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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.