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Organizations continue to assemble and rely upon teams of remote workers as an essential element of their business strategy; however, knowledge processing is particular difficult in such isolated, largely digitally mediated settings. The great challenge for a knowledge-based organization lies not in how individuals should interact using technology but in how to achieve effective cooperation and knowledge exchange. Currently more attention has been paid to technology and the difficulties machines have processing natural language and less to studies of the human aspect—the influence of our own individual cognitive abilities and preferences on the processing of information when interacting online. This thesis draws on four scientific domains involved in the process of interpreting and processing massive, unstructured data—knowledge management, linguistics, cognitive science, and artificial intelligence—to build a model that offers a reliable way to address the ambiguous nature of language and improve workers’ digitally mediated interactions. Human communication can be discouragingly imprecise and is characterized by a strong linguistic ambiguity; this represents an enormous challenge for the computer analysis of natural language. In this thesis, I propose and develop a new data interpretation layer for the processing of natural language based on the human cognitive preferences of the conversants themselves. Such a semantic analysis merges information derived both from the content and from the associated social and individual contexts, as well as the social dynamics that emerge online. At the same time, assessment taxonomies are used to analyze online comportment at the individual and community level in order to successfully identify characteristics leading to greater effectiveness of communication. Measurement patterns for identifying effective methods of individual interaction with regard to individual cognitive and learning preferences are also evaluated; a novel Cyber-Cognitive Identity (CCI)—a perceptual profile of an individual’s cognitive and learning styles—is proposed. Accommodation of such cognitive preferences can greatly facilitate knowledge management in the geographically dispersed and collaborative digital environment. Use of the CCI is proposed for cognitively labeled Latent Dirichlet Allocation (CLLDA), a novel method for automatically labeling and clustering knowledge that does not rely solely on probabilistic methods, but rather on a fusion of machine learning algorithms and the cognitive identities of the associated individuals interacting in a digitally mediated environment. Advantages include: a greater perspicuity of dynamic and meaningful cognitive rules leading to greater tagging accuracy and a higher content portability at the sentence, document, and corpus level with respect to digital communication.
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.
Due to continuously intensifying human usage of the marine environment worldwide ranging cetaceans face an increasing number of threats. Besides whaling, overfishing and by-catch, new technical developments increase the water and noise pollution, which can negatively affect marine species. Cetaceans are especially prone to these influences, being at the top of the food chain and therefore accumulating toxins and contaminants. Furthermore, they are extremely noise sensitive due to their highly developed hearing sense and echolocation ability. As a result, several cetacean species were brought to extinction during the last century or are now classified as critically endangered. This work focuses on two odontocetes. It applies and compares different molecular methods for inference of population status and adaptation, with implications for conservation. The worldwide distributed sperm whale (Physeter macrocephalus) shows a matrilineal population structure with predominant male dispersal. A recently stranded group of male sperm whales provided a unique opportunity to investigate male grouping for the first time. Based on the mitochondrial control region, I was able to infer that male bachelor groups comprise multiple matrilines, hence derive from different social groups, and that they represent the genetic variability of the entire North Atlantic. The harbor porpoise (Phocoena phocoena) occurs only in the northern hemisphere. By being small and occurring mostly in coastal habitats it is especially prone to human disturbance. Since some subspecies and subpopulations are critically endangered, it is important to generate and provide genetic markers with high resolution to facilitate population assignment and subsequent protection measurements. Here, I provide the first harbour porpoise whole genome, in high quality and including a draft annotation. Using it for mapping ddRAD seq data, I identify genome wide SNPs and, together with a fragment of the mitochondrial control region, inferred the population structure of its North Atlantic distribution range. The Belt Sea harbors a distinct subpopulation oppose to the North Atlantic, with a transition zone in the Kattegat. Within the North Atlantic I could detect subtle genetic differentiation between western (Canada-Iceland) and eastern (North Sea) regions, with support for a German North Sea breading ground around the Isle of Sylt. Further, I was able to detect six outlier loci which show isolation by distance across the investigated sampling areas. In employing different markers, I could show that single maker systems as well as genome wide data can unravel new information about population affinities of odontocetes. Genome wide data can facilitate investigation of adaptations and evolutionary history of the species and its populations. Moreover, they facilitate population genetic investigations, providing a high resolution, and hence allowing for detection of subtle population structuring especially important for highly mobile cetaceans.
This thesis investigates how the permafrost microbiota responds to global warming. In detail, the constraints behind methane production in thawing permafrost were linked to methanogenic activity, abundance and composition. Furthermore, this thesis offers new insights into microbial adaptions to the changing environmental conditions during global warming. This was assesed by investigating the potential ecological relevant functions encoded by plasmid DNA within the permafrost microbiota. Permafrost of both interglacial and glacial origin spanning the Holocene to the late Pleistocene, including Eemian, were studied during long-term thaw incubations. Furthermore, several permafrost cores of different stratigraphy, soil type and vegetation cover were used to target the main constraints behind methane production during short-term thaw simulations. Short- and long-term incubations simulating thaw with and without the addition of substrate were combined with activity measurements, amplicon and metagenomic sequencing of permanently frozen and seasonally thawed active layer. Combined, it allowed to address the following questions. i) What constraints methane production when permafrost thaws and how is this linked to methanogenic activity, abundance and composition? ii) How does the methanogenic community composition change during long-term thawing conditions? iii) Which potential ecological relevant functions are encoded by plasmid DNA in active layer soils?
The major outcomes of this thesis are as follows. i) Methane production from permafrost after long-term thaw simulation was found to be constrained mainly by the abundance of methanogens and the archaeal community composition. Deposits formed during periods of warmer temperatures and increased precipitation, (here represented by deposits from the Late Pleistocene of both interstadial and interglacial periods) were found to respond strongest to thawing conditions and to contain an archaeal community dominated by methanogenic archaea (40% and 100% of all detected archaea). Methanogenic population size and carbon density were identified as main predictors for potential methane production in thawing permafrost in short-term incubations when substrate was sufficiently available.
ii) Besides determining the methanogenic activity after long-term thaw, the paleoenvironmental conditions were also found to influence the response of the methanogenic community composition. Substantial shifts within methanogenic community structure and a drop in diversity were observed in deposits formed during warmer periods, but not in deposits from stadials, when colder and drier conditions occurred. Overall, a shift towards a dominance of hydrogenotrophic methanogens was observed in all samples, except for the oldest interglacial deposits from the Eemian, which displayed a potential dominance of acetoclastic methanogens. The Eemian, which is discussed to serve as an analogue to current climate conditions, contained highly active methanogenic communities. However, all potential limitation of methane production after permafrost thaw, it means methanogenic community structure, methanogenic population size, and substrate pool might be overcome after permafrost had thawed on the long-term. iii) Enrichments with soil from the seasonally thawed active layer revealed that its plasmid DNA (‘metaplasmidome’) carries stress-response genes. In particular it encoded antibiotic resistance genes, heavy metal resistance genes, cold shock proteins and genes encoding UV-protection. Those are functions that are directly involved in the adaptation of microbial communities to stresses in polar environments. It was further found that metaplasmidomes from the Siberian active layer originate mainly from Gammaproteobacteria. By applying enrichment cultures followed by plasmid DNA extraction it was possible to obtain a higher average contigs length and significantly higher recovery of plasmid sequences than from extracting plasmid sequences from metagenomes. The approach of analyzing ‘metaplasmidomes’ established in this thesis is therefore suitable for studying the ecological role of plasmids in polar environments in general.
This thesis emphasizes that including microbial community dynamics have the potential to improve permafrost-carbon projections. Microbially mediated methane release from permafrost environments may significantly impact future climate change. This thesis identified drivers of methanogenic composition, abundance and activity in thawing permafrost landscapes. Finally, this thesis underlines the importance to study how the current warming Arctic affects microbial communities in order to gain more insight into microbial response and adaptation strategies.
Towards seasonal prediction: stratosphere-troposphere coupling in the atmospheric model ICON-NWP
(2020)
Stratospheric variability is one of the main potential sources for sub-seasonal to seasonal predictability in mid-latitudes in winter. Stratospheric pathways play an important role for long-range teleconnections between tropical phenomena, such as the quasi-biennial oscillation (QBO) and El Niño-Southern Oscillation (ENSO), and the mid-latitudes on the one hand, and linkages between Arctic climate change and the mid-latitudes on the other hand. In order to move forward in the field of extratropical seasonal predictions, it is essential that an atmospheric model is able to realistically simulate the stratospheric circulation and variability. The numerical weather prediction (NWP) configuration of the ICOsahedral Non-hydrostatic atmosphere model ICON is currently being used by the German Meteorological Service for the regular weather forecast, and is intended to produce seasonal predictions in future. This thesis represents the first extensive evaluation of Northern Hemisphere stratospheric winter circulation in ICON-NWP by analysing a large set of seasonal ensemble experiments.
An ICON control climatology simulated with a default setup is able to reproduce the basic behaviour of the stratospheric polar vortex. However, stratospheric westerlies are significantly too weak and major stratospheric warmings too frequent, especially in January. The weak stratospheric polar vortex in ICON is furthermore connected to a mean sea level pressure (MSLP) bias pattern resembling the negative phase of the Arctic Oscillation (AO). Since a good representation of the drag exerted by gravity waves is crucial for a realistic simulation of the stratosphere, three sensitivity experiments with reduced gravity wave drag are performed. Both a reduction of the non-orographic and orographic gravity wave drag respectively, lead to a strengthening of the stratospheric vortex and thus a bias reduction in winter, in particular in January. However, the effect of the non-orographic gravity wave drag on the stratosphere is stronger. A third experiment, combining a reduced orographic and non-orographic drag, exhibits the largest stratospheric bias reductions. The analysis of stratosphere-troposphere coupling based on an index of the Northern Annular Mode demonstrates that ICON realistically represents downward coupling. This coupling is intensified and more realistic in experiments with a reduced gravity wave drag, in particular with reduced non-orographic drag. Tropospheric circulation is also affected by the reduced gravity wave drag, especially in January, when the strongly improved stratospheric circulation reduces biases in the MSLP patterns. Moreover, a retuning of the subgrid-scale orography parameterisations leads to a significant error reduction in the MSLP in all months. In conclusion, the combination of these adjusted parameterisations is recommended as a current optimal setup for seasonal simulations with ICON.
Additionally, this thesis discusses further possible influences on the stratospheric polar vortex, including the influence of tropical phenomena, such as QBO and ENSO, as well as the influence of a rapidly warming Arctic. ICON does not simulate the quasi-oscillatory behaviour of the QBO and favours weak easterlies in the tropical stratosphere. A comparison with a reanalysis composite of the easterly QBO phase reveals, that the shift towards the easterly QBO in ICON further weakens the stratospheric polar vortex. On the other hand, the stratospheric reaction to ENSO events in ICON is realistic. ICON and the reanalysis exhibit a weakened stratospheric vortex in warm ENSO years. Furthermore, in particular in winter, warm ENSO events favour the negative phase of the Arctic Oscillation, whereas cold events favour the positive phase. The ICON simulations also suggest a significant effect of ENSO on the Atlantic-European sector in late winter. To investigate the influence of Arctic climate change on mid-latitude circulation changes, two differing approaches with transient and fixed sea ice conditions are chosen. Neither ICON approach exhibits the mid-latitude tropospheric negative Arctic Oscillation circulation response to amplified Arctic warming, as it is discussed on the basis of observational evidence. Nevertheless, adding a new model to the current and active discussion on Arctic-midlatitude linkages, further contributes to the understanding of divergent conclusions between model and observational studies.
Philosophische Tugenden
(2020)
Worin besteht gutes Philosophieren? Und weshalb ist gerade John Stuart Mill ein außergewöhnlich guter Philosoph? Joachim Toenges-Hinn verbindet in diesem Band die metaphilosophische Suche danach, was gute Philosophie ausmacht, mit einer historischen Betrachtung des Philosophen John Stuart Mill. Dabei fungiert Mill zugleich als Urheber von und Verkörperung des Strebens nach zwei philosophischen Tugenden, die Toenges-Hinn aus Mills philosophischem Werk ableitet und anschließend systematisch verteidigt. Diese als „Bentham-Ideal“ und „Coleridge-Ideal“ bezeichneten Tugenden stehen dabei ebenso im Fokus seiner Untersuchung wie die Bedeutung von Lebensexperimenten für philosophische Biografien.
Sekundäre Pflanzenstoffe und ihre gesundheitsfördernden Eigenschaften sind in den letzten zwei Jahrzehnten vielfach ernährungsphysiologisch untersucht und spezifische positive Effekte im humanen Organismus zum Teil sehr genau beschrieben worden. Zu den Carotinoiden zählend ist der sekundäre Pflanzenstoff Lutein insbesondere in der Prävention von ophthalmologischen Erkrankungen in den Mittelpunkt der Forschung gerückt. Das ausschließlich von Pflanzen und einigen Algen synthetisierte Xanthophyll wird über die pflanzliche Nahrung insbesondere grünes Blattgemüse in den humanen Organismus aufgenommen. Dort akkumuliert es bevorzugt im Makulapigment der Retina des menschlichen Auges und ist bedeutend im Prozess der Aufrechterhaltung der Funktionsfähigkeit der Photorezeptorzellen. Im Laufe des Alterns kann die Abnahme der Dichte des Makulapigments und der Abbau von Lutein beobachtet werden. Die dadurch eintretende Destabilisierung der Photorezeptorzellen im Zusammenhang mit einer veränderten Stoffwechsellage im alternden Organismus kann zur Ausprägung der altersbedingten Makuladegeneration (AMD) führen. Die pathologische Symptomatik der Augenerkrankung reicht vom Verlust der Sehschärfe bis hin zum irreversiblen Erblinden. Da therapeutische Mittel ausschließlich ein Fortschreiten verhindern, bestehen hier Forschungsansätze präventive Maßnahmen zu finden. Die Supplementierung von luteinhaltigen Präparaten bietet dabei einen Ansatzpunkt. Auf dem Markt finden sich bereits Nahrungsergänzungsmittel (NEM) mit Lutein in verschiedenen Applikationen. Limitierend ist dabei die Stabilität und Bioverfügbarkeit von Lutein, welches teilweise kostenintensiv und mit unbekannter Reinheit zu erwerben ist. Aus diesem Grund wäre die Verwendung von Luteinestern als die pflanzliche Speicherform des Luteins im Rahmen eines NEMs vorteilhaft. Neben ihrer natürlichen, höheren Stabilität sind Luteinester nachhaltig und kostengünstig einsetzbar.
In dieser Arbeit wurden physikochemische und ernährungsphysiologisch relevante Aspekte in dem Produktentwicklungsprozess eines NEMs mit Luteinestern in einer kolloidalen Formulierung untersucht. Die bisher einzigartige Anwendung von Luteinestern in einem Mundspray sollte die Aufnahme des Wirkstoffes insbesondere für ältere Menschen erleichtern und verbessern. Unter Beachtung der Ergebnisse und der ernährungsphysiologischen Bewertung sollten u.a. Empfehlungen für die Rezepturzusammensetzungen einer Miniemulsion (Emulsion mit Partikelgrößen <1,0 µm) gegeben werden. Eine Einschätzung der Bioverfügbarkeit der Luteinester aus den entwickelten, kolloidalen Formulierungen konnte anhand von Studien zur Resorption- und Absorptionsverfügbarkeit in vitro ermöglicht werden.
In physikalischen Untersuchungen wurden zunächst Basisbestandteile für die Formulierungen präzisiert. In ersten wirkstofffreien Musteremulsionen konnten ausgewählte Öle als Trägerphase sowie Emulgatoren und Löslichkeitsvermittler (Peptisatoren) hinsichtlich ihrer Eignung zur Bereitstellung einer Miniemulsion physikalisch geprüft werden. Die beste Stabilität und optimale Eigenschaften einer Miniemulsion zeigten sich bei der Verwendung von MCT-Öl (engl. medium chain triglyceride) bzw. Rapsöl in der Trägerphase sowie des Emulgators Tween® 80 (Tween 80) allein oder in Kombination mit dem Molkenproteinhydrolysat Biozate® 1 (Biozate 1).
Aus den physikalischen Untersuchungen der Musteremulsionen gingen die Präemulsionen als Prototypen hervor. Diese enthielten den Wirkstoff Lutein in verschiedenen Formen. So wurden Präemulsionen mit Lutein, mit Luteinestern sowie mit Lutein und Luteinestern konzipiert, welche den Emulgator Tween 80 oder die Kombination mit Biozate 1 enthielten. Bei der Herstellung der Präemulsionen führte die Anwendung der Emulgiertechniken Ultraschall mit anschließender Hochdruckhomogenisation zu den gewünschten Miniemulsionen. Beide eingesetzten Emulgatoren boten optimale Stabilisierungseffekte. Anschließend erfolgte die physikochemische Charakterisierung der Wirkstoffe. Insbesondere Luteinester aus Oleoresin erwiesen sich hier als stabil gegenüber verschiedenen Lagerungsbedingungen. Ebenso konnte bei einer kurzzeitigen Behandlung der Wirkstoffe unter spezifischen mechanischen, thermischen, sauren und basischen Bedingungen eine Stabilität von Lutein und Luteinestern gezeigt werden. Die Zugabe von Biozate 1 bot dabei nur für Lutein einen zusätzlichen Schutz. Bei längerer physikochemischer Behandlung unterlagen die in den Miniemulsionen eingebrachten Wirkstoffe moderaten Abbauvorgängen. Markant war deren Sensitivität gegenüber dem basischen Milieu. Im Rahmen der Rezepturentwicklung des NEMs war hier die Empfehlung, eine Miniemulsion mit einem leicht saurem pH-Milieu zum Schutz des Wirkstoffes durch kontrollierte Zugabe weiterer Inhaltstoffe zu gestalten.
Im weiteren Entwicklungsprozess des NEMs wurden Fertigrezepturen mit dem Wirkstoff Luteinester aufgestellt. Die alleinige Anwendung des Emulgators Biozate 1 zeigte sich dabei als ungeeignet. Die weiterhin zur Verfügung stehenden Fertigrezepturen enthielten in der Öl-phase neben dem Wirkstoff das MCT-ÖL oder Rapsöl sowie a-Tocopherol zur Stabilisierung. Die Wasserphase bestand aus dem Emulgator Tween 80 oder einer Kombination aus Tween 80 und Biozate 1. Zusatzstoffe waren zudem als mikrobiologischer Schutz Ascorbinsäure und Kaliumsorbat sowie für sensorische Effekte Xylitol und Orangenaroma. Die Anordnung der Basisrezeptur und das angewendete Emulgierverfahren lieferten stabile Miniemulsionen. Weiterhin zeigten langfristige Lagerungsversuche mit den Fertigrezepturen bei 4°C, dass eine Aufrechterhaltung der geforderten Luteinestermenge im Produkt gewährleistet war. Analoge Untersuchungen an einem luteinhaltigen, marktgängigen Präparat bestätigten dagegen eine bereits bei kurzfristiger Lagerung auftretende Instabilität von Lutein.
Abschließend wurde durch Resorptions- und Absorptionsstudien in vitro mit den Präemulsionen und Fertigrezepturen die Bioverfügbarkeit von Luteinestern geprüft. Nach Behandlung in einem etablierten in vitro Verdaumodell konnte eine geringfügige Resorptionsverfügbarkeit der Luteinester definiert werden. Limitiert war eine Micellarisierung des Wirkstoffes aus den konzipierten Formulierungen zu beobachten. Eine enzymatische Spaltung der Luteinester zu freiem Lutein wurde nur begrenzt festgestellt. Spezifität und Aktivität von entsprechenden hydrolytischen Lipasen sind als äußerst gering gegenüber Luteinestern zu bewerten. In sich anschließenden Zellkulturversuchen mit der Zelllinie Caco-2 wurden keine zytotoxischen Effekte durch die relevanten Inhaltsstoffe in den Präemulsionen gezeigt. Dagegen konnten eine Sensibilität gegenüber den Fertigrezepturen beobachtet werden. Diese sollte im Zusammenhang mit Irritationen der Schleimhäute des Magen-Darm-Traktes bedacht werden. Eine weniger komplexe Rezeptur könnte die beobachteten Einschränkungen möglicherweise minimieren. Abschließende Absorptionsstudien zeigten, dass grundsätzlich eine geringfügige Aufnahme von vorrangig Lutein, aber auch Luteinmonoestern in den Enterocyten aus Miniemulsionen erfolgen kann. Dabei hatte weder Tween 80 noch Biozate 1 einen förderlichen Einfluss auf die Absorptionsrate von Lutein oder Luteinestern. Die Metabolisierung der Wirkstoffe durch vorherigen in vitro-Verdau steigerte die zelluläre Aufnahme von Wirkstoffen aus Formulierungen mit Lutein und Luteinestern gleichermaßen. Die beobachtete Aufnahme von Lutein und Luteinmonoestern in den Enterocyten scheint über passive Diffusion zu erfolgen, wobei auch der aktive Transport nicht ausgeschlossen werden kann. Dagegen können Luteindiester aufgrund ihrer Molekülgröße nicht über den Weg der Micellarisierung und einfachen Diffusion in die Enterocyten gelangen. Ihre Aufnahme in die Dünndarmepithelzellen bedarf einer vorherigen hydrolytischen Spaltung durch spezifische Lipasen. Dieser Schritt limitiert wiederum die effektive Aufnahme der Luteinester in die Zellen bzw. stellt eine Einschränkung in ihrer Bioverfügbarkeit im Vergleich zu freiem Lutein dar.
Zusammenfassend konnte für die physikochemisch stabilen Luteinester eine geringe Bioverfügbarkeit aus kolloidalen Formulierungen gezeigt werden. Dennoch ist die Verwendung als Wirkstoffquelle für den sekundären Pflanzenstoff Lutein in einem NEM zu empfehlen. Im Zusammenhang mit der Aufnahme von luteinreichen, pflanzlichen Lebensmitteln kann trotz der zu erwartenden geringen Bioverfügbarkeit der Luteinester aus dem NEM ein Beitrag zur Verbesserung des Luteinstatus erreicht werden. Entsprechende Publikationen zeigten eindeutige Korrelationen zwischen der Aufnahme von luteinesterhaltigen Präparaten und einem Anstieg der Luteinkonzentration im Serum bzw. der Makulapigmentdichte in vivo. Die geringfügig bessere Bioverfügbarkeit von freiem Lutein steht im kritischen Zusammenhang mit seiner Instabilität und Kostenintensität. Bilanzierend wurde im Rahmen dieser Arbeit das marktgängige Produkt Vita Culus® konzipiert. Im Ausblick sollten humane Interventionsstudien mit dem NEM die abschließende Bewertung der Bioverfügbarkeit von Luteinestern aus dem Präparat möglich machen.
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.
