-market responses to the announcement of climate policy targets is performed to investigate impacts of climate policy on financial markets. Results show that 1) international climate negotiations have an effect on asset prices and 2) investors increasingly recognize transition risks in carbon-intensive investments. In Chapter 4, an analysis of equity markets and the interbank market shows that transition risks can potentially affect a large part of the equity market and that financial interconnections can amplify negative shocks. In Chapter 5, an analysis of mortgage loans shows how information on climate policy and the energy performance of buildings can be integrated into risk management and reflected in interest rates.
While costs of climate action have been explored at great depth, this dissertation offers two main contributions. First, it highlights the importance of a green investment program to strengthen the macroeconomic benefits of climate action. Second, it shows different approaches on how to integrate transition risks and opportunities into financial market analysis. Anticipating potential losses and gains in the value of financial assets as early as possible can make the financial system more resilient to transition risks and can stimulate investments into the decarbonization of the economy.
Living cells rely on transport and interaction of biomolecules to perform their diverse functions. A powerful toolbox to study these highly dynamic processes in the native environment is provided by fluorescence fluctuation spectroscopy (FFS) techniques. In more detail, FFS takes advantage of the inherent dynamics present in biological systems, such as diffusion, to infer molecular parameters from fluctuations of the signal emitted by an ensemble of fluorescently tagged molecules. In particular, two parameters are accessible: the concentration of molecules and their transit times through the observation volume. In addition, molecular interactions can be measured by analyzing the average signal emitted per molecule - the molecular brightness - and the cross-correlation of signals detected from differently tagged species.
In the present work, several FFS techniques were implemented and applied in different biological contexts. In particular, scanning fluorescence correlation spectroscopy (sFCS) was performed to measure protein dynamics and interactions at the plasma membrane (PM) of cells, and number and brightness (N&B) analysis to spatially map molecular aggregation. To account for technical limitations and sample related artifacts, e.g. detector noise, photobleaching, or background signal, several correction schemes were explored. In addition, sFCS was combined with spectral detection and higher moment analysis of the photon count distribution to resolve multiple species at the PM.
Using scanning fluorescence cross-correlation spectroscopy and cross-correlation N&B, the interactions of amyloid precursor-like protein 1 (APLP1), a synaptic membrane protein, were investigated. It is shown for the first time directly in living cells, that APLP1 undergoes specific interactions at cell-cell contacts. It is further demonstrated that zinc ions induce formation of large APLP1 clusters that enrich at contact sites and bind to clusters on the opposing cell. Altogether, these results provide direct evidence that APLP1 is a zinc ion dependent neuronal adhesion protein.
In the context of APLP1, discrepancies of oligomeric state estimates were observed, which were attributed to non-fluorescent states of the chosen red fluorescent protein (FP) tag mCardinal (mCard). Therefore, multiple FPs and their performance in FFS based measurements of protein interactions were systematically evaluated. The study revealed superior properties of monomeric enhanced green fluorescent protein (mEGFP) and mCherry2. Furthermore, a simple correction scheme allowed unbiased in situ measurements of protein oligomerization by quantifying non-fluorescent state fractions of FP tags. The procedure was experimentally confirmed for biologically relevant protein complexes consisting of up to 12 monomers.
In the last part of this work, fluorescence correlation spectroscopy (FCS) and single particle tracking (SPT) were used to characterize diffusive transport dynamics in a bacterial biofilm model. Biofilms are surface adherent bacterial communities, whose structural organization is provided by extracellular polymeric substances (EPS) that form a viscous polymer hydrogel. The presented study revealed a probe size and polymer concentration dependent (anomalous) diffusion hindrance in a reconstituted EPS matrix system caused by polymer chain entanglement at physiological concentrations. This result indicates a meshwork-like organization of the biofilm matrix that allows free diffusion of small particles, but strongly hinders diffusion of larger particles such as bacteriophages. Finally, it is shown that depolymerization of the matrix by phage derived enzymes rapidly facilitated free diffusion. In the context of phage infections, such enzymes may provide a key to evade trapping in the biofilm matrix and promote efficient infection of bacteria. In combination with phage application, matrix depolymerizing enzymes may open up novel antimicrobial strategies against multiresistant bacterial strains, as a promising, more specific alternative to conventional antibiotics.
From dawn till dusk
(2020)
Supernova remnants are believed to be the source of cosmic rays with energies up to 10^15 eV that are produced within our Galaxy. The acceleration mechanism associated with the collision-less shocks in supernova remnants - diffusive shock acceleration - predicts a spectral index of the accelerated non-thermal particles of s = 2. However, measurements of non-thermal emission in radio, X-rays and gamma-rays reveal significant deviations of the particles spectral index from the canonical value of s = 2.
The youngest Galactic supernova remnant G1.9+0.3 is an interesting target for next-generation gamma-ray observatories. So far, the remnant is only detected in the radio and the X-ray bands, but its young age of ≈100 yrs and inferred shock speed of ≈ 14, 000 km/s could make it an efficient particle accelerator.
I performed spherical symmetric 1D simulations with the RATPaC code, in which I simultaneously solved the transport equation for cosmic rays, the transport equation for magnetic turbulence, and the hydro-dynamical equations for the gas flow. Separately computed distributions of the particles accelerated at the forward and the reverse shock were then used to calculate the spectra of synchrotron, inverse Compton, and Pion-decay radiation from the source.
