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Institute
Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes
(2017)
Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures.
In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges.
These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure.
Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1.
In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.
Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes.
Steep mountain channels are an important component of the fluvial system. On geological timescales, they shape mountain belts and counteract tectonic uplift by erosion. Their channels are strongly coupled to hillslopes and they are often the main source of sediment transported downstream to low-gradient rivers and to alluvial fans, where commonly settlements in mountainous areas are located. Hence, mountain streams are the cause for one of the main natural hazards in these regions. Due to climate change and a pronounced populating of mountainous regions the attention given to this threat is even growing. Although quantitative studies on sediment transport have significantly advanced our knowledge on measuring and calibration techniques we still lack studies of the processes within mountain catchments. Studies examining the mechanisms of energy and mass exchange on small temporal and spatial scales in steep streams remain sparse in comparison to low-gradient alluvial channels.
In the beginning of this doctoral project, a vast amount of experience and knowledge of a steep stream in the Swiss Prealps had to be consolidated in order to shape the principal aim of this research effort. It became obvious, that observations from within the catchment are underrepresented in comparison to experiments performed at the catchment’s outlet measuring fluxes and the effects of the transported material. To counteract this imbalance, an examination of mass fluxes within the catchment on the process scale was intended. Hence, this thesis is heavily based on direct field observations, which are generally rare in these environments in quantity and quality. The first objective was to investigate the coupling of the channel with surrounding hillslopes, the major sources of sediment. This research, which involved the monitoring of the channel and adjacent hillslopes, revealed that alluvial channel steps play a key role in coupling of channel and hillslopes. The observations showed that hillslope stability is strongly associated with the step presence and an understanding of step morphology and stability is therefore crucial in understanding sediment mobilization. This finding refined the way we think about the sediment dynamics in steep channels and motivated continued research of the step dynamics. However, soon it became obvious that the technological basis for developing field tests and analyzing the high resolution geometry measured in the field was not available. Moreover, for many geometrical quantities in mountain channels definitions and a clear scientific standard was not available. For example, these streams are characterized by a high spatial variability of the channel banks, preventing straightforward calculations of the channel width without a defined reference. Thus, the second and inevitable part of this thesis became the development and evaluation of scientific tools in order to investigate the geometrical content of the study reach thoroughly. The developed framework allowed the derivation of various metrics of step and channel geometry which facilitated research on the a large data set of observations of channel steps. In the third part, innovative, physically-based metrics have been developed and compared to current knowledge on step formation, suggested in the literature. With this analyses it could be demonstrated that the formation of channel steps follow a wide range of hydraulic controls. Due to the wide range of tested parameters channel steps observed in a natural stream were attributed to different mechanisms of step formation, including those based on jamming and those based on key-stones. This study extended our knowledge on step formation in a steep stream and harmonized different, often time seen as competing, processes of step formation. This study was based on observations collected at one point in time. In the fourth part of this project, the findings of the snap-shot observations were extended in the temporal dimension and the derived concepts have been utilized to investigate reach-scale step patterns in response to large, exceptional flood events. The preliminary results of this work based on the long-term analyses of 7 years of long profile surveys showed that the previously observed channel-hillslope mechanism is the responsible for the short-term response of step formation.
The findings of the long-term analyses of step patterns drew a bow to the initial observations of a channel-hillslope system which allowed to join the dots in the dynamics of steep stream. Thus, in this thesis a broad approach has been chosen to gain insights into the complex system of steep mountain rivers. The effort includes in situ field observations (article I), the development of quantitative scientific tools (article II), the reach-scale analyses of step-pool morphology (article III) and its temporal evolution (article IV). With this work our view on the processes within the catchment has been advanced towards a better mechanistic understanding of these fluvial system relevant to improve applied scientific work.
In the here presented work we discuss a series of results that are all in one way or another connected to the phenomenon of trapping in black hole spacetimes.
First we present a comprehensive review of the Kerr-Newman-Taub-NUT-de-Sitter family of black hole spacetimes and their most important properties. From there we go into a detailed analysis of the bahaviour of null geodesics in the exterior region of a sub-extremal Kerr spacetime. We show that most well known fundamental properties of null geodesics can be represented in one plot. In particular, one can see immediately that the ergoregion and trapping are separated in phase space.
We then consider the sets of future/past trapped null geodesics in the exterior region of a sub-extremal Kerr-Newman-Taub-NUT spacetime. We show that from the point of view of any timelike observer outside of such a black hole, trapping can be understood as two smooth sets of spacelike directions on the celestial sphere of the observer. Therefore the topological structure of the trapped set on the celestial sphere of any observer is identical to that in Schwarzschild.
We discuss how this is relevant to the black hole stability problem.
In a further development of these observations we introduce the notion of what it means for the shadow of two observers to be degenerate. We show that, away from the axis of symmetry, no continuous degeneration exists between the shadows of observers at any point in the exterior region of any Kerr-Newman black hole spacetime of unit mass. Therefore, except possibly for discrete changes, an observer can, by measuring the black holes shadow, determine the angular momentum and the charge of the black hole under observation, as well as the observer's radial position and angle of elevation above the equatorial plane. Furthermore, his/her relative velocity compared to a standard observer can also be measured. On the other hand, the black hole shadow does not allow for a full parameter resolution in the case of a Kerr-Newman-Taub-NUT black hole, as a continuous degeneration relating specific angular momentum, electric charge, NUT charge and elevation angle exists in this case.
We then use the celestial sphere to show that trapping is a generic feature of any black hole spacetime.