Organizations incorporate the institutional demands from their environment in order to be deemed legitimate and survive. Yet, complexifying societies promulgate multiple and sometimes inconsistent institutional prescriptions. When these prescriptions collide, organizations are said to face “institutional complexity”. How does an organization then incorporate incompatible demands? What are the consequences of institutional complexity for an organization? The literature provides contradictory conceptual and empirical insights on the matter. A central assumption, however, remains that internal incompatibilities generate tensions that, under certain conditions, can escalate into intractable conflicts, resulting in dysfunctionality and loss of legitimacy. The present research is an inquiry into what happens inside an organization when it incorporates complex institutional demands.
To answer this question, I focus on how individuals inside an organization interpret a complex institutional prescription. I examine how members of the French Development Agency interpret ‘results-based management’, a central but complex concept of organizing in the field of development aid. I use an inductive mixed methods design to systematically explore how different interpretations of results-based management relate to one another and to the organizational context in which they are embedded.
The results reveal that results-based management is a contested concept in the French Development Agency. I find multiple interpretations of the concept, which are attached to partly incompatible rationales about “who we are” and “what we do as an organization”. These rationales nevertheless coexist as balanced forces, without escalating into open conflict. The analysis points to four reasons for this peaceful coexistence of diverging rationales inside one and the same organization: 1) individuals’ capacity to manipulate different interpretations of a complex institutional demand, 2) the nature of interpretations, which makes them more or less prone to conflict, 3) the balanced distribution of rationales across the organizational sub-contexts and 4) the shared rules of interpretation provided by the larger socio-cultural context.
This research shows that an organization that incorporates institutional complexity comes to represent different, partly incompatible things to its members without being at war with itself. In doing so, it contributes to our knowledge of institutional complexity and organizational hybridity. It also advances our understanding of internal organizational legitimacy and of the translation of managerial concepts in organizations.
Comment sections of online news platforms are an essential space to express opinions and discuss political topics. However, the misuse by spammers, haters, and trolls raises doubts about whether the benefits justify the costs of the time-consuming content moderation. As a consequence, many platforms limited or even shut down comment sections completely. In this thesis, we present deep learning approaches for comment classification, recommendation, and prediction to foster respectful and engaging online discussions. The main focus is on two kinds of comments: toxic comments, which make readers leave a discussion, and engaging comments, which make readers join a discussion. First, we discourage and remove toxic comments, e.g., insults or threats. To this end, we present a semi-automatic comment moderation process, which is based on fine-grained text classification models and supports moderators. Our experiments demonstrate that data augmentation, transfer learning, and ensemble learning allow training robust classifiers even on small datasets. To establish trust in the machine-learned models, we reveal which input features are decisive for their output with attribution-based explanation methods. Second, we encourage and highlight engaging comments, e.g., serious questions or factual statements. We automatically identify the most engaging comments, so that readers need not scroll through thousands of comments to find them. The model training process builds on upvotes and replies as a measure of reader engagement. We also identify comments that address the article authors or are otherwise relevant to them to support interactions between journalists and their readership. Taking into account the readers' interests, we further provide personalized recommendations of discussions that align with their favored topics or involve frequent co-commenters. Our models outperform multiple baselines and recent related work in experiments on comment datasets from different platforms.
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.
To find out the future of nowadays reef ecosystem turnover under the environmental stresses such as global warming and ocean acidification, analogue studies from the geologic past are needed. As a critical time of reef ecosystem innovation, the Permian-Triassic transition witnessed the most severe demise of Phanerozoic reef builders, and the establishment of modern style symbiotic relationships within the reef-building organisms. Being the initial stage of this transition, the Middle Permian (Capitanian) mass extinction coursed a reef eclipse in the early Late Permian, which lead to a gap of understanding in the post-extinction Wuchiapingian reef ecosystem, shortly before the radiation of Changhsingian reefs. Here, this thesis presents detailed biostratigraphic, sedimentological, and palaeoecological studies of the Wuchiapingian reef recovery following the Middle Permian (Capitanian) mass extinction, on the only recorded Wuchiapingian reef setting, outcropping in South China at the Tieqiao section.
Conodont biostratigraphic zonations were revised from the Early Permian Artinskian to the Late Permian Wuchiapingian in the Tieqiao section. Twenty main and seven subordinate conodont zones are determined at Tieqiao section including two conodont zone below and above the Tieqiao reef complex. The age of Tieqiao reef was constrained as early to middle Wuchiapingian.
After constraining the reef age, detailed two-dimensional outcrop mapping combined with lithofacies study were carried out on the Wuchiapingian Tieqiao Section to investigate the reef growth pattern stratigraphically as well as the lateral changes of reef geometry on the outcrop scale. Semi-quantitative studies of the reef-building organisms were used to find out their evolution pattern within the reef recovery. Six reef growth cycles were determined within six transgressive-regressive cycles in the Tieqiao section. The reefs developed within the upper part of each regressive phase and were dominated by different biotas. The timing of initial reef recovery after the Middle Permian (Capitanian) mass extinction was updated to the Clarkina leveni conodont zone, which is earlier than previous understanding. Metazoans such as sponges were not the major components of the Wuchiapingian reefs until the 5th and 6th cycles. So, the recovery of metazoan reef ecosystem after the Middle Permian (Capitanian) mass extinction was obviously delayed. In addition, although the importance of metazoan reef builders such as sponges did increase following the recovery process, encrusting organisms such as Archaeolithoporella and Tubiphytes, combined with microbial carbonate precipitation, still played significant roles to the reef building process and reef recovery after the mass extinction.
Based on the results from outcrop mapping and sedimentological studies, quantitative composition analysis of the Tieqiao reef complex were applied on selected thin sections to further investigate the functioning of reef building components and the reef evolution after the Middle Permian (Capitanian) mass extinction. Data sets of skeletal grains and whole rock components were analyzed. The results show eleven biocommunity clusters/eight rock composition clusters dominated by different skeletal grains/rock components. Sponges, Archaeolithoporella and Tubiphytes were the most ecologically important components within the Wuchiapingian Tieqiao reef, while the clotted micrites and syndepositional cements are the additional important rock components for reef cores. The sponges were important within the whole reef recovery. Tubiphytes were broadly distributed in different environments and played a key-role in the initial reef communities. Archaeolithoporella concentrated in the shallower part of reef cycles (i.e., the upper part of reef core) and was functionally significant for the enlargement of reef volume.
In general, the reef recovery after the Middle Permian (Capitanian) mass extinction has some similarities with the reef recovery following the end-Permian mass extinction. It shows a delayed recovery of metazoan reefs and a stepwise recovery pattern that was controlled by both ecological and environmental factors. The importance of encrusting organisms and microbial carbonates are also similar to most of the other post-extinction reef ecosystems. These findings can be instructive to extend our understanding of the reef ecosystem evolution under environmental perturbation or stresses.
Ein Ergebnis der interkulturellen Beziehungen in Südostasien sind die immer noch existierenden portugiesisch-basierten Kreolsprachen Papia Kristang und Macaísta, die zu Muttersprachen von Generationen von Menschen in Malakka und Macau geworden sind. Welche Faktoren bewirken den Sprachwandel dieser Idiome, und wie ist dieser erkennbar? Dieser Band beschäftigt sich nicht nur mit der Sprachdynamik der portugiesisch-basierten Kreolsprachen Südostasiens, sondern auch mit anderen wesentlichen Fragestellungen der Variationslinguistik. Als Basis dienen die Ergebnisse einer empirischen Datenerhebung, die insbesondere die Veränderungen im Sprachgebrauch dokumentieren. Darüber hinaus stellt der Autor neue Resultate hinsichtlich der Sprachidentifikationen vor, die nicht nur für die Kreolistik von Bedeutung sind, sondern auch fachübergreifend für das Interesse der allgemeinen Sprachwissenschaft.
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.
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.
The current thesis is focused on the properties of graphene supported by metallic substrates and specifically on the behaviour of electrons in such systems. Methods of scanning tunneling microscopy, electron diffraction and photoemission spectroscopy were applied to study the structural and electronic properties of graphene. The purpose of the first part of this work is to introduce the most relevant aspects of graphene physics and the methodical background of experimental techniques used in the current thesis.
The scientific part of this work starts with the extensive study by means of scanning tunneling microscopy of the nanostructures that appear in Au intercalated graphene on Ni(111). This study was aimed to explore the possible structural explanations of the Rashba-type spin splitting of ~100 meV experimentally observed in this system — much larger than predicted by theory. It was demonstrated that gold can be intercalated under graphene not only as a dense monolayer, but also in the form of well-periodic arrays of nanoclusters, a structure previously not reported. Such nanocluster arrays are able to decouple graphene from the strongly interacting Ni substrate and render it quasi-free-standing, as demonstrated by our DFT study. At the same time calculations confirm strong enhancement of the proximity-induced SOI in graphene supported by such nanoclusters in comparison to monolayer gold. This effect, attributed to the reduced graphene-Au distance in the case of clusters, provides a large Rashba-type spin splitting of ~60 meV.
The obtained results not only provide a possible mechanism of SOI enhancement in this particular system, but they can be also generalized for graphene on other strongly interacting substrates intercalated by nanostructures of heavy noble d metals.
Even more intriguing is the proximity of graphene to heavy sp-metals that were predicted to induce an intrinsic SOI and realize a spin Hall effect in graphene. Bismuth is the heaviest stable sp-metal and its compounds demonstrate a plethora of exciting physical phenomena. This was the motivation behind the next part of the current thesis, where structural and electronic properties of a previously unreported phase of Bi-intercalated graphene on Ir(111) were studied by means of scanning tunneling microscopy, spin- and angle-resolved photoemission spectroscopy and electron diffraction. Photoemission experiments revealed a remarkable, nearly ideal graphene band structure with strongly suppressed signatures of interaction between graphene and the Ir(111) substrate, moreover, the characteristic moiré pattern observed in graphene on Ir(111) by electron diffraction and scanning tunneling microscopy was strongly suppressed after intercalation. The whole set of experimental data evidences that Bi forms a dense intercalated layer that efficiently decouples graphene from the substrate. The interaction manifests itself only in the n-type charge doping (~0.4 eV) and a relatively small band gap at the Dirac point (~190 meV). The origin of this minor band gap is quite intriguing and in this work it was possible to exclude a wide range of mechanisms that could be responsible for it, such as induced intrinsic spin-orbit interaction, hybridization with the substrate states and corrugation of the graphene lattice. The main origin of the band gap was attributed to the A-B symmetry breaking and this conclusion found support in the careful analysis of the interference effects in photoemission that provided the band gap estimate of ~140 meV.
While the previous chapters were focused on adjusting the properties of graphene by proximity to heavy metals, graphene on its own is a great object to study various physical effects at crystal surfaces. The final part of this work is devoted to a study of surface scattering resonances by means of photoemission spectroscopy, where this effect manifests itself as a distinct modulation of photoemission intensity. Though scattering resonances were widely studied in the past by means of electron diffraction, studies about their observation in photoemission experiments started to appear only recently and they are very scarce.
For a comprehensive study of scattering resonances graphene was selected as a versatile model system with adjustable properties. After the theoretical and historical introduction to the topic of scattering resonances follows a detailed description of the unusual features observed in the photoemission spectra obtained in this work and finally the equivalence between these features and scattering resonances is proven. The obtained photoemission results are in a good qualitative agreement with the existing theory, as verified by our calculations in the framework of the interference model. This simple model gives a suitable explanation for the general experimental observations.
The possibilities of engineering the scattering resonances were also explored. A systematic study of graphene on a wide range of substrates revealed that the energy position of the resonances is in a direct relation to the magnitude of charge transfer between graphene and the substrate. Moreover, it was demonstrated that the scattering resonances in graphene on Ir(111) can be suppressed by nanopatterning either by a superlattice of Ir nanoclusters or by atomic hydrogen. These effects were attributed to strong local variations of tork function and/or destruction of long-range order of thephene lattice. The tunability of scattering resonances can be applied for optoelectronic devices based on graphene. Moreover, the results of this study expand the general understanding of the phenomenon of scattering resonances and are applicable to many other materials besides graphene.
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.
This book endeavours to understand the seemingly direct link between utopianism and the USA, discussing novels that have never been brought together in this combination before, even though they all revolve around intentional communities: Imlay’s The Emigrants (1793), Hawthorne’s The Blithedale Romance (1852), Howland’s Papas Own Girl (1874), Griggs’s Imperium in Imperio (1899), and Du Bois’s The Quest of the Silver Fleece (1911). They relate nation and utopia not by describing perfect societies, but by writing about attempts to immediately live radically different lives. Signposting the respective communal history, the readings provide a literary perspective to communal studies, and add to a deeply necessary historicization for strictly literary approaches to US utopianism, and for studies that focus on Pilgrims/Puritans/Founding Fathers as utopian practitioners. This book therefore highlights how the authors evaluated the USA’s utopian potential and traces the nineteenth-century development of the utopian imagination from various perspectives.
The development of methods such as super-resolution microscopy (Nobel prize in Chemistry, 2014) and multi-scale computer modelling (Nobel prize in Chemistry, 2013) have provided scientists with powerful tools to study microscopic systems. Sub-micron particles or even fluorescently labelled single molecules can now be tracked for long times in a variety of systems such as living cells, biological membranes, colloidal solutions etc. at spatial and temporal resolutions previously inaccessible. Parallel to such single-particle tracking experiments, super-computing techniques enable simulations of large atomistic or coarse-grained systems such as biologically relevant membranes or proteins from picoseconds to seconds, generating large volume of data. These have led to an unprecedented rise in the number of reported cases of anomalous diffusion wherein the characteristic features of Brownian motion—namely linear growth of the mean squared displacement with time and the Gaussian form of the probability density function (PDF) to find a particle at a given position at some fixed time—are routinely violated. This presents a big challenge in identifying the underlying stochastic process and also estimating the corresponding parameters of the process to completely describe the observed behaviour. Finding the correct physical mechanism which leads to the observed dynamics is of paramount importance, for example, to understand the first-arrival time of transcription factors which govern gene regulation, or the survival probability of a pathogen in a biological cell post drug administration. Statistical Physics provides useful methods that can be applied to extract such vital information. This cumulative dissertation, based on five publications, focuses on the development, implementation and application of such tools with special emphasis on Bayesian inference and large deviation theory. Together with the implementation of Bayesian model comparison and parameter estimation methods for models of diffusion, complementary tools are developed based on different observables and large deviation theory to classify stochastic processes and gather pivotal information. Bayesian analysis of the data of micron-sized particles traced in mucin hydrogels at different pH conditions unveiled several interesting features and we gained insights into, for example, how in going from basic to acidic pH, the hydrogel becomes more heterogeneous and phase separation can set in, leading to observed non-ergodicity (non-equivalence of time and ensemble averages) and non-Gaussian PDF. With large deviation theory based analysis we could detect, for instance, non-Gaussianity in seeming Brownian diffusion of beads in aqueous solution, anisotropic motion of the beads in mucin at neutral pH conditions, and short-time correlations in climate data. Thus through the application of the developed methods to biological and meteorological datasets crucial information is garnered about the underlying stochastic processes and significant insights are obtained in understanding the physical nature of these systems.
Lattice dynamics
(2020)
In this thesis I summarize my contribution to the research field of ultrafast structural dynamics in condensend matter. It consists of 17 publications that cover the complex interplay between electron, magnon, and phonon subsystems in solid materials and the resulting lattice dynamics after ultrafast photoexcitation. The investigation of such dynamics is necessary for the physical understanding of the processes in materials that might become important in the future as functional materials for technological applications, for example in data storage applications, information processing, sensors, or energy harvesting.
In this work I present ultrafast x-ray diffraction (UXRD) experiments based on the optical pump – x-ray probe technique revealing the time-resolved lattice strain. To study these dynamics the samples (mainly thin film heterostructures) are excited by femtosecond near-infrared or visible light pulses. The induced strain dynamics caused by stresses of the excited subsystems are measured in a pump-probe scheme with x-ray diffraction (XRD) as a probe. The UXRD setups used during my thesis are a laser-driven table-top x-ray source and large-scale synchrotron facilities with dedicated time-resolved diffraction setups. The UXRD experiments provide quantitative access to heat reservoirs in nanometric layers and monitor the transient responses of these layers with coupled electron, magnon, and phonon subsystems. In contrast to optical probes, UXRD allows accessing the material-specific information, which is unavailable for optical light due to the detection of multiple indistinguishable layers in the range of the penetration depth.
In addition, UXRD facilitates a layer-specific probe for layers buried opaque heterostructures to study the energy flow. I extended this UXRD technique to obtain the driving stress profile by measuring the strain dynamics in the unexcited buried layer after excitation of the adjacent absorbing layers with femtosecond laser pulses. This enables the study of negative thermal expansion (NTE) in magnetic materials, which occurs due to the loss of the magnetic order. Part of this work is the investigation of stress profiles which are the source of coherent acoustic phonon wave packets (hypersound waves). The spatiotemporal shape of these stress profiles depends on the energy distribution profile and the ability of the involved subsystems to produce stress. The evaluation of the UXRD data of rare-earth metals yields a stress profile that closely matches the optical penetration profile: In the paramagnetic (PM) phase the photoexcitation results in a quasi-instantaneous expansive stress of the metallic layer whereas in the antiferromagnetic (AFM) phase a quasi-instantaneous contractive stress and a second contractive stress contribution rising on a 10 ps time scale adds to the PM contribution. These two time scales are characteristic for the magnetic contribution and are in agreement with related studies of the magnetization dynamics of rare-earth materials.
Several publications in this thesis demonstrate the scientific progress in the field of active strain control to drive a second excitation or engineer an ultrafast switch. These applications of ultrafast dynamics are necessary to enable control of functional material properties via strain on ultrafast time scales.
For this thesis I implemented upgrades of the existing laser-driven table-top UXRD setup in order to achieve an enhancement of x-ray flux to resolve single digit nanometer thick layers. Furthermore, I developed and built a new in-situ time-resolved magneto-optic Kerr effect (MOKE) and optical reflectivity setup at the laser-driven table-top UXRD setup to measure the dynamics of lattice, electrons and magnons under the same excitation conditions.
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.
Galaxies are gravitationally bound systems of stars, gas, dust and - probably - dark matter. They are the building blocks of the Universe. The morphology of galaxies is diverse: some galaxies have structures such as spirals, bulges, bars, rings, lenses or inner disks, among others. The main processes that characterise galaxy evolution can be separated into fast violent events that dominated evolution at earlier times and slower processes, which constitute a phase called secular evolution, that became dominant at later times. Internal processes of secular evolution include the gradual rearrangement of matter and angular momentum, the build-up and dissolution of substructures or the feeding of supermassive black holes and their feedback. Galaxy bulges – bright central components in disc galaxies –, on one hand, are relics of galaxy formation and evolution. For instance, the presence of a classical bulge suggests a relatively violent history. In contrast, the presence of a disc-like bulge instead indicates the occurrence of secular evolution processes in the main disc. Galaxy bars – elongated central stellar structures –, on the other hand, are the engines of secular evolution. Studying internal properties of both bars and bulges is key to comprehending some of the processes through which secular evolution takes place. The main objectives of this thesis are (1) to improve the classification of bulges by combining photometric and spectroscopic approaches for a large sample of galaxies, (2) to quantify star formation in bars and verify dependencies on galaxy properties and (3) to analyse stellar populations in bars to aid in understanding the formation and evolution of bars. Integral field spectroscopy is fundamental to the work presented in this thesis, which consists of three different projects as part of three different galaxy surveys: the CALIFA survey, the CARS survey and the TIMER project.
The first part of this thesis constitutes an investigation of the nature of bulges in disc galaxies. We analyse 45 galaxies from the integral-field spectroscopic survey CALIFA by performing 2D image decompositions, growth curve measurements and spectral template fitting to derive stellar kinematics from CALIFA data cubes. From the obtained results, we present a recipe to classify bulges that combines four different parameters from photometry and kinematics: The bulge Sersic index nb, the concentration index C20;50, the Kormendy relation and the inner slope of the radial velocity dispersion profile ∇σ. The results of the different approaches are in good agreement and allow a safe classification for approximately 95% of the galaxies. We also find that our new ‘inner’ concentration index performs considerably better than the traditionally used C50;90 and, in combination with the Kormendy relation, provides a very robust indication of the physical nature of the bulge. In the second part, we study star formation within bars using VLT/MUSE observations for 16 nearby (0.01 < z < 0.06) barred active-galactic-nuclei (AGN)-host galaxies from the CARS survey. We derive spatially-resolved star formation rates (SFR) from Hα emission line fluxes and perform a detailed multi-component photometric decomposition on images derived from the data cubes. We find a clear separation into eight star-forming (SF) and eight non-SF bars, which we interpret as indication of a fast quenching process. We further report a correlation between the SFR in the bar and the shape of the bar surface brightness profile: only the flattest bars (nbar < 0.4) are SF. Both parameters are found to be uncorrelated with Hubble type. Additionally, owing to the high spatial resolution of the MUSE data cubes, for the first time, we are able to dissect the SFR within the bar and analyse trends parallel and perpendicular to the bar major axis. Star formation is 1.75 times stronger on the leading edge of a rotating bar than on the trailing edge and is radially decreasing. Moreover, from testing an AGN feeding scenario, we report that the SFR of the bar is uncorrelated with AGN luminosity. Lastly, we present a detailed analysis of star formation histories and chemical enrichment of stellar populations (SP) in galaxy bars. We use MUSE observations of nine very nearby barred galaxies from the TIMER project to derive spatially resolved maps of stellar ages and metallicities, [α/Fe] abundances, star formation histories, as well as Hα as tracer of star formation. Using these maps, we explore in detail variations of SP perpendicular to the bar major axes. We find observational evidence for a separation of SP, supposedly caused by an evolving bar. Specifically, intermediate-age stars (∼ 2-6 Gyr) get trapped on more elongated orbits forming a thinner bar, while old stars (> 8 Gyr) form a rounder and thicker bar. This evidence is further strengthened by very similar results obtained from barred galaxies in the cosmological zoom-in simulations from the Auriga project. In addition, we find imprints of typical star formation patterns in barred galaxies on the youngest populations (< 2 Gyr), which continuously become more dominant from the major axis towards the sides of the bar. The effect is slightly stronger on the leading side. Furthermore, we find that bars are on average more metal-rich and less α-enhanced than the inner parts of the discs that surrounds them. We interpret this result as an indication of a more prolonged or continuous formation of stars that shape the bar as compared to shorter formation episodes in the disc within the bar region.
