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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.
Hybrid organic-inorganic perovskites have attracted attention in recent years, caused by the incomparable increase in efficiency in energy convergence, which implies the application as an absorber material for solar cells. A disadvantage of these materials is, among others, the instability to moisture and UV-radiation. One possible solution for these problems is the reduction of the size towards the nano world. With that nanosized perovskites are showing superior stability in comparison to e.g. perovskite layers. Additionally to this the nanosize even enables stable perovskite structures, which could not be achieved otherwise at
room temperature.
This thesis is separated into two major parts. The separation is done by the composition and the band gap of the material and at the same time the shape and size of the nanoparticles. Here the division is made by the methylammonium lead tribromide nanoplatelets and the caesium lead triiodide nanocubes.
The first part is focusing on the hybrid organic-inorganic perovskite (methylammonium lead tribromide) nanoplatelets with a band gap of 2.35 eV and their thermal behaviour. Due to the challenging character of this material, several analysis methods are used to investigate the sub nano and nanostructures under the influence of temperature. As a result, a shift of phase-transition temperatures towards higher temperatures is observed. This unusual behaviour can be explained by the ligand, which is incorporated in the perovskite outer structure and adds phase-stability into the system.
The second part of this thesis is focusing on the inorganic caesium lead triiodide nanocubes with a band gap of 1.83 eV. These nanocrystals are first investigated and compared by TEM, XRD and other optical methods. Within these methods, a cuboid and orthorhombic structure are revealed instead of the in literature described cubic shape and structure. Furthermore, these cuboids are investigated towards their self-assembly on a substrate. Here a high degree in self-assembly is shown. As a next step, the ligands of the nanocuboids are exchanged against other ligands to increase the charge carrier mobility. This is further investigated by the above-mentioned methods. The last section is dealing with the enhancement of the CsPbI3 structure, by incorporating potassium in the crystal structure. The results are suggesting here an increase in stability.
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.
Die vorliegende Arbeit widmet sich subjektiven Kompetenzeinschätzungen Lehramtsstudierender in einem zentralen Element des Lehramtsstudiums – den schulischen Praxisphasen. Dabei stehen Selbstwirksamkeitserwartungen als bedeutender Aspekt professioneller Kompetenz sowie deren Bedeutung für das Beraten im schulischen Bereich und für den Umgang mit Beanspruchungsfolgen im Mittelpunkt der Arbeit.
Im ersten Abschnitt werden Ansätze zur Professionsforschung im Lehrberuf sowie das Modell der professionellen Kompetenz dargestellt (Baumert & Kunter, 2011). Zudem werden individuelle Eingangsvoraussetzungen Lehramtsstudierender wie Persönlichkeitsmerkmale und pädagogische Vorerfahrungen als bedeutende Determinanten für den Erwerb professioneller Kompetenz betrachtet (Kunter, Kleickmann, Klusmann & Richter, 2011). Anschließend werden Lerngelegenheiten und zentrale Zielstellungen spezifiziert, die für schulische Praxisphasen kennzeichnend sind (König & Rothland, 2018). Dabei steht das Praxissemester als bedeutende Phase der Schulpraktischen Studien im Mittelpunkt der Betrachtung. Zudem werden spezifische Herausforderungen gekennzeichnet, die mit schulischen Praxisphasen verbunden sind sowie damit in Zusammenhang stehende Belastungen und Beanspruchungsfolgen (z.B. Keller-Schneider 2016b). Anschließend wird die empirische Befundlage zu negativen Beanspruchungsfolgen in schulischen Praxisphasen dargelegt und es wird auf essentielle Ressourcen im Umgang mit emotionaler Erschöpfung und reduzierter Leistungsfähigkeit eingegangen (z.B. Rothland & Klusmann, 2016). Zum einen wird die Bedeutsamkeit sozialer Unterstützung durch Mentoring als zentrale umgebungsbezogene Ressource spezifiziert, zum anderen werden Selbstwirksamkeitserwartungen als bedeutende personengebundene Ressource betrachtet. Danach wird auf den hochrelevanten Kompetenzaspekt Beraten eingegangen. Dabei werden spezifische Fähigkeiten betrachtet, die essentiell für die schulische Beratungsarbeit sind sowie besondere Merkmale, Formen und Beratungsanlässe. Zudem werden Möglichkeiten zur Erfassung von Beratungskompetenz aufgezeigt sowie damit verbundene Forschungsdesiderate. Abschließend wird der Blick auf die Förderung von Beratungskompetenz im Lehramtsstudium gerichtet. Am Ende des Theoriekapitels werden die Forschungsfragen systematisiert, die sich aus der dargestellten Befundlage ergeben sowie damit in Verbindung stehende Forschungsdesiderate.
Studie 1 widmet sich der Fragestellung inwieweit Selbstwirksamkeitserwartungen und soziale Unterstützung durch Mentoring bedeutend sind für den Umgang mit negativen Beanspruchungsfolgen von Burnout wie emotionaler Erschöpfung und verminderter Leistungsfähigkeit. Zudem wird untersucht, inwieweit Mentoring den Effekt von Selbstwirksamkeitserwartungen auf die benannten Burnout-Dimensionen moderiert. In der längsschnittlichen Studie konnte anhand der Daten von 192 Lehramtsstudierenden im Praxissemester gezeigt werden, dass hohe Selbstwirksamkeitserwartungen zu Beginn des Praxissemesters mit geringerer emotionaler Erschöpfung als auch mit höherer Leistungsfähigkeit zum Ende des Praxissemesters einhergehen. Zudem konnte gezeigt werden, dass der Effekt von Selbstwirksamkeitserwartungen auf Leistungsfähigkeit durch Mentoring moderiert wird. Zur Auswertung der Daten wurden multiple Regressionsanalysen berechnet.
Studie 2 widmet sich der Entwicklung und Validierung einer Skala zur Erfassung der Beratungskompetenz, die bereits im Rahmen des Lehramtsstudiums eingesetzt werden kann. In Faktorenanalysen konnte mithilfe der Daten von 200 Lehramtsstudierenden gezeigt werden, dass sich Beratungskompetenz anhand von vier Subskalen beschreiben lässt. Die Skalen wurden als Personale Ressourcen, Kooperation- und Perspektivenübernahme, Berater-Skills sowie Ressourcen- und Lösungsorientierung bezeichnet und erwiesen sich hinsichtlich der internen Konsistenz insgesamt als akzeptabel. Für die einzelnen Subskalen ergaben sich zudem schwache bis mittlere Zusammenhänge mit den Validierungsvariablen Selbstwirksamkeit in Beratungen, der Beratungsmotivation sowie Pädagogische Vorerfahrungen.
Studie 3 ging der Frage nach, inwieweit zentrale individuelle Eingangsvoraussetzungen von Lehramtsstudierenden wie Persönlichkeitsmerkmale und pädagogische Vorerfahrungen bedeutend sind für Selbstwirksamkeitserwartungen in Schüler-Beratungen. Ebenfalls basierend auf Fragebogendaten von 200 Praxissemesterstudierenden konnte anhand multipler Regressionsanalysen gezeigt werden, dass hohe Offenheit für neue Erfahrungen und geringer Neurotizismus mit hohen Selbstwirksamkeitserwartungen einhergehen. Zudem stehen pädagogische Vorerfahrungen in positivem und signifikantem Zusammenhang mit Selbstwirksamkeitserwartungen. Die Studie widmet sich abschließend insbesondere der Förderung von Beratungskompetenz im Lehramtsstudium.
In Studie 4 wird ein Seminarbaustein präsentiert, mithilfe dessen Beratungskompetenz im Lehramtsstudium gefördert werden kann. Mit dem Konzept können sämtliche Aspekte professioneller Kompetenz im Bereich Beraten sowohl theoretisch vermittelt als auch praktisch erprobt werden. Die Rückmeldungen von Lehramtsstudierenden, die den Seminarbaustein erprobt haben, geben erste Hinweise darauf, dass Fähigkeiten im Bereich schulischer Beratungen gefördert werden können.
Die vorliegende Arbeit wird durch die Gesamtdiskussion der Ergebnisse beendet und es werden Grenzen der Arbeit, Anschlussfragen und pädagogischen Implikationen besprochen.
Interactions involving biological interfaces such as lipid-based membranes are of paramount importance for all life processes. The same also applies to artificial interfaces to which biological matter is exposed, for example the surfaces of drug delivery systems or implants. This thesis deals with the two main types of interface interactions, namely (i) interactions between a single interface and the molecular components of the surrounding aqueous medium and (ii) interactions between two interfaces. Each type is investigated with regard to an important scientific problem in the fields of biotechnology and biology:
1.) The adsorption of proteins to surfaces functionalized with hydrophilic polymer brushes; a process of great biomedical relevance in context with harmful foreign-body-response to implants and drug delivery systems.
2.) The influence of glycolipids on the interaction between lipid membranes; a hitherto largely unexplored phenomenon with potentially great biological relevance.
Both problems are addressed with the help of (quasi-)planar, lipid-based model surfaces in combination with x-ray and neutron scattering techniques which yield detailed structural insights into the interaction processes. Regarding the adsorption of proteins to brush-functionalized surfaces, the first scenario considered is the exposure of the surfaces to human blood serum containing a multitude of protein species. Significant blood protein adsorption was observed despite the functionalization, which is commonly believed to act as a protein repellent. The adsorption consists of two distinct modes, namely strong adsorption to the brush grafting surface and weak adsorption to the brush itself. The second aspect investigated was the fate of the brush-functionalized surfaces when exposed to aqueous media containing immune proteins (antibodies) against the brush polymer, an emerging problem in current biomedical applications. To this end, it was found that antibody binding cannot be prevented by variation of the brush grafting density or the polymer length. This result motivates the search for alternative, strictly non-antigenic brush chemistries. With respect to the influence of glycolipids on the interaction between lipid membranes, this thesis focused on the glycolipids’ ability to crosslink and thereby to tightly attract adjacent membranes. This adherence is due to preferential saccharide-saccharide interactions occurring among the glycolipid headgroups. This phenomenon had previously been described for lipids with special oligo-saccharide motifs. Here, it was investigated how common this phenomenon is among glycolipids with a variety of more abundant saccharide-headgroups. It was found that glycolipid-induced membrane crosslinking is equally observed for some of these abundant glycolipid types, strongly suggesting that this under-explored phenomenon is potentially of great biological relevance.
Remembering the dismembered
(2020)
This thesis – written in co-authorship with Tanzanian activist Mnyaka Sururu Mboro – examines different cases of repatriation of ancestral remains to African countries and communities through the prism of postcolonial memory studies. It follows the theft and displacement of prominent ancestors from East and Southern Africa (Sarah Baartman, Dawid Stuurman, Mtwa Mkwawa, Songea Mbano, King Hintsa and the victims of the Ovaherero and Nama genocides) and argues that efforts made for the repatriation of their remains have contributed to a transnational remembrance of colonial violence.
Drawing from cultural studies theories such as "multidirectional memory", "rehumanisation" and "necropolitics", the thesis argues for a new conceptualisation or "re-membrance" in repatriation, through processes of reunion, empowerment, story-telling and belonging. Besides, the afterlives of the dead ancestors, who stand at the centre of political debates on justice and reparations, remind of their past struggles against colonial oppression. They are therefore "memento vita", fostering counter-discourses that recognize them
as people and stories.
This manuscript is accompanied by a “(web)site of memory” where some of the research findings are made available to a wider audience. This blog also hosts important sound material which appears in the thesis as interventions by external contributors. Through QR codes, both the written and the digital version are linked with each other to problematize the idea of a written monograph and bring a polyphonic perspective to those diverse, yet connected, histories.
The Cheb Basin (CZ) is a shallow Neogene intracontinental basin located in the western Eger Rift. The Cheb Basin is characterized by active seismicity and diffuse degassing of mantle-derived CO2 in mofette fields. Within the Cheb Basin, the Hartoušov mofette field shows a daily CO2 flux of 23–97 tons. More than 99% of CO2 released over an area of 0.35 km2. Seismic active periods have been observed in 2000 and 2014 in the Hartoušov mofette field. Due to the active geodynamic processes, the Cheb Basin is considered to be an ideal region for the continental deep biosphere research focussing on the interaction of biological processes with geological processes.
To study the influence of CO2 degassing on microbial community in the surface and subsurface environments, two 3-m shallow drillings and a 108.5-m deep scientific drilling were conducted in 2015 and 2016 respectively. Additionally, the fluid retrieved from the deep drilling borehole was also recovered. The different ecosystems were compared regarding their geochemical properties, microbial abundances, and microbial community structures. The geochemistry of the mofette is characterized by low pH, high TOC, and sulfate contents while the subsurface environment shows a neutral pH, and various TOC and sulfate contents in different lithological settings. Striking differences in the microbial community highlight the substantial impact of elevated CO2 concentrations and high saline groundwater on microbial processes. In general, the microorganisms had low abundance in the deep subsurface sediment compared with the shallow mofette. However, within the mofette and the deep subsurface sediment, the abundance of microbes does not show a typical decrease with depth, indicating that the uprising CO2-rich groundwater has a strong influence on the microbial communities via providing sufficient substrate for anaerobic chemolithoautotrophic microorganisms. Illumina MiSeq sequencing of the 16S rRNA genes and multivariate statistics reveals that the pH strongly influences the microbial community composition in the mofette, while the subsurface microbial community is significantly influenced by the groundwater which motivated by the degassing CO2. Acidophilic microorganisms show a much higher relative abundance in the mofette. Meanwhile, the OTUs assigned to family Comamonadaceae are the dominant taxa which characterize the subsurface communities. Additionally, taxa involved in sulfur cycling characterizing the microbial communities in both mofette and CO2 dominated subsurface environments.