In the last chapter we then prove a generalization of the mode stability result of Whiting (1989) for the Teukolsky equation for the case of real frequencies. The main result of the last chapter states that a separated solution of the Teukolsky equation governing massless test fields on the Kerr spacetime, which is purely outgoing at infinity, and purely ingoing at the horizon, must vanish. This has the consequence, that for real frequencies, there are linearly independent fundamental solutions of the radial Teukolsky equation which are purely ingoing at the horizon, and purely outgoing at infinity, respectively. This fact yields a representation formula for solutions of the inhomogenous Teukolsky equation, and was recently used by Shlapentokh-Rothman (2015) for the scalar wave equation.
The concept of hydrologic connectivity summarizes all flow processes that link separate regions of a landscape. As such, it is a central theme in the field of catchment hydrology, with influence on neighboring disciplines such as ecology and geomorphology. It is widely acknowledged to be an important key in understanding the response behavior of a catchment and has at the same time inspired research on internal processes over a broad range of scales. From this process-hydrological point of view, hydrological connectivity is the conceptual framework to link local observations across space and scales.
This is the context in which the four studies this thesis comprises of were conducted. The focus was on structures and their spatial organization as important control on preferential subsurface flow. Each experiment covered a part of the conceptualized flow path from hillslopes to the stream: soil profile, hillslope, riparian zone, and stream.
For each study site, the most characteristic structures of the investigated domain and scale, such as slope deposits and peat layers were identified based on preliminary or previous investigations or literature reviews. Additionally, further structural data was collected and topographical analyses were carried out. Flow processes were observed either based on response observations (soil moisture changes or discharge patterns) or direct measurement (advective heat transport). Based on these data, the flow-relevance of the characteristic structures was evaluated, especially with regard to hillslope to stream connectivity.
Results of the four studies revealed a clear relationship between characteristic spatial structures and the hydrological behavior of the catchment. Especially the spatial distribution of structures throughout the study domain and their interconnectedness were crucial for the establishment of preferential flow paths and their relevance for large-scale processes. Plot and hillslope-scale irrigation experiments showed that the macropores of a heterogeneous, skeletal soil enabled preferential flow paths at the scale of centimeters through the otherwise unsaturated soil. These flow paths connected throughout the soil column and across the hillslope and facilitated substantial amounts of vertical and lateral flow through periglacial slope deposits.
In the riparian zone of the same headwater catchment, the connectivity between hillslopes and stream was controlled by topography and the dualism between characteristic subsurface structures and the geomorphological heterogeneity of the stream channel. At the small scale (1 m to 10 m) highest gains always occurred at steps along the longitudinal streambed profile, which also controlled discharge patterns at the large scale (100 m) during base flow conditions (number of steps per section). During medium and high flow conditions, however, the impact of topography and parafluvial flow through riparian zone structures prevailed and dominated the large-scale response patterns.
In the streambed of a lowland river, low permeability peat layers affected the connectivity between surface water and groundwater, but also between surface water and the hyporheic zone. The crucial factor was not the permeability of the streambed itself, but rather the spatial arrangement of flow-impeding peat layers, causing increased vertical flow through narrow “windows” in contrast to predominantly lateral flow in extended areas of high hydraulic conductivity sediments.
These results show that the spatial organization of structures was an important control for hydrological processes at all scales and study areas. In a final step, the observations from different scales and catchment elements were put in relation and compared. The main focus was on the theoretical analysis of the scale hierarchies of structures and processes and the direction of causal dependencies in this context. Based on the resulting hierarchical structure, a conceptual framework was developed which is capable of representing the system’s complexity while allowing for adequate simplifications.
The resulting concept of the parabolic scale series is based on the insight that flow processes in the terrestrial part of the catchment (soil and hillslopes) converge. This means that small-scale processes assemble and form large-scale processes and responses. Processes in the riparian zone and the streambed, however, are not well represented by the idea of convergence. Here, the large-scale catchment signal arrives and is modified by structures in the riparian zone, stream morphology, and the small-scale interactions between surface water and groundwater. Flow paths diverge and processes can better be represented by proceeding from large scales to smaller ones. The catchment-scale representation of processes and structures is thus the conceptual link between terrestrial hillslope processes and processes in the riparian corridor.
This paper introduces a novel measure to assess similarity between event hydrographs. It is based on Cross Recurrence Plots and Recurrence Quantification Analysis which have recently gained attention in a range of disciplines when dealing with complex systems. The method attempts to quantify the event runoff dynamics and is based on the time delay embedded phase space representation of discharge hydrographs. A phase space trajectory is reconstructed from the event hydrograph, and pairs of hydrographs are compared to each other based on the distance of their phase space trajectories. Time delay embedding allows considering the multi-dimensional relationships between different points in time within the event. Hence, the temporal succession of discharge values is taken into account, such as the impact of the initial conditions on the runoff event. We provide an introduction to Cross Recurrence Plots and discuss their parameterization. An application example based on flood time series demonstrates how the method can be used to measure the similarity or dissimilarity of events, and how it can be used to detect events with rare runoff dynamics. It is argued that this methods provides a more comprehensive approach to quantify hydrograph similarity compared to conventional hydrological signatures.
Today, more than half of the world’s population lives in urban areas. With a high density of population and assets, urban areas are not only the economic, cultural and social hubs of every society, they are also highly susceptible to natural disasters. As a consequence of rising sea levels and an expected increase in extreme weather events caused by a changing climate in combination with growing cities, flooding is an increasing threat to many urban agglomerations around the globe.