The steadily rising number of investor-State arbitration proceedings within the EU has triggered an extensive backlash and an increased questioning of the international investment law regime by different Member States as well as the EU Commission. This has resulted in the EU's assertion of control over the intra-EU investment regime by promoting the termination of bilateral intra-EU investment treaties (intra-EU BITs) and by opposing the jurisdiction of arbitral tribunals in intra-EU investor-State arbitration proceedings. Against the backdrop of the landmark Achmea decision of the European Court of Justice, the book offers an in depth analysis of the interplay of international investment law and the law of the European Union with regard to intra-EU investments, i.e. investments undertaken by an investor from one EU Member State within the territory of another EU Member State. It specifically analyses the conflict between the two investment protection regimes applicable within the EU with a particular emphasis on the compatibility of the international legal instruments with the law of the European Union. The book thereby addresses the more general question of the relationship between EU law and international law and offers a conceptual framework of intra-European investment protection based on the analysis of all intra-EU BITs, the Energy Charter Treaty and EU law, as well as the arbitral practice in over 180 intra-EU investor-State arbitration proceedings. Finally, the book develops possible solutions to reconcile the international legal standards of protection with the regionalized transnational law of the European Union
Nach lavierenden obiter dicta entspricht die Steueranspruchstheorie wieder der gefestigten Rechtsprechung des 1. Strafsenates des BGH (zuletzt: BGH, Beschl. v. 1.4.2020 – 1 StR 5/20, BeckRS 2020, 23245). Für den prozessualen Nachweis des Steuerhinterziehungsvorsatzes ist damit erforderlich, dass der Steuerpflichtige auch in rechtlicher Hinsicht den verletzten Steueranspruch kannte. Die vorliegende Rechtsprechungsanalyse zum straf- und finanzgerichtlichen Vorsatznachweis bei § 370 AO zeigt, dass die Judikatur mit diesem Konzept besser umgeht als vielfach unterstellt.
Insoweit wird herausgearbeitet, dass die Rechtsprechung mit einem hinreichend etablierten Kanon an Indizien operiert, welche berechtigterweise den Schluss auf vorsätzliches Handeln zulassen. Zugleich kommt die Untersuchung zu dem Ergebnis, dass die Rechtsprechung ebenfalls konsistent entlastende Umstände würdigt und bei entsprechender Indizienlage einen vorsatzausschließenden Irrtum feststellt. Als weiteres Ergebnis liefert die Untersuchung zugleich eine Leitlinie für den Tatrichter bei der Vorsatzfeststellung im Steuerstrafverfahren.
Die Trennung von Werbung und Programm gilt als »Magna Charta« des Medienrechts. In der Medienpraxis scheinen jedoch andere Spielregeln zu herrschen: Werbung soll dort so unauffällig wie möglich in das redaktionelle Programm eingebaut werden, um mit dem potenziellen Käufer erfolgreich zu kommunizieren. Immer neue programmintegrierte Werbeformen entstehen, die Programme darauf ausrichten, Markenprodukte in Szene zu setzen. Dieser Widerspruch zwischen Recht und Praxis bildet den Hintergrund dieser Arbeit. Im Schwerpunkt wird der Rechtsbegriff der Schleichwerbung im nationalen Medienrecht untersucht. Für die Bestimmung der verbotenen programmintegrierten Werbeform im Fernsehen und Internet stellt der Rundfunkstaatsvertrag die entscheidende Rechtsgrundlage dar. Insbesondere spielt die Schleichwerbung im Zusammenhang mit dem Influencer-Marketing eine große Rolle und daher klärt die Arbeit, was Werbebetreibende in sozialen Medien beachten müssen. Ferner werden die Aktualität und Angemessenheit der heutigen Regeln analysiert. Die Arbeit wurde ausgezeichnet mit dem Wolf-Rüdiger-Bub-Preis des Vereins der Freunde und Förderer der Juristischen Fakultät der Universität Potsdam.
In recent years, a substantial number of psycholinguistic studies and of studies on acquired language impairments have investigated the case of morphologically complex words. These have provided evidence for what is known as ‘morphological decomposition’, i.e. a mechanism that decomposes complex words into their constituent morphemes during online processing. This is believed to be a fundamental, possibly universal mechanism of morphological processing, operating irrespective of a word’s specific properties.
However, current accounts of morphological decomposition are mostly based on evidence from suffixed words and compound words, while prefixed words have been comparably neglected. At the same time, it has been consistently observed that, across languages, prefixed words are less widespread than suffixed words. This cross-linguistic preference for suffixing morphology has been claimed to be grounded in language processing and language learning mechanisms. This would predict differences in how prefixed words are processed and therefore also affected in language impairments, challenging the predictions of the major accounts of morphological decomposition.
Against this background, the present thesis aims at reducing the gap between the accounts of morphological decomposition and the accounts of the suffixing preference, by providing a thorough empirical investigation of prefixed words. Prefixed words are examined in three different domains: (i) visual word processing in native speakers; (ii) visual word processing in non-native speakers; (iii) acquired morphological impairments. The processing studies employ the masked priming paradigm, tapping into early stages of visual word recognition. Instead, the studies on morphological impairments investigate the errors produced in reading aloud tasks.
As for native processing, the present work first focuses on derivation (Publication I), specifically investigating whether German prefixed derived words, both lexically restricted (e.g. inaktiv ‘inactive’) and unrestricted (e.g. unsauber ‘unclean’) can be efficiently decomposed. I then present a second study (Publication II) on a Bantu language, Setswana, which offers the unique opportunity of testing inflectional prefixes, and directly comparing priming with prefixed inflected primes (e.g. dikgeleke ‘experts’) to priming with prefixed derived primes (e.g. bokgeleke ‘talent’). With regard to non-native processing (Publication I), the priming effects obtained from the lexically restricted and unrestricted prefixed derivations in native speakers are additionally compared to the priming effects obtained in a group of non-native speakers of German. Finally, in the two studies on acquired morphological impairments, the thesis investigates whether prefixed derived words yield different error patterns than suffixed derived words (Publication III and IV).
For native speakers, the results show evidence for morphological decomposition of both types of prefixed words, i.e. lexically unrestricted and restricted derivations, as well as of prefixed inflected words. Furthermore, non-native speakers are also found to efficiently decompose prefixed derived words, with parallel results to the group of native speakers. I therefore conclude that, for the early stages of visual word recognition, the relative position of stem and affix in prefixed versus suffixed words does not affect how efficiently complex words are decomposed, either in native or in non-native processing. In the studies on acquired language impairments, instead, prefixes are consistently found to be more impaired than suffixes. This is explained in terms of a learnability disadvantage for prefixed words, which may cause weaker representations of the information encoded in affixes when these precede the stem (prefixes) as compared to when they follow it (suffixes). Based on the impairment profiles of the individual participants and on the nature of the task, this dissociation is assumed to emerge from later processing stages than those that are tapped into by masked priming. I therefore conclude that the different characteristics of prefixed and suffixed words do come into play at later processing stages, during which the lexical-semantic information contained in the different constituent morphemes is processed.
The findings presented in the four manuscripts significantly contribute to our current understanding of the mechanisms involved in processing prefixed words. Crucially, the thesis constrains the processing disadvantage for prefixed words to later processing stages, thereby suggesting that theories trying to establish links between language universals and processing mechanisms should more carefully consider the different stages involved in language processing and what factors are relevant for each specific stage.
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.
This thesis is focused on a better understanding of the formation mechanism of bulk birefringence gratings (BBG) and a surface relief gratings (SRG) in photo-sensitive polymer films. A new set-up is developed enabling the in situ investigation how the polymer film is being structured during irradiation with modulated light. The new aspect of the equipment is that it combines several techniques such as a diffraction efficiency (DE) set-up, an atomic force microscope (AFM) and an optical set-up for controlled illumination of the sample. This enables the simultaneous acquiring and differentiation of both gratings (BBG and SRG), while changing the irradiation conditions in desired way.
The dissertation is based on five publications. The first publication (I) is focused on the description of the set-up and interpretation of the measured data. A fine structure within the 1st-order diffraction spot is observed, which is a result of the inhomogeneity of the inscribed gratings.
In the second publication (II) the interplay of BBG and SRG in the DE is discussed. It has been found, that, dependent on the polarization of a weak probe beam, the diffraction components of the SRG and BBG either interfere constructively or destructively in the DE, altering the appearance of the intensity distribution within the diffracted spot.
The third (III) and fourth (IV) publications describe the light-induced reconfiguration of surface structures. Special attention is payed to conditions influencing the erasure of topography and bulk gratings. This can be achieved via thermal treatment or illumination of the polymer film. Using the translation of the interference pattern (IP) in a controlled way, the optical erase speed is significantly increased. Additionally, a dynamic reconfigurable surface is generated, which could move surface attached objects by the continuous translation of the interference pattern during irradiation of the polymer films.
The fifth publication (V) deals with the understanding of polymer deformation under irradiation with SP-IP, which is the only IP generating a half-period topography grating (compared to the period of the IP) on the photo-sensitive polymer film. This mechanism is used, e.g. to generate a SRG below the diffraction limit of light. It also represents an easy way of changing the period of the surface grating just by a small change in polarization angle of the interfering beams without adjusting the optical pass of the two beams. Additionally, complex surface gratings formed in mixed polarization- and intensity interference patterns are shown.
I J. Jelken, C. Henkel and S. Santer, Applied Physics B, 125 (2019), 218
II J. Jelken, C. Henkel and S. Santer, Appl. Phys. Lett., 116 (2020), 051601
III J. Jelken and S. Santer, RSC Advances, 9 (2019), 20295
IV J. Jelken, M. Brinkjans, C. Henkel and S. Santer, SPIE Proceedings, 11367 (2020), 1136710
V J. Jelken, C. Henkel and S. Santer, Formation of Half-Period Surface Relief Gratings in Azobenzene Containing Polymer Films (submitted to Applied Physics B)
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.
Perovskite solar cells have become one of the most studied systems in the quest for new, cheap and efficient solar cell materials. Within a decade device efficiencies have risen to >25% in single-junction and >29% in tandem devices on top of silicon. This rapid improvement was in many ways fortunate, as e. g. the energy levels of commonly used halide perovskites are compatible with already existing materials from other photovoltaic technologies such as dye-sensitized or organic solar cells. Despite this rapid success, fundamental working principles must be understood to allow concerted further improvements. This thesis focuses on a comprehensive understanding of recombination processes in functioning devices.
First the impact the energy level alignment between the perovskite and the electron transport layer based on fullerenes is investigated. This controversial topic is comprehensively addressed and recombination is mitigated through reducing the energy difference between the perovskite conduction band minimum and the LUMO of the fullerene. Additionally, an insulating blocking layer is introduced, which is even more effective in reducing this recombination, without compromising carrier collection and thus efficiency. With the rapid efficiency development (certified efficiencies have broken through the 20% ceiling) and thousands of researchers working on perovskite-based optoelectronic devices, reliable protocols on how to reach these efficiencies are lacking. Having established robust methods for >20% devices, while keeping track of possible pitfalls, a detailed description of the fabrication of perovskite solar cells at the highest efficiency level (>20%) is provided. The fabrication of low-temperature p-i-n structured devices is described, commenting on important factors such as practical experience, processing atmosphere & temperature, material purity and solution age. Analogous to reliable fabrication methods, a method to identify recombination losses is needed to further improve efficiencies. Thus, absolute photoluminescence is identified as a direct way to quantify the Quasi-Fermi level splitting of the perovskite absorber (1.21eV) and interfacial recombination losses the transport layers impose, reducing the latter to ~1.1eV. Implementing very thin interlayers at both the p- and n-interface (PFN-P2 and LiF, respectively), these losses are suppressed, enabling a VOC of up to 1.17eV. Optimizing the device dimensions and the bandgap, 20% devices with 1cm2 active area are demonstrated. Another important consideration is the solar cells’ stability if subjected to field-relevant stressors during operation. In particular these are heat, light, bias or a combination thereof. Perovskite layers – especially those incorporating organic cations – have been shown to degrade if subjected to these stressors. Keeping in mind that several interlayers have been successfully used to mitigate recombination losses, a family of perfluorinated self-assembled monolayers (X-PFCn, where X denotes I/Br and n = 7-12) are introduced as interlayers at the n-interface. Indeed, they reduce interfacial recombination losses enabling device efficiencies up to 21.3%. Even more importantly they improve the stability of the devices. The solar cells with IPFC10 are stable over 3000h stored in the ambient and withstand a harsh 250h of MPP at 85◦C without appreciable efficiency losses. To advance further and improve device efficiencies, a sound understanding of the photophysics of a device is imperative. Many experimental observations in recent years have however drawn an inconclusive picture, often suffering from technical of physical impediments, disguising e. g. capacitive discharge as recombination dynamics. To circumvent these obstacles, fully operational, highly efficient perovskites solar cells are investigated by a combination of multiple optical and optoelectronic probes, allowing to draw a conclusive picture of the recombination dynamics in operation. Supported by drift-diffusion simulations, the device recombination dynamics can be fully described by a combination of first-, second- and third-order recombination and JV curves as well as luminescence efficiencies over multiple illumination intensities are well described within the model. On this basis steady state carrier densities, effective recombination constants, densities-of-states and effective masses are calculated, putting the devices at the brink of the radiative regime. Moreover, a comprehensive review of recombination in state-of-the-art devices is given, highlighting the importance of interfaces in nonradiative recombination. Different strategies to assess these are discussed, before emphasizing successful strategies to reduce interfacial recombination and pointing towards the necessary steps to further improve device efficiency and stability. Overall, the main findings represent an advancement in understanding loss mechanisms in highly efficient solar cells. Different reliable optoelectronic techniques are used and interfacial losses are found to be of grave importance for both efficiency and stability. Addressing the interfaces, several interlayers are introduced, which mitigate recombination losses and degradation.
Ammonia is a chemical of fundamental importance for nature`s vital nitrogen cycle. It is crucial for the growth of living organisms as well as food and energy source. Traditionally, industrial ammonia production is predominated by Haber- Bosch process (HBP) which is based on direct conversion of N2 and H2 gas under high temperature and high pressure (~500oC, 150-300 bar). However, it is not the favorite route because of its thermodynamic and kinetic limitations, and the need for the energy intense production of hydrogen gas by reforming processes. All these disfavors of HBP open a target to search for an alternative technique to perform efficient ammonia synthesis via electrochemical catalytic processes, in particular via water electrolysis, using water as the hydrogen source to save the process from gas reforming.
In this study, the investigation of the interface effects between imidazolium-based ionic liquids and the surface of porous carbon materials with a special interest in the nitrogen absorption capability. As the further step, the possibility to establish this interface as the catalytically active area for the electrochemical N2 reduction to NH3 has been evaluated. This particular combination has been chosen because the porous carbon materials and ionic liquids (IL) have a significant importance in many scientific fields including catalysis and electrocatalysis due to their special structural and physicochemical properties. Primarily, the effects of the confinement of ionic liquid (EmimOAc, 1-Ethyl-3-methylimidazolium acetate) into carbon pores have been investigated. The salt-templated porous carbons, which have different porosity (microporous and mesoporous) and nitrogen species, were used as model structures for the comparison of the IL confinement at different loadings. The nitrogen uptake of EmimOAc can be increased by about 10 times by the confinement in the pores of carbon materials compared to the bulk form. In addition, the most improved nitrogen absorption was observed by IL confinement in micropores and in nitrogen-doped carbon materials as a consequence of the maximized structural changes of IL. Furthermore, the possible use of such interfaces between EmimOAc and porous carbon for the catalytic activation of dinitrogen during the kinetically challenging NRR due to the limited gas absorption in the electrolyte, was examined. An electrocatalytic NRR system based on the conversion of water and nitrogen gas to ammonia at ambient operation conditions (1 bar, 25 °C) was performed in a setup under an applied electric potential with a single chamber electrochemical cell, which consists of the combination of EmimOAc electrolyte with the porous carbon-working electrode and without a traditional electrocatalyst. Under a potential of -3 V vs. SCE for 45 minutes, a NH3 production rate of 498.37 μg h-1 cm-2 and FE of 12.14% were achieved. The experimental observations show that an electric double-layer, which serves the catalytically active area, occurs between a microporous carbon material and ions of the EmimOAc electrolyte in the presence of sufficiently high provided electric potential. Comparing with the typical NRR systems which have been reported in the literature, the presented electrochemical ammonia synthesis approach provides a significantly higher ammonia production rate with a chance to avoid the possible kinetic limitations of NRR. In terms of operating conditions, ammonia production rate and the faradic efficiency without the need for any synthetic electrocatalyst can be resulted of electrocatalytic activation of nitrogen in the double-layer formed between carbon and IL ions.
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.
In this dissertation we introduce a concept of light driven active and passive manipulation of colloids trapped at solid/liquid interface. The motion is induced due to generation of light driven diffusioosmotic flow (LDDO) upon irradiation with light of appropriate wavelength. The origin of the flow is due to osmotic pressure gradient resulting from a concentration gradient at the solid/liquid interface of the photosensitive surfactant present in colloidal dispersion. The photosensitive surfactant consists of a cationic head group and a hydrophobic tail in which azobenzene group is integrated in. The azobenzene is known to undergo reversible photo-isomerization from a stable trans to a meta stable cis state under irradiation with UV light. Exposure to light of larger wavelength results in back photo-isomerization from cis to trans state. The two isomers have different molecular properties, for instance, trans isomer has a rod like structure and low polarity (0 dipole moment), whereas cis one is bent and has a dipole moment of ~3 Debye. Being integrated in the hydrophobic tail of the surfactant molecule, the azobenzene state determines the hydrophobicity of the whole molecule: in the trans state the surfactant is more hydrophobic than in the cis-state. In this way many properties of the surfactant such as the CMC, solubility and the interaction potential with a solid surface can be altered by light. When the solution containing such a surfactant is irradiated with focused light, a concentration gradient of different isomers is formed near the boundary of the irradiated area near the solid surface resulting in osmotic pressure gradient. The generated diffusioosmotic (DO) flow carries the particles passively along.
The local-LDDO flow can be generated around and by each particle when mesoporous silica colloids are dispersed in the surfactant solution. This is because porous particles act as a sink/source which absorbs azobenzene molecule in trans state and expels it when it is in the cis state. The DO flows generated at each particle interact resulting in aggregation or separation depending upon the initial state of surfactant molecules. The kinetic of aggregation and separation can be controlled and manipulated by altering the parameters such as the wavelength and intensity of the applied light, as well as surfactant and particle concentration. Using two wavelengths simultaneously allows for dynamic gathering and separation creating fascinating patterns such as 2D disk of well separated particles or establishing collective complex behaviour of particle ensemble as described in this thesis.
The mechanism of l-LDDO is also used to generate self-propelled motion. This is possible when half of the porous particle is covered by metal layer, basically blocking the pores on one side. The LDDO flow generated on uncapped side pushes the particle forward resulting in a super diffusive motion. The system of porous particle and azobenzene containing surfactant molecule can be utilized for various application such as drug delivery, cargo transportation, self-assembling, micro motors/ machines or micro patterning.
Lava domes are severely hazardous, mound-shaped extrusions of highly viscous lava and commonly erupt at many active stratovolcanoes around the world. Due to gradual growth and flank oversteepening, such lava domes regularly experience partial or full collapses, resulting in destructive and far-reaching pyroclastic density currents. They are also associated with cyclic explosive activity as the complex interplay of cooling, degassing, and solidification of dome lavas regularly causes gas pressurizations on the dome or the underlying volcano conduit. Lava dome extrusions can last from days to decades, further highlighting the need for accurate and reliable monitoring data.
This thesis aims to improve our understanding of lava dome processes and to contribute to the monitoring and prediction of hazards posed by these domes. The recent rise and sophistication of photogrammetric techniques allows for the extraction of observational data in unprecedented detail and creates ideal tools for accomplishing this purpose. Here, I study natural lava dome extrusions as well as laboratory-based analogue models of lava dome extrusions and employ photogrammetric monitoring by Structure-from-Motion (SfM) and Particle-Image-Velocimetry (PIV) techniques. I primarily use aerial photography data obtained by helicopter, airplanes, Unoccupied Aircraft Systems (UAS) or ground-based timelapse cameras. Firstly, by combining a long time-series of overflight data at Volcán de Colima, México, with seismic and satellite radar data, I construct a detailed timeline of lava dome and crater evolution. Using numerical model, the impact of the extrusion on dome morphology and loading stress is further evaluated and an impact on the growth direction is identified, bearing important implications for the location of collapse hazards. Secondly, sequential overflight surveys at the Santiaguito lava dome, Guatemala, reveal surface motion data in high detail. I quantify the growth of the lava dome and the movement of a lava flow, showing complex motions that occur on different timescales and I provide insight into rock properties relevant for hazard assessment inferred purely by photogrammetric processing of remote sensing data. Lastly, I recreate artificial lava dome and spine growth using analogue modelling under controlled conditions, providing new insights into lava extrusion processes and structures as well as the conditions in which they form.
These findings demonstrate the capabilities of photogrammetric data analyses to successfully monitor lava dome growth and evolution while highlighting the advantages of complementary modelling methods to explain the observed phenomena. The results presented herein further bear important new insights and implications for the hazards posed by lava domes.
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.
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 transfer of particulate organic carbon from continents to the ocean is an important component of the global carbon cycle. Transfer to and burial of photosynthetically fixed biospheric organic carbon in marine sediments can effectively sequester atmospheric carbon dioxide over geological timescales. The exhumation and erosion of fossil organic carbon contained in sedimentary rocks, i.e. petrogenic carbon, can result in remineralization, releasing carbon to the atmosphere. In contrast, eroded petrogenic organic carbon that gets transferred back to the ocean and reburied does not affect atmospheric carbon content.
Mountain ranges play a key role in this transfer since they can source vast amounts of sediment including particulate organic carbon. Globally, the export of both, biospheric and petrogenic organic carbon has been linked to sediment export. Additionally, short transfer times from mountains to the ocean and high sediment concentrations have been shown to increase the likelihood of organic carbon burial. While the importance of mountain ranges in the organic carbon cycle is now widely recognized, the processes acting within mountain ranges to influence the storage, cycling and mobilization of organic carbon, as well as carbon fluxes from mountain ranges remain poorly constrained.
In this thesis, I employ different methods to assess the nature and fate of particulate organic carbon in mountain belts, ranging from the molecular to regional landscape scale. These studies are located along the Trans-Himalayan Kali Gandaki River in Central Nepal. This river traverses all major geological and climatic zones of the Himalaya, from the dry northern Tibetan plateau to the high-relief, monsoon dominated steep High Himalaya and the lower relief and abundant vegetation of the Lesser Himalayan region.
First, I document how biospheric organic matter has accumulated during the Holocene in the headwaters of the Kali Gandaki River valley, by combining compound specific isotope measurements with different dating methods and grain size data, and investigate the stability of this organic carbon reservoir on millennial timescales. I show, that around 1.6 ka an eco-geomorphic tipping point occurred leading to a destabilization of the landscape resulting in today’s high erosion rates and the excavation of the aged organic carbon reservoir. This study highlights the climatic and geomorphic controls on biospheric organic carbon storage and release from mountain ranges.