The emission from G1.9+0.3 can be self-consistently explained within the test-particle limit. I find that the X-ray flux is dominated by emission from the forward shock while most of the radio emission originates near the reverse shock, which makes G1.9+0.3 the first remnant with non-thermal radiation detected from the reverse shock. The flux of very-high-energy gamma-ray emission from G1.9+0.3 is expected to be close to the sensitivity threshold of the Cherenkov Telescope Array. The limited time available to grow large-scale turbulence limits the maximum energy of particles to values below 100 TeV, hence G1.9+0.3 is not a PeVatron.
Although there are many models for the acceleration of cosmic rays in Supernova remnants, the escape of cosmic rays from these sources is yet understudied.
I use our time-dependent acceleration code RATPaC to study the acceleration of cosmic rays and their escape in post-adiabatic Supernova remnants and calculate the subsequent gamma-ray emission from inverse-Compton scattering and Pion decay. My simulations span 100,000 years, thus covering the free-expansion, the Sedov-Taylor, and the beginning of the post-adiabatic phase of the remnant’s evolution.
At later stages of the evolution cosmic rays over a wide range of energy can reside outside of the remnant, creating spectra that are softer than predicted by standard diffusive shock acceleration and feature breaks in the 10 - 100 GeV-range. The total spectrum of cosmic rays released into the interstellar medium has a spectral index of s ≈ 2.4 above roughly 10 GeV which is close to that required by Galactic propagation models. I further find the gamma-ray luminosity to peak around an age of 4,000 years for inverse-Compton-dominated high-energy emission. Remnants expanding in low-density media emit generally more inverse-Compton radiation matching the fact that the brightest known supernova remnants - RCW86, Vela Jr, HESSJ1721-347 and RXJ1713.7-3946 - are all expanding in low density environments.
The importance of feedback from the cosmic-rays on the hydrodynamical evolution of the remnants is debated as a possibility to obtain soft cosmic-ray spectra at low energies.
I performed spherically symmetric 1-D simulations with a modified version of the RATPaC code, in which I simultaneously solve the transport equation for cosmic rays and the hydrodynamical equations, including the back-reaction of the cosmic-ray pressure on the flow profiles.
Besides the known modification of the flow profiles and the consequently curved cosmic-ray spectra, steady-state models for non-linear diffusive shock acceleration overpredict the total compression ratio that can be reached with cosmic-ray feedback, as there is limited time for building these modifications. Further, I find modifications to the downstream flow structure that change the evolutionary behavior of the remnant and trigger a cosmic-ray-induced instability close to the contact discontinuity, if and when the cosmic-ray pressure becomes dominant there.
The development of bioinspired self-assembling materials, such as hydrogels, with promising applications in cell culture, tissue engineering and drug delivery is a current focus in material science. Biogenic or bioinspired proteins and peptides are frequently used as versatile building blocks for extracellular matrix (ECM) mimicking hydrogels. However, precisely controlling and reversibly tuning the properties of these building blocks and the resulting hydrogels remains challenging. Precise control over the viscoelastic properties and self-healing abilities of hydrogels are key factors for developing intelligent materials to investigate cell matrix interactions. Thus, there is a need to develop building blocks that are self-healing, tunable and self-reporting. This thesis aims at the development of α-helical peptide building blocks, called coiled coils (CCs), which integrate these desired properties. Self-healing is a direct result of the fast self-assembly of these building blocks when used as material cross-links. Tunability is realized by means of reversible histidine (His)-metal coordination bonds. Lastly, implementing a fluorescent readout, which indicates the CC assembly state, self-reporting hydrogels are obtained.
Coiled coils are abundant protein folding motifs in Nature, which often have mechanical function, such as in myosin or fibrin. Coiled coils are superhelices made up of two or more α-helices wound around each other. The assembly of CCs is based on their repetitive sequence of seven amino acids, so-called heptads (abcdefg). Hydrophobic amino acids in the a and d position of each heptad form the core of the CC, while charged amino acids in the e and g position form ionic interactions. The solvent-exposed positions b, c and f are excellent targets for modifications since they are more variable. His-metal coordination bonds are strong, yet reversible interactions formed between the amino acid histidine and transition metal ions (e.g. Ni2+, Cu2+ or Zn2+). His-metal coordination bonds essentially contribute to the mechanical stability of various high-performance proteinaceous materials, such as spider fangs, Nereis worm jaws and mussel byssal threads. Therefore, I bioengineered reversible His-metal coordination sites into a well-characterized heterodimeric CC that served as tunable material cross-link. Specifically, I took two distinct approaches facilitating either intramolecular (Chapter 4.2) and/or intermolecular (Chapter 4.3) His-metal coordination.
Previous research suggested that force-induced CC unfolding in shear geometry starts from the points of force application. In order to tune the stability of a heterodimeric CC in shear geometry, I inserted His in the b and f position at the termini of force application (Chapter 4.2). The spacing of His is such that intra-CC His-metal coordination bonds can form to bridge one helical turn within the same helix, but also inter-CC coordination bonds are not generally excluded. Starting with Ni2+ ions, Raman spectroscopy showed that the CC maintained its helical structure and the His residues were able to coordinate Ni2+. Circular dichroism (CD) spectroscopy revealed that the melting temperature of the CC increased by 4 °C in the presence of Ni2+. Using atomic force microscope (AFM)-based single molecule force spectroscopy, the energy landscape parameters of the CC were characterized in the absence and the presence of Ni2+. His-Ni2+ coordination increased the rupture force by ~10 pN, accompanied by a decrease of the dissociation rate constant. To test if this stabilizing effect can be transferred from the single molecule level to the bulk viscoelastic material properties, the CC building block was used as a non-covalent cross-link for star-shaped poly(ethylene glycol) (star-PEG) hydrogels. Shear rheology revealed a 3-fold higher relaxation time in His-Ni2+ coordinating hydrogels compared to the hydrogel without metal ions. This stabilizing effect was fully reversible when using an excess of the metal chelator ethylenediaminetetraacetate (EDTA). The hydrogel properties were further investigated using different metal ions, i.e. Cu2+, Co2+ and Zn2+. Overall, these results suggest that Ni2+, Cu2+ and Co2+ primarily form intra-CC coordination bonds while Zn2+ also participates in inter-CC coordination bonds. This may be a direct result of its different coordination geometry.