To mitigate the destructive consequences of flooding, appropriate risk management and adaptation strategies are required. So far, flood risk management in urban areas is almost exclusively focused on managing river and coastal flooding. Often overlooked is the risk from small-scale rainfall-triggered flooding, where the rainfall intensity of rainstorms exceeds the capacity of urban drainage systems, leading to immediate flooding. Referred to as pluvial flooding, this flood type exclusive to urban areas has caused severe losses in cities around the world. Without further intervention, losses from pluvial flooding are expected to increase in many urban areas due to an increase of impervious surfaces compounded with an aging drainage infrastructure and a projected increase in heavy precipitation events. While this requires the integration of pluvial flood risk into risk management plans, so far little is known about the adverse consequences of pluvial flooding due to a lack of both detailed data sets and studies on pluvial flood impacts. As a consequence, methods for reliably estimating pluvial flood losses, needed for pluvial flood risk assessment, are still missing.
Therefore, this thesis investigates how pluvial flood losses to private households can be reliably estimated, based on an improved understanding of the drivers of pluvial flood loss. For this purpose, detailed data from pluvial flood-affected households was collected through structured telephone- and web-surveys following pluvial flood events in Germany and the Netherlands.
Pluvial flood losses to households are the result of complex interactions between impact characteristics such as the water depth and a household’s resistance as determined by its risk awareness, preparedness, emergency response, building properties and other influencing factors. Both exploratory analysis and machine-learning approaches were used to analyze differences in resistance and impacts between households and their effects on the resulting losses. The comparison of case studies showed that the awareness around pluvial flooding among private households is quite low. Low awareness not only challenges the effective dissemination of early warnings, but was also found to influence the implementation of private precautionary measures. The latter were predominately implemented by households with previous experience of pluvial flooding. Even cases where previous flood events affected a different part of the same city did not lead to an increase in preparedness of the surveyed households, highlighting the need to account for small-scale variability in both impact and resistance parameters when assessing pluvial flood risk.
While it was concluded that the combination of low awareness, ineffective early warning and the fact that only a minority of buildings were adapted to pluvial flooding impaired the coping capacities of private households, the often low water levels still enabled households to mitigate or even prevent losses through a timely and effective emergency response.
These findings were confirmed by the detection of loss-influencing variables, showing that cases in which households were able to prevent any loss to the building structure are predominately explained by resistance variables such as the household’s risk awareness, while the degree of loss is mainly explained by impact variables.
Based on the important loss-influencing variables detected, different flood loss models were developed. Similar to flood loss models for river floods, the empirical data from the preceding data collection was used to train flood loss models describing the relationship between impact and resistance parameters and the resulting loss to building structures. Different approaches were adapted from river flood loss models using both models with the water depth as only predictor for building structure loss and models incorporating additional variables from the preceding variable detection routine.
The high predictive errors of all compared models showed that point predictions are not suitable for estimating losses on the building level, as they severely impair the reliability of the estimates. For that reason, a new probabilistic framework based on Bayesian inference was introduced that is able to provide predictive distributions instead of single loss estimates. These distributions not only give a range of probable losses, they also provide information on how likely a specific loss value is, representing the uncertainty in the loss estimate.
Using probabilistic loss models, it was found that the certainty and reliability of a loss estimate on the building level is not only determined by the use of additional predictors as shown in previous studies, but also by the choice of response distribution defining the shape of the predictive distribution. Here, a mix between a beta and a Bernoulli distribution to account for households that are able to prevent losses to their building’s structure was found to provide significantly more certain and reliable estimates than previous approaches using Gaussian or non-parametric response distributions.
The successful model transfer and post-event application to estimate building structure loss in Houston, TX, caused by pluvial flooding during Hurricane Harvey confirmed previous findings, and demonstrated the potential of the newly developed multi-variable beta model for future risk assessments. The highly detailed input data set constructed from openly available data sources containing over 304,000 affected buildings in Harris County further showed the potential of data-driven, building-level loss models for pluvial flood risk assessment.
In conclusion, pluvial flood losses to private households are the result of complex interactions between impact and resistance variables, which should be represented in loss models. The local occurrence of pluvial floods requires loss estimates on high spatial resolutions, i.e. on the building level, where losses are variable and uncertainties are high.
Therefore, probabilistic loss estimates describing the uncertainty of the estimate should be used instead of point predictions. While the performance of probabilistic models on the building level are mainly driven by the choice of response distribution, multi-variable models are recommended for two reasons:
First, additional resistance variables improve the detection of cases in which households were able to prevent structural losses.
Second, the added variability of additional predictors provides a better representation of the uncertainties when loss estimates from multiple buildings are aggregated.
This leads to the conclusion that data-driven probabilistic loss models on the building level allow for a reliable loss estimation at an unprecedented level of detail, with a consistent quantification of uncertainties on all aggregation levels. This makes the presented approach suitable for a wide range of applications, from decision support in spatial planning to impact- based early warning systems.
Over the last years there is an increasing awareness that historical land cover changes and associated land use legacies may be important drivers for present-day species richness and biodiversity due to time-delayed extinctions or colonizations in response to historical environmental changes. Historically altered habitat patches may therefore exhibit an extinction debt or colonization credit and can be expected to lose or gain species in the future. However, extinction debts and colonization credits are difficult to detect and their actual magnitudes or payments have rarely been quantified because species richness patterns and dynamics are also shaped by recent environmental conditions and recent environmental changes.