Second, I systematically investigate the spatial variation of particulate organic carbon fluxes across the Himalaya along the Kali Gandaki River, using bulk stable and radioactive isotopes combined with a new Bayesian modeling approach. The detailed dataset allows the distinction of aged and modern biospheric organic carbon as well as petrogenic organic carbon across the Himalayan mountain range and the investigation of the role of climatic and geomorphic factors in their riverine export. The data suggest a decoupling of the particulate organic carbon from the sediment yield along the Kali Gandaki River, partially driven by climatic and geomorphic processes. In contrast to the suspended sediment, a large part of the particulate organic carbon exported by the river originates from the Tibetan part of the catchment and is dominated by petrogenic organic carbon derived from Jurassic shales with only minor contributions of modern and aged biospheric organic carbon. These findings emphasize the importance of organic carbon source distribution and erosion mechanisms in determining the organic carbon export from mountain ranges.
In a third step, I explore the potential of ultra-high resolution mass spectrometry for particulate organic carbon transport studies. I have generated a novel and unprecedented high-resolution molecular dataset, which contains up to 103 molecular formulas of the lipid fraction of particulate organic matter for modern and aged biospheric carbon, petrogenic organic carbon and river sediments. First, I test if this dataset can be used to better resolve different organic carbon sources and to identify new geochemical tracers. Using multivariate statistics, I identify up to 10² characteristic molecular formulas for the major organic carbon sources in the upper part of the Kali Gandaki catchment, and trace their transfer from the surrounding landscape into the river sediment. Second, I test the potential of the molecular dataset to trace molecular transformations along source-to-sink pathways. I identify changes in molecular metrics derived from the dataset, which are characteristic of transformation processes during incorporation of litter into soil, the aging of soil material, and the mobilization of the organic carbon into the river. These two studies demonstrate that high-resolution molecular datasets open a promising analytical window on particulate organic carbon and can provide novel insights into the composition, sourcing and transformation of riverine particulate organic carbon.
Collectively, these studies advance our understanding of the processes contributing to the storage and mobilization of organic carbon in the Central Himalaya, the mountain belt that dominates global erosional fluxes. They do so by identifying the major sources of particulate organic carbon to the Trans-Himalayan Kali Gandaki River, by elucidating their sensitivity to climate and geomorphic processes, and by identifying some of the transformations of this material on the molecular scale. As a result, the thesis demonstrates that the amount and composition of organic carbon routed from mountain belts is a function of the dynamic interactions of geologic, biologic, geomorphic and climatic processes within the mountain belt. This understanding will ultimately help in answering whether the build-up and erosion of mountain ranges over geological time represents a net carbon source or sink to the atmosphere. Beyond this, the thesis contributes to our technical ability to characterize organic matter and attribute it to sources by scoping the potential of high-end molecular analysis.
Grenzen des Organisierbaren
(2020)
With populations growing worldwide and climate change threatening food production there is an urgent need to find ways to ensure food security. Increasing carbon fixation rate in plants is a promising approach to boost crop yields. The carbon-fixing enzyme Rubisco catalyzes, beside the carboxylation reaction, also an oxygenation reaction that generates glycolate-2P, which needs to be recycled via a metabolic route termed photorespiration. Photorespiration dissipates energy and most importantly releases previously fixed CO2, thus significantly lowering carbon fixation rate and yield. Engineering plants to omit photorespiratory CO2 release is the goal of the FutureAgriculture consortium and this thesis is part of this collaboration. The consortium aims to establish alternative glycolate-2P recycling routes that do not release CO2. Ultimately, they are expected to increase carbon fixation rates and crop yields. Natural and novel reactions, which require enzyme engineering, were considered in the pathway design process. Here I describe the engineering of two pathways, the arabinose-5P and the erythrulose shunt. They were designed to recycle glycolate-2P via glycolaldehyde into a sugar phosphate and thereby reassimilate glycolate-2P to the Calvin cycle. I used Escherichia coli gene deletion strains to validate and characterize the activity of both synthetic shunts. The strains’ auxotrophies can be alleviated by the activity of the synthetic route, thus providing a direct way to select for pathway activity. I introduced all pathway components to these dedicated selection strains and discovered inhibitions, limitations and metabolic cross talk interfering with pathway activity. After resolving these issues, I was able to show the in vivo activity of all pathway components and combine them into functional modules.. Specifically, I demonstrate the activity of a new-to-nature module of glycolate reduction to glycolaldehyde. Also, I successfully show a new glycolaldehyde assimilation route via arabinose-5P to ribulose-5P. In addition, all necessary enzymes for glycolaldehyde assimilation via L-erythrulose were shown to be active and an L-threitol assimilation route via L-erythrulose was established in E. coli. On their own, these findings demonstrate the power of using an easily engineerable microbe to test novel pathways; combined, they will form the basis for implementing photorespiration bypasses in plants.
Das Ziel der vorliegenden Dissertation war es herauszuarbeiten, ob Nachhaltigkeitsbewusstsein den Konsum von Luxusgütern beeinflusst und ob verschiedene Moderatoren einen Einfluss auf diesen Zusammenhang ausüben. Das Nachhaltigkeitsbewusstsein wurde dabei basierend auf dem von Balderjahn et al. (2013) entwickelten Consciousness-for-sustainable-consumption-Modell durch die ökologische, soziale und die ökonomische Nachhaltigkeit sowie ergänzend durch das Tierschutzbewusstsein und Bewusstsein für lokale Produktion repräsentiert. Als Moderatoren dienten das Streben nach sozialer Anerkennung und Prestige, Materialismus, Hedonismus und Traditionsbewusstsein. Für die Aufdeckung möglicher Zusammenhänge zwischen den verschiedenen Dimensionen der Nachhaltigkeit und Luxuskonsum wurde eine Prädiktorenanalyse durchgeführt. Moderatorenanalysen offenbarten zusätzlich, ob ein Einfluss der verschiedenen Moderatoren auf die einzelnen Zusammenhänge vorlag. Die Untersuchung zeigte, dass jeweils das Umweltbewusstsein, das Bewusstsein für genügsamen Konsum sowie das Bewusstsein für schuldenfreien Konsum als Teil der ökonomischen Nachhaltigkeit und das Tierschutzbewusstsein einen Einfluss auf den Luxuskonsum ausüben. Darüber hinaus konnten insgesamt sieben Einflüsse durch die verschiedenen Moderatorvariablen auf die unterschiedlichen Zusammenhänge zwischen den Nachhaltigkeitsdimensionen und Luxuskonsum aufgedeckt werden.
Giant unilamellar vesicles are an important tool in todays experimental efforts to understand the structure and behaviour of biological cells. Their simple structure allows the isolation of the physical elastic properties of the lipid membrane. A central physical
property is the bending energy of the membrane, since the many different shapes of giant vesicles can be obtained by finding the minimum of the bending energy. In the spontaneous curvature model the bending energy is a function of the bending rigidity as well as the mean curvature and an additional parameter called the spontaneous curvature, which describes an internal preference of the lipid-bilayer to bend towards one side or the other. The spontaneous and mean curvature are local properties of the membrane.
Additional constraints arise from the conservation of the membrane surface area and the enclosed volume, which are global properties.
In this thesis the spontaneous curvature model is used to explain the experimental observation of a periodic shape oscillation of a giant unilamellar vesicle that was filled with a protein complex that periodically binds to and unbinds from the membrane.
By assuming that the binding of the proteins to the membrane induces a change in the spontaneous curvature the experimentally observed shapes could successfully be explained. This involves the numerical solution of the differential equations as obtained from the minimization of the bending energy respecting the area and volume constraints, the so called shape equations. Vice versa this approach can be used to estimate the spontaneous curvature from experimentally measurable quantities.
The second topic of this thesis is the analysis of concentration gradients in rigid conic membrane compartments. Gradients of an ideal gas due to gravity and gradients generated by the directed stochastic movement of molecular motors along a microtubulus were considered. It was possible to calculate the free energy and the bending energy analytically for the ideal gas. In the case of the non-equilibrium system with molecular motors, the characteristic length of the density profile, the jam-length, and its dependency on the opening angle of the conic compartment have been calculated in the mean-field limit.
The mean field results agree qualitatively with stochastic particle simulations.
In der vorliegenden Arbeit wird untersucht, in wie weit physikalische Experimente ein flow-Erleben bei Lernenden hervorrufen. Flow-Erleben wird als Motivationsursache gesehen und soll den Weg zu Freude und Glück darstellen. Insbesondere wegen dem oft zitierten Fachkräftemangel in naturwissenschaftlichen und technischen Berufen ist eine Motivationssteigerung in naturwissenschaftlichen Unterrichtsfächern wichtig. Denn trotz Leistungssteigerungen in internationalen Vergleichstests möchten in Deutschland deutlich weniger Schüler*innen einen solchen Beruf ergreifen als in anderen Industriestaaten. Daher gilt es, möglichst früh Schüler*innen für naturwissenschaftlich-technische Fächer zu begeistern und insbesondere im regelrecht verhassten Physikunterricht flow-Erleben zu erzeugen.
Im Rahmen dieser Arbeit wird das flow-Erleben von Studierenden in klassischen Laborexperimenten und FELS (Forschend-Entdeckendes Lernen mit dem Smartphone) als Lernumgebung untersucht. FELS ist eine an die Lebenswelt der Schüler*innen angepasste Lernumgebung, in der sie mit Smartphones ihre eigene Lebenswelt experimentell untersuchen.
Es zeigt sich, dass sowohl klassische Laborexperimente als auch in der Lebenswelt durchgeführte, smartphonebasierte Experimente flow-Erleben erzeugen. Allerdings verursachen die smartphonebasierten Experimente kaum Stressgefühle.
Die in dieser Arbeit herausgefundenen Ergebnisse liefern einen ersten Ansatz, der durch Folgestudien erweitert werden sollte.
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.
After endosymbiosis, chloroplasts lost most of their genome. Many former endosymbiotic genes are now nucleus-encoded and the products are re-imported post-translationally. Consequently, photosynthetic complexes are built of nucleus- and plastid-encoded subunits in a well-defined stoichiometry. In Chlamydomonas, the translation of chloroplast-encoded photosynthetic core subunits is feedback-regulated by the assembly state of the complexes they reside in. This process is called Control by Epistasy of Synthesis (CES) and enables the efficient production of photosynthetic core subunits in stoichiometric amounts. In chloroplasts of embryophytes, only Rubisco subunits have been shown to be feedback-regulated. That opens the question if there is additional CES regulation in embryophytes. I analyzed chloroplast gene expression in tobacco and Arabidopsis mutants with assembly defects for each photosynthetic complex to broadly answer this question. My results (i) confirmed CES within Rubisco and hint to potential translational feedback regulation in the synthesis of (ii) cytochrome b6f (Cyt b6f) and (iii) photosystem II (PSII) subunits. This work suggests a CES network in PSII that links psbD, psbA, psbB, psbE, and potentially psbH expression by a feedback mechanism that at least partially differs from that described in Chlamydomonas. Intriguingly, in the Cyt b6f complex, a positive feedback regulation that coordinates the synthesis of PetA and PetB was observed, which was not previously reported in Chlamydomonas. No evidence for CES interactions was found in the expression of NDH and ATP synthase subunits of embryophytes. Altogether, this work provides solid evidence for novel assembly-dependent feedback regulation mechanisms controlling the expression of photosynthetic genes in chloroplasts of embryophytes.
In order to obtain a comprehensive inventory of the rbcL and psbA RNA-binding proteomes (including factors that regulate their expression, especially factors involved in CES), an aptamer based affinity purification method was adapted and refined for the specific purification these transcripts from tobacco chloroplasts. To this end, three different aptamers (MS2, Sephadex ,and streptavidin binding) were stably introduced into the 3’ UTRs of psbA and rbcL by chloroplast transformation. RNA aptamer based purification and subsequent chip analysis (RAP Chip) demonstrated a strong enrichment of psbA and rbcL transcripts and currently, ongoing mass spectrometry analyses shall reveal potential regulatory factors. Furthermore, the suborganellar localization of MS2 tagged psbA and rbcL transcripts was analyzed by a combined affinity, immunology, and electron microscopy approach and demonstrated the potential of aptamer tags for the examination of the spatial distribution of chloroplast transcripts.
The plasmasphere is a dynamic region of cold, dense plasma surrounding the Earth. Its shape and size are highly susceptible to variations in solar and geomagnetic conditions. Having an accurate model of plasma density in the plasmasphere is important for GNSS navigation and for predicting hazardous effects of radiation in space on spacecraft. The distribution of cold plasma and its dynamic dependence on solar wind and geomagnetic conditions remain, however, poorly quantified. Existing empirical models of plasma density tend to be oversimplified as they are based on statistical averages over static parameters. Understanding the global dynamics of the plasmasphere using observations from space remains a challenge, as existing density measurements are sparse and limited to locations where satellites can provide in-situ observations. In this dissertation, we demonstrate how such sparse electron density measurements can be used to reconstruct the global electron density distribution in the plasmasphere and capture its dynamic dependence on solar wind and geomagnetic conditions.
First, we develop an automated algorithm to determine the electron density from in-situ measurements of the electric field on the Van Allen Probes spacecraft. In particular, we design a neural network to infer the upper hybrid resonance frequency from the dynamic spectrograms obtained with the Electric and Magnetic Field Instrument Suite and Integrated Science (EMFISIS) instrumentation suite, which is then used to calculate the electron number density. The developed Neural-network-based Upper hybrid Resonance Determination (NURD) algorithm is applied to more than four years of EMFISIS measurements to produce the publicly available electron density data set.
We utilize the obtained electron density data set to develop a new global model of plasma density by employing a neural network-based modeling approach. In addition to the location, the model takes the time history of geomagnetic indices and location as inputs, and produces electron density in the equatorial plane as an output. It is extensively validated using in-situ density measurements from the Van Allen Probes mission, and also by comparing the predicted global evolution of the plasmasphere with the global IMAGE EUV images of He+ distribution. The model successfully reproduces erosion of the plasmasphere on the night side as well as plume formation and evolution, and agrees well with data.
The performance of neural networks strongly depends on the availability of training data, which is limited during intervals of high geomagnetic activity. In order to provide reliable density predictions during such intervals, we can employ physics-based modeling. We develop a new approach for optimally combining the neural network- and physics-based models of the plasmasphere by means of data assimilation. The developed approach utilizes advantages of both neural network- and physics-based modeling and produces reliable global plasma density reconstructions for quiet, disturbed, and extreme geomagnetic conditions.
Finally, we extend the developed machine learning-based tools and apply them to another important problem in the field of space weather, the prediction of the geomagnetic index Kp. The Kp index is one of the most widely used indicators for space weather alerts and serves as input to various models, such as for the thermosphere, the radiation belts and the plasmasphere. It is therefore crucial to predict the Kp index accurately. Previous work in this area has mostly employed artificial neural networks to nowcast and make short-term predictions of Kp, basing their inferences on the recent history of Kp and solar wind measurements at L1. We analyze how the performance of neural networks compares to other machine learning algorithms for nowcasting and forecasting Kp for up to 12 hours ahead. Additionally, we investigate several machine learning and information theory methods for selecting the optimal inputs to a predictive model of Kp. The developed tools for feature selection can also be applied to other problems in space physics in order to reduce the input dimensionality and identify the most important drivers.
Research outlined in this dissertation clearly demonstrates that machine learning tools can be used to develop empirical models from sparse data and also can be used to understand the underlying physical processes. Combining machine learning, physics-based modeling and data assimilation allows us to develop novel methods benefiting from these different approaches.
Today’s focus on the 1930s as a time of radical politics paving the way for the apocalypse of the Second World War ignores the complexity of the decade’s cultural responses, especially those by British women writers who highlighted gender issues within their contemporary political climate. The decade’s literature is often understood to capture the political unrest, either narrating people’s chaotic movement or their paralysed shock. This book argues that 1930s novels collapse the distinction between movement and standstill and calls this phenomenon Dynamic Stasis. This Dynamic Stasis thematically and structurally informs the novels of Nancy Mitford, Stevie Smith, Rosamond Lehmann and Jean Rhys. By disrupting the oft-repeated cliché of the 1930s as the age of political extremes, gender politics and negotiations of femininity can emerge from the discursive periphery. This book therefore corrects a persistent gender blind spot, which opens up a (re)consideration of authors that have been overlooked in literary criticism of 1930s to this day.
Advanced hybrid materials are recognized as one of the most significant enablers for new technologies, which holds true especially on the quest for sustainable energy sources and energy production schemes (e.g., semiconductor based photocatalytic materials). Usually, a single component is far from meeting all the demands needed for these advanced applications. Hybrid materials are composed of at least two components commonly an inorganic and an organic material on the molecular level, which feature novel properties exceeding the sum of the individual parts and might be the milestones of next-generation applications. This dissertation aims to provide novel combinations of the metal-free semiconductor graphitic carbon nitride (g-C3N4) with polymers to obtain materials with advanced properties and applications. Visible light constitutes the core of the present work as it is the only energy source utilized either in synthesis or in the application process. In the area of applications by combination of g-C3N4 and polymers, two different hybrids were thoroughly elucidated, i.e.. their design and construction as well as potential application in photocatalysis. Novel soft 3D liquid objects were formed via charge-interaction driven interfacial jamming between polyelectrolytes in aqueous environment and colloidal dispersions of g-C3N4 in edible sunflower oil. As such, stable liquid objects could be molded into specific shapes and utilized for photodegradation of organic dyes in water. Furthermore, the grafting of polymers onto g-C3N4 was investigated. Allyl-end functionalized polymers were grafted onto g-C3N4 by a photoinitiated process to yield g-C3N4 with versatile and improved properties, e.g. advanced dispersibility enabling processing via spin coating. As g-C3N4 produces radicals under visible light irradiation, which is of significant interest for polymer science, g-C3N4 containing polymer latex and macrogel beads (MGB) were synthesized by emulsion photopolymerization and inverse suspension photopolymerization, respectively. A well-controlled emulsion photopolymerization process via g-C3N4 initiation was designed, which features synthesis of well-defined and cross-linked polymer particles. Furthermore, the polymerization process was investigated thoroughly, indicating an ad-layer polymerization in early stages of the process. The utilization of functionalized g-C3N4 allowed the polymerization of various monomer types. Moreover, g-C3N4 was utilized as photoinitiator in hydrogel MGB formation. The formed MGB properties could be tailored via process design, e.g. stirring rate, cross-linker content and g-C3N4 content. Finally, MGBs were introduced as photocatalyst for waste water remediation, i.e. the degradation of Rhodamine B in aqueous solution was studied. The present thesis therefore builds a bridge between g-C3N4 and polymers and provides strategies for hybrid material formation. Furthermore, several potential applications are revealed with significant implications for photocatalysis, polymerization processes and polymer materials.
Bilder des Glaubens
(2020)
Medien prägen maßgeblich das öffentliche Bild von Religion in der modernen Gesellschaft, weshalb die Kirchen frühzeitig mediale Wege der Verkündigung suchten. Das Fernsehen als bedeutendstes Massenmedium in der zweiten Hälfte des 20. Jahrhunderts spielte dabei eine Schlüsselrolle. Von den Kirchen produzierte Unterhaltungsserien erreichten große Reichweiten, gleichzeitig entwickelte sich das bundesdeutsche Fernsehen zu einem Experimentierfeld für neue Praktiken der Religionsausübung. Alternative Glaubensformen gewannen an Aufmerksamkeit, etwa nichtchristliche Weltreligionen wie der Islam, Gläubige am Rande der Kirchen wie die Evangelikalen oder als »Sekten« geschmähte Gruppen wie die Zeugen Jehovas, aber auch spirituelle Phänomene wie Wahrsagerei, Okkultismus und »New Age«. Ronald Funke analysiert die zwischen den 1950er und 1980er Jahren im Fernsehen gezeigten Bilder des Glaubens in der Bundesrepublik und verdeutlicht, wie deren Inhalte durch enge Zusammenarbeit, aber auch durch Konflikte ausgehandelt wurden.