Intermolecular His-metal coordination bonds in the terminal regions of the protein building blocks of mussel byssal threads are primarily formed by Zn2+ and were found to be intimately linked to higher-order assembly and self-healing of the thread. In the above example, the contribution of intra-CC and inter-CC His-Zn2+ cannot be disentangled. In Chapter 4.3, I redesigned the CC to prohibit the formation of intra-CC His-Zn2+ coordination bonds, focusing only on inter-CC interactions. Specifically, I inserted His in the solvent-exposed f positions of the CC to focus on the effect of metal-induced higher-order assembly of CC cross-links. Raman and CD spectroscopy revealed that this CC building block forms α-helical Zn2+ cross-linked aggregates. Using this CC as a cross-link for star-PEG hydrogels, I showed that the material properties can be switched from viscoelastic in the absence of Zn2+ to elastic-like in the presence of Zn2+. Moreover, the relaxation time of the hydrogel was tunable over three orders of magnitude when using different Zn2+:His ratios. This tunability is attributed to a progressive transformation of single CC cross-links into His-Zn2+ cross-linked aggregates, with inter-CC His-Zn2+ coordination bonds serving as an additional, cross-linking mode.
Rheological characterization of the hydrogels with inter-CC His-Zn2+ coordination raised the question whether the His-Zn2+ coordination bonds between CCs or also the CCs themselves rupture when shear strain is applied. In general, the amount of CC cross-links initially formed in the hydrogel as well as the amount of CC cross-links breaking under force remains to be elucidated. In order to more deeply probe these questions and monitor the state of the CC cross-links when force is applied, a fluorescent reporter system based on Förster resonance energy transfer (FRET) was introduced into the CC (Chapter 4.4). For this purpose, the donor-acceptor pair carboxyfluorescein and tetramethylrhodamine was used. The resulting self-reporting CC showed a FRET efficiency of 77 % in solution. Using this fluorescently labeled CC as a self-reporting, reversible cross-link in an otherwise covalently cross-linked star-PEG hydrogel enabled the detection of the FRET efficiency change under compression force. This proof-of-principle result sets the stage for implementing the fluorescently labeled CCs as molecular force sensors in non-covalently cross-linked hydrogels.
In summary, this thesis highlights that rationally designed CCs are excellent reversibly tunable, self-healing and self-reporting hydrogel cross-links with high application potential in bioengineering and biomedicine. For the first time, I demonstrated that His-metal coordination-based stabilization can be transferred from the single CC level to the bulk material with clear viscoelastic consequences. Insertion of His in specific sequence positions was used to implement a second non-covalent cross-linking mode via intermolecular His-metal coordination. This His-metal binding induced aggregation of the CCs enabled for reversibly tuning the hydrogel properties from viscoelastic to elastic-like. As a proof-of-principle to establish self-reporting CCs as material cross-links, I labeled a CC with a FRET pair. The fluorescently labelled CC acts as a molecular force sensor and first preliminary results suggest that the CC enables the detection of hydrogel cross-link failure under compression force. In the future, fluorescently labeled CC force sensors will likely not only be used as intelligent cross-links to study the failure of hydrogels but also to investigate cell-matrix interactions in 3D down to the single molecule level.
The impact that catalysis has on global economy and environment is substantial, since 85% of all chemical industrial processes are catalytic. Among those, 80% of the processes are heterogeneously catalyzed, 17% make use of homogeneous catalysts, and 3% are biocatalytic processes. Especially in the pharmaceutical and agrochemical industry, a significant part of these processes involves chiral compounds. Obtaining enantiomerically pure compounds is necessary and it is usually accomplished by asymmetric synthesis and catalysis, as well as chiral separation. The efficiency of these processes may be vastly improved if the chiral selectors are positioned on a porous solid support, thereby increasing the available surface area for chiral recognition. Similarly, the majority of commercial catalysts are also supported, usually comprising of metal nanoparticles (NPs) dispersed on highly porous oxide or nanoporous carbon material.
Materials that have exceptional thermal and chemical stability, and are electrically conductive are porous carbons. Their stability in extreme pH regions and temperatures, the possibility to tailor their pore architecture and chemical functionalization, and their electric conductivity have already established these materials in the fields of separation and catalysis. However, their heterogeneous chemical structure with abundant defects make it challenging to develop reliable models for the investigation of structure-performance relationships. Therefore, there is a necessity for expanding the fundamental understanding of these robust materials under experimental conditions to allow for their further optimization for particular applications. This thesis gives a contribution to our knowledge about carbons, through different aspects, and in different applications.
On the one hand, a rather exotic novel application was investigated by attempts in synthesizing porous carbon materials with an enantioselective surface. Chapter 4.1 described an approach for obtaining mesoporous carbons with an enantioselective surface by direct carbonization of a chiral precursor. Two enantiomers of chiral ionic liquids (CIL) based on amino acid tyrosine were used as carbon precursors and ordered mesoporous silica SBA-15 served as a hard template for obtaining porosity. The chiral recognition of the prepared carbons has been tested in the solution by isothermal titration calorimetry with enantiomers of Phenylalanine as probes, as well as chiral vapor adsorption with 2-butanol enantiomers. Measurements in both solution and the gas phase revealed the differences in the affinity of carbons towards two enantiomers.