In this thesis we aimed to determine patterns of herb-layer species richness and recent species richness dynamics of forest herb layer plants and link those patterns and dynamics to historical land cover changes and associated land use legacies. The study was conducted in the Prignitz, NE-Germany, where the forest distribution remained stable for the last ca. 100 years but where a) the deciduous forest area had declined by more than 90 per cent (leaving only remnants of "ancient forests"), b) small new forests had been established on former agricultural land ("post-agricultural forests"). Here, we analyzed the relative importance of land use history and associated historical land cover changes for herb layer species richness compared to recent environmental factors and determined magnitudes of extinction debt and colonization credit and their payment in ancient and post-agricultural forests, respectively.
We showed that present-day species richness patterns were still shaped by historical land cover changes that ranged back to more than a century. Although recent environmental conditions were largely comparable we found significantly more forest specialists, species with short-distance dispersal capabilities and clonals in ancient forests than in post-agricultural forests. Those species richness differences were largely contingent to a colonization credit in post-agricultural forests that ranged up to 9 species (average 4.7), while the extinction debt in ancient forests had almost completely been paid. Environmental legacies from historical agricultural land use played a minor role for species richness differences. Instead, patch connectivity was most important. Species richness in ancient forests was still dependent on historical connectivity, indicating a last glimpse of an extinction debt, and the colonization credit was highest in isolated post-agricultural forests. In post-agricultural forests that were better connected or directly adjacent to ancient forest patches the colonization credit was way smaller and we were able to verify a gradual payment of the colonization credit from 2.7 species to 1.5 species over the last six decades.
Thermoresponsive Zellkultursubstrate für zeitlich-räumlich gesteuertes Auswachsen neuronaler Zellen
(2019)
Ein wichtiges Ziel der Neurowissenschaften ist das Verständnis der komplexen und zugleich faszinierenden, hochgeordneten Vernetzung der Neurone im Gehirn, welche neuronalen Prozessen, wie zum Beispiel dem Wahrnehmen oder Lernen wie auch Neuropathologien zu Grunde liegt. Für verbesserte neuronale Zellkulturmodelle zur detaillierten Untersuchung dieser Prozesse ist daher die Rekonstruktion von geordneten neuronalen Verbindungen dringend erforderlich. Mit Oberflächenstrukturen aus zellattraktiven und zellabweisenden Beschichtungen können neuronale Zellen und ihre Neuriten in vitro strukturiert werden. Zur Kontrolle der neuronalen Verbindungsrichtung muss das Auswachsen der Axone zu benachbarten Zellen dynamisch gesteuert werden, zum Beispiel über eine veränderliche Zugänglichkeit der Oberfläche.
In dieser Arbeit wurde untersucht, ob mit thermoresponsiven Polymeren (TRP) beschichtete Zellkultursubstrate für eine dynamische Kontrolle des Auswachsens neuronaler Zellen geeignet sind. TRP können über die Temperatur von einem zellabweisenden in einen zellattraktiven Zustand geschaltet werden, womit die Zugänglichkeit der Oberfläche für Zellen dynamisch gesteuert werden kann. Die TRP-Beschichtung wurde mikrostrukturiert, um einzelne oder wenige neuronale Zellen zunächst auf der Oberfläche anzuordnen und das Auswachsen der Zellen und Neuriten über definierte TRP-Bereiche in Abhängigkeit der Temperatur zeitlich und räumlich zu kontrollieren. Das Protokoll wurde mit der neuronalen Zelllinie SH-SY5Y etabliert und auf humane induzierte Neurone übertragen. Die Anordnung der Zellen konnte bei Kultivierung im zellabweisenden Zustand des TRPs für bis zu 7 Tage aufrecht erhalten werden. Durch Schalten des TRPs in den zellattraktiven Zustand konnte das Auswachsen der Neuriten und Zellen zeitlich und räumlich induziert werden. Immunozytochemische Färbungen und Patch-Clamp-Ableitungen der Neurone demonstrierten die einfache Anwendbarkeit und Zellkompatibilität der TRP-Substrate.
Eine präzisere räumliche Kontrolle des Auswachsens der Zellen sollte durch lokales Schalten der TRP-Beschichtung erreicht werden. Dafür wurden Mikroheizchips mit Mikroelektroden zur lokalen Jouleschen Erwärmung der Substratoberfläche entwickelt. Zur Evaluierung der generierten Temperaturprofile wurde eine Temperaturmessmethode entwickelt und die erhobenen Messwerte mit numerisch simulierten Werten abgeglichen. Die Temperaturmessmethode basiert auf einfach zu applizierenden Sol-Gel-Schichten, die den temperatursensitiven Fluoreszenzfarbstoff Rhodamin B enthalten. Sie ermöglicht oberflächennahe Temperaturmessungen in trockener und wässriger Umgebung mit hoher Orts- und Temperaturauflösung. Numerische Simulationen der Temperaturprofile korrelierten gut mit den experimentellen Daten. Auf dieser Basis konnten Geometrie und Material der Mikroelektroden hinsichtlich einer lokal stark begrenzten Temperierung optimiert werden. Ferner wurden für die Kultvierung der Zellen auf den Mikroheizchips eine Zellkulturkammer und Kontaktboard für die elektrische Kontaktierung der Mikroelektroden geschaffen.
Die vorgestellten Ergebnisse demonstrieren erstmalig das enorme Potential thermoresponsiver Zellkultursubstrate für die zeitlich und räumlich gesteuerte Formation geordneter neuronaler Verbindungen in vitro. Zukünftig könnte dies detaillierte Studien zur neuronalen Informationsverarbeitung oder zu Neuropathologien an relevanten, humanen Zellmodellen ermöglichen.