Grenzen des Organiesierbaren
(2020)
Interessiert man sich für den gesellschaftlichen Einfluss der Organisationssoziologie auf die Praxis des Organisierens, so muss der Befund ernüchtern. Stärker als auf organisationssoziologische Wissensbestände wird in Unternehmen oder Verwaltungen auf aktuelle Managementtrends rekurriert. Man könnte diesen Befund beklagen und als fehlerhafte Rezeption der Praxis beiseitelegen. Alternativ ließe sich aber auch diskutieren, welchen Beitrag die Disziplin selbst zu dieser Rezeption leistet. Mit einer solchen Diskussion begibt man sich fast unweigerlich auf einen schwierigen Pfad. Zum einen kann die Soziologie gerade dann, wenn sie ihren Blick auf die Erforschung von Unternehmen oder Verwaltungen richtet, nicht die von der Praxis erwarteten positiven Antworten liefern. Gerade die Organisationssoziologie begibt sich zum anderen jedoch in direkte Konkurrenz zu Nachbardisziplinen wie die Betriebswirtschaftslehre oder die Organisationspsychologie, die die Rezeptionsfähigkeit ihrer Wissensbestände im Praxisfeld in den letzten Jahren unter Beweis gestellt haben. Die Erwartungen an die Umsetzbarkeit wissenschaftlicher Erkenntnisse in der Praxis sind dadurch gestiegen. Eine Soziologie, die ihre Erkenntniskraft in der kritischen Distanz sieht, mag das skeptisch stimmen. Es gilt daher, die Frage zu beantworten, wie die Praxisrelevanz einer Wissenschaft des zweiten Blicks auf Organisationen konkret aussehen kann. Diesem Vorhaben widmet sich das vorgelegte Promotionsprojekt. Die in der kumulativen Dissertation versammelten Beiträge verstehen sich allesamt als Erkundungen und Erprobungen der Praxisrelevanz der Organisationssoziologie anhand aktueller Managementfragen in Unternehmen. Die These lautet dabei, dass sich diese Praxisrelevanz nur als Kritik entfalten kann. Eine solche Kritik kann dabei zwei grundsätzliche Formen annehmen: Als Strukturkritik bezieht sie sich auf konkrete Organisationen, deren spezifische Eigenlogiken und strukturelle Verstrickungen. Sie beschreibt dabei für den Einzelfall Funktionen und Folgen von Erwartungsstrukturen, die sich dann z. B. fallvergleichend generalisieren oder typisieren lassen. Organisationssoziologische Strukturkritik kann sich damit sowohl als vergleichender, praxissensibler Forschungsansatz realisieren, als auch die Grundlage einer soziologisch orientierten Beratung bilden. Als Schematakritik richtet sie sich gegen verkürzte Vorstellungen des Organisierens, die sich etwa in Managementmoden finden lassen. Dem Kumulus zugrunde liegen fünf Beiträge, die konkrete Ausprägungen beider Kritikformen ausloten. Der erste Beitrag „Datafizierung und Organisation“ zeigt, wie Schematakritik an Nachbardisziplinen aussehen kann, indem er Organisation als blinden Fleck der Digitalisierungsforschung diskutiert und Anschlussstellen für interdisziplinäre Forschung ausweist. Daher liefert der Beitrag einen systematischen Zugang zu organisationalen Implikationen der Digitalisierung. Neben der Anreicherung der Digitalisierungsforschung kann die entwickelte Argumentation auch für die Praxis Erkenntniskraft haben, indem z. B. problematisiert wird, dass im Managementdiskurs um Digitalisierung überzogene Rationalisierungserwartungen herrschen oder durch digitale Infrastrukturen entstehende Informalitäten systematisch ausgeblendet werden Der zweite Beitrag „Führung als erfolgreiche Einflussnahme in kritischen Momenten“ legt eine Umdeutung des populären Managementbegriffs Führung durch Schematakritik vor. Damit trägt er in mehrfacher Hinsicht zu einer praxisrelevanten Neubestimmung von Führung bei. Für Führungskräfte ermöglicht er beispielsweise die Einsicht, dass sie ihre Führungsaufgaben auf kritische Momente konzentrieren können und postuliert die Abkehr vom heroischen Bild des dauerhaft Führenden. Diese Umdeutung kann auch für Führungskräfte in Organisationen entlastend sein, weist sie doch auf den Zusammenhang zwischen der organisationalen Verfasstheit und Führungschancen hin und eröffnet damit Gestaltungschancen jenseits der Führungskräfte- und Personalentwicklung. Für die Organisationsforschung liefert der Beitrag einen theoretisch integrierten Führungsbegriff, der Führung sowohl organisational als auch situativ bestimmt. Er steht somit exemplarisch für eine organisationssoziologische Schematakritik, die etablierte Managementbegriffe neu deutet. Der dritte Beitrag kritisiert mit dem Konzept der transformationalen Führung eine Managementmode und zeigt auf, wie das darin enthaltene Führungsmodell durch die Bildung moralischer Kategorien Organisationsprobleme auf Organisationsmitglieder (hier: Führungskräfte) verschiebt. Es wird einerseits eine organisationssoziologische Kritik am populären Managementkonzept der transformationalen Führung vorgelegt. Andererseits verdeutlicht der Beitrag anhand systemtheoretischer Konzepte wie elementarer Verhaltensweisen, Moral oder Rollentrennung exemplarisch, dass organisationssoziologisches Denken den Managementdiskurs bereichern kann, indem es Verkürzungen und Simplifizierungen aufdeckt und alternative Analyse- und Gestaltungsansätze bereitstellt. Dafür lässt sich auch im Praxisdiskurs Gehör finden, weil man annehmen darf, dass mit den Heilsversprechen von Kompaktlösungen auch Enttäuschungen einhergehen, für die die Organisationssoziologie Erklärungen liefern kann. Die Möglichkeiten und Grenzen von Strukturkritik werden in den letzten beiden Beiträgen diskutiert. Das Potenzial von Strukturkritik für die soziologisch orientierte Beratung von Organisationen exploriert der Beitrag „Die schwierige Liaison von Organisationssoziologie und Praxisbezug am Beispiel der Beratung“. Ausgehend vom Theorie-Praxis-Komplex wird eruiert, wie soziologischer Praxisbezug im Feld der Beratung aussehen kann. Dafür systematisiert der Beitrag organisationssoziologische Ansätze von Beratung und zeigt auf, wie ein genuin soziologischer Beratungsansatz aussehen könnte. Der letzte Beitrag stellt Grundzüge einer Methodologie strukturkritischer Forschung vor und illustriert diese an einem durchgeführten Forschungsprojekt zu Managementmoden. Anhand der Forschung in einem Produktionsbetrieb wird gezeigt, wie strukturkritische Forschung konkret aussehen kann. Solch strukturkritische Forschung steht im Forschungsprozess vor drei Herausforderungen: dem qualitativ hochwertigen Feldzugang, der Entwicklung einer für Forschung und Praxis instruktiven Fragestellung und der Rückspiegelung der Ergebnisse in das Feld. Der Beitrag stellt Grundzüge einer Methodologie strukturkritischer Organisationsforschung vor, die sich sachlich, zeitlich und sozial entlang der drei beschriebenen Momente des Feldzugangs, der Ausgangsfragestellung und der Rückspiegelung der Ergebnisse spezifizieren lassen.
TrainTrap
(2020)
The Willmore functional is a function that maps an immersed Riemannian manifold to its total mean curvature. Finding closed surfaces that minimizes the Willmore energy, or more generally finding critical surfaces, is a classic problem of differential geometry.
In this thesis we will develop the concept of generalized Willmore functionals for surfaces in Riemannian manifolds. We are guided by models in mathematical physics, such as the Hawking energy of general relativity and the bending energies for thin membranes.
We prove the existence of minimizers under area constraint for these generalized Willmore functionals in a suitable class of generalized surfaces. In particular, we construct minimizers of the bending energy mentioned above for prescribed area and enclosed volume.
Furthermore, we prove that critical surfaces of generalized Willmore functionals with prescribed area are smooth, away from finitely many points. These results and the following are based on the existing theory for the Willmore functional.
This general discussion is succeeded by a detailed analysis of the Hawking energy. In the context of general relativity the surrounding manifold describes the space at a given time, hence we strive to understand the interplay between the Hawking energy and the ambient space. We characterize points in the surrounding manifold for which there are small critical spheres with prescribed area in any neighborhood. These points are interpreted as concentration points of the Hawking energy.
Additionally, we calculate an expansion of the Hawking energy on small, round spheres. This allows us to identify a kind of energy density of the Hawking energy.
It needs to be mentioned that our results stand in contrast to previous expansions of the Hawking energy. However, these expansions are obtained on spheres along the light cone at a given point. At this point it is not clear how to explain the discrepancy.
Finally, we consider asymptotically Schwarzschild manifolds. They are a special case of asymptotically flat manifolds, which serf as models for isolated systems. The Schwarzschild spacetime itself is a classical solution to the Einstein equations and yields a simple description of a black hole.
In these asymptotically Schwarzschild manifolds we construct a foliation of the exterior region by critical spheres of the Hawking energy with prescribed large area. This foliation can be seen as a generalized notion of the center of mass of the isolated system. Additionally, the Hawking energy of grows along the foliation as the area of the surfaces grows.
Die Verweigerung des Militärdienstes und seine Folgen sind angesichts andauernder bewaffneter Konflikte immer häufiger Gegenstand von Asylanträgen. Die Autorin untersucht die Voraussetzungen für die Flüchtlingsanerkennung von Wehrdienstverweigerern anhand verschiedener Fallgruppen und unter Einbeziehung zahlreicher Entscheidungen von angloamerikanischen, europäischen und deutschen Gerichten. Dabei widmet sie sich dem Spannungsfeld zwischen dem Wehrdienst als Grundpflicht und dem Recht auf Kriegsdienstverweigerung aus Gewissensgründen. Zudem beleuchtet sie das Verhältnis des Flüchtlingsrechts zum humanitären Völkerrecht und Völkerstrafrecht, bettet also das Flüchtlingsrecht in andere Teilbereiche des Völkerrechts ein.
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.
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.
Sie senden den Wandel
(2020)
Altbekannt ist, welch wichtige Rolle Medien bei der Konsolidierung oder aber auch bei der Transformation einer Gesellschaft spielen. Was aber geschieht, wenn Medien von unten aus agieren und dies in großer Zahl geschieht, unter Einbindung vieler gesellschaftlicher Akteure sowie gegenüber einem umfassenden Publikum? In Argentinien hat sich eine faszinierende Radiolandschaft gebildet, die kollektiv, partizipativ und progressiv arbeitet: Die Community-Radios. Viviana Uriona nimmt uns mit auf eine ethnografische Reise durch die Geschichte dieser Radios, analysiert ihre Arbeitsweise und sucht nach den Gründen ihres Erfolges. Am Ende der Lektüre bleibt eine Frage nicht mehr offen: Könnte hierzulande in gleicher Weise gelingen, was dort geschah?
Using individual-based modeling to understand grassland diversity and resilience in the Anthropocene
(2020)
The world’s grassland systems are increasingly threatened by anthropogenic change. Susceptible to a variety of different stressors, from land-use intensification to climate change, understanding the mechanisms driving the maintenance of these systems’ biodiversity and stability, and how these mechanisms may shift under human-mediated disturbance, is thus critical for successfully navigating the next century. Within this dissertation, I use an individual-based and spatially-explicit model of grassland community assembly (IBC-grass) to examine several processes, thought key to understanding their biodiversity and stability and how it changes under stress. In the first chapter of my thesis, I examine the conditions under which intraspecific trait variation influences the diversity of simulated grassland communities. In the second and third chapters of my thesis, I shift focus towards understanding how belowground herbivores influence the stability of these grassland systems to either a disturbance that results in increased, stochastic, plant mortality, or eutrophication.
Intraspecific trait variation (ITV), or variation in trait values between individuals of the same species, is fundamental to the structure of ecological communities. However, because it has historically been difficult to incorporate into theoretical and statistical models, it has remained largely overlooked in community-level analyses. This reality is quickly shifting, however, as a consensus of research suggests that it may compose a sizeable proportion of the total variation within an ecological community and that it may play a critical role in determining if species coexist. Despite this increasing awareness that ITV matters, there is little consensus of the magnitude and direction of its influence. Therefore, to better understand how ITV changes the assembly of grassland communities, in the first chapter of my thesis, I incorporate it into an established, individual-based grassland community model, simulating both pairwise invasion experiments as well as the assembly of communities with varying initial diversities. By varying the amount of ITV in these species’ functional traits, I examine the magnitude and direction of ITV’s influence on pairwise invasibility and community coexistence. During pairwise invasion, ITV enables the weakest species to more frequently invade the competitively superior species, however, this influence does not generally scale to the community level. Indeed, unless the community has low alpha- and beta- diversity, there will be little effect of ITV in bolstering diversity. In these situations, since the trait axis is sparsely filled, the competitively inferior may suffer less competition and therefore ITV may buffer the persistence and abundance of these species for some time.
In the second and third chapters of my thesis, I model how one of the most ubiquitous trophic interactions within grasslands, herbivory belowground, influences their diversity and stability. Until recently, the fundamental difficulty in studying a process within the soil has left belowground herbivory “out of sight, out of mind.” This dilemma presents an opportunity for simulation models to explore how this understudied process may alter community dynamics. In the second chapter of my thesis, I implement belowground herbivory – represented by the weekly removal of plant biomass – into IBC-grass. Then, by introducing a pulse disturbance, modelled as the stochastic mortality of some percentage of the plant community, I observe how the presence of belowground herbivores influences the resistance and recovery of Shannon diversity in these communities. I find that high resource, low diversity, communities are significantly more destabilized by the presence of belowground herbivores after disturbance. Depending on the timing of the disturbance and whether the grassland’s seed bank persists for more than one season, the impact of the disturbance – and subsequently the influence of the herbivores – can be greatly reduced. However, because human-mediated eutrophication increases the amount of resources in the soil, thus pressuring grassland systems, our results suggest that the influence of these herbivores may become more important over time.
In the third chapter of my thesis, I delve further into understanding the mechanistic underpinnings of belowground herbivores on the diversity of grasslands by replicating an empirical mesocosm experiment that crosses the presence of herbivores above- and below-ground with eutrophication. I show that while aboveground herbivory, as predicted by theory and frequently observed in experiments, mitigates the impact of eutrophication on species diversity, belowground herbivores counterintuitively reduce biodiversity. Indeed, this influence positively interacts with the eutrophication process, amplifying its negative impact on diversity. I discovered the mechanism underlying this surprising pattern to be that, as the herbivores consume roots, they increase the proportion of root resources to root biomass. Because root competition is often symmetric, herbivory fails to mitigate any asymmetries in the plants’ competitive dynamics. However, since the remaining roots have more abundant access to resources, the plants’ competition shifts aboveground, towards asymmetric competition for light. This leads the community towards a low-diversity state, composed of mostly high-performance, large plant species. We further argue that this pattern will emerge unless the plants’ root competition is asymmetric, in which case, like its counterpart aboveground, belowground herbivory may buffer diversity by reducing this asymmetry between the competitively superior and inferior plants.
I conclude my dissertation by discussing the implications of my research on the state of the art in intraspecific trait variation and belowground herbivory, with emphasis on the necessity of more diverse theory development in the study of these fundamental interactions. My results suggest that the influence of these processes on the biodiversity and stability of grassland systems is underappreciated and multidimensional, and must be thoroughly explored if researchers wish to predict how the world’s grasslands will respond to anthropogenic change. Further, should researchers myopically focus on understanding central ecological interactions through only mathematically tractable analyses, they may miss entire suites of potential coexistence mechanisms that can increase the coviability of species, potentially leading to coexistence over ecologically-significant timespans. Individual-based modelling, therefore, with its focus on individual interactions, will prove a critical tool in the coming decades for understanding how local interactions scale to larger contexts, and how these interactions shape ecological communities and further predicting how these systems will change under human-mediated stress.
Lehrkräftefortbildungen werden in der Forschung als vielversprechende Möglichkeit angesehen, Lehrkräfte dabei zu unterstützen, den an sie gestellten Anforderungen gerecht zu werden (Darling-Hammond, Hyler & Gardner, 2017). Über verschiedene Studien hinweg konnte hierbei gezeigt werden, dass die Teilnahme einer Lehrkraft an Fortbildungen positiv mit der Entwicklung ihrer Schüler*innen zusammenhängt (Kalinowski, Egert, Gronostaj & Vock, 2020; Yoon, Duncan, Lee, Scarloss & Shapley, 2007). Während ein Teil der Forschung ihren Fokus auf die Wirksamkeit von Fortbildungsangeboten richtet, nehmen andere Untersuchungen stärker die Nutzung dieser Angebote in den Blick. Die vorliegende Arbeit knüpft an die bisherige Forschung zur Lehrkräftefortbildung an und versucht, Aspekte der Nutzung und des Angebots der Lehrkräftefortbildung in Deutschland im Rahmen des Comprehensive Lifelong Learning Participation Models stärker gemeinsam zu betrachten (Boeren, Nicaise & Baert, 2010). Hierbei handelt es sich um ein Mehrebenen-Modell zur Erklärung von Weiterbildungsverhalten, welches verschiedene Akteursgruppen (z.B. Fortbildungsteilnehmer*innen, Fortbildungsinstitute) auf der Nachfrage- und der Angebotsseite berücksichtigt und deren Interdependenz in den Blick nimmt. Vor diesem Hintergrund beschäftigt sich die vorliegende Arbeit in vier Teilstudien mit den Merkmalen der Fortbildungsteilnehmer*innen und des Fortbildungsangebots. Sie untersucht zudem die Prädiktoren für Fortbildungsbeteiligung von Lehrkräften auf der Nachfrage- und Angebotsseite. Studie 1 fokussiert zunächst die Nachfrageseite des Comprehensive Lifelong Learning Participation Models (Boeren et al., 2010) und betrachtet die in der Forschung wenig beachtete Gruppe der Nicht-Teilnehmer*innen. An Befunde der allgemeinen Weiterbildungsforschung anknüpfend, beschäftigt sich diese Teilstudie mit den Teilnahmebarrieren von Lehrkräften an Fortbildungen und untersucht, wie diese mit der Fortbildungsaktivität von Lehrkräften zusammenhängen. Die Beantwortung der Forschungsfragen basiert auf einer Sekundärdatenanalyse des IQB-Ländervergleichs 2012 (Pant et al., 2013), auf dessen Grundlage ein Gruppenvergleich von Teilnehmer*innen und Nicht-Teilnehmer*innen an Fortbildung sowie eine faktoranalytische Betrachtung der berichteten Teilnahmebarrieren durchgeführt wurde. Studie 2 greift die Frage auf, welche Lehrkräfte intensiv von Angeboten der Fortbildung Gebrauch machen. Ausgangspunkt der Arbeit ist die Beobachtung eines Matthäus-Effektes durch die allgemeine Weiterbildungsforschung. Demnach beteiligen sich insbesondere jene Personen stärker an beruflichen Lerngelegenheiten, die bereits vor der Maßnahme über günstige Ausgangsvoraussetzungen, etwa in Form eines höheren Kompetenzniveaus im Vergleich zu Personen, die nicht oder weniger an Angeboten der Fort- und Weiterbildung partizipieren, verfügen. In Anlehnung an diese Befunde diskutiert Teilstudie 2 verschiedene Aspekte der Qualität von Lehrkräften und geht anhand bivariater Zusammenhangsanalysen der Frage nach, welche Zusammenhänge zwischen der Voraussetzung der Lehrkraft und der Nutzung von Fortbildung bestehen. Dabei berücksichtigt die Studie das von Boeren et al. (2010) eingeführte Comprehensive Lifelong Learning Participation Model, indem sie die Befunde der Wirksamkeits- und Angebotsforschung aufgreift und differentielle Effekte in Abhängigkeit der Merkmale der Fortbildungen (fachlich vs. nicht-fachlich) in den Blick nimmt. Die durchgeführten Analysen beruhen auf einer Sekundärdatenanalyse des COACTIV-Forschungsprojekts (Kunter, Baumert & Blum, 2011). Auch in Studie 3 steht die Interaktion von Nachfrage- und Angebotsseite im Mittelpunkt. Während in Studie 2 jedoch konzeptionelle Merkmale der Fortbildung fokussiert wurden, liegt der Fokus in Studie 3 auf dem strukturellen Merkmal Zeit. Zeiten zum (beruflichen) Lernen werden hierbei zunächst auf Basis empirischer Befunde als Grundvoraussetzung für das Zustandekommen von Fortbildungsbeteiligung herausgearbeitet. Die Studie geht dann der Frage nach, welche zeitlichen Merkmale das Fortbildungsangebot für Lehrkräfte aufweist und wie diese Merkmale des Angebots im Zusammenhang mit der Nutzung durch Lehrkräfte stehen. Zur Beantwortung der Forschungsfragen werden eine Programmanalyse sowie polynomiale Regressionen durchgeführt. Die der Analyse zugrundeliegenden Daten beruhen hierbei auf den in der elektronischen Datenbank hinterlegten Fortbildungsangebotsdaten für das Land Brandenburg aus dem akademischen Jahr 2016/2017. Studie 4 fokussiert schließlich die Gruppe der Lehrerfortbildner*innen und somit die Angebotsseite des Comprehensive Lifelong Learning Participation Models (Boeren et al., 2010). In Anlehnung an theoretische Arbeiten zur professionellen Identität wird dabei der Frage nachgegangen, wie Lehrerfortbildner*innen ihre Aufgaben wahrnehmen und wie diese Wahrnehmung mit weiteren Aspekten ihrer professionellen Identität und der Gestaltung ihrer Fortbildungsveranstaltungen zusammenhängt. Hierzu wurden selbsterhobene Daten einer schriftlichen Befragung von Lehrerfortbildner*innen im Jahr 2019 zunächst faktoranalytisch betrachtet und anschließend mithilfe bivariater Zusammenhangsanalysen untersucht. Die zentralen Ergebnisse der vorliegenden Arbeit werden abschließend zusammengefasst diskutiert. Sie deuten insgesamt darauf hin, dass das derzeitige Fortbildungssystem in Deutschland nicht dazu geeignet erscheint, alle Lehrkräfte mit qualitativ hochwertigen Fortbildungen so zu erreichen, dass sie an ihren Schwächen arbeiten können. Die Befunde zeigen weiter, dass Fortbildner*innen eine mögliche Stellschraube für die Veränderung von Teilen des Fortbildungsangebots darstellen. Die Befunde bieten somit die Grundlage für zukünftige Forschungsarbeiten und mögliche Implikationen in der Fortbildungspraxis und Bildungspolitik.
Small moonlets or moons embedded in dense planetary rings create S-shaped density modulations called propellers if their masses are smaller than a certain threshold, alternatively they create a circumferential gap in the disk if the embedded body’s mass exceeds this threshold (Spahn and Sremčević, 2000). The gravitational perturber scatters the ring particles, depletes the disk’s density, and, thus, clears a gap, whereas counteracting viscous diffusion of the ring material has the tendency to close the created gap, thereby forming a propeller. Propeller objects were predicted by Spahn and Sremčević (2000) and Sremčević et al. (2002) and were later discovered by the Cassini space probe (Tiscareno et al., 2006, Sremčević et al., 2007, Tiscareno et al., 2008, and Tiscareno et al., 2010). The ring moons Pan and Daphnis are massive enough to maintain the circumferential Encke and Keeler gaps in Saturn’s A ring and were detected by Showalter (1991) and Porco (2005) in Voyager and Cassini images, respectively. In this thesis, a nonlinear axisymmetric diffusion model is developed to describe radial density profiles of circumferential gaps in planetary rings created by embedded moons (Grätz et al., 2018). The model accounts for the gravitational scattering of the ring particles by the embedded moon and for the counteracting viscous diffusion of the ring matter back into the gap. With test particle simulations it is shown that the scattering of the ring particles passing the moon is larger for small impact parameters than estimated by Goldreich and Tremaine (1980). This is especially significant for the modeling of the Keeler gap. The model is applied to the Encke and Keeler gaps with the aim to estimate the shear viscosity of the ring in their vicinities. In addition, the model is used to analyze whether tiny icy moons whose dimensions lie below Cassini’s resolution capabilities would be able to cause the poorly understood gap structure of the C ring and the Cassini Division. One of the most intriguing facets of Saturn’s rings are the extremely sharp edges of the Encke and Keeler gaps: UVIS-scans of their gap edges show that the optical depth drops from order unity to zero over a range of far less than 100 m, a spatial scale comparable to the ring’s vertical extent. This occurs despite the fact that the range over which a moon transfers angular momentum onto the ring material is much larger. Borderies et al. (1982, 1989) have shown that this striking feature is likely related to the local reversal of the usually outward-directed viscous transport of angular momentum in strongly perturbed regions. We have revised the Borderies et al. (1989) model using a granular flow model to define the shear and bulk viscosities, ν and ζ, in order to incorporate the angular momentum flux reversal effect into the axisymmetric diffusion model for circumferential gaps presented in this thesis (Grätz et al., 2019). The sharp Encke and Keeler gap edges are modeled and conclusions regarding the shear and bulk viscosities of the ring are discussed. Finally, we explore the question of whether the radial density profile of the central and outer A ring, recently measured by Tiscareno and Harris (2018) in the highest resolution to date, and in particular, the sharp outer A ring edge can be modeled consistently from the balance of gravitational scattering by several outer moons and the mass and momentum transport. To this aim, the developed model is extended to account for the inward drifts caused by multiple discrete and overlapping resonances with multiple outer satellites and is then used to hydrodynamically simulate the normalized surface mass density profile of the A ring. This section of the thesis is based on studies by Tajeddine et al. (2017a) who recently discussed the common misconception that the 7:6 resonance with Janus alone maintains the outer A ring edge, showing that the combined effort of several resonances with several outer moons is required to confine the A ring as observed by the Cassini spacecraft.