The atomic efficiency of the CIL precursors was increased in Chapter 4.2, and the porosity was developed independently from the development of chiral carbons, through the formation of stable composites of pristine carbon and CIL-derived coating. After the same set of experiments for the investigation of chirality, the enantiomeric ratios of the composites reported herein were even higher than in the previous chapter.
On the other hand, the structure‒activity relationship of carbons as supports for gold nanoparticles in a rather traditional catalytic model reaction, on the interface between gas, liquid, and solid, was studied. In Chapter 5.1 it was shown on the series of catalysts with different porosities that the kinetics of ᴅ-glucose oxidation reaction can be enhanced by increasing the local concentration of the reactants around the active phase of the catalyst. A large amount of uniform narrow mesopores connected to the surface of the Au catalyst supported on ordered mesoporous carbon led to the water confinement, which increased the solubility of the oxygen in the proximity of the catalyst and thereby increased the apparent catalytic activity of this catalyst.
After increasing the oxygen concentration in the internal area of the catalyst, in Chapter 5.2 the concentration of oxygen was increased in the external environment of the catalyst, by the introduction of less cohesive liquids that serve as efficient solvent for oxygen, perfluorinated compounds, near the active phase of the catalyst. This was achieved by a formation of catalyst particle-stabilized emulsions of perfluorocarbon in aqueous ᴅ-glucose solution, that further promoted the catalytic activity of gold-on-carbon catalyst.
The findings reported within this thesis are an important step in the understanding of the structure-related properties of carbon materials.
The Milky Way is a spiral galaxy consisting of a disc of gas, dust and stars embedded in a halo of dark matter. Within this dark matter halo there is also a diffuse population of stars called the stellar halo, that has been accreting stars for billions of years from smaller galaxies that get pulled in and disrupted by the large gravitational potential of the Milky Way. As they are disrupted, these galaxies leave behind long streams of stars that can take billions of years to mix with the rest of the stars in the halo. Furthermore, the amount of heavy elements (metallicity) of the stars in these galaxies reflects the rate of chemical enrichment that occurred in them, since the Universe has been slowly enriched in heavy elements (e.g. iron) through successive generations of stars which produce them in their cores and supernovae explosions. Therefore, stars that contain small amounts of heavy elements (metal-poor stars) either formed at early times before the Universe was significantly enriched, or in isolated environments. The aim of this thesis is to develop a better understanding of the substructure content and chemistry of the Galactic stellar halo, in order to gain further insight into the formation and evolution of the Milky Way.
The Pristine survey uses a narrow-band filter which specifically targets the Ca II H & K spectral absorption lines to provide photometric metallicities for a large number of stars down to the extremely metal-poor (EMP) regime, making it a very powerful data set for Galactic archaeology studies. In Chapter 2, we quantify the efficiency of the survey using a preliminary spectroscopic follow-up sample of ~ 200 stars. We also use this sample to establish a set of selection criteria to improve the success rate of selecting EMP candidates for follow-up spectroscopy. In Chapter 3, we extend this work and present the full catalogue of ~ 1000 stars from a three year long medium resolution spectroscopic follow-up effort conducted as part of the Pristine survey. From this sample, we compute success rates of 56% and 23% for recovering stars with [Fe/H] < -2.5 and [Fe/H] < -3.0, respectively. This demonstrates a high efficiency for finding EMP stars as compared to previous searches with success rates of 3-4%.
In Chapter 4, we select a sample of ~ 80000 halo stars using colour and magnitude cuts to select a main sequence turnoff population in the distance range 6 < dʘ < 20 kpc. We then use the spectroscopic follow-up sample presented in Chapter 3 to statistically rescale the Pristine photometric metallicities of this sample, and present the resulting corrected metallicity distribution function (MDF) of the halo. The slope at the metal-poor end is significantly shallower than previous spectroscopic efforts have shown, suggesting that there may be more metal-poor stars with [Fe/H] < -2.5 in the halo than previously thought. This sample also shows evidence that the MDF of the halo may not be bimodal as was proposed by previous works, and that the lack of globular clusters in the Milky Way may be the result of a physical truncation of the MDF rather than just statistical under-sampling.
Chapter 5 showcases the unexpected capability of the Pristine filter for separating blue horizontal branch (BHB) stars from Blue Straggler (BS) stars. We demonstrate a purity of 93% and completeness of 91% for identifying BHB stars, a substantial improvement over previous works. We then use this highly pure and complete sample of BHB stars to trace the halo density profile out to d > 100 kpc, and the Sagittarius stream substructure out to ~ 130 kpc.
In Chapter 6 we use the photometric metallicities from the Pristine survey to perform a clustering analysis of the halo as a function of metallicity. Separating the Pristine sample into four metallicity bins of [Fe/H] < -2, -2 < [Fe/H] < -1.5, -1.5 < [Fe/H] < -1 and -0.9 < [Fe/H] < -0.8, we compute the two-point correlation function to measure the amount of clustering on scales of < 5 deg. For a smooth comparison sample we make a mock Pristine data set generated using the Galaxia code based on the Besançon model of the Galaxy. We find enhanced clustering on small scales (< 0.5 deg) for some regions of the Galaxy for the most metal-poor bin ([Fe/H] < -2), while in others we see large scale signals that correspond to known substructures in those directions. This confirms that the substructure content of the halo is highly anisotropic and diverse in different Galactic environments. We discuss the difficulties of removing systematic clustering signals from the data and the limitations of disentangling weak clustering signals from real substructures and residual systematic structure in the data.