Another investigated important geo–bio interaction is the influence of the seismic activity. During seismic events, released H2 may serve as the electron donor for microbial hydrogenotrophic processes, such as methanogenesis. To determine whether the seismic events can potentially trigger methanogenesis by the elevated geogenic H2 concentration, we performed laboratory simulation experiments with sediments retrieved from the drillings. The simulation results indicate that after the addition of hydrogen, substantial amounts of methane were produced in incubated mofette sediments and deep subsurface sediments. The methanogenic hydrogenotrophic genera Methanobacterium was highly enriched during the incubation. The modeling of the in-situ observation of the earthquake swarm period in 2000 at the Novy Kostel focal area/Czech Republic and our laboratory simulation experiments reveals a close relation between seismic activities and microbial methane production via earthquake-induced H2 release. We thus conclude that H2 – which is released during seismic activity – can potentially trigger methanogenic activity in the deep subsurface. Based on this conclusion, we further hypothesize that the hydrogenotrophic early life on Earth was boosted by the Late Heavy Bombardment induced seismic activity in approximately 4.2 to 3.8 Ga.
The Andean Plateau (Altiplano-Puna Plateau) of the southern Central Andes is the second-highest orogenic plateau on our planet after Tibet. The Andean Plateau and its foreland exhibit a pronounced segmentation from north to south regarding the style and magnitude of deformation. In the Altiplano (northern segment), more than 300 km of tectonic shortening has been recorded, which started during the Eocene. A well-developed thin-skinned thrust wedge located at the eastern flank of the plateau (Subandes) indicates a simple-shear shortening mode. In contrast, the Puna (southern segment) records approximately half of the shortening of the Altiplano - and the shortening started later. The tectonic style in the Puna foreland switches to a thick-skinned mode, which is related to pure-shear shortening. In this study, carried out in the framework of the StRATEGy project, high-resolution 2D thermomechanical models were developed to systematically investigate controls of deformation patterns in the orogen-foreland pair. The 2D and 3D models were subsequently applied to study the evolution of foreland deformation and surface topography in the Altiplano-Puna Plateau. The models demonstrate that three principal factors control the foreland-deformation patterns: (i) strength differences in the upper lithosphere between the orogen and its foreland, rather than a strength difference in the entire lithosphere; (ii) gravitational potential energy of the orogen (GPE) controlled by crustal and lithospheric thicknesses, and (iii) the strength and thickness of foreland-basin sediments. The high-resolution 2D models are constrained by observations and successfully reproduce deformation structures and surface topography of different segments of the Altiplano-Puna plateau and its foreland. The developed 3D models confirm these results and suggest that a relatively high shortening rate in the Altiplano foreland (Subandean foreland fold-and-thrust belt) is due to simple-shear shortening facilitated by thick and mechanically weak sediments, a process which requires a much lower driving force than the pure-shear shortening deformation mode in the adjacent broken foreland of the Puna, where these thick sedimentary basin fills are absent. Lower shortening rate in the Puna foreland is likely accommodated in the forearc by the slab retreat.
Lately, the integration of upconverting nanoparticles (UCNP) in industrial, biomedical and scientific applications has been increasingly accelerating, owing to the exceptional photophysical properties that UCNP offer. Some of the most promising applications lie in the field of medicine and bioimaging due to such advantages as, among others, deeper tissue penetration, reduced optical background, possibility for multicolor imaging, and lower toxicity, compared to many known luminophores. However, some questions regarding not only the fundamental photophysical processes, but also the interaction of the UCNP with other luminescent reporters frequently used for bioimaging and the interaction with biological media remain unanswered. These issues were the primary motivation for the presented work.
This PhD thesis investigated several aspects of various properties and possibilities for bioapplications of Yb3+,Tm3+-doped NaYF4 upconverting nanoparticles. First, the effect of Gd3+ doping on the structure and upconverting behaviour of the nanocrystals was assessed. The ageing process of the UCNP in cyclohexane was studied over 24 months on the samples with different Gd3+ doping concentrations. Structural information was gathered by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), dynamic light scattering (DLS), and discussed in relation to spectroscopic results, obtained through multiparameter upconversion luminescence studies at various temperatures (from 4 K to 295 K). Time-resolved and steady-state emission spectra recorded over this ample temperature range allowed for a deeper understanding of photophysical processes and their dependence on structural changes of UCNP.
A new protocol using a commercially available high boiling solvent allowed for faster and more controlled production of very small and homogeneous UCNP with better photophysical properties, and the advantages of a passivating NaYF4 shell were shown.
Förster resonance energy transfer (FRET) between four different species of NaYF4: Yb3+, Tm3+ UCNP (synthesized using the improved protocol) and a small organic dye was studied. The influence of UCNP composition and the proximity of Tm3+ ions (donors in the process of FRET) to acceptor dye molecules have been assessed. The brightest upconversion luminescence was observed in the UCNP with a protective inert shell. UCNP with Tm3+ ions only in the shell were the least bright, but showed the most efficient energy transfer.
In the final part, two surface modification strategies were applied to make UCNP soluble in water, which simultaneously allowed for linking them via a non-toxic copper-free click reaction to the liposomes, which served as models for further cell experiments. The results were assessed on a confocal microscope system, which was made possible by lesser known downshifting properties of Yb3+, Tm3+-doped UCNP. Preliminary antibody-staining tests using two primary and one dye-labelled secondary antibodies were performed on MDCK-II cells.
מחקר זה מתמקד במשנתו ההלכתית של הרב כלפון, כפי שהשתקפה בחיבוריו 'שואל ונשאל' ו'ברית כהונה' שהם ספרי שו"ת (responsa) הפורשים היקף נרחב של יחסיו לתמורות שחלו באותן שנים בקהילה היהודית באי ג'רבה שליד תוניס. נבחנים יחסו למודרנה, לחינוך כללי, למעמד האשה ועוד. כמו"כ נבדקה דרכו ההלכתית, הדומיננטיות שהעניק למסורת הג'רבאית גם לעומת פסיקותיו של רבי יוסף קארו.
In the present study, we employ the angle-resolved photoemission spectroscopy (ARPES) technique to study the electronic structure of topological states of matter. In particular, the so-called topological crystalline insulators (TCIs) Pb1-xSnxSe and Pb1-xSnxTe, and the Mn-doped Z2 topological insulators (TIs) Bi2Te3 and Bi2Se3. The Z2 class of strong topological insulators is protected by time-reversal symmetry and is characterized by an odd number of metallic Dirac type surface states in the surface Brillouin zone. The topological crystalline insulators on the other hand are protected by the individual crystal symmetries and exhibit an even number of Dirac cones.
The topological properties of the lead tin chalcogenides topological crystalline insulators can be tuned by temperature and composition. Here, we demonstrate that Bi-doping of the Pb1-xSnxSe(111) epilayers induces a quantum phase transition from a topological crystalline insulator to a Z2 topological insulator. This occurs because Bi-doping lifts the fourfold valley degeneracy in the bulk. As a consequence a gap appears at ⌈¯, while the three Dirac cones at the M̅ points of the surface Brillouin zone remain intact. We interpret this new phase transition is caused by lattice distortion. Our findings extend the topological phase diagram enormously and make strong topological insulators switchable by distortions or electric field. In contrast, the bulk Bi doping of epitaxial Pb1-xSnxTe(111) films induces a giant Rashba splitting at the surface that can be tuned by the doping level. Tight binding calculations identify their origin as Fermi level pinning by trap states at the surface.
Magnetically doped topological insulators enable the quantum anomalous Hall effect (QAHE) which provide quantized edge states for lossless charge transport applications. The edge states are hosted by a magnetic energy gap at the Dirac point which has not been experimentally observed to date. Our low temperature ARPES studies unambiguously reveal the magnetic gap of Mn-doped Bi2Te3. Our analysis shows a five times larger gap size below the Tc than theoretically predicted. We assign this enhancement to a remarkable structure modification induced by Mn doping. Instead of a disordered impurity system, a self-organized alternating sequence of MnBi2Te4 septuple and Bi2Te3quintuple layers is formed. This enhances the wave-function overlap and gives rise to a large magnetic gap. Mn-doped Bi2Se3 forms similar heterostructure, but only a nonmagnetic gap is observed in this system. This correlates with the difference in magnetic anisotropy due to the much larger spin-orbit interaction in Bi2Te3 compared to Bi2Se3. These findings provide crucial insights for pushing lossless transport in topological insulators towards room-temperature applications.
Percolation process, which is intrinsically a phase transition process near the critical point, is ubiquitous in nature. Many of its applications embrace a wide spectrum of natural phenomena ranging from the forest fires, spread of contagious diseases, social behaviour dynamics to mathematical finance, formation of bedrocks and biological systems. The topology generated by the percolation process near the critical point is a random (stochastic) fractal. It is fundamental to the percolation theory that near the critical point, a unique infinite fractal structure, namely the infinite cluster, would emerge. As de Gennes suggested, the properties of the infinite cluster could be deduced by studying the dynamical behaviour of the random walk process taking place on it. He coined the term the ant in the labyrinth. The random walk process on such an infinite fractal cluster exhibits a subdiffusive dynamics in the sense that the mean squared displacement grows as ~t2/dw, where dw, called the fractal dimension of the random walk path, is greater than 2. Thus, the random walk process on the infinite cluster is classified as a process exhibiting the properties of anomalous diffusions. Yet near the critical point, the infinite cluster is not the sole emergent topology, but it coexists with other clusters whose size is finite. Though finite, on specific length scales these finite clusters exhibit fractal properties as well. In this work, it is assumed that the random walk process could take place on these finite size objects as well. Bearing this assumption in mind requires one address the non-equilibrium initial condition. Due to the lack of knowledge on the propagator of the random walk process in stochastic random environments, a phenomenological correspondence between the renowned Ornstein-Uhlenbeck process and the random walk process on finite size clusters is established. It is elucidated that when an ensemble of these finite size clusters and the infinite cluster is considered, the anisotropy and size of these finite clusters effects the mean squared displacement and its time averaged counterpart to grow in time as ~t(d+df (t-2))/dw, where d is the embedding Euclidean dimension, df is the fractal dimension of the infinite cluster, and , called the Fisher exponent, is a critical exponent governing the power-law distribution of the finite size clusters. Moreover, it is demonstrated that, even though the random walk process on a specific finite size cluster is ergodic, it exhibits a persistent non-ergodic behaviour when an ensemble of finite size and the infinite clusters is considered.
Abstract. Catalysis is one of the most effective tools for the highly efficient assembly of complex molecular structures. Nevertheless, it is mainly represented by transition metal-based catalysts and typically is an energy consuming process. Therefore, photocatalysis utilizing solar energy is one of the appealing approaches to overcome these problems. A great alternative to classic transition metal-based photocatalysts, carbon nitrides, a group of organic polymeric semiconductors, have already shown their efficiency in water splitting, CO2 reduction, and organic pollutants degradation. However, these materials have also a great potential for the use in functionalization of complex organic molecules for synthetic needs as it was shown in recent years.
This work addresses the challenge to develop efficient system for heterogeneous organic photocatalysis, employing cheap and environmentally benign photocatalysts – carbon nitrides. Herein, fundamental properties of semiconductors are studied from the organic chemistry standpoint; the inherent properties of carbon nitrides, such as ability to accumulate electrons, are deeply investigated and their effect on the reaction outcome is established. Thus, understanding of the electron charging processes allowed for the synthesis of otherwise hardly-achieved diazetidines-1,3 by tetramerization of benzylamines. Furthermore, the high electron capacity of Potassium Poly(heptazine imide)s (K-PHI) made possible a multi-electron reduction of aromatic nitro compounds to bare or formylated anilines. Additionally, two deep eutectic solvents (DES) were designed as a sustainable reaction media and reducing reagent for this reaction. Eventually, the high oxidation ability of carbon nitride K-PHI is employed in a challenging reaction of halide anion oxidation (Cl―, Br―) to accomplish electrophilic substitution in aromatic ring. The possibility to utilize NaCl solution (seawater mimetic) for the chlorination of electron rich arenes was shown. Eventually, light itself is used as a tool in a chromoselective photocatalytic oxidation of aromatic thiols and thioacetatas to three different compounds, using UV, blue, and red LEDs.
All in all, the work enhances understanding the mechanism of heterogeneous photocatalysis in synthetic organic reactions and therefore, is a step forward to the sustainable methods of synthesis in organic chemistry.
Pre-service physics teachers often have difficulties seeing the relevance of the content of the content knowledge courses they attend in their study; they regularly do not see the connection with the physics they need in their later profession as a secondary school teacher. A lower perceived relevance is however connected to motivational problems which leads to both a qualitative and quantitative problem: not only is there a relation between the drop-out of students and their motivation, but their level of conceptual understanding is also suffering under this lower motivation.
In order to increase the perceived relevance of the problems that pre-service physics teachers have to solve for the courses Experimentalphysik 1 and 2, an intervention study has been designed and implemented. In these content knowledge courses, first- and second semester students attend lectures, do experiments and they solve problems on weekly problem sets which are discussed in tutorial sessions. The problems on a typical problem set are however mainly quantitative problems that have no connection to school. In the intervention study, regular, quantitative problems are used next to two newly designed conceptual (qualitative) problem types. One of these problem types are conceptual problems that have no implicit or explicit school-relevance; the other problems are based on school-related content knowledge. This content knowledge category describes knowledge that leads to a deeper understanding of school knowledge, relevant for teachers: a teacher-specific content knowledge. A new model for this category, SRCK, has been conceptualised and operationalised as a cross-disciplinary model that consists of conceptual knowledge and skills necessary for this deeper understanding of content that is relevant to teaching at a secondary school.
During two semesters in both the courses Experimentalphysik 1 and 2 (N = 75 and N = 43 respectively) students had to solve the problems on the problem sets. At the start of every tutorial session, they were asked to rate all the problems with respect to perceived relevance and difficulty. Analyses show that the problems based on SRCK were perceived as more relevant than the regular, quantitative problems. However, this difference is only statistically significant for the course Experimentalphysik 2.