The Earth's inner magnetosphere is a very dynamic system, mostly driven by the external solar wind forcing exerted upon the magnetic field of our planet. Disturbances in the solar wind, such as coronal mass ejections and co-rotating interaction regions, cause geomagnetic storms, which lead to prominent changes in charged particle populations of the inner magnetosphere - the plasmasphere, ring current, and radiation belts. Satellites operating in the regions of elevated energetic and relativistic electron fluxes can be damaged by deep dielectric or surface charging during severe space weather events. Predicting the dynamics of the charged particles and mitigating their effects on the infrastructure is of particular importance, due to our increasing reliance on space technologies.
The dynamics of particles in the plasmasphere, ring current, and radiation belts are strongly coupled by means of collisions and collisionless interactions with electromagnetic fields induced by the motion of charged particles. Multidimensional numerical models simplify the treatment of transport, acceleration, and loss processes of these particles, and allow us to predict how the near-Earth space environment responds to solar storms. The models inevitably rely on a number of simplifications and assumptions that affect model accuracy and complicate the interpretation of the results. In this dissertation, we quantify the processes that control electron dynamics in the inner magnetosphere, paying particular attention to the uncertainties of the employed numerical codes and tools.
We use a set of convenient analytical solutions for advection and diffusion equations to test the accuracy and stability of the four-dimensional Versatile Electron Radiation Belt (VERB-4D) code. We show that numerical schemes implemented in the code converge to the analytical solutions and that the VERB-4D code demonstrates stable behavior independent of the assumed time step. The order of the numerical scheme for the convection equation is demonstrated to affect results of ring current and radiation belt simulations, and it is crucially important to use high-order numerical schemes to decrease numerical errors in the model.
Using the thoroughly tested VERB-4D code, we model the dynamics of the ring current electrons during the 17 March 2013 storm. The discrepancies between the model and observations above 4.5 Earth's radii can be explained by uncertainties in the outer boundary conditions. Simulation results indicate that the electrons were transported from the geostationary orbit towards the Earth by the global-scale electric and magnetic fields.
We investigate how simulation results depend on the input models and parameters. The model is shown to be particularly sensitive to the global electric field and electron lifetimes below 4.5 Earth's radii. The effects of radial diffusion and subauroral polarization streams are also quantified.
We developed a data-assimilative code that blends together a convection model of energetic electron transport and loss and Van Allen Probes satellite data by means of the Kalman filter. We show that the Kalman filter can correct model uncertainties in the convection electric field, electron lifetimes, and boundary conditions. It is also demonstrated how the innovation vector - the difference between observations and model prediction - can be used to identify physical processes missing in the model of energetic electron dynamics.
We computed radial profiles of phase space density of ultrarelativistic electrons, using Van Allen Probes measurements. We analyze the shape of the profiles during geomagnetically quiet and disturbed times and show that the formation of new local minimums in the radial profiles coincides with the ground observations of electromagnetic ion-cyclotron (EMIC) waves. This correlation indicates that EMIC waves are responsible for the loss of ultrarelativistic electrons from the heart of the outer radiation belt into the Earth's atmosphere.
In the last decade the photovoltaic research has been preponderantly overturned by the arrival of metal halide perovskites. The introduction of this class of materials in the academic research for renewable energy literally shifted the focus of a large number of research groups and institutions. The attractiveness of halide perovskites lays particularly on their skyrocketing efficiencies and relatively simple and cheap fabrication methods. Specifically, the latter allowed for a quick development of this research in many universities and institutes around the world at the same time. The outcome has been a fast and beneficial increase in knowledge with a consequent terrific improvement of this new technology. On the other side, the enormous amount of research promoted an immense outgrowth of scientific literature, perpetually published. Halide perovskite solar cells are now effectively competing with other established photovoltaic technologies in terms of power conversion efficiencies and production costs. Despite the tremendous improvement, a thorough understanding of the energy losses in these systems is of imperative importance to unlock the full thermodynamic potential of this material. This thesis focuses on the understanding of the non-radiative recombination processes in the neat perovskite and in complete devices. Specifically, photoluminescence quantum yield (PLQY) measurements were applied to multilayer stacks and cells under different illumination conditions to accurately determine the quasi-Fermi levels splitting (QFLS) in the absorber, and compare it with the external open-circuit voltage of the device (V_OC). Combined with drift-diffusion simulations, this approach allowed us to pinpoint the sites of predominant recombination, but also to investigate the dynamics of the underlying processes. As such, the internal and external ideality factors, associated to the QFLS and V_OC respectively, are studied with the aim of understanding the type of recombination processes taking place in the multilayered architecture of the device. Our findings highlight the failure of the equality between QFLS and V_OC in the case of strong interface recombination, as well as the detrimental effect of all commonly used transport layers in terms of V_OC losses. In these regards, we show how, in most perovskite solar cells, different recombination processes can affect the internal QFLS and the external V_OC and that interface recombination dictates the V_OC losses. This line of arguments allowed to rationalize that, in our devices, the external ideality factor is completely dominated by interface recombination, and that this process can alone be responsible for values of the ideality factor between 1 and 2, typically observed in perovskite solar cells. Importantly, our studies demonstrated how strong interface recombination can lower the ideality factor towards values of 1, often misinterpreted as pure radiative second order recombination. As such, a comprehensive understanding of the recombination loss mechanisms currently limiting the device performance was achieved. In order to reach the full thermodynamic potential of the perovskite absorber, the interfaces of both the electron and hole transport layers (ETL/HTL) must be properly addressed and improved. From here, the second part of the research work is devoted on reducing the interfacial non-radiative energy losses by optimizing the structure and energetics of the relevant interface in our solar cell devices, with the aim of bringing their quasi-Fermi level splitting closer to its radiative limit. As such, the interfaces have been carefully addressed and optimized with different methodologies. First, a small amount of Sr is added into the perovskite precursor solution with the effect of effectively reducing surface and interface recombination. In this case, devices with V_OC up to 1.23 V were achieved and the energy losses were minimized to as low as 100 meV from the radiative limit of the material. Through a combination of different methods, we showed that these improvements are related to a strong n-type surface doping, which repels the holes in the perovskite from the surface and the interface with the ETL. Second, a more general device improvement was achieved by depositing a defect-passivating poly(ionic-liquid) layer on top of the perovskite absorber. The resulting devices featured a concomitant improvement of the V_OC and fill factor, up to 1.17 V and 83% respectively, reaching efficiency as high as 21.4%. Moreover, the protecting polymer layer helped to enhance the stability of the devices under prolonged maximum power point tracking measurements. Lastly, PLQY measurements are used to investigate the recombination mechanisms in halide-segregated large bandgap perovskite materials. Here, our findings showed how few iodide-rich low-energy domains act as highly efficient radiative recombination centers, capable of generating PLQY values up to 25%. Coupling these results with a detailed microscopic cathodoluminescence analysis and absorption profiles allowed to demonstrate how the emission from these low energy domains is due to the trapping of the carriers photogenerated in the Br-rich high-energy domains. Thereby, the strong implications of this phenomenon are discussed in relation to the failure of the optical reciprocity between absorption and emission and on the consequent applicability of the Shockley-Queisser theory for studying the energy losses such systems. In conclusion, the identification and quantification of the non-radiative QFLS and V_OC losses provided a base knowledge of the fundamental limitation of perovskite solar cells and served as guidance for future optimization and development of this technology. Furthermore, by providing practical examples of solar cell improvements, we corroborated the correctness of our fundamental understanding and proposed new methodologies to be further explored by new generations of scientists.
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.
Abstract. Catalysis is one of the most effective tools for the highly efficient assembly of complex molecular structures. Nevertheless, it is mainly represented by transition metal-based catalysts and typically is an energy consuming process. Therefore, photocatalysis utilizing solar energy is one of the appealing approaches to overcome these problems. A great alternative to classic transition metal-based photocatalysts, carbon nitrides, a group of organic polymeric semiconductors, have already shown their efficiency in water splitting, CO2 reduction, and organic pollutants degradation. However, these materials have also a great potential for the use in functionalization of complex organic molecules for synthetic needs as it was shown in recent years.
This work addresses the challenge to develop efficient system for heterogeneous organic photocatalysis, employing cheap and environmentally benign photocatalysts – carbon nitrides. Herein, fundamental properties of semiconductors are studied from the organic chemistry standpoint; the inherent properties of carbon nitrides, such as ability to accumulate electrons, are deeply investigated and their effect on the reaction outcome is established. Thus, understanding of the electron charging processes allowed for the synthesis of otherwise hardly-achieved diazetidines-1,3 by tetramerization of benzylamines. Furthermore, the high electron capacity of Potassium Poly(heptazine imide)s (K-PHI) made possible a multi-electron reduction of aromatic nitro compounds to bare or formylated anilines. Additionally, two deep eutectic solvents (DES) were designed as a sustainable reaction media and reducing reagent for this reaction. Eventually, the high oxidation ability of carbon nitride K-PHI is employed in a challenging reaction of halide anion oxidation (Cl―, Br―) to accomplish electrophilic substitution in aromatic ring. The possibility to utilize NaCl solution (seawater mimetic) for the chlorination of electron rich arenes was shown. Eventually, light itself is used as a tool in a chromoselective photocatalytic oxidation of aromatic thiols and thioacetatas to three different compounds, using UV, blue, and red LEDs.
All in all, the work enhances understanding the mechanism of heterogeneous photocatalysis in synthetic organic reactions and therefore, is a step forward to the sustainable methods of synthesis in organic chemistry.
To meet the demands of a growing world population while reducing carbon dioxide (CO2) emissions, it is necessary to capture CO2 and convert it into value-added compounds. In recent years, metabolic engineering of microbes has gained strong momentum as a strategy for the production of valuable chemicals. As common microbial feedstocks like glucose directly compete with human consumption, the one carbon (C1) compound formate was suggested as an alternative feedstock. Formate can be easily produced by various means including electrochemical reduction of CO2 and could serve as a feedstock for microbial production, hence presenting a novel entry point for CO2 to the biosphere and a storage option for excess electricity. Compared to the gaseous molecule CO2, formate is a highly soluble compound that can be easily handled and stored. It can serve as a carbon and energy source for natural formatotrophs, but these microbes are difficult to cultivate and engineer. In this work, I present the results of several projects that aim to establish efficient formatotrophic growth of E. coli – which cannot naturally grow on formate – via synthetic formate assimilation pathways. In the first study, I establish a workflow for growth-coupled metabolic engineering of E. coli. I demonstrate this approach by presenting an engineering scheme for the PFL-threonine cycle, a synthetic pathway for anaerobic formate assimilation in E. coli. The described methods are intended to create a standardized toolbox for engineers that aim to establish novel metabolic routes in E. coli and related organisms. The second chapter presents a study on the catalytic efficiency of C1-oxidizing enzymes in vivo. As formatotrophic growth requires generation of both energy and biomass from formate, the engineered E. coli strains need to be equipped with a highly efficient formate dehydrogenase, which provides reduction equivalents and ATP for formate assimilation. I engineered a strain that cannot generate reducing power and energy for cellular growth, when fed on acetate. Under this condition, the strain depends on the introduction of an enzymatic system for NADH regeneration, which could further produce ATP via oxidative phosphorylation. I show that the strain presents a valuable testing platform for C1-oxidizing enzymes by testing different NAD-dependent formate and methanol dehydrogenases in the energy auxotroph strain. Using this platform, several candidate enzymes with high in vivo activity, were identified and characterized as potential energy-generating systems for synthetic formatotrophic or methylotrophic growth in E. coli. In the third chapter, I present the establishment of the serine threonine cycle (STC) – a synthetic formate assimilation pathway – in E. coli. In this pathway, formate is assimilated via formate tetrahydrofolate ligase (FtfL) from Methylobacterium extorquens (M. extorquens). The carbon from formate is attached to glycine to produce serine, which is converted into pyruvate entering central metabolism. Via the natural threonine synthesis and cleavage route, glycine is regenerated and acetyl-CoA is produced as the pathway product. I engineered several selection strains that depend on different STC modules for growth and determined key enzymes that enable high flux through threonine synthesis and cleavage. I could show that expression of an auxiliary formate dehydrogenase was required to achieve growth via threonine synthesis and cleavage on pyruvate. By overexpressing most of the pathway enzymes from the genome, and applying adaptive laboratory evolution, growth on glycine and formate was achieved, indicating the activity of the complete cycle. The fourth chapter shows the establishment of the reductive glycine pathway (rGP) – a short, linear formate assimilation route – in E. coli. As in the STC, formate is assimilated via M. extorquens FtfL. The C1 from formate is condensed with CO2 via the reverse reaction of the glycine cleavage system to produce glycine. Another carbon from formate is attached to glycine to form serine, which is assimilated into central metabolism via pyruvate. The engineered E. coli strain, expressing most of the pathway genes from the genome, can grow via the rGP with formate or methanol as a sole carbon and energy source.
This thesis offers new insights on the effects of Start-Up Subsidies (SUS) for unemployed individuals as a special kind of active labor market program (ALMP) that aims to re-integrate individuals into the labor market via the route of self-employment. Moreover, this thesis contributes to the literature on methods for causal inference when the treatment variable is continuous rather than binary. For example, this is the case when individuals differ in their degree of exposure to a common treatment.
The analysis of the effects of SUS focuses on the main current German program called “Gründungszuschuss” (New Start-Up Subsidy, NSUS) after its reform in 2011. Average Effects on participants' labor market outcomes - as measured by employment and earnings - as well as subjective well-being are estimated mainly based on propensity score matching (PSM) techniques. PSM aims to achieve balance in terms of observed characteristics by matching participants with at least one comparable non-participant in terms of their probability to receive the treatment. This estimation strategy is valid as long as all relevant characteristics that explain selection patterns into treatment are observed and included in the estimation of the propensity score. To make our analysis as credible as possible, we control for a large vector of characteristics as observed through the combination of rich administrative data from the Federal Employment Agency as well as through survey data.
Chapters two to four of this thesis puts special emphasis on aspects regarding (the evaluation of) SUS programs that have received no or only limited attention thus far. The first aspect relates to the interplay of institutional details of the program and its effectiveness. So far, relatively little is known about the importance of SUS program features such as the duration of support. Second, there is no experimental benchmark evaluation of SUS available and thus, the reliability of non-experimental estimation techniques such as PSM is of crucial importance as estimates are biased when relevant confounders are omitted from the analysis. Third, there may be potentially detrimental effects of transitioning into (relatively risky) self-employment on subjective well-being among subsidized founders out of unemployment. These were to remain undetected if the analysis would focus exclusively on labor market outcomes of participants. The results indicate positive long-term effects of SUS participation on employment and earnings among participants. These effects are substantially larger than what estimated before the reform, indicating room for improvement in program design via changes in institutional details. Moreover, non-experimental estimates of treatment effects are remarkably robust to hidden confounding. Regarding subjective well-being, this thesis finds a positive long-run impact on job satisfaction and a detrimental effect on satisfaction with social security. The latter appears to be driven by adverse effects on social insurance contributions.
In chapter five, a novel automated covariate balancing technique for the estimation of causal effects in the context of continuous treatments is derived and assessed regarding its performance compared to other (automated) balancing techniques. Although binary research designs that only differentiate between participants and non-participants of some treatment remain the most-common case in empirical practice, many applications can be adapted to include continuous treatments as well. Often, this will allow for more meaningful estimates of causal effects in order to further improve the design of programs. In the context of SUS, one may further investigate the effects of the size of monetary support or its duration on participants' labor market outcomes. Both Monte-Carlo investigations and analysis of two well-known datasets suggests superior performance of the proposed Entropy Balancing for continuous treatments (EBCT) compared to other existing estimation strategies.
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.
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.
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.
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.
In beiden deutschen Teilstaaten gehörten die Rentenversicherungen zu den ersten Nutzern von Computern. Bereits seit Mitte der 1950er Jahre berechneten diese die Altersruhegelder im Westen, zehn Jahre später auch in der DDR. Die digitale Datenverarbeitung versprach große Rationalisierungs- und Beschleunigungseffekte. Gleichwohl führten die verschiedenen Staats- und Versicherungsformen zu einer unterschiedlichen Nutzung von Computern.
Die Studie von Thomas Kasper zeigt, unter welchen Bedingungen sich die elektronische Datenverarbeitung in der Sozialverwaltung durchsetzen konnte. Sie verdeutlicht, welchen bisher unbekannten Einfluss sie auf sozialpolitische Entscheidungen sowie auf die Arbeitsverhältnisse und den Datenschutz in beiden deutschen Teilstaaten hatte. Nach der Wiedervereinigung ließ nur die gemeinsame Nutzung der vorhandenen digitalen Strukturen die Zusammenführung beider Sozialsysteme gelingen.
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.
Water quality in river systems is of growing concern due to rising anthropogenic pressures and climate change. Mitigation efforts have been placed under the guidelines of different governance conventions during last decades (e.g., the Water Framework Directive in Europe). Despite significant improvement through relatively straightforward measures, the environmental status has likely reached a plateau. A higher spatiotemporal accuracy of catchment nitrate modeling is, therefore, needed to identify critical source areas of diffuse nutrient pollution (especially for nitrate) and to further guide implementation of spatially differentiated, cost-effective mitigation measures. On the other hand, the emerging high-frequency sensor monitoring upgrades the monitoring resolution to the time scales of biogeochemical processes and enables more flexible monitoring deployments under varying conditions. The newly available information offers new prospects in understanding nitrate spatiotemporal dynamics. Formulating such advanced process understanding into catchment models is critical for model further development and environmental status evaluation. This dissertation is targeting on a comprehensive analysis of catchment and in-stream nitrate dynamics and is aiming to derive new insights into their spatial and temporal variabilities through the new fully distributed model development and the new high-frequency data.
Firstly, a new fully distributed, process-based catchment nitrate model (the mHM-Nitrate model) is developed based on the mesoscale Hydrological Model (mHM) platform. Nitrate process descriptions are adopted from the Hydrological Predictions for the Environment (HYPE), with considerable improved implementations. With the multiscale grid-based discretization, mHM-Nitrate balances the spatial representation and the modeling complexity. The model has been thoughtfully evaluated in the Selke catchment (456 km2), central Germany, which is characterized by heterogeneous physiographic conditions. Results show that the model captures well the long-term discharge and nitrate dynamics at three nested gauging stations. Using daily nitrate-N observations, the model is also validated in capturing short-term fluctuations due to changes in runoff partitioning and spatial contribution during flooding events. By comparing the model simulations with the values reported in the literature, the model is capable of providing detailed and reliable spatial information of nitrate concentrations and fluxes. Therefore, the model can be taken as a promising tool for environmental scientists in advancing environmental modeling research, as well as for stakeholders in supporting their decision-making, especially for spatially differentiated mitigation measures.
Secondly, a parsimonious approach of regionalizing the in-stream autotrophic nitrate uptake is proposed using high-frequency data and further integrated into the new mHM-Nitrate model. The new regionalization approach considers the potential uptake rate (as a general parameter) and effects of above-canopy light and riparian shading (represented by global radiation and leaf area index data, respectively). Multi-parameter sensors have been continuously deployed in a forest upstream reach and an agricultural downstream reach of the Selke River. Using the continuous high-frequency data in both streams, daily autotrophic uptake rates (2011-2015) are calculated and used to validate the regionalization approach. The performance and spatial transferability of the approach is validated in terms of well-capturing the distinct seasonal patterns and value ranges in both forest and agricultural streams. Integrating the approach into the mHM-Nitrate model allows spatiotemporal variability of in-stream nitrate transport and uptake to be investigated throughout the river network.
Thirdly, to further assess the spatial variability of catchment nitrate dynamics, for the first time the fully distributed parameterization is investigated through sensitivity analysis. Sensitivity results show that parameters of soil denitrification, in-stream denitrification and in-stream uptake processes are the most sensitive parameters throughout the Selke catchment, while they all show high spatial variability, where hot-spots of parameter sensitivity can be explicitly identified. The Spearman rank correlation is further analyzed between sensitivity indices and multiple catchment factors. The correlation identifies that the controlling factors vary spatially, reflecting heterogeneous catchment responses in the Selke catchment. These insights are, therefore, informative in informing future parameter regionalization schemes for catchment water quality models. In addition, the spatial distributions of parameter sensitivity are also influenced by the gauging information that is being used for sensitivity evaluation. Therefore, an appropriate monitoring scheme is highly recommended to truly reflect the catchment responses.
Hydrological models are important tools for the simulation and quantification of the water cycle.
They therefore aid in the understanding of hydrological processes, prediction of river discharge, assessment of the impacts of land use and climate changes, or the management of water resources.
However, uncertainties associated with hydrological modelling are still large.
While significant research has been done on the quantification and reduction of uncertainties, there are still fields which have gained little attention so far, such as model structural uncertainties that are related to the process implementations in the models.
This holds especially true for complex process-based models in contrast to simpler conceptual models.
Consequently, the aim of this thesis is to improve the understanding of structural uncertainties with focus on process-based hydrological modelling, including methods for their quantification.
To identify common deficits of frequently used hydrological models and develop further strategies on how to reduce them, a survey among modellers was conducted.
It was found that there is a certain degree of subjectivity in the perception of modellers, for instance with respect to the distinction of hydrological models into conceptual groups.
It was further found that there are ambiguities on how to apply a certain hydrological model, for instance how many parameters should be calibrated, together with a large diversity of opinion regarding the deficits of models.
Nevertheless, evapotranspiration processes are often represented in a more physically based manner, while processes of groundwater and soil water movement are often simplified, which many survey participants saw as a drawback.
A large flexibility, for instance with respect to different alternative process implementations or a small number of parameters that needs to be calibrated, was generally seen as strength of a model.
Flexible and efficient software, which is straightforward to apply, has been increasingly acknowledged by the hydrological community.
This work further elaborated on this topic in a twofold way.
First, a software package for semi-automated landscape discretisation has been developed, which serves as a tool for model initialisation.
This was complemented by a sensitivity analysis of important and commonly used discretisation parameters, of which the size of hydrological sub-catchments as well as the size and number of hydrologically uniform computational units appeared to be more influential than information considered for the characterisation of hillslope profiles.
Second, a process-based hydrological model has been implemented into a flexible simulation environment with several alternative process representations and a number of numerical solvers.
It turned out that, even though computation times were still long, enhanced computational capabilities nowadays in combination with innovative methods for statistical analysis allow for the exploration of structural uncertainties of even complex process-based models, which up to now was often neglected by the modelling community.