Taken together, the work presented in this thesis approaches the problem of better understanding the halo of our Galaxy from multiple angles. Firstly, presenting a sizeable sample of EMP stars and improving the selection efficiency of EMP stars for the Pristine survey, paving the way for the further discovery of metal-poor stars to be used as probes to early chemical evolution. Secondly, improving the selection of BHB distance tracers to map out the halo to large distances, and finally, using the large samples of metal-poor stars to derive the MDF of the inner halo and analyse the substructure content at different metallicities. The results of this thesis therefore expand our understanding of the physical and chemical properties of the Milky Way stellar halo, and provide insight into the processes involved in its formation and evolution.
During a dark night, it is possible to observe thousands of stars by eye. All these stars are located within the Milky Way, our home. Not all stars are the same, they can have different sizes, masses, temperatures and ages. Heavy stars do not live long (in astronomical terms), only a few million years, but stars less massive than the Sun can get more than ten billion years old. Such small stars that formed in the beginning of the Universe still shine today. These ancient stars are very helpful to learn more about the early Universe, the First Stars and the history of the Milky Way. But how do you recognise an ancient star? Using their chemical fingerprints! In the beginning of the Universe, there were only two chemical elements: hydrogen and helium (and a tiny bit of lithium). All the heavier elements like carbon, calcium and iron were only made later within stars and their explosions. The amount of chemical elements in the Universe increases with the number of stars that are born, evolve and explode. Stars that form later are born with more heavy elements, or a greater metallicity. In the field of astronomy that is called “Galactic Archaeology”, stars of various metallicities are used to study the history of the Milky Way. In this doctoral thesis, the focus is on metal-poor stars because these are expected to be the oldest and can therefore tell us a lot about the early history of our Galaxy.
Until today, we still have not discovered a metal-free star. The most metal-poor stars, however, give us important insights in the lives and deaths of the First Stars. Many of the oldest, most metal-poor stars have an unexpectedly large amount of carbon, compared to for example iron. These carbon-enhanced metal-poor (CEMP) stars tell us something about the very first stars in the Universe: they somehow produced a lot of carbon. If we look at the precise chemical fingerprints of the CEMP stars, we can learn a lot more. But our interpretation depends on the assumption that the chemical fingerprint of a star does not change during its life. In this thesis, new data is presented that shows that this assumption may be too simple: many extremely metal-poor CEMP stars are members of binary systems. Interactions between two stars in a binary system can pollute the surface of the stars. Likely not all of the CEMP stars in binary systems were actually polluted, but we should be very careful in our interpretations of the fingerprints of these stars.
The CEMP stars and other metal-poor stars are also important for our understanding of the early history of the Milky Way. Most researchers who study metal-poor stars look for these stars in the halo of the Milky Way: a huge diffuse Galactic component containing about 1% of the stars in our Galaxy. However, models predict that the oldest metal-poor stars are located in the center of the Milky Way, in the bulge. The metal-poor inner Galaxy is unfortunately difficult to study due to large amounts of dust between us and the center and an overwhelming majority of metal-rich stars. This thesis presents results from the successful Pristine Inner Galaxy Survey (PIGS), a new survey looking for (and finding) the oldest stars in the bulge of the Milky Way. PIGS is using images with a specific color that is sensitive to the metallicity of stars, and can therefore efficiently select the metal-poor stars among millions of other, more metal-rich stars. The interesting candidates are followed up with spectroscopy, which is then analysed using two independent methods. With this strategy, PIGS has discovered the largest sample of metal-poor stars in the inner Galaxy to date. A new result from the PIGS data is that the metal-poor stars rotate more slowly around the Galactic center compared to the more metal-rich stars, and they show larger randomness in their motions as well. Another important contribution from PIGS is the discovery of tens of CEMP stars in the inner Galaxy, where previously only two such stars were known.
The new results from this thesis help us to understand the First Stars and the early history of the Milky Way. Ongoing and future large surveys will provide us with a lot of additional data in the coming years. It is an exciting time for the field of Galactic Archaeology.
Geomechanical and petrological characterisation of exposed slip zones, Alpine Fault, New Zealand
(2020)
The Alpine Fault is a large, plate-bounding, strike-slip fault extending along the north-western edge of the Southern Alps, South Island, New Zealand. It regularly accommodates large (MW > 8) earthquakes and has a high statistical probability of failure in the near future, i.e., is late in its seismic cycle. This pending earthquake and associated co-seismic landslides are expected to cause severe infrastructural damage that would affect thousands of people, so it presents a substantial geohazard. The interdisciplinary study presented here aims to characterise the fault zone’s 4D (space and time) architecture, because this provides information about its rheological properties that will enable better assessment of the hazard
the fault poses.
The studies undertaken include field investigations of principal slip zone fault gouges exposed
along strike of the fault, and subsequent laboratory analyses of these outcrop and additional borehole samples. These observations have provided new information on (I) characteristic microstructures down to the nanoscale that indicate which deformation mechanisms operated within the rocks, (II) mineralogical information that constrains the fault’s geomechanical behaviour and (III) geochemical compositional information that allows the influence of fluid- related alteration processes on material properties to be unraveled.