The SRCK-problems show the connection between the content of the problems and school physics and are therefore seen as more relevant. In Experimentalphysik 1, the content is not that distant to school physics. This might be the reason that the students see all the problem types as just as relevant to them. When we however only look at the final third of the first semester, where more advanced subjects - that are not necessarily discussed in secondary school physics – are discussed, we see that in this part the SRCK-problems are seen as more relevant than the regular problems too. We can therefore conclude that if the content is distant to school physics, the SRCK-problems are seen as more relevant than the regular problems. We do not see a statistically significant difference between the (conceptual) problems based on SRCK and the conceptual problems that are not based on SRCK (and therefore have no school relevance). This means that we do not know whether the conceptual problems based on SRCK are more relevant because they are based on SRCK or because they are conceptual.
In order to find out what problem properties have an influence on the perceived relevance of these problems by pre-service teachers, an interview study with N = 7 pre-service teachers was conducted.
This interview was done using the repertory grid technique, based on the personal construct theory by Kelly (1955). This technique makes it possible to find personal constructs of students: how do students determine for themselves how relevant a problem is to them? It allows to capture their intuition or gut feeling. These personal constructs could then give us information about the problem properties that have a positive influence on relevance.
Six categories of personal constructs were found that have a high similarity to relevance. According to the personal constructs that were generated in the interviews, physics problems are more relevant when they are more conceptual (compared to calculational), are close to everyday life, have a lower level of mathematical requirement, have a content that is more school-relevant, give the students the idea that they have learned something, and contain a situation that has to be analysed.
Of the six problem properties described above, one can be connected to the facets of SRCK: many problems based on SRCK contain a situation (e.g. a textbook with a simplified explanation, a student solution with an error) that has to be analysed.
The expectation is that problems that are based on the six properties described above would be perceived as more relevant to pre-service physics teachers.
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.
This dissertation aims to deliver a transcendental interpretation of Immanuel Kant's Kritik der Urteilskraft, considering both its coherence with other critical works as well as the internal coherence of the work itself. This interpretation is called transcendental insofar as special emphasis is placed on the newly introduced cognitive power, namely the reflective power of judgement, guided by the a priori principle of purposiveness. In this way the seeming manifold of themes, varying from judgements of taste through culture to teleological judgements about natural purposes, are discussed exclusively in regard of their dependence on this faculty and its transcendental principle. In contrast, in contemporary scholarship the book is often treated as a fragmented work, consisting of different independent parts, while my focus lies on the continuity comprised primarily of the activity of the power of judgement.
Going back to certain central yet silently presupposed concepts, adopted from previous critical works, the main contribution of this study is to integrate the KU within the overarching critical project. More specifically, I have argue how the need for the presupposition by the reflective power of judgement follows from the peculiar character of our sense-dependent discursive mind. Because we are sense-dependent discursive minds, we do not and cannot have immediate insight into all of nature's features. The particular constitution of our mind rather demands conceptually informed representations which mediately refer to objects.
Having said that, the principle of purposiveness, namely the presupposition that nature is organized in concert with the particular constitution of our mind, is a necessary condition for the possibility of reflection on nature's empirical features. Reflection refers on my account to a process of selecting features in order to allow a classification, including reflection on the method, means and selection criteria. Rather than directly contributing to cognition, like the categories, reflective judgements thus express our ignorance when it comes to the motivation behind nature's design, and this is most forcefully expressed by judgements of taste and teleological judgements about organized matter. In this way, reflection, regardless whether it is manifested in concept acquisition, scientific systematization, judgements of taste or judgements about organized matter, relies on a principle of the power of judgement which is revealed and justified in this transcendental inquiry.
Salt pans also termed playas are common landscape features of hydrologically closed basins in arid and semiarid zones, where evaporation significantly exceeds the local precipitation. The analysis and monitoring of salt pan environments is important for the evaluation of current and future impact of these landscape features. Locally, salt pans have importance for the ecosystem, wildlife and human health, and through dust emissions they influence the climate on regional and global scales. Increasing economic exploitation of these environments in the last years, e.g. by brine extraction for raw materials, as well as climate change severely affect the water, material and energy balance of these systems. Optical remote sensing has the potential to characterise salt pan environments and to increase the understanding of processes in playa basins, as well as to assess wider impacts and feedbacks that exist between climate forcing and human intervention in their regions. Remote sensing techniques can provide information for extensive regions on a high temporal basis compared to traditional field samples and ground observations. Specifically, for salt pans that are often challenging to study because of their large size, remote location, and limited accessibility due to missing infrastructure and ephemeral flooding. Furthermore, the availability of current and upcoming hyperspectral remote sensing data opened the opportunity for the analyses of the complex reflectance signatures that relate to the mineralogical mixtures found in the salt pan sediments. However, these new advances in sensor technology, as well as increased data availability currently have not been fully explored for the study of salt pan environments. The potential of new sensors needs to be assessed and state of the art methods need to be adapted and improved to provide reliable information for in depth analysis of processes and characterisation of the recent condition, as well as to support long-term monitoring and to evaluate environmental impacts of changing climate and anthropogenic activity.
This thesis provides an assessment of the capabilities of optical remote sensing for the study of salt pan environments that combines the information of hyperspectral data with the increased temporal coverage of multispectral observations for a more complete understanding of spatial and temporal complexity of salt pan environments using the Omongwa salt pan located in the south-west Kalahari as a test site. In particular, hyperspectral data are used for unmixing of the mineralogical surface composition, spectral feature-based modelling for quantification of main crust components, as well as time-series based classification of multispectral data for the assessment of the long-term dynamic and the analysis of the seasonal process regime. The results show that the surface of the Omongwa pan can be categorized into three major crust types based on diagnostic absorption features and mineralogical ground truth data. The mineralogical crust types can be related to different zones of surface dynamic as well as pan morphology that influences brine flow during the pan inundation and desiccation cycles. Using current hyperspectral imagery, as well as simulated data of upcoming sensors, robust quantification of the gypsum component could be derived. For the test site the results further indicate that the crust dynamic is mainly driven by flooding events in the wet season, but it is also influenced by temperature and aeolian activity in the dry season. Overall, the scientific outcomes show that optical remote sensing can provide a wide range of information helpful for the study of salt pan environments. The thesis also highlights that remote sensing approaches are most relevant, when they are adapted to the specific site conditions and research scenario and that upcoming sensors will increase the potential for mineralogical, sedimentological and geomorphological analysis, and will improve the monitoring capabilities with increased data availability.
The Arctic region is especially impacted by global warming as temperatures in high latitude regions have increased and are predicted to further rise at levels above the global average. This is crucial to Arctic soils and the shallow shelves of the Arctic Ocean as they are underlain by permafrost. Perennially frozen ground is a habitat for a large number and great diversity of viable microorganisms, which can remain active even under freezing conditions. Warming and thawing of permafrost makes trapped soil organic carbon more accessible to microorganisms. They can transform it to the greenhouse gases carbon dioxide, methane and nitrous oxide. On the other hand, it is assumed that thawing of the frozen ground stimulates microbial activity and carbon turnover. This can lead to a positive feedback loop of warming and greenhouse gas release.
Submarine permafrost covers most areas of the Siberian Arctic Shelf and contains a large though unquantified carbon pool. However, submarine permafrost is not only affected by changes in the thermal regime but by drastic changes in the geochemical composition as it formed under terrestrial conditions and was inundated by Holocene sea level rise and coastal erosion. Seawater infiltration into permafrost sediments resulted in an increase of the pore water salinity and, thus, in thawing of permafrost in the upper sediment layers even at subzero temperatures. The permafrost below, which was not affected by seawater, remained ice-bonded, but warmed through seawater heat fluxes.
The objective of this thesis was to study microbial communities in submarine permafrost with a focus on their response to seawater influence and long-term warming using a combined approach of molecular biological and physicochemical analyses. The microbial abundance, community composition and structure as well as the diversity were investigated in drill cores from two locations in the Laptev Sea, which were subjected to submarine conditions for centuries to millennia. The microbial abundance was measured through total cell counts and copy numbers of the 16S rRNA gene and of functional genes. The latter comprised genes which are indicative for methane production (mcrA) and sulfate reduction (dsrB). The microbial community was characterized by high-throughput-sequencing of the 16S rRNA gene. Physicochemical analyses included the determination of the pore water geochemical and stable isotopic composition, which were used to describe the degree of seawater influence. One major outcome of the thesis is that the submarine permafrost stratified into different so-called pore water units centuries as well as millennia after inundation: (i) sediments that were mixed with seafloor sediments, (ii) sediments that were infiltrated with seawater, and (iii) sediments that were unaffected by seawater. This stratification was reflected in the submarine permafrost microbial community composition only millennia after inundation but not on time-scales of centuries.
Changes in the community composition as well as abundance were used as a measure for microbial activity and the microbial response to changing thermal and geochemical conditions. The results were discussed in the context of permafrost temperature, pore water composition, paleo-climatic proxies and sediment age. The combination of permafrost warming and increasing salinity as well as permafrost warming alone resulted in a disturbance of the microbial communities at least on time-scales of centuries. This was expressed by a loss of microbial abundance and bacterial diversity. At the same time, the bacterial community of seawater unaffected but warmed permafrost was mainly determined by environmental and climatic conditions at the time of sediment deposition. A stimulating effect of warming was observed only in seawater unaffected permafrost after millennia-scale inundation, visible through increased microbial abundance and reduced amounts of substrate.
Despite submarine exposure for centuries to millennia, the community of bacteria in submarine permafrost still generally resembled the community of terrestrial permafrost. It was dominated by phyla like Actinobacteria, Chloroflexi, Firmicutes, Gemmatimonadetes and Proteobacteria, which can be active under freezing conditions.
Moreover, the archaeal communities of both study sites were found to harbor high abundances of marine and terrestrial anaerobic methane oxidizing archaea (ANME). Results also suggested ANME populations to be active under in situ conditions at subzero temperatures. Modeling showed that potential anaerobic oxidation of methane (AOM) could mitigate the release of almost all stored or microbially produced methane from thawing submarine permafrost.
Based on the findings presented in this thesis, permafrost warming and thawing under submarine conditions as well as permafrost warming without thaw are supposed to have marginal effects on the microbial abundance and community composition, and therefore likely also on carbon mobilization and the formation of methane. Thawing under submarine conditions even stimulates AOM and thus mitigates the release of methane.
The political legacy of the Martinican poet, novelist and philosopher Édouard Glissant (1928–2011) is the subject of an ongoing debate among postcolonial literary scholars. Responding to an influential view shaping this debate, that Glissant’s work can be categorised into an early political and late apolitical phase, this dissertation claims that this division is based on a narrow conception of 'engaged political writing' that prevents a more comprehensive view of the changing political strategies Glissant pursued throughout his life from emerging. Proceeding from this conceptual basis, the dissertation is concerned with re-reading the dimensions of Glissant's work that have hitherto been relegated as apolitical, literary or poetic, with the aim of conceptualising the politics of relation as an integral part of his overall poetic project. In methodological terms, the dissertation therefore proposes a relational reading of Glissant’s life-work across literary genres, epochs, as well as the conventional divisions between political thought, writing and activism. This perspective is informed by Glissant's philosophy of relation, and draws on a conception of political practice that includes both explicit engagements with established political systems and institutions, as well as literary and cultural interventions geared towards their transformation and the creation of alternatives to them. Theoretically the work thus combines a poststructuralist lens on the conceptual difference between 'politics' and 'the political' with arguments for an inherent political quality of literature, and perspectives from the Afro-Caribbean radical tradition, in which writers and intellectuals have historically sought to combine discursive interventions with organisational actions. Applying this theoretical angle to the analysis of Glissant's politics of relation results in an interdisciplinary research framework designed to explore the synergies between postcolonial political and literary studies.
In order to comprehensively describe Glissant's politics of relation without recourse to evolutionary or digressive models, the concept of an intellectual marronage is proposed as a framework to map the strategies making up Glissant's political archive. Drawing on a variety of historic, political theoretical and literary sources, intellectual marronage is understood as a mode of radical resistance to the neocolonial subjugation for which the plantation system stands historically and metaphorically, as an inherently innovative political practice invested in the creation of communities marked by relational ontologies, and as a commitment to fostering an imagination of the world and the human that differs fundamentally from the Enlightenment paradigm. This specific conception of intellectual marronage forms the basis on which three key strategies that consistently shape Glissant's political practice are identified and mapped. They revolve around Glissant's engagement with history (chapter 2), his commitment to fostering an imagination of the Tout-Monde (whole-world) as a political point of reference (chapter 3), and the continuous exploration of alternative forms of community on the levels of the island, the archipelago and the Tout-Monde (chapter 4). Together these strategies constitute Glissant's personal politics of relation. Its abstract characteristics can be put in a productive conversation with related theoretical traditions invested in exploring the political potentials of fugitivity (chapters 5), as well as with the work of other postcolonial actors whose holistic practice warrants to be described as a politics of relation (chapter 6).
Die Praktische Fahrerlaubnisprüfung dient der Erfassung und Beurteilung der Fahrkompe-tenz von Fahrerlaubnisbewerbern. Die aus dieser Prüfung gewonnenen Rückschlüsse auf das Niveau der Fahrkompetenz sollen insbesondere auch der Weiterentwicklung des Bewerbers dienen. Bisher erhalten Bewerber nur bei nicht bestandener Praktischer Fahrerlaubnisprü-fung eine Auflistung der wichtigsten Fehler, die zum Nichtbestehen geführt haben. Für ein zielgerichtetes Weiterlernen ist es aber notwendig, dass die Ergebnisse der Leistungserfas-sung und der Leistungsbewertung gemäß prüfungsdidaktischer Grundsätze pädagogisch an-spruchsvoll an alle Fahranfänger (unabhängig vom Prüfungsergebnis) zurückgemeldet wer-den.