The natural abundance of Coiled Coil (CC) motifs in cytoskeleton and extracellular matrix proteins suggests that CCs play an important role as passive (structural) and active (regulatory) mechanical building blocks. CCs are self-assembled superhelical structures consisting of 2-7 α-helices. Self-assembly is driven by hydrophobic and ionic interactions, while the helix propensity of the individual helices contributes additional stability to the structure. As a direct result of this simple sequence-structure relationship, CCs serve as templates for protein design and sequences with a pre-defined thermodynamic stability have been synthesized de novo. Despite this quickly increasing knowledge and the vast number of possible CC applications, the mechanical function of CCs has been largely overlooked and little is known about how different CC design parameters determine the mechanical stability of CCs. Once available, this knowledge will open up new applications for CCs as nanomechanical building blocks, e.g. in biomaterials and nanobiotechnology.
With the goal of shedding light on the sequence-structure-mechanics relationship of CCs, a well-characterized heterodimeric CC was utilized as a model system. The sequence of this model system was systematically modified to investigate how different design parameters affect the CC response when the force is applied to opposing termini in a shear geometry or separated in a zipper-like fashion from the same termini (unzip geometry). The force was applied using an atomic force microscope set-up and dynamic single-molecule force spectroscopy was performed to determine the rupture forces and energy landscape properties of the CC heterodimers under study. Using force as a denaturant, CC chain separation is initiated by helix uncoiling from the force application points. In the shear geometry, this allows uncoiling-assisted sliding parallel to the force vector or dissociation perpendicular to the force vector. Both competing processes involve the opening of stabilizing hydrophobic (and ionic) interactions. Also in the unzip geometry, helix uncoiling precedes the rupture of hydrophobic contacts.
In a first series of experiments, the focus was placed on canonical modifications in the hydrophobic core and the helix propensity. Using the shear geometry, it was shown that both a reduced core packing and helix propensity lower the thermodynamic and mechanical stability of the CC; however, with different effects on the energy landscape of the system. A less tightly packed hydrophobic core increases the distance to the transition state, with only a small effect on the barrier height. This originates from a more dynamic and less tightly packed core, which provides more degrees of freedom to respond to the applied force in the direction of the force vector. In contrast, a reduced helix propensity decreases both the distance to the transition state and the barrier height. The helices are ‘easier’ to unfold and the remaining structure is less thermodynamically stable so that dissociation perpendicular to the force axis can occur at smaller deformations.
Having elucidated how canonical sequence modifications influence CC mechanics, the pulling geometry was investigated in the next step. Using one and the same sequence, the force application points were exchanged and two different shear and one unzipping geometry were compared. It was shown that the pulling geometry determines the mechanical stability of the CC. Different rupture forces were observed in the different shear as well as in the unzipping geometries, suggesting that chain separation follows different pathways on the energy landscape. Whereas the difference between CC shearing and unzipping was anticipated and has also been observed for other biological structures, the observed difference for the two shear geometries was less expected. It can be explained with the structural asymmetry of the CC heterodimer. It is proposed that the direction of the α-helices, the different local helix propensities and the position of a polar asparagine in the hydrophobic core are responsible for the observed difference in the chain separation pathways. In combination, these factors are considered to influence the interplay between processes parallel and perpendicular to the force axis.
To obtain more detailed insights into the role of helix stability, helical turns were reinforced locally using artificial constraints in the form of covalent and dynamic ‘staples’. A covalent staple bridges to adjacent helical turns, thus protecting them against uncoiling. The staple was inserted directly at the point of force application in one helix or in the same terminus of the other helix, which did not experience the force directly. It was shown that preventing helix uncoiling at the point of force application reduces the distance to the transition state while slightly increasing the barrier height. This confirms that helix uncoiling is critically important for CC chain separation. When inserted into the second helix, this stabilizing effect is transferred across the hydrophobic core and protects the force-loaded turns against uncoiling. If both helices were stapled, no additional increase in mechanical stability was observed. When replacing the covalent staple with a dynamic metal-coordination bond, a smaller decrease in the distance to the transition was observed, suggesting that the staple opens up while the CC is under load.
Using fluorinated amino acids as another type of non-natural modification, it was investigated how the enhanced hydrophobicity and the altered packing at the interface influences CC mechanics. The fluorinated amino acid was inserted into one central heptad of one or both α-helices. It was shown that this substitution destabilized the CC thermodynamically and mechanically. Specifically, the barrier height was decreased and the distance to the transition state increased. This suggests that a possible stabilizing effect of the increased hydrophobicity is overruled by a disturbed packing, which originates from a bad fit of the fluorinated amino acid into the local environment. This in turn increases the flexibility at the interface, as also observed for the hydrophobic core substitution described above. In combination, this confirms that the arrangement of the hydrophobic side chains is an additional crucial factor determining the mechanical stability of CCs.
In conclusion, this work shows that knowledge of the thermodynamic stability alone is not sufficient to predict the mechanical stability of CCs. It is the interplay between helix propensity and hydrophobic core packing that defines the sequence-structure-mechanics relationship. In combination, both parameters determine the relative contribution of processes parallel and perpendicular to the force axis, i.e. helix uncoiling and uncoiling-assisted sliding as well as dissociation. This new mechanistic knowledge provides insight into the mechanical function of CCs in tissues and opens up the road for designing CCs with pre-defined mechanical properties. The library of mechanically characterized CCs developed in this work is a powerful starting point for a wide spectrum of applications, ranging from molecular force sensors to mechanosensitive crosslinks in protein nanostructures and synthetic extracellular matrix mimics.
Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells
(2019)
Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell’s cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C.
A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts.
Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8%.
Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9% relative to 26.5% absolute. The results also reveal general guidelines for further performance gains of the technology.
The trace gases CO2 and CH4 pertain to the most relevant greenhouse gases and are important exchange fluxes of the global carbon (C) cycle. Their atmospheric quantity increased significantly as a result of the intensification of anthropogenic activities, such as especially land-use and land-use change, since the mid of the 18th century. To mitigate global climate change and ensure food security, land-use systems need to be developed, which favor reduced trace gas emissions and a sustainable soil carbon management. This requires the accurate and precise quantification of the influence of land-use and land-use change on CO2 and CH4 emissions. A common method to determine the trace gas dynamics and C sink or source function of a particular ecosystem is the closed chamber method. This method is often used assuming that accuracy and precision are high enough to determine differences in C gas emissions for e.g., treatment comparisons or different ecosystem components.
However, the broad range of different chamber designs, related operational procedures and data-processing strategies which are described in the scientific literature contribute to the overall uncertainty of closed chamber-based emission estimates. Hence, the outcomes of meta-analyses are limited, since these methodical differences hamper the comparability between studies. Thus, a standardization of closed chamber data acquisition and processing is much-needed.
Within this thesis, a set of case studies were performed to: (I) develop standardized routines for an unbiased data acquisition and processing, with the aim of providing traceable, reproducible and comparable closed chamber based C emission estimates; (II) validate those routines by comparing C emissions derived using closed chambers with independent C emission estimates; and (III) reveal processes driving the spatio-temporal dynamics of C emissions by developing (data processing based) flux separation approaches.
The case studies showed: (I) the importance to test chamber designs under field conditions for an appropriate sealing integrity and to ensure an unbiased flux measurement. Compared to the sealing integrity, the use of a pressure vent and fan was of minor importance, affecting mainly measurement precision; (II) that the developed standardized data processing routines proved to be a powerful and flexible tool to estimate C gas emissions and that this tool can be successfully applied on a broad range of flux data sets from very different ecosystem; (III) that automatic chamber measurements display temporal dynamics of CO2 and CH4 fluxes very well and most importantly, that they accurately detect small-scale spatial differences in the development of soil C when validated against repeated soil inventories; and (IV) that a simple algorithm to separate CH4 fluxes into ebullition and diffusion improves the identification of environmental drivers, which allows for an accurate gap-filling of measured CH4 fluxes.
Overall, the proposed standardized data acquisition and processing routines strongly improved the detection accuracy and precision of source/sink patterns of gaseous C emissions. Hence, future studies, which consider the recommended improvements, will deliver valuable new data and insights to broaden our understanding of spatio-temporal C gas dynamics, their particular environmental drivers and underlying processes.
In my doctoral thesis, I examine continuous gravity measurements for monitoring of the geothermal site at Þeistareykir in North Iceland. With the help of high-precision superconducting gravity meters (iGravs), I investigate underground mass changes that are caused by operation of the geothermal power plant (i.e. by extraction of hot water and reinjection of cold water). The overall goal of this research project is to make a statement about the sustainable use of the geothermal reservoir, from which also the Icelandic energy supplier and power plant operator Landsvirkjun should benefit.
As a first step, for investigating the performance and measurement stability of the gravity meters, in summer 2017, I performed comparative measurements at the gravimetric observatory J9 in Strasbourg. From the three-month gravity time series, I examined calibration, noise and drift behaviour of the iGravs in comparison to stable long-term time series of the observatory superconducting gravity meters. After preparatory work in Iceland (setup of gravity stations, additional measuring equipment and infrastructure, discussions with Landsvirkjun and meetings with the Icelandic partner institute ISOR), gravity monitoring at Þeistareykir was started in December 2017. With the help of the iGrav records of the initial 18 months after start of measurements, I carried out the same investigations (on calibration, noise and drift behaviour) as in J9 to understand how the transport of the superconducting gravity meters to Iceland may influence instrumental parameters.
In the further course of this work, I focus on modelling and reduction of local gravity contributions at Þeistareykir. These comprise additional mass changes due to rain, snowfall and vertical surface displacements that superimpose onto the geothermal signal of the gravity measurements. For this purpose, I used data sets from additional monitoring sensors that are installed at each gravity station and adapted scripts for hydro-gravitational modelling. The third part of my thesis targets geothermal signals in the gravity measurements.
Together with my PhD colleague Nolwenn Portier from France, I carried out additional gravity measurements with a Scintrex CG5 gravity meter at 26 measuring points within the geothermal field in the summers of 2017, 2018 and 2019. These annual time-lapse gravity measurements are intended to increase the spatial coverage of gravity data from the three continuous monitoring stations to the entire geothermal field. The combination of CG5 and iGrav observations, as well as annual reference measurements with an FG5 absolute gravity meter represent the hybrid gravimetric monitoring method for Þeistareykir. Comparison of the gravimetric data to local borehole measurements (of groundwater levels, geothermal extraction and injection rates) is used to relate the observed gravity changes to the actually extracted (and reinjected) geothermal fluids. An approach to explain the observed gravity signals by means of forward modelling of the geothermal production rate is presented at the end of the third (hybrid gravimetric) study. Further modelling with the help of the processed gravity data is planned by Landsvirkjun. In addition, the experience from time-lapse and continuous gravity monitoring will be used for future gravity measurements at the Krafla geothermal field 22 km south-east of Þeistareykir.