Results show that along-strike variations of fault rock properties such as microstructures and mineralogical composition are minor and / or do not substantially influence fault zone architecture. They furthermore provide evidence that the architecture of the fault zone, particularly its fault core, is more complex than previously considered, and also more complex than expected for this sort of mature fault cutting quartzofeldspathic rocks. In particular our results strongly suggest that the fault has more than one principal slip zone, and that these form an anastomosing network extending into the basement below the cover of Quaternary sediments.
The observations detailed in this thesis highlight that two major processes, (I) cataclasis and (II) authigenic mineral formation, are the major controls on the rheology of the Alpine Fault. The velocity-weakening behaviour of its fault gouge is favoured by abundant nanoparticles
promoting powder lubrication and grain rolling rather than frictional sliding. Wall-rock fragmentation is accompanied by co-seismic, fluid-assisted dilatancy that is recorded by calcite cementation. This mineralisation, along with authigenic formation of phyllosilicates, quickly alters the petrophysical fault zone properties after each rupture, restoring fault competency. Dense networks of anastomosing and mutually cross-cutting calcite veins and intensively reworked gouge matrix demonstrate that strain repeatedly localised within the narrow fault gouge. Abundantly undeformed euhedral chlorite crystallites and calcite veins cross-cutting both fault gouge and gravels that overlie basement on the fault’s footwall provide evidence that the processes of authigenic phyllosilicate growth, fluid-assisted dilatancy and associated fault healing are processes active particularly close to the Earth’s surface in this fault zone.
Exposed Alpine Fault rocks are subject to intense weathering as direct consequence of abundant orogenic rainfall associated with the fault’s location at the base of the Southern Alps. Furthermore, fault rock rheology is substantially affected by shallow-depth conditions such as the juxtaposition of competent hanging wall fault rocks on poorly consolidated footwall sediments. This means microstructural, mineralogical and geochemical properties of the exposed fault rocks may differ substantially from those at deeper levels, and thus are not characteristic of the majority of the fault rocks’ history. Examples are (I) frictionally weak smectites found within the fault gouges being artefacts formed at temperature conditions, and imparting petrophysical properties that are not typical for most of fault rocks of the Alpine Fault, (II) grain-scale dissolution resulting from subaerial weathering rather than deformation by pressure-solution processes and (III) fault gouge geometries being more complex than expected for deeper counterparts.
The methodological approaches deployed in analyses of this, and other fault zones, and the major results of this study are finally discussed in order to contextualize slip zone investigations of fault zones and landslides. Like faults, landslides are major geohazards, which highlights the importance of characterising their geomechanical properties. Similarities between faults, especially those exposed to subaerial processes, and landslides, include mineralogical composition and geomechanical behaviour. Together, this ensures failure occurs predominantly by cataclastic processes, although aseismic creep promoted by weak phyllosilicates is not uncommon. Consequently, the multidisciplinary approach commonly used to investigate fault zones may contribute to increase the understanding of landslide faulting processes and the assessment of their hazard potential.
Glycosylphosphatidylinositols (GPIs) are highly complex glycolipids that serve as membrane anchors to a large variety of eukaryotic proteins. These are covalently attached to a group of peripheral proteins called GPI-anchored proteins (GPI-APs) through a post-translational modification in the endoplasmic reticulum. The GPI anchor is a unique structure composed of a glycan, with phospholipid tail at one end and a phosphoethanolamine linker at the other where the protein attaches. The glycan part of the GPI comprises a conserved pseudopentasaccharide core that could branch out to carry additional glycosyl or phosphoethanolamine units. GPI-APs are involved in a diverse range of cellular processes, few of which are signal transduction, protein trafficking, pathogenesis by protozoan parasites like the malaria- causing parasite Plasmodium falciparum. GPIs can also exist freely on the membrane surface without an attached protein such as those found in parasites like Toxoplasma gondii, the causative agent of Toxoplasmosis. These molecules are both structurally and functionally diverse, however, their structure-function relationship is still poorly understood. This is mainly because no clear picture exists regarding how the protein and the glycan arrange with respect to the lipid layer. Direct experimental evidence is rather scarce, due to which inconclusive pictures have emerged, especially regarding the orientation of GPIs and GPI-APs on membrane surfaces and the role of GPIs in membrane organization. It appears that computational modelling through molecular dynamics simulations would be a useful method to make progress. In this thesis, we attempt to explore characteristics of GPI anchors and GPI-APs embedded in lipid bilayers by constructing molecular models at two different resolutions – all-atom and coarse-grained.
First, we show how to construct a modular molecular model of GPIs and GPI-anchored proteins that can be readily extended to a broad variety of systems, addressing the micro-heterogeneity of GPIs. We do so by creating a hybrid link to which GPIs of diverse branching and lipid tails of varying saturation with their optimized force fields, GLYCAM06 and Lipid14 respectively, can be attached. Using microsecond simulations, we demonstrate that GPI prefers to “flop-down” on the membrane, thereby, strongly interacting with the lipid heads, over standing upright like a “lollipop”. Secondly, we extend the model of the GPI core to carry out a systematic study of the structural aspects of GPIs carrying different side chains (parasitic and human GPI variants) inserted in lipid bilayers. Our results demonstrate the importance of the side branch residues as these are the most accessible, and thereby, recognizable epitopes. This finding qualitatively agrees with experimental observations that highlight the role of the side branches in immunogenicity of GPIs and the specificity thereof. The overall flop-down orientation of the GPIs with respect to the bilayer surface presents the side chain residues to face the solvent. Upon attaching the green fluorescent protein (GFP) to the GPI, it is seen to lie in close proximity to the bilayer, interacting both with the lipid heads and glycan part of the GPI. However the orientation of GFP is sensitive to the type of GPI it is attached to. Finally, we construct a coarse-grained model of the GPI and GPI-anchored GFP using a modified version of the MARTINI force-field, using which the timescale is enhanced by at least an order of magnitude compared to the atomistic system.