Das Ziel der vorliegenden Arbeit besteht darin, die Gestaltungsgrundlagen und einen Umset-zungsvorschlag für ein kompetenzbezogenes und lernförderliches Rückmeldesystem für die Praktische Fahrerlaubnisprüfung zu erarbeiten. Dieses Rückmeldesystem soll in der Praxis erprobt werden. Darüber hinaus sollen anhand einer Bewerberbefragung zur Nutzerzufrie-denheit Erkenntnisse für die Weiterentwicklung gewonnen werden. Der Entwicklungs- und Erprobungsprozess des optimierten Rückmeldesystems lässt sich in drei Projektphasen auf-teilen:
1. Im Zuge der Optimierungsarbeiten zur Praktischen Fahrerlaubnisprüfung wurde in der ersten Projektphase ein neues Rückmeldesystem erarbeitet, das aus einem kompetenz-bezogenen mündlichen Auswertungsgespräch und einer ergänzenden schriftlichen Rückmeldung einschließlich weiterführender Lernhinweise für alle Bewerber besteht. Dieses Rückmeldesystem soll einerseits die Fahranfänger dabei unterstützen, die Leis-tungsbewertung inhaltlich besser zu verstehen sowie ein zielgerichtetes Weiterlernen ermöglichen. Andererseits soll es die Bewerber dazu motivieren, die festgestellten Kompetenzdefizite weiter zu bearbeiten, und dadurch Lernzuwachs fördern.
2. Das Rückmeldesystem wurde in der zweiten Projektphase in verschiedenen Modell-
regionen Deutschlands anhand von ca. 9.000 realen Praktischen Fahrerlaubnisprüfun-gen erprobt. Die Fahrerlaubnisbewerber, die in den Modellregionen an einer optimier-ten Praktischen Fahrerlaubnisprüfung teilgenommen und somit eine schriftliche Rückmeldung gemäß der optimierten Vorgaben bzw. einen individuellen Zugangscode zum Downloadbereich erhalten haben, wurden zu einer Befragung eingeladen. Dabei wurden vor allem Aspekte der Akzeptanz und der Lernwirksamkeit aus Sicht der Be-werber erfasst. Ziel war es, die Qualität der verkehrspädagogischen Gestaltung des Rückmeldesystems und seinen Nutzen zu untersuchen, um die erprobte Rückmeldung weiterzuentwickeln. Für die Bewerberbefragung wurde eine Onlinebefragung mit ei-nem standardisierten Fragebogen durchgeführt.
3. Die Erprobungs- und Befragungsergebnisse dienten in der dritten Projektphase der Ableitung von Schlussfolgerungen für die Weiterentwicklung des Rückmeldesystems. Die vorliegenden Ergebnisse der Felderprobung deuten darauf hin, dass die Bereitstel-lung einer schriftlichen, ausführlichen Rückmeldung zu den Prüfungsleistungen der Praktischen Fahrerlaubnisprüfungen insgesamt als nützlich und gewinnbringend ange-sehen wird. Allerdings wurde auch deutlich, dass bezüglich der Umsetzung noch Op-timierungspotenzial besteht. Im Anschluss an die Erprobung wurde die schriftliche Rückmeldung daher – ausgehend von den Nutzererfahrungen während der Felderpro-bung – umfassend überarbeitet und eine revidierte Version vorgelegt.
Als Ergebnis der Arbeit liegt ein in mehreren Schritten entwickeltes, empirisch fundiertes und erprobtes Rückmeldesystem vor, das eine differenzierte Kompetenzrückmeldung er-möglicht. Die umfassende Rückmeldung bietet künftig einerseits eine verbesserte Ausgangs-lage für eine ggf. anschließende Wiederholungsprüfung und andererseits ist es dem Bewer-ber anhand der aufgezeigten Stärken und Schwächen auch nach einer bestandenen Prüfung möglich, diese Rückmeldung für das weitere Lernen zu nutzen.
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.
The current thesis contains the results from two experimental and one modelling study focused on the topic of ductile strain localization in the presence of material heterogeneities. Localization of strain in the high temperature regime is a well known feature of rock deformation occurring in nature at different scales and in a variety of lithologies. Large scale shear zones at the roots of major crustal fault zones are considered responsible for the activity of plate tectonics on our planet. A large number of mechanisms are suggested to be associated with strain softening and nucleation of localization. Among these, the presence of material heterogeneities within homogeneous host rocks is frequently observed in field examples to trigger shear zone development. Despite a number of studies conducted on the topic, the mechanisms controlling initiation and evolution of localization are not fully understood yet. We investigated, experimentally and by means of numerical modelling, phenomenological and microphysical aspects of high temperature strain localization in a homogeneous body containing single and paired inclusions of weaker material. A monomineralic carbonate system composed of Carrara marble (homogeneous, strong matrix) and Solnhofen limestone (weak planar inclusions) is selected for our studies based on its versatility as an experimental material and on the frequent occurrence of carbonate rocks at the core of natural shear zones.
To explore the influence of different loading conditions on heterogeneity-induced high temperature shear zones we conducted torsion experiments under constant twist (deformation) rate and constant torque (stress) conditions in a Paterson-type deformation apparatus on hollow cylinders of marble containing single planar inclusions of limestone. At the imposed experimental conditions (900 ◦C temperature and 400 MPa confining pressure) both materials deform plastically and the marble is ≈ 9 times stronger than the limestone. The viscosity contrast between the two materials induces a perturbation of the stress field within the marble matrix at the tip of the planar inclusion. Early on along the deformation path (at bulk shear strains ≈ 0.3), heterogeneous distribution of strain can be observed under both loading conditions and a small area of incipient strain localization is formed at the tip of the weak limestone inclusion. Strongly deformed grains, incipient dynamic recrystallization and a weak crystallographic preferred orientation characterize the marble within an area a few mm in front of the inclusion. As the bulk strain is increased (up to γ ≈ 1), the area of microstructural modification is expanded along the inclusion plane, the texture strengthens and grain size refinement by dynamic recrystallization becomes pervasive. Locally, evidences for coexisting brittle deformation are also observed regardless of the imposed loading conditions. A shear zone is effectively formed within the deforming Carrara marble, its geometry controlled by the plane containing the thin plate of limestone. Thorough microstructural and textural analysis, however, do not reveal substantial differences in the mechanisms or magnitude of strain localization at the different loading conditions. We conclude that, in the presence of material heterogeneities capable of inducing strain softening, the imposed loading conditions do not affect ductile localization in its nucleating and transient stages.
As the ultimate goal of experimental rock deformation is the extrapolation of results to geologically relevant time and space scales, we developed 2D numerical models reproducing (and benchmarked to) our experimental results. Our cm-scaled models have been implemented with a first-order strain-dependent softening law to reproduce the effect of rheological weakening in the deforming material. We successfully reproduced the local stress concentration at the inclusion tips and the strain localization initiated in the marble matrix. The heterogeneous distribution of strain and its evolution with imposed bulk deformation (i.e. the shape and extent of the nucleating shear zone) are observed to depend on the degree of softening imposed to the deforming matrix. When a second (artificial) softening step is introduced at elevated bulk strains in the model, the formation of a secondary high strain layer is observed at the core of the initial shear zone, analogous to the development of ultramylonite bands in high strain natural shear zones. Our results do not only reproduce the nucleation and transient evolution of a heterogeneity-induced high temperature shear zone with high accuracy, but also confirm the importance of introducing reliable softening laws capable of mimicking strain weakening to numerical models of crustal scale ductile processes.
Material heterogeneities inducing strain localization in the field are often consisting of brittle precursors (joints and fractures). More generally, the interaction of brittle and ductile deformation mechanisms and its effect on the localization of strain have been a key topic in the structural geology community for a long time. The positive feedback between (micro)fracturing and ductile strain localization is a well recognized effect in a number of field examples. We experimentally investigated the influence of brittle deformation on the initiation and evolution of high temperature shear zones in a strong matrix containing pairs of weak material heterogeneities. Our Carrara marble-Solnhofen limestone inclusions system was tested in triaxial compression under constant strain rate and high temperature (900 ◦C) conditions in a Paterson deformation apparatus. The inclusion pairs were arranged in non-overlapping step-over geometries of either compressional or extensional nature. Experimental runs were conducted at different confining pressures (30, 50, 100 and 300 MPa) to induce various amounts of brittle deformation within the marble matrix. At low confinement (30 and 50 MPa) abundant brittle deformation is observed in all configurations, but the spatial distribution of cracks is dependent on the kinematics of the step-over region: concentrated along the shearing plane between the inclusions in the extensional samples, or broadly distributed around the inclusions but outside the step-over region in the compressional configuration. Accordingly, brittle-assisted ductile processes tend to localize deformation along the inclusions plane in the extensional geometry or to distribute widely across large areas of the matrix in the compressional step-over. At pressures of 100 and 300 MPa fracturing is mostly suppressed in both configurations and strain is accommodated almost entirely by viscous creep. In extensional samples this leads to progressive de-localization with increasing confinement. Our results show that, while ductile localization of strain is indeed more efficient where assisted by brittle processes, these latter are only effective if themselves heterogeneously distributed, ultimately a function of the local stress perturbations.
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.
Seismological agencies play an important role in seismological research and seismic hazard mitigation by providing source parameters of seismic events (location, magnitude, mechanism), and keeping these data accessible in the long term. The availability of catalogues of seismic source parameters is an important requirement for the evaluation and mitigation of seismic hazards, and the catalogues are particularly valuable to the research community as they provide fundamental long-term data in the geophysical sciences. This work is well motivated by the rising demand for developing more robust and efficient methods for routine source parameter estimation, and ultimately generation of reliable catalogues of seismic source parameters. Specifically, the aim of this work is to develop some methods to determine hypocentre location and temporal evolution of seismic sources based on regional and teleseismic observations more accurately, and investigate the potential of these methods to be integrated in near real-time processing.
To achieve this, a location method that considers several events simultaneously and improves the relative location accuracy among nearby events has been provided. This method tries to reduce the biasing effects of the lateral velocity heterogeneities (or equivalently to compensate for limitations and inaccuracies in the assumed velocity model) by calculating a set of timing corrections for each seismic station. The systematic errors introduced into the locations by the inaccuracies in the assumed velocity structure can be corrected without explicitly solving for a velocity model. Application to sets of multiple earthquakes in complex tectonic environments with strongly heterogeneous structure such as subduction zones and plate boundary region demonstrate that this relocation process significantly improves the hypocentre locations compared to standard locations.
To meet the computational demands of this location process, a new open-source software package has been developed that allows for efficient relocation of large-scale multiple seismic events using arrival time data. Upon that, a flexible location framework is provided which can be tailored to various application cases on local, regional, and global scales. The latest version of the software distribution including source codes, a user guide, an example data set, and a change history, is freely available to the community.
The developed relocation algorithm has been modified slightly and then its performance in a simulated near real-time processing has been evaluated. It has been demonstrated that applying the proposed technique significantly reduces the bias in routine locations and enhance the ability to locate the lower magnitude events using only regional arrival data.
Finally, to return to emphasis on global seismic monitoring, an inversion framework has been developed to determine the seismic source time function through direct waveform fitting of teleseismic recordings. The inversion technique can be systematically applied to moderate- size seismic events and has the potential to be performed in near real-time applications. It is exemplified by application to an abnormal seismic event; the 2017 North Korean nuclear explosion.
The presented work and application case studies in this dissertation represent the first step in an effort to establish a framework for automatic, routine generation of reliable catalogues of seismic event locations and source time functions.
Die Fehlerkorrektur in der Codierungstheorie beschäftigt sich mit der Erkennung und Behebung von Fehlern bei der Übertragung und auch Sicherung von Nachrichten.
Hierbei wird die Nachricht durch zusätzliche Informationen in ein Codewort kodiert.
Diese Kodierungsverfahren besitzen verschiedene Ansprüche, wie zum Beispiel die maximale Anzahl der zu korrigierenden Fehler und die Geschwindigkeit der Korrektur.
Ein gängiges Codierungsverfahren ist der BCH-Code, welches industriell für bis zu vier Fehler korrigiere Codes Verwendung findet. Ein Nachteil dieser Codes ist die technische Durchlaufzeit für die Berechnung der Fehlerstellen mit zunehmender Codelänge.
Die Dissertation stellt ein neues Codierungsverfahren vor, bei dem durch spezielle Anordnung kleinere Codelängen eines BCH-Codes ein langer Code erzeugt wird. Diese Anordnung geschieht über einen weiteren speziellen Code, einem LDPC-Code, welcher für eine schneller Fehlererkennung konzipiert ist.
Hierfür wird ein neues Konstruktionsverfahren vorgestellt, welches einen Code für einen beliebige Länge mit vorgebbaren beliebigen Anzahl der zu korrigierenden Fehler vorgibt. Das vorgestellte Konstruktionsverfahren erzeugt zusätzlich zum schnellen Verfahren der Fehlererkennung auch eine leicht und schnelle Ableitung eines Verfahrens zu Kodierung der Nachricht zum Codewort. Dies ist in der Literatur für die LDPC-Codes bis zum jetzigen Zeitpunkt einmalig.
Durch die Konstruktion eines LDPC-Codes wird ein Verfahren vorgestellt wie dies mit einem BCH-Code kombiniert wird, wodurch eine Anordnung des BCH-Codes in Blöcken erzeugt wird. Neben der allgemeinen Beschreibung dieses Codes, wird ein konkreter Code für eine 2-Bitfehlerkorrektur beschrieben. Diese besteht aus zwei Teilen, welche in verschiedene Varianten beschrieben und verglichen werden. Für bestimmte Längen des BCH-Codes wird ein Problem bei der Korrektur aufgezeigt, welche einer algebraischen Regel folgt.