In a further study it could be shown that process-based models may even be employed as tools for seasonal operational forecasting.
In contrast to statistical models, which are faster to initialise and to apply, process-based models produce more information in addition to the target variable, even at finer spatial and temporal scales, and provide more insights into process behaviour and catchment functioning.
However, the process-based model was much more dependent on reliable rainfall forecasts.
It seems unlikely that there exists a single best formulation for hydrological processes, even for a specific catchment.
This supports the use of flexible model environments with alternative process representations instead of a single model structure.
However, correlation and compensation effects between process formulations, their parametrisation, and other aspects such as numerical solver and model resolution, may lead to surprising results and potentially misleading conclusions.
In future studies, such effects should be more explicitly addressed and quantified.
Moreover, model functioning appeared to be highly dependent on the meteorological conditions and rainfall input generally was the most important source of uncertainty.
It is still unclear, how this could be addressed, especially in the light of the aforementioned correlations.
The use of innovative data products, e.g.\ remote sensing data in combination with station measurements, and efficient processing methods for the improvement of rainfall input and explicit consideration of associated uncertainties is advisable to bring more insights and make hydrological simulations and predictions more reliable.
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.
Plants are an attractive platform for the production of medicinal compounds because of their potential to generate large amounts of biomass cheaply. The use of chloroplast transformation is an attractive way to achieve the recombinant production of proteins in plants, because of the chloroplasts’ high capacity to produce foreign proteins in comparison to nuclear transformed plants. In this thesis, the production of two different types of antimicrobial polypeptides in chloroplasts is explored.
The first example is the production of the potent HIV entry inhibitor griffithsin. Griffithsin has the potential to prevent HIV infections by blocking the entry of the virus into human cells. Here the use of transplastomic plants as an inexpensive production method for griffithsin was explored. Transplastomic plants grew healthily and were able to accumulate griffithsin to up to 5% of the total soluble protein. Griffithsin could easily be purified from tobacco leaf tissue and had a similarly high neutralization activity as griffithsin recombinantly produced in bacteria. Griffithsin could be purified from dried tobacco leaves, demonstrating that dried leaves could be used as a storable starting material for griffithsin purification, circumventing the need for immediate purification after harvest.
The second example is the production of antimicrobial peptides (AMPs) that have the capacity to kill bacteria and are an attractive alternative to currently used antibiotics that are increasingly becoming ineffective. The production of antimicrobial peptides was considerably more challenging than the production of griffithsin. Small AMPs are prone to degradation in plastids. This problem was overcome by fusing AMPs to generate larger polypeptides. In one approach, AMPs were fused to each other to increase size and combine the mode of action of multiple AMPs. This improved the accumulation of AMPs but also resulted in impaired plant growth. This was solved by the use of two different inducible systems, which could largely restore plant growth. Fusions of multiple AMPs were insoluble and could not be purified.
In addition to fusing AMPs to each other, the fusion of AMPs to small ubiquitin-like modifier (SUMO), was tested as an approach to improve the accumulation, facilitate purification, and reduce the toxicity of AMPs to chloroplasts. Fusion of AMPs to SUMO indeed increased accumulation while reducing the toxicity to the plants. SUMO fusions produced inside chloroplasts could be purified, and SUMO could be efficiently cleaved off with the SUMO protease. Such fusions therefore provide a promising strategy for the production of AMPs and other small polypeptides inside chloroplasts.
The earth’s ecosystems undergo considerable changes characterized by human-induced alterations of environmental factors. In order to develop conservation goals for vulnerable ecosystems, research on ecosystem functioning is required.. Therefore, it is crucial to explore organismal interactions, such as trophic interaction or competition, which are decisive for key processes in ecosystems. These interactions are determined by the performance responses of organisms to environmental changes, which in turn, are shaped by the organism’s functional traits. Exploring traits, their variation, and the environmental factors that act on them may provide insights on how ecological interactions affect
populations, community structures and dynamics, and thus ecosystem
functioning. In aquatic ecosystems, global warming intensifies
phytoplankton blooms, which are more frequently dominated by
cyanobacteria. As cyanobacteria are poor in polyunsaturated fatty acids
(PUFA) and sterols, this compositional change alters the biochemical
food quality of phytoplankton for consumer species with potential
effects on ecological interactions. Within this thesis, I studied the
effects of biochemical food quality on consumer traits and performance responses at the phytoplankton-zooplankton interface using different strains of two closely related generalist rotifer species Brachionus calyciflorus and Brachionus fernandoi and three phytoplankton species that differ in their biochemical food quality, i.e. in their content and composition of PUFA and sterols. In a series of laboratory feeding experiments I found that biochemical food quality affected rotifer’s performance, i.e. fecundity, survival, and population growth, across a broad range of food quantities. Biochemical food quality constraints,
which are often underestimated as influencing environmental factors, had strong impacts on performance responses. I further explored the potential of biochemical food quality in mediating consumer response variation between species and among strains of one species. Co-limitation by food quantity and biochemical food quality resulted in differences in performance responses, which were more pronounced within than between rotifer species. Furthermore, I demonstrated that the body PUFA compositions of rotifer species and strains were differently affected by the dietary PUFA supply, which indicates inter- and intraspecific differences in physiological traits, such as PUFA retention, allocation, and/or bioconversion capacity, within the genus Brachionus. This indicates that dietary PUFA are involved in shaping traits and performance responses of rotifers. This thesis reveals that biochemical food quality is an environmental factor with strong effects on individual traits and performance responses of consumers. Biochemical food quality constraints can further mediate trait and response variation among species or strains. Consequently, they carry the potential to shape ecological interactions and evolutionary processes with effects on community structures and dynamics. Trait-based approaches, which include food quality research, thus may provide further insights into the linkage between functional diversity and the maintenance of crucial ecosystem functions.
Fiktion und Wirklichkeit
(2020)
Die Untersuchung widmet sich mit der Besteuerung von Ordensgemeinschaften einem bisher in der Rechtswissenschaft vernachlässigten Thema, aus dem größeren Themenbereich der Besteuerung des Dritten Sektors. Die Vernachlässigung verwundert, kommt den Ordensgemeinschaften doch seit Jahrhunderten mit denen von ihnen in Deutschland betriebenen sozialen Einrichtungen eine erhebliche Bedeutung zu. Die vorliegende Arbeit schließt diese Lücke in ansprechender Weise. Durch die Bearbeitung entsteht auch ein übergreifendes Bild des geltenden Besteuerungsregimes im Dritten Sektor und seiner Problemfelder.
Die §§ 299a, 299b StGB sind das Ergebnis eines legitimen gesetzgeberischen Anliegens, die Umsetzung erfolgte indes defizitär.
Der Rechtsgüterschutz ist nicht konsistent, was zu dessen Weiterentwicklung zwingt.
Die unkritische Übernahme der Auslegungsergebnisse zu § 299 StGB – obwohl vom Gesetzgeber intendiert – ist darüber hinaus oftmals verfehlt. Die Arbeit hinterfragt diesen Ansatz und zeigt Lösungen auf.
Um existente Strafbarkeitslücken zu schließen ist es ferner unerlässlich eine verfassungskonforme „Pflichtverletzungsvariante“ einzuführen. Ferner böte eine Clearingstelle Rechtssicherheit, insbesondere mit der Möglichkeit zur Genehmigung von Austauschverhältnissen im Gesundheitswesen. Hierzu werden Vorschläge gemacht.
Algorithmen in der Justiz
(2020)
Unter welchen Bedingungen dürfen Gerichte in Deutschland digitale Anwendungen zur Entscheidungsfindung einsetzen? Das Werk zeigt die engen Grenzen und einen Lösungsweg hierfür auf. Neben rechtstheoretischen und durch die computerspezifische Arbeitsweise gesetzten Grenzen ist der durch das Grundgesetz und das Europarecht abgesteckte Rechtsrahmen zu beachten. Im Zentrum der Bearbeitung steht die Garantie der richterlichen Unabhängigkeit, die durch den Technikeinsatz nicht infrage gestellt werden darf. Zur Auflösung des daraus resultierenden Konflikts wird ein Zertifizierungsverfahren für determinierte Programme vorgeschlagen. Schließlich werden konkrete Anwendungsbeispiele beleuchtet.
Urbanization and agricultural land use are two of the main drivers of global changes with effects on ecosystem functions and human wellbeing. Green Infrastructure is a new approach in spatial planning contributing to sustainable urban development, and to address urban challenges, such as biodiversity conservation, climate change adaptation, green economy development, and social cohesion. Because the research focus has been mainly on open green space structures, such as parks, urban forest, green building, street green, but neglected spatial and functional potentials of utilizable agricultural land, this thesis aims at fill this gap.
This cumulative thesis addresses how agricultural land in urban and peri-urban landscapes can contribute to the development of urban green infrastructure as a strategy to promote sustainable urban development. Therefore, a number of different research approaches have been applied. First, a quantitative, GIS-based modeling approach looked at spatial potentials, addressing the heterogeneity of peri-urban landscape that defines agricultural potentials and constraints. Second, a participatory approach was applied, involving stakeholder opinions to evaluate multiple urban functions and benefits. Finally, an evidence synthesis was conducted to assess the current state of research on evidence to support future policy making at different levels.
The results contribute to the conceptual understanding of urban green infrastructures as a strategic spatial planning approach that incorporates inner-urban utilizable agricultural land and the agriculturally dominated landscape at the outer urban fringe. It highlights the proposition that the linkage of peri-urban farmland with the green infrastructure concept can contribute to a network of multifunctional green spaces to provide multiple benefits to the urban system and to successfully address urban challenges. Four strategies are introduced for spatial planning with the contribution of peri-urban farmland to a strategically planned multifunctional network, namely the connecting, the productive, the integrated, and the adapted way. Finally, this thesis sheds light on the opportunities that arise from the integration of the peri- urban farmland in the green infrastructure concept to support transformation towards a more sustainable urban development. In particular, the inherent core planning principle of multifunctionality endorses the idea of co-benefits that are considered crucial to trigger transformative processes.
This work concludes that the linkage of peri-urban farmland with the green infrastructure concept is a promising action field for the development of new pathways for urban transformation towards sustainable urban development. Along with these outcomes, attention is drawn to limitations that remain to be addressed by future research, especially the identification of further mechanisms required to support policy integration at all levels.
Um auch die unbeabsichtigten Folgen ihrer Politik zu ermitteln, unternehmen Regierungen umfassende Gesetzesfolgenabschätzungen. Immer häufiger lassen sie sich dabei von unabhängigen Expertengremien kontrollieren. Doch: Wie erzielen diese Gremien Einfluss? Und welche Rolle spielen sie als Politikberater für Bürokratieabbau und bessere Rechtsetzung? Das Buch eröffnet neue Einblicke in die Entwicklungshistorie und Handlungsrealität der drei erfahrensten Normenkontrollräte in Europa. Vor dem Hintergrund unterschiedlicher Verwaltungskulturen werden die Ratstypen „Wachhund“, „Torwächter“ und „Kritischer Freund“ herausgearbeitet. Die Ergebnisse schärfen die politische und wissenschaftliche Debatte um die Leistungsfähigkeit von Normenkontrollräten.
‘The Territorialities of U.S. Imperialisms’ sets into relation U.S. imperial and Indigenous conceptions of territoriality as articulated in U.S. legal texts and Indigenous life writing in the 19th century. It analyzes the ways in which U.S. legal texts as “legal fictions” narratively press to affirm the United States’ territorial sovereignty and coherence in spite of its reliance on a variety of imperial practices that flexibly disconnect and (re)connect U.S. sovereignty, jurisdiction and territory.
At the same time, the book acknowledges Indigenous life writing as legal texts in their own right and with full juridical force, which aim to highlight the heterogeneity of U.S. national territory both from their individual perspectives and in conversation with these legal fictions. Through this, the book’s analysis contributes to a more nuanced understanding of the coloniality of U.S. legal fictions, while highlighting territoriality as a key concept in the fashioning of the narrative of U.S. imperialism.
A large body of research now supports the presence of both syntactic and lexical predictions in sentence processing. Lexical predictions, in particular, are considered to indicate a deep level of predictive processing that extends past the structural features of a necessary word (e.g. noun), right down to the phonological features of the lexical identity of a specific word (e.g. /kite/; DeLong et al., 2005). However, evidence for lexical predictions typically focuses on predictions in very local environments, such as the adjacent word or words (DeLong et al., 2005; Van Berkum et al., 2005; Wicha et al., 2004). Predictions in such local environments may be indistinguishable from lexical priming, which is transient and uncontrolled, and as such may prime lexical items that are not compatible with the context (e.g. Kukona et al., 2014). Predictive processing has been argued to be a controlled process, with top-down information guiding preactivation of plausible upcoming lexical items (Kuperberg & Jaeger, 2016). One way to distinguish lexical priming from prediction is to demonstrate that preactivated lexical content can be maintained over longer distances.
In this dissertation, separable German particle verbs are used to demonstrate that preactivation of lexical items can be maintained over multi-word distances. A self-paced reading time and an eye tracking experiment provide some support for the idea that particle preactivation triggered by a verb and its context can be observed by holding the sentence context constant and manipulating the predictabilty of the particle. Although evidence of an effect of particle predictability was only seen in eye tracking, this is consistent with previous evidence suggesting that predictive processing facilitates only some eye tracking measures to which the self-paced reading modality may not be sensitive (Staub, 2015; Rayner1998). Interestingly, manipulating the distance between the verb and the particle did not affect reading times, suggesting that the surprisal-predicted faster reading times at long distance may only occur when the additional distance is created by information that adds information about the lexical identity of a distant element (Levy, 2008; Grodner & Gibson, 2005). Furthermore, the results provide support for models proposing that temporal decay is not major influence on word processing (Lewandowsky et al., 2009; Vasishth et al., 2019).
In the third and fourth experiments, event-related potentials were used as a method for detecting specific lexical predictions. In the initial ERP experiment, we found some support for the presence of lexical predictions when the sentence context constrained the number of plausible particles to a single particle. This was suggested by a frontal post-N400 positivity (PNP) that was elicited when a lexical prediction had been violated, but not to violations when more than one particle had been plausible. The results of this study were highly consistent with previous research suggesting that the PNP might be a much sought-after ERP marker of prediction failure (DeLong et al., 2011; DeLong et al., 2014; Van Petten & Luka, 2012; Thornhill & Van Petten, 2012; Kuperberg et al., 2019). However, a second experiment in a larger sample experiment failed to replicate the effect, but did suggest the relationship of the PNP to predictive processing may not yet be fully understood. Evidence for long-distance lexical predictions was inconclusive.
The conclusion drawn from the four experiments is that preactivation of the lexical entries of plausible upcoming particles did occur and was maintained over long distances. The facilitatory effect of this preactivation at the particle site therefore did not appear to be the result of transient lexical priming. However, the question of whether this preactivation can also lead to lexical predictions of a specific particle remains unanswered. Of particular interest to future research on predictive processing is further characterisation of the PNP. Implications for models of sentence processing may be the inclusion of long-distance lexical predictions, or the possibility that preactivation of lexical material can facilitate reading times and ERP amplitude without commitment to a specific lexical item.
Escaping the plant cell
(2020)
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.
Most reading theories assume that readers aim at word centers for optimal information processing. During reading, saccade targeting turns out to be imprecise: Saccades’ initial landing positions often miss the word centers and have high variance, with an additional systematic error that is modulated by the distance from the launch site to the center of the target word. The performance of the oculomotor system, as reflected in the statistics of within-word landing positions, turns out to be very robust and mostly affected by the spatial information during reading. Hence, it is assumed that the saccade generation is highly automated.
The main goal of this thesis is to explore the performance of the oculomotor system under various reading conditions where orthographic information and the reading direction were manipulated. Additionally, the challenges in understanding the eye movement data to represent the oculomotor process during reading are addressed.
Two experimental studies and one simulation study were conducted for this thesis, which resulted in the following main findings:
(i) Reading texts with orthographic manipulations leads to specific changes in the eye movement patterns, both in temporal and spatial measures. The findings indicate that the oculomotor control of eye movements during reading is dependent on reading conditions (Chapter 2 & 3).
(ii) Saccades’ accuracy and precision can be simultaneously modulated under reversed reading condition, supporting the assumption that the random and systematic oculomotor errors are not independent. By assuming that readers increase the precision of sensory observation while maintaining the learned prior knowledge when reading direction was reversed, a process-oriented Bayesian model for saccade targeting can account for the simultaneous reduction of oculomotor errors (Chapter 2).
(iii) Plausible parameter values serving as proxies for the intended within-word landing positions can be estimated by using the maximum a posteriori estimator from Bayesian inference. Using the mean value of all observations as proxies is insufficient for studies focusing on the launch-site effect because the method exhibits the strongest bias when estimating the size of the effect. Mislocated fixations remain a challenge for the currently known estimation methods, especially when the systematic oculomotor error is large (Chapter 4).
The results reported in this thesis highlight the role of the oculomotor system, together with underlying cognitive processes, in eye movements during reading. The modulation of oculomotor control can be captured through a precise analysis of landing positions.
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.
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.
Bacteria are one of the most widespread kinds of microorganisms that play essential roles in many biological and ecological processes. Bacteria live either as independent individuals or in organized communities. At the level of single cells, interactions between bacteria, their neighbors, and the surrounding physical and chemical environment are the foundations of microbial processes. Modern microscopy imaging techniques provide attractive and promising means to study the impact of these interactions on the dynamics of bacteria. The aim of this dissertation is to deepen our understanding four fundamental bacterial processes – single-cell motility, chemotaxis, bacterial interactions with environmental constraints, and their communication with neighbors – through a live cell imaging technique. By exploring these processes, we expanded our knowledge on so far unexplained mechanisms of bacterial interactions.
Firstly, we studied the motility of the soil bacterium Pseudomonas putida (P. putida), which swims through flagella propulsion, and has a complex, multi-mode swimming tactic. It was recently reported that P. putida exhibits several distinct swimming modes – the flagella can push and pull the cell body or wrap around it. Using a new combined phase-contrast and fluorescence imaging set-up, the swimming mode (push, pull, or wrapped) of each run phase was automatically recorded, which provided the full swimming statistics of the multi-mode swimmer. Furthermore, the investigation of cell interactions with a solid boundary illustrated an asymmetry for the different swimming modes; in contrast to the push and pull modes, the curvature of runs in wrapped mode was not affected by the solid boundary. This finding suggested that having a multi-mode swimming strategy may provide further versatility to react to environmental constraints.
Then we determined how P. putida navigates toward chemoattractants, i.e. its chemotaxis strategies. We found that individual run modes show distinct chemotactic responses in nutrition gradients. In particular, P. putida cells exhibited an asymmetry in their chemotactic responsiveness; the wrapped mode (slow swimming mode) was affected by the chemoattractant, whereas the push mode (fast swimming mode) was not. These results can be seen as a starting point to understand more complex chemotaxis strategies of multi-mode swimmers going beyond the well-known paradigm of Escherichia coli, that exhibits only one swimming mode.
Finally we considered the cell dynamics in a dense population. Besides physical interactions with their neighbors, cells communicate their activities and orchestrate their population behaviors via quorum-sensing. Molecules that are secreted to the surrounding by the bacterial cells, act as signals and regulate the cell population behaviour. We studied P. putida’s motility in a dense population by exposing the cells to environments with different concentrations of chemical signals. We found that higher amounts of chemical signals in the surrounding influenced the single-cell behaviourr, suggesting that cell-cell communications may also affect the flagellar dynamics.
In summary, this dissertation studies the dynamics of a bacterium with a multi-mode swimming tactic and how it is affected by the surrounding environment using microscopy imaging. The detailed description of the bacterial motility in fundamental bacterial processes can provide new insights into the ecology of microorganisms.