In the frame of a world fighting a dramatic global warming caused by human-related activities, research towards the development of renewable energies plays a crucial role. Solar energy is one of the most important clean energy sources and its role in the satisfaction of the global energy demand is set to increase. In this context, a particular class of materials captured the attention of the scientific community for its attractive properties: halide perovskites. Devices with perovskite as light-absorber saw an impressive development within the last decade, reaching nowadays efficiencies comparable to mature photovoltaic technologies like silicon solar cells. Yet, there are still several roadblocks to overcome before a wide-spread commercialization of this kind of devices is enabled. One of the critical points lies at the interfaces: perovskite solar cells (PSCs) are made of several layers with different chemical and physical features. In order for the device to function properly, these properties have to be well-matched.
This dissertation deals with some of the challenges related to interfaces in PSCs, with a focus on the interface between the perovskite material itself and the subsequent charge transport layer. In particular, molecular assemblies with specific properties are deposited on the perovskite surface to functionalize it. The functionalization results in energy level alignment adjustment, interfacial losses reduction, and stability improvement.
First, a strategy to tune the perovskite’s energy levels is introduced: self-assembled monolayers of dipolar molecules are used to functionalize the surface, obtaining simultaneously a shift in the vacuum level position and a saturation of the dangling bonds at the surface. A shift in the vacuum level corresponds to an equal change in work function, ionization energy, and electron affinity. The direction of the shift depends on the direction of the collective interfacial dipole. The magnitude of the shift can be tailored by controlling the deposition parameters, such as the concentration of the solution used for the deposition. The shift for different molecules is characterized by several non-invasive techniques, including in particular Kelvin probe. Overall, it is shown that it is possible to shift the perovskite energy levels in both directions by several hundreds of meV. Moreover, interesting insights on the molecules deposition dynamics are revealed.
Secondly, the application of this strategy in perovskite solar cells is explored. Devices with different perovskite compositions (“triple cation perovskite” and MAPbBr3) are prepared. The two resulting model systems present different energetic offsets at the perovskite/hole-transport layer interface. Upon tailored perovskite surface functionalization, the devices show a stabilized open circuit voltage (Voc) enhancement of approximately 60 meV on average for devices with MAPbBr3, while the impact is limited on triple-cation solar cells. This suggests that the proposed energy level tuning method is valid, but its effectiveness depends on factors such as the significance of the energetic offset compared to the other losses in the devices.
Finally, the above presented method is further developed by incorporating the ability to interact with the perovskite surface directly into a novel hole-transport material (HTM), named PFI. The HTM can anchor to the perovskite halide ions via halogen bonding (XB). Its behaviour is compared to that of another HTM (PF) with same chemical structure and properties, except for the ability of forming XB. The interaction of perovskite with PFI and PF is characterized through UV-Vis, atomic force microscopy and Kelvin probe measurements combined with simulations. Compared to PF, PFI exhibits enhanced resilience against solvent exposure and improved energy level alignment with the perovskite layer. As a consequence, devices comprising PFI show enhanced Voc and operational stability during maximum-power-point tracking, in addition to hysteresis reduction. XB promotes the formation of a high-quality interface by anchoring to the halide ions and forming a stable and ordered interfacial layer, showing to be a particularly interesting candidate for the development of tailored charge transport materials in PSCs.
Overall, the results exposed in this dissertation introduce and discuss a versatile tool to functionalize the perovskite surface and tune its energy levels. The application of this method in devices is explored and insights on its challenges and advantages are given. Within this frame, the results shed light on XB as ideal interaction for enhancing stability and efficiency in perovskite-based devices.
The spread of antibiotic-resistant bacteria poses a globally increasing threat to public health care. The excessive use of antibiotics in animal husbandry can develop resistances in the stables. Transmission through direct contact with animals and contamination of food has already been proven. The excrements of the animals combined with a binding material enable a further potential path of spread into the environment, if they are used as organic manure in agricultural landscapes. As most of the airborne bacteria are attached to particulate matter, the focus of the work will be the atmospheric dispersal via the dust fraction.
Field measurements on arable lands in Brandenburg, Germany and wind erosion studies in a wind tunnel were conducted to investigate the risk of a potential atmospheric dust-associated spread of antibiotic-resistant bacteria from poultry manure fertilized agricultural soils. The focus was to (i) characterize the conditions for aerosolization and (ii) qualify and quantify dust emissions during agricultural operations and wind erosion.
PM10 (PM, particulate matter with an aerodynamic diameter smaller than 10 µm) emission factors and bacterial fluxes for poultry manure application and incorporation have not been previously reported before. The contribution to dust emissions depends on the water content of the manure, which is affected by the manure pretreatment (fresh, composted, stored, dried), as well as by the intensity of manure spreading from the manure spreader. During poultry manure application, PM10 emission ranged between 0.05 kg ha-1 and 8.37 kg ha-1. For comparison, the subsequent land preparation contributes to 0.35 – 1.15 kg ha-1 of PM10 emissions. Manure particles were still part of dust emissions but they were accounted to be less than 1% of total PM10 emissions due to the dilution of poultry manure in the soil after manure incorporation. Bacterial emissions of fecal origin were more relevant during manure application than during the subsequent manure incorporation, although PM10 emissions of manure incorporation were larger than PM10 emissions of manure application for the non-dried manure variants.