Der BCH-Code wird sehr allgemein beschrieben, doch existiert durch bestimmte Voraussetzungen ein BCH-Code im engerem Sinne, welcher den Standard vorgibt. Dieser BCH-Code im engerem Sinne wird in dieser Dissertation modifiziert, so dass das algebraische Problem bei der 2-Bitfehler Korrektur bei der Kombination mit dem LDPC-Code nicht mehr existiert. Es wird gezeigt, dass nach der Modifikation der neue Code weiterhin ein BCH-Code im allgemeinen Sinne ist, welcher 2-Bitfehler korrigieren und 3-Bitfehler erkennen kann. Bei der technischen Umsetzung der Fehlerkorrektur wird des Weiteren gezeigt, dass die Durchlaufzeiten des modifizierten Codes im Vergleich zum BCH-Code schneller ist und weiteres Potential für Verbesserungen besitzt.
Im letzten Kapitel wird gezeigt, dass sich dieser modifizierte Code mit beliebiger Länge eignet für die Kombination mit dem LDPC-Code, wodurch dieses Verfahren nicht nur umfänglicher in der Länge zu nutzen ist, sondern auch durch die schnellere Dekodierung auch weitere Vorteile gegenüber einem BCH-Code im engerem Sinne besitzt.
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.
Metal halide perovskites have merged as an attractive class of materials for photovoltaic applications due to their excellent optoelectronic properties. However, the long term stability is a roadblock for this class of material’s industrial pathway. Increasing evidence shows that intrinsic defects in perovskite promote material degradation. Consequently, understanding defect behaviours in perovskite materials is essential to further improve device stability and performance. This dissertation, hence, focuses on the topic of defect chemistry in halide perovskites.
The first part of the dissertation gives a brief overview of the defect properties in halide perovskite. Subsequently, the second part shows that doping methylammonium lead iodide with a small amount of alkaline earth metals (Sr and Mg) creates a higher quality, less defective material resulted in high open circuit voltages in both n-i-p and p-i-n architecture. It has been found that the mechanism of doping has two distinct regimes in which a low doping concentration enables the inclusion of the dopants into the lattice whereas higher doping concentrations lead to phase segregation. The material can be more n-doped in the low doping regime while being less n-doped in the high doping regime. The threshold of these two regimes is based on the atomic size of the dopants.
The next part of the dissertation examines the photo-induced degradation in methylammonium lead iodide. This degradation mechanism links closely to the formation and migration of ionic defects. After they are formed, these ionic defects can migrate, however, not freely depending on the defect concentration and their distribution. In fact, a highly concentrated defect region such as the grain boundaries can inhibit the migration of ionic defects. This has implications for material design as perovskite solar cells normally employ a polycrystalline thin-film which has a high density of grain boundary.
The final study presented in this PhD dissertation focuses on the stability of the state-of-the-art triple cation perovskite-based solar devices under external bias. Prolonged bias (more than three hours) is found to promote amorphization in halide perovskite. The amorphous phase is suspected to accumulate at the interfaces especially between the hole selective layer and perovskite. This amorphous phase inhibits the charge collection and severely affects the device performance. Nonetheless, the devices can recover after resting without bias in the dark. This amorphization is attributed to ionic defect migration most likely halides. This provides a new understanding of the potential degradation mechanisms in perovskite solar cells under operational conditions.
This cumulative thesis is concerned with the evolution of geomagnetic activity since the beginning of the 20th century, that is, the time-dependent response of the geomagnetic field to solar forcing. The focus lies on the description of the magnetospheric response field at ground level, which is particularly sensitive to the ring current system, and an interpretation of its variability in terms of the solar wind driving. Thereby, this work contributes to a comprehensive understanding of long-term solar-terrestrial interactions.
The common basis of the presented publications is formed by a reanalysis of vector magnetic field measurements from geomagnetic observatories located at low and middle geomagnetic latitudes. In the first two studies, new ring current targeting geomagnetic activity indices are derived, the Annual and Hourly Magnetospheric Currents indices (A/HMC). Compared to existing indices (e.g., the Dst index), they do not only extend the covered period by at least three solar cycles but also constitute a qualitative improvement concerning the absolute index level and the ~11-year solar cycle variability. The analysis of A/HMC shows that (a) the annual geomagnetic activity experiences an interval-dependent trend with an overall linear decline during 1900–2010 of ~5 % (b) the average trend-free activity level amounts to ~28 nT (c) the solar cycle related variability shows amplitudes of ~15–45 nT (d) the activity level for geomagnetically quiet conditions (Kp<2) lies slightly below 20 nT. The plausibility of the last three points is ensured by comparison to independent estimations either based on magnetic field measurements from LEO satellite missions (since the 1990s) or the modeling of geomagnetic activity from solar wind input (since the 1960s). An independent validation of the longterm trend is problematic mainly because the sensitivity of the locally measured geomagnetic activity depends on geomagnetic latitude. Consequently, A/HMC is neither directly comparable to global geomagnetic activity indices (e.g., the aa index) nor to the partly reconstructed open solar magnetic flux, which requires a homogeneous response of the ground-based measurements to the interplanetary magnetic field and the solar wind speed.
The last study combines a consistent, HMC-based identification of geomagnetic storms from 1930–2015 with an analysis of the corresponding spatial (magnetic local time-dependent) disturbance patterns. Amongst others, the disturbances at dawn and dusk, particularly their evolution during the storm recovery phases, are shown to be indicative of the solar wind driving structure (Interplanetary Coronal Mass Ejections vs. Stream or Co-rotating Interaction Regions), which enables a backward-prediction of the storm driver classes. The results indicate that ICME-driven geomagnetic storms have decreased since 1930 which is consistent with the concurrent decrease of HMC. Out of the collection of compiled follow-up studies the inclusion of measurements from high-latitude geomagnetic observatories into the third study’s framework seems most promising at this point.
Hydrological models are important tools for the simulation and quantification of the water cycle.
They therefore aid in the understanding of hydrological processes, prediction of river discharge, assessment of the impacts of land use and climate changes, or the management of water resources.
However, uncertainties associated with hydrological modelling are still large.
While significant research has been done on the quantification and reduction of uncertainties, there are still fields which have gained little attention so far, such as model structural uncertainties that are related to the process implementations in the models.
This holds especially true for complex process-based models in contrast to simpler conceptual models.
Consequently, the aim of this thesis is to improve the understanding of structural uncertainties with focus on process-based hydrological modelling, including methods for their quantification.
To identify common deficits of frequently used hydrological models and develop further strategies on how to reduce them, a survey among modellers was conducted.
It was found that there is a certain degree of subjectivity in the perception of modellers, for instance with respect to the distinction of hydrological models into conceptual groups.
It was further found that there are ambiguities on how to apply a certain hydrological model, for instance how many parameters should be calibrated, together with a large diversity of opinion regarding the deficits of models.
Nevertheless, evapotranspiration processes are often represented in a more physically based manner, while processes of groundwater and soil water movement are often simplified, which many survey participants saw as a drawback.
A large flexibility, for instance with respect to different alternative process implementations or a small number of parameters that needs to be calibrated, was generally seen as strength of a model.
Flexible and efficient software, which is straightforward to apply, has been increasingly acknowledged by the hydrological community.
This work further elaborated on this topic in a twofold way.
First, a software package for semi-automated landscape discretisation has been developed, which serves as a tool for model initialisation.
This was complemented by a sensitivity analysis of important and commonly used discretisation parameters, of which the size of hydrological sub-catchments as well as the size and number of hydrologically uniform computational units appeared to be more influential than information considered for the characterisation of hillslope profiles.
Second, a process-based hydrological model has been implemented into a flexible simulation environment with several alternative process representations and a number of numerical solvers.
It turned out that, even though computation times were still long, enhanced computational capabilities nowadays in combination with innovative methods for statistical analysis allow for the exploration of structural uncertainties of even complex process-based models, which up to now was often neglected by the modelling community.
In a further study it could be shown that process-based models may even be employed as tools for seasonal operational forecasting.
In contrast to statistical models, which are faster to initialise and to apply, process-based models produce more information in addition to the target variable, even at finer spatial and temporal scales, and provide more insights into process behaviour and catchment functioning.
However, the process-based model was much more dependent on reliable rainfall forecasts.
It seems unlikely that there exists a single best formulation for hydrological processes, even for a specific catchment.
This supports the use of flexible model environments with alternative process representations instead of a single model structure.
However, correlation and compensation effects between process formulations, their parametrisation, and other aspects such as numerical solver and model resolution, may lead to surprising results and potentially misleading conclusions.
In future studies, such effects should be more explicitly addressed and quantified.
Moreover, model functioning appeared to be highly dependent on the meteorological conditions and rainfall input generally was the most important source of uncertainty.
It is still unclear, how this could be addressed, especially in the light of the aforementioned correlations.
The use of innovative data products, e.g.\ remote sensing data in combination with station measurements, and efficient processing methods for the improvement of rainfall input and explicit consideration of associated uncertainties is advisable to bring more insights and make hydrological simulations and predictions more reliable.
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.
Geomorphology seeks to characterize the forms, rates, and magnitudes of sediment and water transport that sculpt landscapes. This is generally referred to as earth surface processes, which incorporates the influence of biologic (e.g., vegetation), climatic (e.g., rainfall), and tectonic (e.g., mountain uplift) factors in dictating the transport of water and eroded material. In mountains, high relief and steep slopes combine with strong gradients in rainfall and vegetation to create dynamic expressions of earth surface processes. This same rugged topography presents challenges in data collection and process measurement, where traditional techniques involving detailed observations or physical sampling are difficult to apply at the scale of entire catchments. Herein lies the utility of remote sensing. Remote sensing is defined as any measurement that does not disturb the natural environment, typically via acquisition of images in the visible- to radio-wavelength range of the electromagnetic spectrum. Remote sensing is an especially attractive option for measuring earth surface processes, because large areal measurements can be acquired at much lower cost and effort than traditional methods. These measurements cover not only topographic form, but also climatic and environmental metrics, which are all intertwined in the study of earth surface processes. This dissertation uses remote sensing data ranging from handheld camera-based photo surveying to spaceborne satellite observations to measure the expressions, rates, and magnitudes of earth surface processes in high-mountain catchments of the Eastern Central Andes in Northwest Argentina. This work probes the limits and caveats of remote sensing data and techniques applied to geomorphic research questions, and presents important progress at this disciplinary intersection.
The significant environmental and socioeconomic consequences of hydrometeorological extreme events, such as extreme rainfall, are constituted as a most important motivation for analyzing these events in the south-central Andes of NW Argentina. The steep topographic and climatic gradients and their interactions frequently lead to the formation of deep convective storms and consequently trigger extreme rainfall generation.
In this dissertation, I focus on identifying the dominant climatic variables and atmospheric conditions and their spatiotemporal variability leading to deep convection and extreme rainfall in the south-central Andes.
This dissertation first examines the significant contribution of temperature on atmospheric humidity (dew-point temperature, Td) and on convection (convective available potential energy, CAPE) for deep convective storms and hence, extreme rainfall along the topographic and climatic gradients. It was found that both climatic variables play an important role in extreme rainfall generation. However, their contributions differ depending on topographic and climatic sub-regions, as well as rainfall percentiles.
Second, this dissertation explores if (near real-time) the measurements conducted by the Global Navigation Satellite System (GNSS) on integrated water vapor (IWV) provide reliable data for explaining atmospheric humidity. I argue that GNSS-IWV, in conjunction with other atmospheric stability parameters such as CAPE, is able to decipher the extreme rainfall in the eastern central Andes. In my work, I rely on a multivariable regression analysis described by a theoretical relationship and fitting function analysis.
Third, this dissertation identifies the local impact of convection on extreme rainfall in the eastern Andes. Relying on a Principal Component Analysis (PCA) it was found that during the existence of moist and warm air, extreme rainfall is observed more often during local night hours. The analysis includes the mechanisms for this observation.
Exploring the atmospheric conditions and climatic variables leading to extreme rainfall is one of the main findings of this dissertation. The conditions and variables are a prerequisite for understanding the dynamics of extreme rainfall and predicting these events in the eastern Andes.
This thesis is concerned with Data Assimilation, the process of combining model predictions with observations. So called filters are of special interest. One is inter- ested in computing the probability distribution of the state of a physical process in the future, given (possibly) imperfect measurements. This is done using Bayes’ rule. The first part focuses on hybrid filters, that bridge between the two main groups of filters: ensemble Kalman filters (EnKF) and particle filters. The first are a group of very stable and computationally cheap algorithms, but they request certain strong assumptions. Particle filters on the other hand are more generally applicable, but computationally expensive and as such not always suitable for high dimensional systems. Therefore it exists a need to combine both groups to benefit from the advantages of each. This can be achieved by splitting the likelihood function, when assimilating a new observation and treating one part of it with an EnKF and the other part with a particle filter.
The second part of this thesis deals with the application of Data Assimilation to multi-scale models and the problems that arise from that. One of the main areas of application for Data Assimilation techniques is predicting the development of oceans and the atmosphere. These processes involve several scales and often balance rela- tions between the state variables. The use of Data Assimilation procedures most often violates relations of that kind, which leads to unrealistic and non-physical pre- dictions of the future development of the process eventually. This work discusses the inclusion of a post-processing step after each assimilation step, in which a minimi- sation problem is solved, which penalises the imbalance. This method is tested on four different models, two Hamiltonian systems and two spatially extended models, which adds even more difficulties.
In unserer digitalisierten Welt verlagert sich das Lernen in die Cloud. Vom Unterricht in der Schule und der Tafel zum Tablet, hin zu einem lebenslangen Lernen in der Arbeitswelt und sogar darüber hinaus. Wie erfolgreich und attraktiv dieses zeitgemäße Lernen erfolgt, hängt nicht unwesentlich von den technologischen Möglichkeiten ab, die digitale Lernplattformen rund um MOOCs und Schul-Clouds bieten.