The PhD thesis entitled “Actions through the lens of communicative cues. The influence of verbal cues and emotional cues on action processing and action selection in the second year of life” is based on four studies, which examined the cognitive integration of another person’s communicative cues (i.e., verbal cues, emotional cues) with behavioral cues in 18- and 24-month-olds. In the context of social learning of instrumental actions, it was investigated how the intention-related coherence of either a verbally announced action intention or an emotionally signaled action evaluation with an action demonstration influenced infants’ neuro-cognitive processing (Study I) and selection (Studies II, III, IV) of a novel object-directed action. Developmental research has shown that infants benefit from another’s behavioral cues (e.g., action effect, persistency, selectivity) to infer the underlying goal or intention, respectively, of an observed action (e.g., Cannon & Woodward, 2012; Woodward, 1998). Particularly action effects support infants in distinguishing perceptual action features (e.g., target object identity, movement trajectory, final target object state) from conceptual action features such as goals and intentions. However, less is known about infants’ ability to cognitively integrate another’s behavioral cues with additional action-related communicative cues. There is some evidence showing that in the second year of life, infants selectively imitate a novel action that is verbally (“There!”) or emotionally (positive expression) marked as aligning with the model’s action intention over an action that is verbally (“Whoops!”) or emotionally (negative expression) marked as unintentional (Carpenter, Akhtar, & Tomasello, 1998; Olineck & Poulin-Dubois, 2005, 2009; Repacholi, 2009; Repacholi, Meltzoff, Toub, & Ruba, 2016). Yet, it is currently unclear which role the specific intention-related coherence of a communicative cue with a behavioral cue plays in infants’ action processing and action selection that is, whether the communicative cue confirms, contrasts, clarifies, or is unrelated to the behavioral cue. Notably, by using both verbal cues and emotional cues, we examined not only two domains of communicative cues but also two qualitatively distinct relations between behavioral cues on the one hand and communicative cues on the other hand. More specifically, a verbal cue has the potential to communicate an action intention in the absence of an action demonstration and thus a prior-intention (Searle, 1983), whereas an emotional cue evaluates an ongoing or past action demonstration and thus signals an intention-in-action (Searle, 1983). In a first research focus, this thesis examined infants’ capacity to cognitively integrate another’s intention-related communicative cues and behavioral cues, and also focused on the role of the social cues’ coherence in infants’ action processing and action selection. In a second research focus, and to gain more elaborate insights into how the sub-processes of social learning (attention, encoding, response; cf. Bandura, 1977) are involved in this coherence-sensitive integrative processing, we employed a multi-measures approach. More specifically, we used Electroencephalography (EEG) and looking times to examine how the cues’ coherence influenced the compound of attention and encoding, and imitation (including latencies to first-touch and first-action) to address the compound of encoding and response. Based on the action-reconstruction account (Csibra, 2007), we predicted that infants use extra-motor information (i.e., communicative cues) together with behavioral cues to reconstruct another’s action intention. Accordingly, we expected infants to possess a flexibly organized internal action hierarchy, which they adapt according to the cues’ coherence that is, according to what they inferred to be the overarching action goal. More specifically, in a social-learning situation that comprised an adult model, who demonstrated an action on a novel object that offered two actions, we expected the demonstrated action to lead infants’ action hierarchy when the communicative (i.e., verbal, emotional) cue conveyed similar (confirming coherence) or no additional (un-related coherence) intention-related information relative to the behavioral cue. In terms of action selection, this action hierarchy should become evident in a selective imitation of the demonstrated action. However, when the communicative cue questioned (contrasting coherence) the behaviorally implied action goal or was the only cue conveying meaningful intention-related information (clarifying coherence), the verbally/emotionally intended action should ascend infants’ action hierarchy. Consequently, infants’ action selection should align with the verbally/emotionally intended action (goal emulation). Notably, these predictions oppose the direct-matching perspective (Rizzolatti & Craighero, 2004), according to which the observation of another’s action directly resonates with the observer’s motor repertoire, with this motor resonance enabling the identification of the underlying action goal. Importantly, the direct-matching perspective predicts a rather inflexible action hierarchy inasmuch as the process of goal identification should solely rely on the behavioral cue, irrespective of the behavioral cue’s coherence with extra-motor intention-related information, as it may be conveyed via communicative cues. As to the role of verbal cues, Study I used EEG to examine the influence of a confirming (Congruent) versus contrasting (Incongruent) coherence of a verbal action intention with the same action demonstration on 18-month-olds’ conceptual action processing (as measured via mid-latency mean negative ERP amplitude) and motor activation (as measured via central mu-frequency band power). The action was demonstrated on a novel object that offered two action alternatives from a neutral position. We expected mid-latency ERP negativity to be enhanced in Incongruent compared to Congruent, because past EEG research has demonstrated enhanced conceptual processing for stimuli that mismatched rather than matched the semantic context (Friedrich & Friederici, 2010; Kaduk et al., 2016). Regarding motor activation, Csibra (2007) posited that the identification of a clear action goal constitutes a crucial basis for motor activation to occur. We therefore predicted reduced mu power (indicating enhanced motor activation) for Congruent than Incongruent, because in Congruent, the cues’ match provides unequivocal information about the model’s action goal, whereas in Incongruent, the conflict may render the model’s action goal more unclear. Unexpectedly, in the entire sample, 18-month-olds’ mid-latency ERP negativity during the observation of the same action demonstration did not differ significantly depending on whether this action was congruent or incongruent with the model’s verbal action intention. Yet, post hoc analyses revealed the presence of two subgroups of infants, each of which exhibited significantly different mid-latency ERP negativity for Congruent versus Incongruent, but in opposing directions. The subgroups differed in their productive action-related language skills, with the linguistically more advanced infants exhibiting the expected response pattern of enhanced ERP mean negativity in Incongruent than Congruent, indicating enhanced conceptual processing of an action demonstration that was contrasted rather than confirmed by the verbal action context. As expected, central mu power in the entire sample was reduced in Congruent relative to Incongruent, indicating enhanced motor activation when the action demonstration was preceded by a confirming relative to a contrasting verbal action intention. This finding may indicate the covert preparation for a preferential imitation of the congruent relative to the incongruent action (Filippi et al., 2016; Frey & Gerry, 2006). Overall, these findings are in line with the action-reconstruction account (Csibra, 2007), because they suggest a coherence-sensitive attention to and encoding of the same perceptual features of another’s behavior and thus a cognitive integration of intention-related verbal cues and behavioral cues. Yet, because the subgroup constellation in infants’ ERPs was only discovered post hoc, future research is clearly required to substantiate this finding. Also, future research should validate our interpretation that enhanced motor activation may reflect an electrophysiological marker of subsequent imitation by employing EEG and imitation in a within-subjects design. Study II built on Study I by investigating the impact of coherence of a verbal cue and a behavioral cue on 18- and 24-month-olds’ action selection in an imitation study. When infants of both age groups observed a confirming (Congruent) or unrelated (Pseudo-word: action demonstration was associated with novel verb-like cue) coherence, they selectively imitated the demonstrated action over the not demonstrated, alternative action, with no difference between these two conditions. These findings suggest that, as expected, infants’ action hierarchy was led by the demonstrated action when the verbal cue provided similar (Congruent) or no additional (Pseudo-word) intention-related information relative to a meaningful behavioral cue. These findings support the above-mentioned interpretation that enhanced motor activation during action observation may reflect a covert preparation for imitation (Study I). Interestingly, infants did not seem to benefit from the intention-highlighting effect of the verbal cue in Congruent, suggesting that the verbal cue had an unspecific (e.g., attention-guiding) effect on infants’ action selection. Contrary, when infants observed a contrasting (Incongruent) or clarifying (Failed-attempt: model failed to manipulate the object but verbally announced a certain action intention) coherence, their action selection varied with age and also varied across the course of the experiment (block 1 vs. block 2). More specifically, the 24-month-olds made stronger use of the verbal cue for their action selection in block 1 than did the 18-month-olds. However, while the 18-month-olds’ use of the verbal cue increased across blocks, particularly in Incongruent, the 24-month-olds’ use of the verbal cue decreased across blocks. Overall, these results suggest that, as expected, infants’ action hierarchy in Incongruent (both age groups) and Failed-attempt (only 24-month-olds) drew on the verbal action intention, because in both age groups, infants emulated the verbal intention about as often as they imitated the demonstrated action or even emulated the verbal action intention preferentially. Yet, these findings were confined to certain blocks. It may be argued that the younger age group had a harder time inferring and emulating the intended, yet never observed action, because this requirement is more demanding in cognitive and motor terms. These demands may explain why the 18-month-olds needed some time to take account of the verbal action intention. Contrary, it seems that the 24-month-olds, although demonstrating their principle capacity to take account of the verbal cue in block 1, lost trust in the model’s verbal cue, maybe because the verbal cue did not have predictive value for the model’s actual behavior. Supporting this interpretation, research on selective trust has demonstrated that already infants evaluate another’s reliability or competence, respectively, based on how that model handles familiar objects (behavioral reliability) or labels familiar objects (verbal reliability; for reviews, see Mills, 2013; Poulin-Dubois & Brosseau-Liard, 2016). Relatedly, imitation research has demonstrated that the interpersonal aspects of a social-learning situation gain increasing relevance for infants during the second year of life (Gellén & Buttelmann, 2019; Matheson, Moore, & Akhtar, 2013; Uzgiris, 1981). It may thus be argued that when the 24-month-olds were repeatedly faced with a verbally unreliable model, they de-evaluated the verbal cue as signaling the model’s action intention and instead relied more heavily on alternative cues such as the behavioral cue (Incongruent) or the action context (e.g., object affordances, salience; Failed-attempt). Infants’ first-action latencies were higher in Incongruent and Failed-attempt than in both Congruent and Pseudo-word, and were also higher in Failed-attempt than in Incongruent. These latency-findings thus indicate that situations involving a meaningful verbal cue that deviated from the behavioral cue are cognitively more demanding, resulting in a delayed initiation of a behavioral response. In sum, the findings of Study II suggest that both age groups were highly flexible in their integration of a verbal cue and behavioral cue. Moreover, our results do not indicate a general superiority of either cue. Instead, it seems to depend on the informational gain conveyed by the verbal cue whether it exerts a specific, intention-highlighting effect (Incongruent, Failed-attempt) or an unspecific (e.g., attention-guiding) effect (Congruent, Pseudo-word). Studies III and IV investigated the impact of another’s action-related emotional cues on 18-month-olds’ action selection. In Study III, infants observed a model, who demonstrated two actions on a novel object in direct succession, and who combined one of the two actions with a positive (happy) emotional expression and the other action with a negative (sad) emotional expression. As expected, infants imitated the positively emoted (PE) action more often than the negatively emoted (NE) action. This preference arose from an increase in infants’ readiness to perform the PE action from the baseline period (prior to the action demonstrations) to the test period (following the action demonstrations), rather than from a decrease in readiness to the perform the NE action. The positive cue thus had a stronger behavior-regulating effect than the negative cue. Notably, infants’ more general object-directed behavior in terms of first-touch latencies remained unaffected by the emotional cues’ valence, indicating that infants had linked the emotional cues specifically to the corresponding action and not the object as a whole (Repacholi, 2009). Also, infants’ looking times during the action demonstration did not differ significantly as a function of emotional valence and were characterized by a predominant attentional focus to the action/object rather than to the model’s face. Together with the findings on infants’ first-touch latencies, these results indicate a sensitivity for the notion that emotions can have very specific referents (referential specificity; Martin, Maza, McGrath, & Phelps, 2014). Together, Study III provided evidence for selective imitation based on another’s intention-related (particularly positive) emotional cues in an action-selection task, and thus indicates that infants’ action hierarchy flexibly responds to another’s emotional evaluation of observed actions. According to Repacholi (2009), we suggest that infants used the model’s emotional evaluation to re-appraise the corresponding action (effect), for instance in terms of desirability. Study IV followed up on Study III by investigating the role of the negative emotional cue for infants’ action selection in more detail. Specifically, we investigated whether a contrasting (negative) emotional cue alone would be sufficient to differentially rank the two actions along infants’ action hierarchy or whether instead infants require direct information about the model’s action intention (in the form of a confirming action-emotion pair) to align their action selection with the emotional cues. Also, we examined whether the absence of a direct behavior-regulating effect of the negative cue in Study III was due to the negative cue itself or to the concurrently available positive cue masking the negative cue’s potential effect. To this end, we split the demonstration of the two action-emotion pairs across two trials. In each trial, one action was thus demonstrated and emoted (PE, NE action), and one action was not demonstrated and un-emoted (UE action). For trial 1, we predicted that infants, who observed a PE action demonstration, would selectively imitate the PE action, whereas infants, who observed a NE action demonstration would selectively emulate the UE action. As to trial 2, we expected the complementary action-emotion pair to provide additional clarifying information as the model’s emotional evaluation of both actions, which should either lead to adaptive perseveration (if infants’ action selection in trial 1 had already drawn on the emotional cue) or adaptive change (if infants’ action selection in trial 1 signaled a disregard of the emotional cue). As to trial 1, our findings revealed that, as expected, infants imitated the PE action more often than they emulated the UE action. Like in Study III, this selectivity arose from an increase in infants’ propensity to perform the PE action from baseline to trial 1. Also like in Study III, infants performed the NE action about equally often in baseline and trial 1, which speaks against a direct behavior-regulating effect of the negative cue also when presented in isolation. However, after a NE action demonstration, infants emulated the UE action more often in trial 1 than in baseline, suggesting an indirect behavior-regulating effect of the negative cue. Yet, this indirect effect did not yield a selective emulation of the UE action, because infants performed both action alternatives about equally often in trial 1. Unexpectedly, infants’ action selection in trial 2 was unaffected by the emotional cue. Instead, infants perseverated their action selection of trial 1 in trial 2, irrespective of whether it was adaptive or non-adaptive with respect to the model’s emotional evaluation of the action. It seems that infants changed their strategy across trials, from an initial adherence to the emotional (particularly positive) cue, towards bringing about a salient action effect (Marcovich & Zelazo, 2009). In sum, Studies III and IV indicate a dynamic interplay of different action-selection strategies, depending on valence and presentation order. Apparently, at least in infancy, action reconstruction as one basis for selective action performance reaches its limits when infants can only draw on indirect intention-related information (i.e., which action should be avoided). Overall, our findings favor the action-reconstruction account (Csibra, 2007), according to which actions are flexibly organized along a hierarchy, depending on inferential processes based on extra-motor intention-related information. At the same time, the findings question the direct-matching hypothesis (Rizzolatti & Craighero, 2004), according to which the identification (and pursuit) of action goals hinges on a direct simulation of another’s behavioral cues. Based on the studies’ findings, a preliminary working model is introduced, which seeks to integrate the two theoretical accounts by conceptualizing the routes that activation induced by social cues may take to eventually influence an infant’s action selection. Our findings indicate that it is useful to strive a differentiated conceptualization of communicative cues, because they seem to operate at different places within the process of cue integration, depending on their potential to convey direct intention-related information. Moreover, we suggest that there is bidirectional exchange within each compound of adjacent sub-processes (i.e., between attention and encoding, and encoding and response), and between the compounds. Hence, our findings highlight the benefits of a multi-measures approach when studying the development of infants’ social-cognitive abilities, because it provides a more comprehensive picture how the concerted use of social cues from different domains influences infants’ processing and selection of instrumental actions. Finally, this thesis points to potential future directions to substantiate our current interpretation of the findings.. Moreover, an extension to additional kinds of coherence is suggested to get closer to infants’ everyday-world of experience.
Lately, the integration of upconverting nanoparticles (UCNP) in industrial, biomedical and scientific applications has been increasingly accelerating, owing to the exceptional photophysical properties that UCNP offer. Some of the most promising applications lie in the field of medicine and bioimaging due to such advantages as, among others, deeper tissue penetration, reduced optical background, possibility for multicolor imaging, and lower toxicity, compared to many known luminophores. However, some questions regarding not only the fundamental photophysical processes, but also the interaction of the UCNP with other luminescent reporters frequently used for bioimaging and the interaction with biological media remain unanswered. These issues were the primary motivation for the presented work.
This PhD thesis investigated several aspects of various properties and possibilities for bioapplications of Yb3+,Tm3+-doped NaYF4 upconverting nanoparticles. First, the effect of Gd3+ doping on the structure and upconverting behaviour of the nanocrystals was assessed. The ageing process of the UCNP in cyclohexane was studied over 24 months on the samples with different Gd3+ doping concentrations. Structural information was gathered by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS), and discussed in relation to spectroscopic results, obtained through multiparameter upconversion luminescence studies at various temperatures (from 4 K to 295 K). Time-resolved and steady-state emission spectra recorded over this ample temperature range allowed for a deeper understanding of photophysical processes and their dependence on structural changes of UCNP.
A new protocol using a commercially available high boiling solvent allowed for faster and more controlled production of very small and homogeneous UCNP with better photophysical properties, and the advantages of a passivating NaYF4 shell were shown.
Förster resonance energy transfer (FRET) between four different species of NaYF4: Yb3+, Tm3+ UCNP (synthesized using the improved protocol) and a small organic dye was studied. The influence of UCNP composition and the proximity of Tm3+ ions (donors in the process of FRET) to acceptor dye molecules have been assessed. The brightest upconversion luminescence was observed in the UCNP with a protective inert shell. UCNP with Tm3+ ions only in the shell were the least bright, but showed the most efficient energy transfer.
In the final part, two surface modification strategies were applied to make UCNP soluble in water, which simultaneously allowed for linking them via a non-toxic copper-free click reaction to the liposomes, which served as models for further cell experiments. The results were assessed on a confocal microscope system, which was made possible by lesser known downshifting properties of Yb3+, Tm3+-doped UCNP. Preliminary antibody-staining tests using two primary and one dye-labelled secondary antibodies were performed on MDCK-II cells.
Hybrid organic-inorganic perovskites have attracted attention in recent years, caused by the incomparable increase in efficiency in energy convergence, which implies the application as an absorber material for solar cells. A disadvantage of these materials is, among others, the instability to moisture and UV-radiation. One possible solution for these problems is the reduction of the size towards the nano world. With that nanosized perovskites are showing superior stability in comparison to e.g. perovskite layers. Additionally to this the nanosize even enables stable perovskite structures, which could not be achieved otherwise at
room temperature.
This thesis is separated into two major parts. The separation is done by the composition and the band gap of the material and at the same time the shape and size of the nanoparticles. Here the division is made by the methylammonium lead tribromide nanoplatelets and the caesium lead triiodide nanocubes.
The first part is focusing on the hybrid organic-inorganic perovskite (methylammonium lead tribromide) nanoplatelets with a band gap of 2.35 eV and their thermal behaviour. Due to the challenging character of this material, several analysis methods are used to investigate the sub nano and nanostructures under the influence of temperature. As a result, a shift of phase-transition temperatures towards higher temperatures is observed. This unusual behaviour can be explained by the ligand, which is incorporated in the perovskite outer structure and adds phase-stability into the system.
The second part of this thesis is focusing on the inorganic caesium lead triiodide nanocubes with a band gap of 1.83 eV. These nanocrystals are first investigated and compared by TEM, XRD and other optical methods. Within these methods, a cuboid and orthorhombic structure are revealed instead of the in literature described cubic shape and structure. Furthermore, these cuboids are investigated towards their self-assembly on a substrate. Here a high degree in self-assembly is shown. As a next step, the ligands of the nanocuboids are exchanged against other ligands to increase the charge carrier mobility. This is further investigated by the above-mentioned methods. The last section is dealing with the enhancement of the CsPbI3 structure, by incorporating potassium in the crystal structure. The results are suggesting here an increase in stability.
The Cheb Basin (CZ) is a shallow Neogene intracontinental basin located in the western Eger Rift. The Cheb Basin is characterized by active seismicity and diffuse degassing of mantle-derived CO2 in mofette fields. Within the Cheb Basin, the Hartoušov mofette field shows a daily CO2 flux of 23–97 tons. More than 99% of CO2 released over an area of 0.35 km2. Seismic active periods have been observed in 2000 and 2014 in the Hartoušov mofette field. Due to the active geodynamic processes, the Cheb Basin is considered to be an ideal region for the continental deep biosphere research focussing on the interaction of biological processes with geological processes.
To study the influence of CO2 degassing on microbial community in the surface and subsurface environments, two 3-m shallow drillings and a 108.5-m deep scientific drilling were conducted in 2015 and 2016 respectively. Additionally, the fluid retrieved from the deep drilling borehole was also recovered. The different ecosystems were compared regarding their geochemical properties, microbial abundances, and microbial community structures. The geochemistry of the mofette is characterized by low pH, high TOC, and sulfate contents while the subsurface environment shows a neutral pH, and various TOC and sulfate contents in different lithological settings. Striking differences in the microbial community highlight the substantial impact of elevated CO2 concentrations and high saline groundwater on microbial processes. In general, the microorganisms had low abundance in the deep subsurface sediment compared with the shallow mofette. However, within the mofette and the deep subsurface sediment, the abundance of microbes does not show a typical decrease with depth, indicating that the uprising CO2-rich groundwater has a strong influence on the microbial communities via providing sufficient substrate for anaerobic chemolithoautotrophic microorganisms. Illumina MiSeq sequencing of the 16S rRNA genes and multivariate statistics reveals that the pH strongly influences the microbial community composition in the mofette, while the subsurface microbial community is significantly influenced by the groundwater which motivated by the degassing CO2. Acidophilic microorganisms show a much higher relative abundance in the mofette. Meanwhile, the OTUs assigned to family Comamonadaceae are the dominant taxa which characterize the subsurface communities. Additionally, taxa involved in sulfur cycling characterizing the microbial communities in both mofette and CO2 dominated subsurface environments.
Another investigated important geo–bio interaction is the influence of the seismic activity. During seismic events, released H2 may serve as the electron donor for microbial hydrogenotrophic processes, such as methanogenesis. To determine whether the seismic events can potentially trigger methanogenesis by the elevated geogenic H2 concentration, we performed laboratory simulation experiments with sediments retrieved from the drillings. The simulation results indicate that after the addition of hydrogen, substantial amounts of methane were produced in incubated mofette sediments and deep subsurface sediments. The methanogenic hydrogenotrophic genera Methanobacterium was highly enriched during the incubation. The modeling of the in-situ observation of the earthquake swarm period in 2000 at the Novy Kostel focal area/Czech Republic and our laboratory simulation experiments reveals a close relation between seismic activities and microbial methane production via earthquake-induced H2 release. We thus conclude that H2 – which is released during seismic activity – can potentially trigger methanogenic activity in the deep subsurface. Based on this conclusion, we further hypothesize that the hydrogenotrophic early life on Earth was boosted by the Late Heavy Bombardment induced seismic activity in approximately 4.2 to 3.8 Ga.
"How Wenzel and Cassie were wrong" – this was the eye-catching title of an article published by Lichao Gao and Thomas McCarthy in 2007, in which fundamental interpretations of wetting behavior were put into question. The authors initiated a discussion on a subject, which had been generally accepted a long time ago and they showed that wetting phenomena were not as fully understood as imagined. Similarly, this thesis tries to put a focus on certain aspects of liquid wetting, which so far have been widely neglected in terms of interpretation and experimental proof. While the effect of surface roughness on the macroscopically observed wetting behavior is commonly and reliably interpreted according to the well-known models of Wenzel and Cassie/Baxter, the size-scale of the structures responsible for the surface's rough texture has not been of further interest. Analogously, the limits of these models have not been described and exploited. Thus, the question arises, what will happen when the size of surface structures is reduced to the size of the contacting liquid molecules itself? Are common methods still valid or can deviations from macroscopic behavior be observed?
This thesis wants to create a starting point regarding these questions. In order to investigate the effect of smallest-scale surface structures on liquid wetting, a suitable model system is developed by means of self-assembled monolayer (SAM) formation from (fluoro)organic thiols of differing lengths of the alkyl chain. Surface topographies are created which rely on size differences of several Ångströms and exhibit surprising wetting behavior depending on the choice of the individual precursor system. Thus, contact angles are experimentally detected, which deviate considerably from theoretical calculations based on Wenzel and Cassie/Baxter models and confirm that sub-nm surface topographies affect wetting. Moreover, experimentally determined wetting properties are found to correlate well to an assumed scale-dependent surface tension of the contacting liquid. This behavior has already been described for scattering experiments taking into account capillary waves on the liquid surface induced by temperature and had been predicted earlier by theoretical calculations.
However, the investigation of model surfaces requires the provision of suitable precursor molecules, which are not commercially available and opens up a door to the exotic chemistry of fluoro-organic materials. During the course of this work, the synthesis of long-chain precursors is examined with a particular focus put on oligomerically pure semi-fluorinated n-alkyl thiols and n-alkyl trichlorosilanes. For this, general protocols for the syntheses of the desired compounds are developed and product mixtures are assayed to be separated into fractions of individual chain lengths by fluorous-phase high-performance liquid chromatography (F-HPLC).
The transition from model systems to technically more relevant surfaces and applications is initiated through the deposition of SAMs from long-chain fluorinated n-alkyl trichlorosilanes. Depositions are accomplished by a vapor-phase deposition process conducted on a pilot-scale set-up, which enables the exact control of relevant process parameters. Thus, the influence of varying deposition conditions on the properties of the final coating is examined and analyzed for the most important parameters. The strongest effect is observed for the partial pressure of reactive water vapor, which directly controls the extent of precursor hydrolysis during the deposition process. Experimental results propose that the formation of ordered monolayers rely on the amount of hydrolyzed silanol species present in the deposition system irrespective of the exact grade of hydrolysis. However, at increased amounts of species which are able to form cross-linked molecules due to condensation reactions, films deteriorate in quality. This effect is assumed to be caused by the introduction of defects within the film and the adsorption of cross linked agglomerates. Deposition conditions are also investigated for chain extended precursor species and reveal distinct differences caused by chain elongation.