This study provides a theoretical perspective on the conformational behavior of the GPI core and some of its branched variations in presence of lipid bilayers, as well as draws comparisons with experimental observations. Our modular atomistic model of GPI can be further employed to study GPIs of variable branching, and thereby, aid in designing future experiments especially in the area of vaccines and drug therapies. Our coarse-grained model can be used to study dynamic aspects of GPIs and GPI-APs w.r.t plasma membrane organization. Furthermore, the backmapping technique of converting coarse-grained trajectory back to the atomistic model would enable in-depth structural analysis with ample conformational sampling.
Gold at the nanoscale
(2020)
In this cumulative dissertation, I want to present my contributions to the field of plasmonic nanoparticle science. Plasmonic nanoparticles are characterised by resonances of the free electron gas around the spectral range of visible light. In recent years, they have evolved as promising components for light based nanocircuits, light harvesting, nanosensors, cancer therapies, and many more.
This work exhibits the articles I authored or co-authored in my time as PhD student at the University of Potsdam. The main focus lies on the coupling between localised plasmons and excitons in organic dyes. Plasmon–exciton coupling brings light–matter coupling to the nanoscale. This size reduction is accompanied by strong enhancements of the light field which can, among others, be utilised to enhance the spectroscopic footprint of molecules down to single molecule detection, improve the efficiency of solar cells, or establish lasing on the nanoscale. When the coupling exceeds all decay channels, the system enters the strong coupling regime. In this case, hybrid light–matter modes emerge utilisable as optical switches, in quantum networks, or as thresholdless lasers. The present work investigates plasmon–exciton coupling in gold–dye core–shell geometries and contains both fundamental insights and technical novelties. It presents a technique which reveals the anticrossing in coupled systems without manipulating the particles themselves. The method is used to investigate the relation between coupling strength and particle size. Additionally, the work demonstrates that pure extinction measurements can be insufficient when trying to assess the coupling regime. Moreover, the fundamental quantum electrodynamic effect of vacuum induced saturation is introduced. This effect causes the vacuum fluctuations to diminish the polarisability of molecules and has not yet been considered in the plasmonic context.
The work additionally discusses the reaction of gold nanoparticles to optical heating. Such knowledge is of great importance for all potential optical applications utilising plasmonic nanoparticles since optical excitation always generates heat. This heat can induce a change in the optical properties, but also mechanical changes up to melting can occur. Here, the change of spectra in coupled plasmon–exciton particles is discussed and explained with a precise model. Moreover, the work discusses the behaviour of gold nanotriangles exposed to optical heating. In a pump–probe measurement, X-ray probe pulses directly monitored the particles’ breathing modes. In another experiment, the triangles were exposed to cw laser radiation with varying intensities and illumination areas. X-ray diffraction directly measured the particles’ temperature. Particle melting was investigated with surface enhanced Raman spectroscopy and SEM imaging demonstrating that larger illumination areas can cause melting at lower intensities. An elaborate methodological and theoretical introduction precedes the articles. This way, also readers without specialist’s knowledge get a concise and detailed overview of the theory and methods used in the articles. I introduce localised plasmons in metal nanoparticles of different shapes. For this work, the plasmons were mostly coupled to excitons in J-aggregates. Therefore, I discuss these aggregates of organic dyes with sharp and intense resonances and establish an understanding of the coupling between the two systems. For ab initio simulations of the coupled systems, models for the systems’ permittivites are presented, too. Moreover, the route to the sample fabrication – the dye coating of gold nanoparticles, their subsequent deposition on substrates, and the covering with polyelectrolytes – is presented together with the measurement methods that were used for the articles.
Lifelong learning plays an increasingly important role in many societies. Technology is changing faster than ever and what has been important to learn today, may be obsolete tomorrow. The role of informal programs is becoming increasingly important. Particularly, Massive Open Online Courses have become popular among learners and instructors. In 2008, a group of Canadian education enthusiasts started the first Massive Open Online Courses or MOOCs to prove their cognitive theory of Connectivism. Around 2012, a variety of American start-ups redefined the concept of MOOCs. Instead of following the connectivist doctrine they returned to a more traditional approach. They focussed on video lecturing and combined this with a course forum that allowed the participants to discuss with each other and the teaching team. While this new version of the concept was enormously successful in terms of massiveness—hundreds of thousands of participants from all over the world joined the first of these courses—many educators criticized the re-lapse to the cognitivist model. In the early days, the evolving platforms often did not have more features than a video player, simple multiple-choice quizzes, and the course forum. It soon became a major interest of research to allow the scaling of more modern approaches of learning and teaching for the massiveness of these courses. Hands-on exercises, alternative forms of assessment, collaboration, and teamwork are some of the topics on the agenda. The insights provided by cognitive and pedagogical theories, however, do not necessarily always run in sync with the needs and the preferences of the majority of participants. While the former promote action-learning, hands-on-learning, competence-based-learning, project-based-learning, team-based-learning as the holy grail, many of the latter often rather prefer a more laid-back style of learning, sometimes referred to as edutainment. Obviously, given the large numbers of participants in these courses, there is not just one type of learners. Participants are not a homogeneous mass but a potpourri of individuals with a wildly heterogeneous mix of backgrounds, previous knowledge, familial and professional circumstances, countries of origin, gender, age, and so on. For the majority of participants, a full-time job and/or a family often just does not leave enough room for more time intensive tasks, such as practical exercises or teamwork. Others, however, particularly enjoy these hands-on or collaborative aspects of MOOCs. Furthermore, many subjects particularly require these possibilities and simply cannot be taught or learned in courses that lack collaborative or hands-on features. In this context, the thesis discusses how team assignments have been implemented on the HPI MOOC platform. During the recent years, several experiments have been conducted and a great amount of experience has been gained by employing team assignments in courses in areas, such as Object-Oriented Programming, Design Thinking, and Business Innovation on various instances of this platform: openHPI, openSAP, and mooc.house