Bei deren Weiterentwicklung sollten statt ökonomischen Messgrößen und KPIs die Lernenden und ihre Lernerfahrungen im Vordergrund stehen.
Hierfür wurde ein Optimierungsframework entwickelt, das für die Entwicklung von Lernplattformen anhand verschiedener qualitativer und quantitative Methoden Verbesserungen identifiziert, priorisiert und deren Beurteilung und Umsetzung steuert.
Datengestützte Entscheidungen sollten auf einer ausreichenden Datenbasis aufbauen. Moderne Web-Anwendungen bestehen aber oft aus mehreren Microservices mit jeweils eigener Datenhaltung. Viele Daten sind daher nicht mehr einfach zugänglich. Daher wird in dieser Arbeit ein Learning Analytics Dienst eingeführt, der diese Daten sammelt und verarbeitet. Darauf aufbauend werden Metriken eingeführt, auf deren Grundlage die erfassten Daten nutzbar werden und die somit zu verschiedenen Zwecken verwendet werden können.
Neben der Visualisierung der Daten in Dashboards werden die Daten für eine automatisierte Qualitätskontrolle herangezogen. So kann festgestellt werden, wenn Tests zu schwierig oder die soziale Interaktion in einem MOOC zu gering ist.
Die vorgestellte Infrastruktur lässt sich aber auch verwenden, um verschiedene A/B/n-Tests durchzuführen. In solchen Tests gibt es mehrere Varianten, die an verschiedene Nutzergruppen in einem kontrollierten Experiment erprobt werden. Dank der vorgestellten Testinfrastruktur, die in der HPI MOOC Plattform eingebaut wurde, kann ermittelt werden, ob sich für diese Gruppen statistisch signifikante Änderungen in der Nutzung feststellen lassen. Dies wurde mit fünf verschiedenen Verbesserungen der HPI MOOC Plattform evaluiert, auf der auch openHPI und openSAP basieren.
Dabei konnte gezeigt werden, dass sich Lernende mit reaktivierenden Mails zurück in den Kurs holen lassen. Es ist primär die Kommunikation der unbearbeiteten Lerninhalte des Nutzers, die eine reaktivierende Wirkung hat.
Auch Übersichtsmails, die die Forenaktivität zusammenfassen, haben einen positiven Effekt erzielt.
Ein gezieltes On-Boarding kann dazu führen, dass die Nutzer die Plattform besser verstehen und hierdurch aktiver sind.
Der vierte Test konnte zeigen, dass die Zuordnung von Forenfragen zu einem bestimmten Zeitpunkt im Video und die grafische Anzeige dieser Informationen zu einer erhöhten Forenaktivität führt.
Auch die experimentelle Erprobung von unterschiedlichen Lernmaterialien, wie sie im fünften Test durchgeführt wurde, ist in MOOCs hilfreich, um eine Verbesserung der Kursmaterialien zu erreichen.
Neben diesen funktionalen Verbesserungen wird untersucht wie MOOC Plattformen und Schul-Clouds einen Nutzen bieten können, wenn Nutzern nur eine schwache oder unzuverlässige Internetanbindung zur Verfügung steht (wie dies in vielen deutschen Schulen der Fall ist). Hier wird gezeigt, dass durch ein geschicktes Vorausladen von Daten die Internetanbindungen entlastet werden können. Teile der Lernanwendungen funktionieren dank dieser Anpassungen, selbst wenn keine Verbindung zum Internet besteht.
Als Letztes wird gezeigt, wie Endgeräte sich in einem lokalen Peer-to-Peer CDN gegenseitig mit Daten versorgen können, ohne dass diese aus dem Internet heruntergeladen werden müssen.
Seit Jahrzehnten stellen die molekularen Schalter ein wachsendes Forschungsgebiet dar. Im Rahmen dieser Dissertation stand die Verbesserung der thermischen Stabilität, der Auslesbarkeit und Schaltbarkeit dieser molekularen Schalter in komplexen Umgebungen mithilfe computergestützter Chemie im Vordergrund.
Im ersten Projekt wurde die Kinetik der thermischen E → Z-Isomerisierung und die damit verbundene thermische Stabilität eines Azobenzol-Derivats untersucht. Dafür wurde Dichtefunktionaltheorie (DFT) in Verbindung mit der Eyring-Theorie des Übergangszustandes (TST) angewendet. Das Azobenzol-Derivat diente als vereinfachtes Modell für das Schalten in einer komplexen Umgebung (hier in metallorganischen Gerüsten). Es wurden thermodynamische und kinetische Größen unter verschiedenen Einflüssen berechnet, wobei gute Übereinstimmungen mit dem Experiment gefunden wurden. Die hier verwendete Methode stellte einen geeigneten Ansatz dar, um diese Größen mit angemessener Genauigkeit vorherzusagen.
Im zweiten Projekt wurde die Auslesbarkeit der Schaltzustände in Form des nichtlinearen optischen (NLO) Kontrastes für die Molekülklasse der Fulgimide untersucht. Die dafür benötigten dynamischen Hyperpolarisierbarkeiten unter Berücksichtigung der Elektronenkorrelation wurden mittels einer etablierten Skalierungsmethode berechnet. Es wurden verschiedene Fulgimide analysiert, wobei viele experimentelle Befunde bestätigt werden konnten. Darüber hinaus legte die theoretische Vorhersage für ein weiteres System nahe, dass insbesondere die Erweiterung des π-Elektronensystems ein vielversprechender Ansatz zur Verbesserung von NLO-Kontrasten darstellt. Die Fulgimide verfügen somit über nützliche Eigenschaften, sodass diese in Zukunft als Bauelemente in photonischen und optoelektronischen Bereichen Anwendungen finden könnten.
Im dritten Projekt wurde die E → Z-Isomerisierung auf ein quantenmechanisch (QM) behandeltes Dimer mit molekularmechanischer (MM) Umgebung und zwei Fluorazobenzol-Monomeren durch Moleküldynamik simuliert. Dadurch wurde die Schaltbarkeit in komplexer Umgebung (hier selbstorgansierte Einzelschichten = SAMs) bzw. von Azobenzolderivaten analysiert. Mit dem QM/MM Modell wurden sowohl Van-der-Waals-Interaktionen mit der Umgebung als auch elektronische Kopplung (nur zwischen QM-Molekülen) berücksichtigt. Dabei wurden systematische Untersuchungen zur Packungsdichte durchgeführt. Es zeigte sich, dass bereits bei einem Molekülabstand von 4.5 Å die Quantenausbeute (prozentuale Anzahl erfolgreicher Schaltprozesse) des Monomers erreicht wird. Die größten Quantenausbeuten wurden für die beiden untersuchten Fluorazobenzole erzielt. Es wurden die Effekte des Molekülabstandes und der Einfluss von Fluorsubstituenten auf die Dynamik eingehend untersucht, sodass der Weg für darauf aufbauende Studien geebnet ist.
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.
Near-Earth space represents a significant scientific and technological challenge. Particularly at magnetic low-latitudes, the horizontal magnetic field geometry at the dip equator and its closed field-lines support the existence of a distinct electric current system, abrupt electric field variations and the development of plasma irregularities. Of particular interest are small-scale irregularities associated with equatorial plasma depletions (EPDs). They are responsible for the disruption of trans-ionospheric radio waves used for navigation, communication, and Earth observation. The fast increase of satellite missions makes it imperative to study the near-Earth space, especially the phenomena known to harm space technology or disrupt their signals. EPDs correspond to the large-scale structure (i.e., tens to hundreds of kilometers) of topside F region irregularities commonly known as Spread F. They are observed as depleted-plasma density channels aligned with the ambient magnetic field in the post-sunset low-latitude ionosphere. Although the climatological variability of their occurrence in terms of season, longitude, local time and solar flux is well-known, their day to day variability is not. The sparse observations from ground-based instruments like radars and the few simultaneous measurements of ionospheric parameters by space-based instruments have left gaps in the knowledge of EPDs essential to comprehend their variability.
In this dissertation, I profited from the unique observations of the ESA’s Swarm constellation mission launched in November 2013 to tackle three issues that revealed novel and significant results on the current knowledge of EPDs. I used Swarm’s measurements of the electron density, magnetic, and electric fields to answer, (1.) what is the direction of propagation of the electromagnetic energy associated with EPDs?, (2.) what are the spatial and temporal characteristics of the electric currents (field-aligned and diamagnetic currents) related to EPDs, i.e., seasonal/geographical, and local time dependencies?, and (3.) under what conditions does the balance between magnetic and plasma pressure across EPDs occur?
The results indicate that: (1.) The electromagnetic energy associated with EPDs presents a preference for interhemispheric flows; that is, the related Poynting flux directs from one magnetic hemisphere to the other and varies with longitude and season. (2.) The field-aligned currents at the edges of EPDs are interhemispheric. They generally close in the hemisphere with the highest Pedersen conductance. Such hemispherical preference presents a seasonal/longitudinal dependence. The diamagnetic currents increase or decrease the magnetic pressure inside EPDs. These two effects rely on variations of the plasma temperature inside the EPDs that depend on longitude and local time. (3.) EPDs present lower or higher plasma pressure than the ambient. For low-pressure EPDs the plasma pressure gradients are mostly dominated by variations of the plasma density so that variations of the temperature are negligible. High-pressure EPDs suggest significant temperature variations with magnitudes of approximately twice the ambient. Since their occurrence is more frequent in the vicinity of the South Atlantic magnetic anomaly, such high temperatures are suggested to be due to particle precipitation.
In a broader context, this dissertation shows how dedicated satellite missions with high-resolution capabilities improve the specification of the low-latitude ionospheric electrodynamics and expand knowledge on EPDs which is valuable for current and future communication, navigation, and Earth-observing missions. The contributions of this investigation represent several ’firsts’ in the study of EPDs: (1.) The first observational evidence of interhemispheric electromagnetic energy flux and field-aligned currents. (2.) The first spatial and temporal characterization of EPDs based on their associated field-aligned and diamagnetic currents. (3.) The first evidence of high plasma pressure in regions of depleted plasma density in the ionosphere. These findings provide new insights that promise to advance our current knowledge of not only EPDs but the low-latitude post-sunset ionosphere environment.
Urbanization and agricultural land use are two of the main drivers of global changes with effects on ecosystem functions and human wellbeing. Green Infrastructure is a new approach in spatial planning contributing to sustainable urban development, and to address urban challenges, such as biodiversity conservation, climate change adaptation, green economy development, and social cohesion. Because the research focus has been mainly on open green space structures, such as parks, urban forest, green building, street green, but neglected spatial and functional potentials of utilizable agricultural land, this thesis aims at fill this gap.
This cumulative thesis addresses how agricultural land in urban and peri-urban landscapes can contribute to the development of urban green infrastructure as a strategy to promote sustainable urban development. Therefore, a number of different research approaches have been applied. First, a quantitative, GIS-based modeling approach looked at spatial potentials, addressing the heterogeneity of peri-urban landscape that defines agricultural potentials and constraints. Second, a participatory approach was applied, involving stakeholder opinions to evaluate multiple urban functions and benefits. Finally, an evidence synthesis was conducted to assess the current state of research on evidence to support future policy making at different levels.
The results contribute to the conceptual understanding of urban green infrastructures as a strategic spatial planning approach that incorporates inner-urban utilizable agricultural land and the agriculturally dominated landscape at the outer urban fringe. It highlights the proposition that the linkage of peri-urban farmland with the green infrastructure concept can contribute to a network of multifunctional green spaces to provide multiple benefits to the urban system and to successfully address urban challenges. Four strategies are introduced for spatial planning with the contribution of peri-urban farmland to a strategically planned multifunctional network, namely the connecting, the productive, the integrated, and the adapted way. Finally, this thesis sheds light on the opportunities that arise from the integration of the peri- urban farmland in the green infrastructure concept to support transformation towards a more sustainable urban development. In particular, the inherent core planning principle of multifunctionality endorses the idea of co-benefits that are considered crucial to trigger transformative processes.
This work concludes that the linkage of peri-urban farmland with the green infrastructure concept is a promising action field for the development of new pathways for urban transformation towards sustainable urban development. Along with these outcomes, attention is drawn to limitations that remain to be addressed by future research, especially the identification of further mechanisms required to support policy integration at all levels.
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.
Die Gesundheitswirtschaft in Deutschland steht vor zahlreichen Veränderungen in ihrem Umfeld. Dabei mangelt es der Krankenhauslandschaft an ärztlichem Personal. Es fehlt insbesondere an Arztstunden bei zugleich steigendem Bedarf an medizinischen Leistungen. Der demografische Wandel, Abwanderung ins Ausland (z. B. in die Schweiz) und Extrapolationen wie Feminisierung des Arztberufs und der Wertewandel respektive Generationenforschung begünstigen diese
Entwicklung. Zudem wird der Arbeitsplatz Krankenhaus zunehmend als unattraktiv von zukünftigen Arbeitnehmerkohorten angesehen. Nachwuchsärzte entscheiden sich bereits im Studium vermehrt gegen die kurative Medizin beziehungsweise gegen eine medizinisch-klinische Tätigkeit. Ein virulentes Beschaffungsproblem zeichnet sich ab, das es zu lösen gilt.
Das Forschungsziel ist die Entwicklung eines ganzheitlichen strategischen Lösungsansatzes mit marktorientierter Akzentuierung für den Arbeitgeber Krankenhaus. Dabei wird das Krankenhaus als wissens- und kompetenzintensive Dienstleistungsorganisation definiert. Employer Branding stellt den Bezugsrahmen eines marktorientierten Personalmanagements dar. Ein forschungstheoretischer Unterbau wird durch strategische Managementansätze integriert. Employer Branding schlägt die Brücke vom Market-based View zum Competence-based View und ist Markenmanagement im Kontext des strategischen Personalmanagements. In der vorliegenden Arbeit wird ein holistischer Bezugsrahmen vorgestellt, der die Wirkungszusammenhänge respektive Employer Branding darstellt. Das Herzstück ist die Employer Value Proposition, die auf der Markenidentität der Organisation basiert. Ziel des Employer Branding Ansatzes ist es, unter anderem eine präferenzerzeugende Wirkung im Prozess der Arbeitsplatzwahl sicherzustellen.
Die Zielrichtung und die Erkenntnis-Interessen erfordern einen breit angelegten Forschungsansatz, der qualitative und quantitative Methoden kombiniert. Ziel der leitfadengesteuerten Tiefeninterviews (exploratives Studiendesign) ist es, bestehende und noch zu entwickelnde Kompetenzstärken der Krankenhausorganisationen zu identifizieren. Bei der Stichprobe handelt es sich um ein „Typical Case Sampling“ (N=12). Defizitäre Befunde, welche Werte und Attraktivitätsfaktoren bei angehenden Ärzten ausgeprägt sind, werden bestätigt. In der Krankenhauslandschaft wird eine fragmentarische und reaktive Herangehensweise identifiziert, die die erfolgreiche Rekrutierung von qualifiziertem Krankenhauspersonal erschwert.
Durch die qualitative Marktforschung werden Anforderungen des Marktes – also zukünftiges, ärztliches Krankenhauspersonal – auf faktorenanalytischer Basis analysiert. Die Stichprobe (N=475) ist isomorph. Dabei wird der Prozess der Einstellungsbildung in das neobehavioristische Erklärungsmodell des Käuferverhaltens eingeordnet. Die Vereinbarkeit von Beruf, Karriere und Familie sowie die betriebliche Kinderbetreuung werden als Schlüsselkomponenten erkannt.
Wichtigste Arbeitswerte in Bezug auf einen attraktiven Arbeitgeber sind Verlässlichkeit, Verantwortung und Respekt. Diese Komponenten haben kommunikativen Nutzen und Differenzierungskraft. Schließlich bewerten Bewerber ein Krankenhaus positiver im Prozess der Arbeitsplatzwahl, je mehr die Werte des potentiellen Arbeitnehmers mit dem Werteprofil der Person übereinstimmen (Person-Organisation Fit).
Krankenhausorganisationen, die den Employer Branding Ansatz implementieren und als Chance zur Definition ihrer Stärken, ihrer Vorzüge und ihres Leistungsangebots als Arbeitgeber annehmen, rüsten sich für das verstärkte Werben um Jungmediziner. Schließlich setzt Employer Branding als marktorientierter Strategieansatz intern und extern Kräfte frei, die Differenzierungsvorteile gegenüber anderen Arbeitgebern bringen. Dabei hat Employer Branding positive Auswirkungen auf den Human Ressource-Bereich entlang der Wertschöpfungskette und mindert das gesamtwirtschaftliche Problem.
Even though the majority of individuals know that exercising is healthy, a high percentage struggle to achieve the recommended amount of exercise. The (social-cognitive) theories that are commonly applied to explain exercise motivation refer to the assumption that people base their decisions mainly on rational reasoning. However, behavior is not only bound to reflection. In recent years, the role of automaticity and affect for exercise motivation has been increasingly discussed. In this dissertation, central assumptions of the affective–reflective theory of physical inactivity and exercise (ART; Brand & Ekkekakis, 2018), an exercise-specific dual-process theory that emphasizes the role of a momentary automatic affective reaction for exercise-decisions, were examined. The central aim of this dissertation was to investigate exercisers and non-exercisers automatic affective reactions to exercise-related stimuli (i.e., type-1 process). In particular, the two components of the ART’s type-1 process, that are, automatic associations with exercise and the automatic affective valuation to exercise, were under study.
In the first publication (Schinkoeth & Antoniewicz, 2017), research on automatic (evaluative) associations with exercise was summarized and evaluated in a systematic review. The results indicated that automatic associations with exercise appeared to be relevant predictors for exercise behavior and other exercise-related variables, providing evidence for a central assumption of the ART’s type-1 process. Furthermore, indirect methods seem to be suitable to assess automatic associations. The aim of the second publication (Schinkoeth, Weymar, & Brand, 2019) was to approach the somato-affective core of the automatic valuation of exercise using analysis of reactivity in vagal HRV while viewing exercise-related pictures. Results revealed that differences in exercise volume could be regressed on HRV reactivity. In light of the ART, these findings were interpreted as evidence of an inter-individual affective reaction elicited at the thought of exercise and triggered by exercise-stimuli. In the third publication (Schinkoeth & Brand, 2019, subm.), it was sought to disentangle and relate to each other the ART’s type-1 process components—automatic associations and the affective valuation of exercise. Automatic associations to exercise were assessed with a recoding-free variant of an implicit association test (IAT). Analysis of HRV reactivity was applied to approach a somatic component of the affective valuation, and facial reactions in a facial expression (FE) task served as indicators of the automatic affective reaction’s valence. Exercise behavior was assessed via self-report. The measurement of the affective valuation’s valence with the FE task did not work well in this study. HRV reactivity was predicted by the IAT score and did also statistically predict exercise behavior. These results thus confirm and expand upon the results of publication two and provide empirical evidence for the type-1 process, as defined in the ART. This dissertation advances the field of exercise psychology concerning the influence of automaticity and affect on exercise motivation. Moreover, both methodical implications and theoretical extensions for the ART can be derived from the results.
Geomechanical and petrological characterisation of exposed slip zones, Alpine Fault, New Zealand
(2020)
The Alpine Fault is a large, plate-bounding, strike-slip fault extending along the north-western edge of the Southern Alps, South Island, New Zealand. It regularly accommodates large (MW > 8) earthquakes and has a high statistical probability of failure in the near future, i.e., is late in its seismic cycle. This pending earthquake and associated co-seismic landslides are expected to cause severe infrastructural damage that would affect thousands of people, so it presents a substantial geohazard. The interdisciplinary study presented here aims to characterise the fault zone’s 4D (space and time) architecture, because this provides information about its rheological properties that will enable better assessment of the hazard
the fault poses.
The studies undertaken include field investigations of principal slip zone fault gouges exposed
along strike of the fault, and subsequent laboratory analyses of these outcrop and additional borehole samples. These observations have provided new information on (I) characteristic microstructures down to the nanoscale that indicate which deformation mechanisms operated within the rocks, (II) mineralogical information that constrains the fault’s geomechanical behaviour and (III) geochemical compositional information that allows the influence of fluid- related alteration processes on material properties to be unraveled.
Results show that along-strike variations of fault rock properties such as microstructures and mineralogical composition are minor and / or do not substantially influence fault zone architecture. They furthermore provide evidence that the architecture of the fault zone, particularly its fault core, is more complex than previously considered, and also more complex than expected for this sort of mature fault cutting quartzofeldspathic rocks. In particular our results strongly suggest that the fault has more than one principal slip zone, and that these form an anastomosing network extending into the basement below the cover of Quaternary sediments.
The observations detailed in this thesis highlight that two major processes, (I) cataclasis and (II) authigenic mineral formation, are the major controls on the rheology of the Alpine Fault. The velocity-weakening behaviour of its fault gouge is favoured by abundant nanoparticles
promoting powder lubrication and grain rolling rather than frictional sliding. Wall-rock fragmentation is accompanied by co-seismic, fluid-assisted dilatancy that is recorded by calcite cementation. This mineralisation, along with authigenic formation of phyllosilicates, quickly alters the petrophysical fault zone properties after each rupture, restoring fault competency. Dense networks of anastomosing and mutually cross-cutting calcite veins and intensively reworked gouge matrix demonstrate that strain repeatedly localised within the narrow fault gouge. Abundantly undeformed euhedral chlorite crystallites and calcite veins cross-cutting both fault gouge and gravels that overlie basement on the fault’s footwall provide evidence that the processes of authigenic phyllosilicate growth, fluid-assisted dilatancy and associated fault healing are processes active particularly close to the Earth’s surface in this fault zone.
Exposed Alpine Fault rocks are subject to intense weathering as direct consequence of abundant orogenic rainfall associated with the fault’s location at the base of the Southern Alps. Furthermore, fault rock rheology is substantially affected by shallow-depth conditions such as the juxtaposition of competent hanging wall fault rocks on poorly consolidated footwall sediments. This means microstructural, mineralogical and geochemical properties of the exposed fault rocks may differ substantially from those at deeper levels, and thus are not characteristic of the majority of the fault rocks’ history. Examples are (I) frictionally weak smectites found within the fault gouges being artefacts formed at temperature conditions, and imparting petrophysical properties that are not typical for most of fault rocks of the Alpine Fault, (II) grain-scale dissolution resulting from subaerial weathering rather than deformation by pressure-solution processes and (III) fault gouge geometries being more complex than expected for deeper counterparts.
The methodological approaches deployed in analyses of this, and other fault zones, and the major results of this study are finally discussed in order to contextualize slip zone investigations of fault zones and landslides. Like faults, landslides are major geohazards, which highlights the importance of characterising their geomechanical properties. Similarities between faults, especially those exposed to subaerial processes, and landslides, include mineralogical composition and geomechanical behaviour. Together, this ensures failure occurs predominantly by cataclastic processes, although aseismic creep promoted by weak phyllosilicates is not uncommon. Consequently, the multidisciplinary approach commonly used to investigate fault zones may contribute to increase the understanding of landslide faulting processes and the assessment of their hazard potential.
Die vorliegende Untersuchung analysierte den direkten Zusammenhang eines berufsbezogenen Angebots Sozialer Gruppenarbeit mit dem Ergebnis beruflicher Wiedereingliederung bei Rehabilitandinnen und Rehabilitanden in besonderen beruflichen Problemlagen. Sie wurde von der Deutschen Rentenversicherung Bund als Forschungsprojekt vom 01.01.2013 bis 31.12. 2015 gefördert und an der Professur für Rehabilitationswissenschaften der Universität Potsdam realisiert.
Die Forschungsfrage lautete: Kann eine intensive sozialarbeiterische Gruppenintervention im Rahmen der stationären medizinischen Rehabilitation soweit auf die Stärkung sozialer Kompetenzen und die Soziale Unterstützung von Rehabilitandinnen und Rehabilitanden einwirken, dass sich dadurch langfristige Verbesserungen hinsichtlich der beruflichen Wiedereingliederung im Vergleich zur konventionellen Behandlung ergeben?
Die Studie gliederte sich in eine qualitative und eine quantitative Erhebung mit einer zwischenliegenden Intervention. Eingeschlossen waren 352 Patientinnen und Patienten im Alter zwischen 18 und 65 Jahren mit kardiovaskulären Diagnosen, deren Krankheitsbilder häufig von komplexen Problemlagen begleitet sind, verbunden mit einer schlechten sozialmedizinischen Prognose.
Die Evaluation der Gruppenintervention erfolgte in einem clusterrandomisierten kontrollierten Studiendesign, um einen empirischen Nachweis darüber zu erbringen, inwieweit die Intervention gegenüber der regulären sozialarbeiterischen Behandlung höhere Effekte erzielen kann. Die Interventionsgruppen nahmen am Gruppenprogramm teil, die Kontrollgruppen erhielten die reguläre sozialarbeiterische Behandlung.
Im Ergebnis konnte mit dieser Stichprobe kein Nachweis zur Verbesserung der beruflichen Wiedereingliederung, der gesundheitsbezogenen Arbeitsfähigkeit, der Lebensqualität sowie der Sozialen Unterstützung durch die Teilnahme am sozialarbeiterischen Gruppenprogramm erbracht werden. Die Return-To-Work-Rate betrug 43,7 %, ein Viertel der Untersuchungsgruppe befand sich nach einem Jahr in Arbeitslosigkeit. Die durchgeführte Gruppenintervention ist dem konventionellen Setting Sozialer Arbeit als gleichwertig anzusehen.
Schlussfolgernd wurde auf eine sozialarbeiterische Unterstützung der beruflichen Wiedereingliederung über einen längeren Zeitraum nach einer kardiovaskulären Erkrankung verwiesen, insbesondere durch wohnortnahe Angebote zu einem späteren Zeitpunkt bei stabilerer Gesundheit. Aus den Erhebungen ließen sich mögliche Erfolge bei engerer Kooperation zwischen dem Fachbereich der Sozialen Arbeit und der Psychologie ableiten. Ebenfalls gab es Hinweise auf die einflussreiche Rolle der Angehörigen, die durch Einbindung in die Soziale Beratung unterstützend auf den Wiedereingliederungsprozess wirken könnten. Die Passgenauigkeit der untersuchten sozialarbeiterischen Gruppeninterventionen ist durch eine gezielte Soziale Diagnostik zu verbessern.
Chloroplasts are the photosynthetic organelles in plant and algae cells that enable photoautotrophic growth. Due to their prokaryotic origin, modern-day chloroplast genomes harbor 100 to 200 genes. These genes encode for core components of the photosynthetic complexes and the chloroplast gene expression machinery, making most of them essential for the viability of the organism. The regulation of those genes is predominated by translational adjustments. The powerful technique of ribosome profiling was successfully used to generate highly resolved pictures of the translational landscape of Arabidopsis thaliana cytosol, identifying translation of upstream open reading frames and long non-coding transcripts. In addition, differences in plastidial translation and ribosomal pausing sites were addressed with this method. However, a highly resolved picture of the chloroplast translatome is missing. Here, with the use of chloroplast isolation and targeted ribosome affinity purification, I generated highly enriched ribosome profiling datasets of the chloroplasts translatome for Nicotiana tabacum in the dark and light. Chloroplast isolation was found unsuitable for the unbiased analysis of translation in the chloroplast but adequate to identify potential co-translational import. Affinity purification was performed for the small and large ribosomal subunit independently. The enriched datasets mirrored the results obtained from whole-cell ribosome profiling. Enhanced translational activity was detected for psbA in the light. An alternative translation initiation mechanism was not identified by selective enrichment of small ribosomal subunit footprints. In sum, this is the first study that used enrichment strategies to obtain high-depth ribosome profiling datasets of chloroplasts to study ribosome subunit distribution and chloroplast associated translation.