Studies on the unsustainable use of groundwater resources are still considered incipient since it is frequently a poorly understood and managed, devalued and inadequately protected natural resource. Groundwater Recharge (GWR) is one of the most challenging elements to estimate since it can rarely be measured directly and cannot easily be derived from existing data. To overcome these limitations, many hydro(geo)logists have combined different approaches to estimate large-scale GWR, namely: remote sensing products, such as IMERG product; Water Budget Equation, also in combination with hydrological models, and; Geographic Information System (GIS), using estimation formulas. For intermediary-scale GWR estimation, there exist: Non-invasive Cosmic-Ray Neutron Sensing (CRNS); wireless networks from local soil probes; and soil hydrological models, such as HYDRUS. Accordingly, this PhD thesis aims, on the one hand, to demonstrate a GIS-based model coupling for estimating the GWR distribution on a large scale in tropical wet basins. On the other hand, it aims to use the time series from CRNS and invasive soil moisture probes to inversely calibrate the soil hydraulic properties, and based on this, estimating the intermediary-scale GWR using a soil hydrological model. For such purpose, two tropical wet basins located in a complex sedimentary aquifer in the coastal Northeast region of Brazil were selected. These are the João Pessoa Case Study Area and the Guaraíra Experimental Basin. Several satellite products in the first area were used as input to the GIS-based water budget equation model for estimating the water balance components and GWR in 2016 and 2017. In addition, the point-scale measurement and CRNS data were used in the second area to determine the soil hydraulic properties, and to estimate the GWR in the 2017-2018 and 2018-2019 hydrological years. The resulting values of GWR on large- and intermediary-scale were then compared and validated by the estimates obtained by groundwater table fluctuations. The GWR rates for IMERG- and rain-gauge-based scenarios showed similar coefficients between 68% and 89%, similar mean errors between 30% and 34%, and slightly-different bias between -13% and 11%. The results of GWR rates for soil probes and CRNS soil moisture scenarios ranged from -5.87 to -61.81 cm yr-1, which corresponds to 5% and 38% of the precipitation. The calculations of the mean GWR rates on large-scale, based on remote sensing data, and on intermediary-scale, based on CRNS data, held similar results for the Podzol soil type, namely 17.87% and 17% of the precipitation. It is then concluded that the proposed methodologies allowed for estimating realistically the GWR over the study areas, which can be a ground-breaking step towards improving the water management and decision-making in the Northeast of Brazil.
Chloroplasts are the photosynthetic organelles in plant and algae cells that enable photoautotrophic growth. Due to their prokaryotic origin, modern-day chloroplast genomes harbor 100 to 200 genes. These genes encode for core components of the photosynthetic complexes and the chloroplast gene expression machinery, making most of them essential for the viability of the organism. The regulation of those genes is predominated by translational adjustments. The powerful technique of ribosome profiling was successfully used to generate highly resolved pictures of the translational landscape of Arabidopsis thaliana cytosol, identifying translation of upstream open reading frames and long non-coding transcripts. In addition, differences in plastidial translation and ribosomal pausing sites were addressed with this method. However, a highly resolved picture of the chloroplast translatome is missing. Here, with the use of chloroplast isolation and targeted ribosome affinity purification, I generated highly enriched ribosome profiling datasets of the chloroplasts translatome for Nicotiana tabacum in the dark and light. Chloroplast isolation was found unsuitable for the unbiased analysis of translation in the chloroplast but adequate to identify potential co-translational import. Affinity purification was performed for the small and large ribosomal subunit independently. The enriched datasets mirrored the results obtained from whole-cell ribosome profiling. Enhanced translational activity was detected for psbA in the light. An alternative translation initiation mechanism was not identified by selective enrichment of small ribosomal subunit footprints. In sum, this is the first study that used enrichment strategies to obtain high-depth ribosome profiling datasets of chloroplasts to study ribosome subunit distribution and chloroplast associated translation.
Ever-changing light intensities are challenging the photosynthetic capacity of photosynthetic organism. Increased light intensities may lead to over-excitation of photosynthetic reaction centers resulting in damage of the photosystem core subunits. Additional to an expensive repair mechanism for the photosystem II core protein D1, photosynthetic organisms developed various features to reduce or prevent photodamage. In the long-term, photosynthetic complex contents are adjusted for the efficient use of experienced irradiation. However, the contribution of chloroplastic gene expression in the acclimation process remained largely unknown. Here, comparative transcriptome and ribosome profiling was performed for the early time points of high-light acclimation in Nicotiana tabacum chloroplasts in a genome-wide scale. The time- course data revealed stable transcript level and only minor changes in translational activity of specific chloroplast genes during high-light acclimation. Yet, psbA translation was increased by two-fold in the high light from shortly after the shift until the end of the experiment. A stress-inducing shift from low- to high light exhibited increased translation only of psbA. This study indicate that acclimation fails to start in the observed time frame and only short-term responses to reduce photoinhibition were observed.