Ever-changing light intensities are challenging the photosynthetic capacity of photosynthetic organism. Increased light intensities may lead to over-excitation of photosynthetic reaction centers resulting in damage of the photosystem core subunits. Additional to an expensive repair mechanism for the photosystem II core protein D1, photosynthetic organisms developed various features to reduce or prevent photodamage. In the long-term, photosynthetic complex contents are adjusted for the efficient use of experienced irradiation. However, the contribution of chloroplastic gene expression in the acclimation process remained largely unknown. Here, comparative transcriptome and ribosome profiling was performed for the early time points of high-light acclimation in Nicotiana tabacum chloroplasts in a genome-wide scale. The time- course data revealed stable transcript level and only minor changes in translational activity of specific chloroplast genes during high-light acclimation. Yet, psbA translation was increased by two-fold in the high light from shortly after the shift until the end of the experiment. A stress-inducing shift from low- to high light exhibited increased translation only of psbA. This study indicate that acclimation fails to start in the observed time frame and only short-term responses to reduce photoinhibition were observed.
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.
The hepatokine FGF21 and the adipokine chemerin have been implicated as metabolic regulators and mediators of inter-tissue crosstalk. While FGF21 is associated with beneficial metabolic effects and is currently being tested as an emerging therapeutic for obesity and diabetes, chemerin is linked to inflammation-mediated insulin resistance. However, dietary regulation of both organokines and their role in tissue interaction needs further investigation.
The LEMBAS nutritional intervention study investigated the effects of two diets differing in their protein content in obese human subjects with non-alcoholic fatty liver disease (NAFLD). The study participants consumed hypocaloric diets containing either low (LP: 10 EN%, n = 10) or high (HP: 30 EN%, n = 9) dietary protein 3 weeks prior to bariatric surgery. Before and after the intervention the participants were anthropometrically assessed, blood samples were drawn, and hepatic fat content was determined by MRS. During bariatric surgery, paired subcutaneous and visceral adipose tissue biopsies as well as liver biopsies were collected. The aim of this thesis was to investigate circulating levels and tissue-specific regulation of (1) FGF21 and (2) chemerin in the LEMBAS cohort. The results were compared to data obtained in 92 metabolically healthy subjects with normal glucose tolerance and normal liver fat content.
(1) Serum FGF21 concentrations were elevated in the obese subjects, and strongly associated with intrahepatic lipids (IHL). In accordance, FGF21 serum concentrations increased with severity of NAFLD as determined histologically in the liver biopsies. Though both diets were successful in reducing IHL, the effect was more pronounced in the HP group. FGF21 serum concentrations and mRNA expression were bi-directionally regulated by dietary protein, independent from metabolic improvements. In accordance, in the healthy study subjects, serum FGF21 concentrations dropped by more than 60% in response to the HP diet. A short-term HP intervention confirmed the acute downregulation of FGF21 within 24 hours. Lastly, experiments in HepG2 cell cultures and primary murine hepatocytes identified nitrogen metabolites (NH4Cl and glutamine) to dose-dependently suppress FGF21 expression.
(2) Circulating chemerin concentrations were considerably elevated in the obese versus lean study participants and differently associated with markers of obesity and NAFLD in the two cohorts. The adipokine decreased in response to the hypocaloric interventions while an unhealthy high-fat diet induced a rise in chemerin serum levels. In the lean subjects, mRNA expression of RARRES2, encoding chemerin, was strongly and positively correlated with expression of several cytokines, including MCP1, TNFα, and IL6, as well as markers of macrophage infiltration in the subcutaneous fat depot. However, RARRES2 was not associated with any cytokine assessed in the obese subjects and the data indicated an involvement of chemerin not only in the onset but also resolution of inflammation. Analyses of the tissue biopsies and experiments in human primary adipocytes point towards a role of chemerin in adipogenesis while discrepancies between the in vivo and in vitro data were detected.
Taken together, the results of this thesis demonstrate that circulating FGF21 and chemerin levels are considerably elevated in obesity and responsive to dietary interventions. FGF21 was acutely and bi-directionally regulated by dietary protein in a hepatocyte-autonomous manner. Given that both, a lack in essential amino acids and excessive nitrogen intake, exert metabolic stress, FGF21 may serve as an endocrine signal for dietary protein balance. Lastly, the data revealed that chemerin is derailed in obesity and associated with obesity-related inflammation. However, future studies on chemerin should consider functional and regulatory differences between secreted and tissue-specific isoforms.
To investigate the reliability and stability of spherical harmonic models based on archeo/-paleomagnetic data, 2000 Geomagnetic models were calculated. All models are based on the same data set but with randomized uncertainties. Comparison of these models to the geomagnetic field model gufm1 showed that large scale magnetic field structures up to spherical harmonic degree 4 are stable throughout all models. Through a ranking of all models by comparing the dipole coefficients to gufm1 more realistic uncertainty estimates were derived than the authors of the data provide.
The derived uncertainty estimates were used in further modelling, which combines archeo/-paleomagnetic and historical data. The huge difference in data count, accuracy and coverage of these two very different data sources made it necessary to introduce a time dependent spatial damping, which was constructed to constrain the spatial complexity of the model. Finally 501 models were calculated by considering that each data point is a Gaussian random variable, whose mean is the original value and whose standard deviation is its uncertainty. The final model arhimag1k is calculated by taking the mean of the 501 sets of Gauss coefficients. arhimag1k fits different dependent and independent data sets well. It shows an early reverse flux patch at the core-mantle boundary between 1000 AD and 1200 AD at the location of the South Atlantic Anomaly today. Another interesting feature is a high latitude flux patch over Greenland between 1200 and 1400 AD. The dipole moment shows a constant behaviour between 1600 and 1840 AD.
In the second part of the thesis 4 new paleointensities from 4 different flows of the island Fogo, which is part of Cape Verde, are presented. The data is fitted well by arhimag1k with the exception of the value at 1663 of 28.3 microtesla, which is approximately 10 microtesla lower than the model suggest.
In today's world, many applications produce large amounts of data at an enormous rate. Analyzing such datasets for metadata is indispensable for effectively understanding, storing, querying, manipulating, and mining them. Metadata summarizes technical properties of a dataset which rang from basic statistics to complex structures describing data dependencies. One type of dependencies is inclusion dependency (IND), which expresses subset-relationships between attributes of datasets. Therefore, inclusion dependencies are important for many data management applications in terms of data integration, query optimization, schema redesign, or integrity checking. So, the discovery of inclusion dependencies in unknown or legacy datasets is at the core of any data profiling effort.
For exhaustively detecting all INDs in large datasets, we developed S-indd++, a new algorithm that eliminates the shortcomings of existing IND-detection algorithms and significantly outperforms them. S-indd++ is based on a novel concept for the attribute clustering for efficiently deriving INDs. Inferring INDs from our attribute clustering eliminates all redundant operations caused by other algorithms. S-indd++ is also based on a novel partitioning strategy that enables discording a large number of candidates in early phases of the discovering process. Moreover, S-indd++ does not require to fit a partition into the main memory--this is a highly appreciable property in the face of ever-growing datasets. S-indd++ reduces up to 50% of the runtime of the state-of-the-art approach.
None of the approach for discovering INDs is appropriate for the application on dynamic datasets; they can not update the INDs after an update of the dataset without reprocessing it entirely. To this end, we developed the first approach for incrementally updating INDs in frequently changing datasets. We achieved that by reducing the problem of incrementally updating INDs to the incrementally updating the attribute clustering from which all INDs are efficiently derivable. We realized the update of the clusters by designing new operations to be applied to the clusters after every data update. The incremental update of INDs reduces the time of the complete rediscovery by up to 99.999%.
All existing algorithms for discovering n-ary INDs are based on the principle of candidate generation--they generate candidates and test their validity in the given data instance. The major disadvantage of this technique is the exponentially growing number of database accesses in terms of SQL queries required for validation. We devised Mind2, the first approach for discovering n-ary INDs without candidate generation. Mind2 is based on a new mathematical framework developed in this thesis for computing the maximum INDs from which all other n-ary INDs are derivable. The experiments showed that Mind2 is significantly more scalable and effective than hypergraph-based algorithms.
Distance Education or e-Learning platform should be able to provide a virtual laboratory to let the participants have hands-on exercise experiences in practicing their skill remotely. Especially in Cybersecurity e-Learning where the participants need to be able to attack or defend the IT System. To have a hands-on exercise, the virtual laboratory environment must be similar to the real operational environment, where an attack or a victim is represented by a node in a virtual laboratory environment. A node is usually represented by a Virtual Machine (VM). Scalability has become a primary issue in the virtual laboratory for cybersecurity e-Learning because a VM needs a significant and fix allocation of resources. Available resources limit the number of simultaneous users. Scalability can be increased by increasing the efficiency of using available resources and by providing more resources. Increasing scalability means increasing the number of simultaneous users.
In this thesis, we propose two approaches to increase the efficiency of using the available resources. The first approach in increasing efficiency is by replacing virtual machines (VMs) with containers whenever it is possible. The second approach is sharing the load with the user-on-premise machine, where the user-on-premise machine represents one of the nodes in a virtual laboratory scenario. We also propose two approaches in providing more resources. One way to provide more resources is by using public cloud services. Another way to provide more resources is by gathering resources from the crowd, which is referred to as Crowdresourcing Virtual Laboratory (CRVL).
In CRVL, the crowd can contribute their unused resources in the form of a VM, a bare metal system, an account in a public cloud, a private cloud and an isolated group of VMs, but in this thesis, we focus on a VM. The contributor must give the credential of the VM admin or root user to the CRVL system. We propose an architecture and methods to integrate or dis-integrate VMs from the CRVL system automatically. A Team placement algorithm must also be investigated to optimize the usage of resources and at the same time giving the best service to the user. Because the CRVL system does not manage the contributor host machine, the CRVL system must be able to make sure that the VM integration will not harm their system and that the training material will be stored securely in the contributor sides, so that no one is able to take the training material away without permission. We are investigating ways to handle this kind of threats.
We propose three approaches to strengthen the VM from a malicious host admin. To verify the integrity of a VM before integration to the CRVL system, we propose a remote verification method without using any additional hardware such as the Trusted Platform Module chip. As the owner of the host machine, the host admins could have access to the VM's data via Random Access Memory (RAM) by doing live memory dumping, Spectre and Meltdown attacks. To make it harder for the malicious host admin in getting the sensitive data from RAM, we propose a method that continually moves sensitive data in RAM. We also propose a method to monitor the host machine by installing an agent on it. The agent monitors the hypervisor configurations and the host admin activities.
To evaluate our approaches, we conduct extensive experiments with different settings. The use case in our approach is Tele-Lab, a Virtual Laboratory platform for Cyber Security e-Learning. We use this platform as a basis for designing and developing our approaches. The results show that our approaches are practical and provides enhanced security.
Redox signalling in plants
(2020)
Once proteins are synthesized, they can additionally be modified by post-translational modifications (PTMs). Proteins containing reactive cysteine thiols, stabilized in their deprotonated form due to their local environment as thiolates (RS-), serve as redox sensors by undergoing a multitude of oxidative PTMs (Ox-PTMs). Ox-PTMs such as S-nitrosylation or formation of inter- or intra-disulfide bridges induce functional changes in these proteins. Proteins containing cysteines, whose thiol oxidation state regulates their functions, belong to the so-called redoxome. Such Ox-PTMs are controlled by site-specific cellular events that play a crucial role in protein regulation, affecting enzyme catalytic sites, ligand binding affinity, protein-protein interactions or protein stability. Reversible protein thiol oxidation is an essential regulatory mechanism of photosynthesis, metabolism, and gene expression in all photosynthetic organisms. Therefore, studying PTMs will remain crucial for understanding plant adaptation to external stimuli like fluctuating light conditions. Optimizing methods suitable for studying plants Ox-PTMs is of high importance for elucidation of the redoxome in plants. This study focusses on thiol modifications occurring in plant and provides novel insight into in vivo redoxome of Arabidopsis thaliana in response to light vs. dark. This was achieved by utilizing a resin-assisted thiol enrichment approach. Furthermore, confirmation of candidates on the single protein level was carried out by a differential labelling approach. The thiols and disulfides were differentially labelled, and the protein levels were detected using immunoblot analysis. Further analysis was focused on light-reduced proteins. By the enrichment approach many well studied redox-regulated proteins were identified. Amongst those were fructose 1,6-bisphosphatase (FBPase) and sedoheptulose-1,7-bisphosphatase (SBPase) which have previously been described as thioredoxin system targeted enzymes. The redox regulated proteins identified in the current study were compared to several published, independent results showing redox regulated proteins in Arabidopsis leaves, root, mitochondria and specifically S-nitrosylated proteins. These proteins were excluded as potential new candidates but remain as a proof-of-concept to the enrichment experiments to be effective. Additionally, CSP41A and CSP41B proteins, which emerged from this study as potential targets of redox-regulation, were analyzed by Ribo-Seq. The active translatome study of csp41a mutant vs. wild-type showed most of the significant changes at end of the night, similarly as csp41b. Yet, in both mutants only several chloroplast-encoded genes were altered. Further studies of CSP41A and CSP41B proteins are needed to reveal their functions and elucidate the role of redox regulation of these proteins.