Wind erosion leads to preferred detachment of manure particles from sandy soils, when poultry manure has been recently incorporated. Sorting effects were determined between the low-density organic particles of manure origin and the soil particles of mineral origin close above the threshold of 7 m s-1. In dependence to the wind speed, potential erosion rates between 101 and 854 kg ha-1 were identified, if 6 t ha-1 of poultry manure were applied. Microbial investigation showed that manure bacteria got detached more easily from the soil surface during wind erosion, due to their attachment on manure particles.
Although antibiotic-resistant bacteria (ESBL-producing E. coli) were still found in the poultry barns, no further contamination could be detected with them in the manure, fertilized soils or in the dust generated by manure application, land preparation or wind erosion. Parallel studies of this project showed that storage of poultry manure for a few days (36 – 72 h) is sufficient to inactivate ESBL-producing E. coli. Further antibiotic-resistant bacteria, i.e. MRSA and VRE, were only found sporadically in the stables and not at all in the dust. Therefore, based on the results of this work, the risk of a potential infection by dust-associated antibiotic-resistant bacteria can be considered as low.
Climate change is one of the greatest challenges to humanity in this century, and most noticeable consequences are expected to be impacts on the water cycle – in particular the distribution and availability of water, which is fundamental for all life on Earth. In this context, it is essential to better understand where and when water is available and what processes influence variations in water storages. While estimates of the overall terrestrial water storage (TWS) variations are available from the GRACE satellites, these represent the vertically integrated signal over all water stored in ice, snow, soil moisture, groundwater and surface water bodies. Therefore, complementary observational data and hydrological models are still required to determine the partitioning of the measured signal among different water storages and to understand the underlying processes. However, the application of large-scale observational data is limited by their specific uncertainties and the incapacity to measure certain water fluxes and storages. Hydrological models, on the other hand, vary widely in their structure and process-representation, and rarely incorporate additional observational data to minimize uncertainties that arise from their simplified representation of the complex hydrologic cycle.
In this context, this thesis aims to contribute to improving the understanding of global water storage variability by combining simple hydrological models with a variety of complementary Earth observation-based data. To this end, a model-data integration approach is developed, in which the parameters of a parsimonious hydrological model are calibrated against several observational constraints, inducing GRACE TWS, simultaneously, while taking into account each data’s specific strengths and uncertainties. This approach is used to investigate 3 specific aspects that are relevant for modelling and understanding the composition of large-scale TWS variations.
The first study focusses on Northern latitudes, where snow and cold-region processes define the hydrological cycle. While the study confirms previous findings that seasonal dynamics of TWS are dominated by the cyclic accumulation and melt of snow, it reveals that inter-annual TWS variations on the contrary, are determined by variations in liquid water storages. Additionally, it is found to be important to consider the impact of compensatory effects of spatially heterogeneous hydrological variables when aggregating the contribution of different storage components over large areas. Hence, the determinants of TWS variations are scale-dependent and underlying driving mechanism cannot be simply transferred between spatial and temporal scales. These findings are supported by the second study for the global land areas beyond the Northern latitudes as well.
This second study further identifies the considerable impact of how vegetation is represented in hydrological models on the partitioning of TWS variations. Using spatio-temporal varying fields of Earth observation-based data to parameterize vegetation activity not only significantly improves model performance, but also reduces parameter equifinality and process uncertainties. Moreover, the representation of vegetation drastically changes the contribution of different water storages to overall TWS variability, emphasizing the key role of vegetation for water allocation, especially between sub-surface and delayed water storages. However, the study also identifies parameter equifinality regarding the decay of sub-surface and delayed water storages by either evapotranspiration or runoff, and thus emphasizes the need for further constraints hereof.
The third study focuses on the role of river water storage, in particular whether it is necessary to include computationally expensive river routing for model calibration and validation against the integrated GRACE TWS. The results suggest that river routing is not required for model calibration in such a global model-data integration approach, due to the larger influence other observational constraints, and the determinability of certain model parameters and associated processes are identified as issues of greater relevance. In contrast to model calibration, considering river water storage derived from routing schemes can already significantly improve modelled TWS compared to GRACE observations, and thus should be considered for model evaluation against GRACE data.
Beyond these specific findings that contribute to improved understanding and modelling of large-scale TWS variations, this thesis demonstrates the potential of combining simple modeling approaches with diverse Earth observational data to improve model simulations, overcome inconsistencies of different observational data sets, and identify areas that require further research. These findings encourage future efforts to take advantage of the increasing number of diverse global observational data.
Sustainable urban growth
(2022)
This dissertation explores the determinants for sustainable and socially optimalgrowth in a city. Two general equilibrium models establish the base for this evaluation, each adding its puzzle piece to the urban sustainability discourse and examining the role of non-market-based and market-based policies for balanced growth and welfare improvements in different theory settings. Sustainable urban growth either calls for policy actions or a green energy transition. Further, R&D market failures can pose severe challenges to the sustainability of urban growth and the social optimality of decentralized allocation decisions. Still, a careful (holistic) combination of policy instruments can achieve sustainable growth and even be first best.
Die vorliegende kumulative Promotionsarbeit beschäftigt sich mit leistungsstarken Schülerinnen und Schülern, die seit 2015 in der deutschen Bildungspolitik, zum Beispiel im Rahmen von Förderprogrammen wieder mehr Raum einnehmen, nachdem in Folge des „PISA-Schocks“ im Jahr 2000 zunächst der Fokus stärker auf den Risikogruppen lag. Während leistungsstärkere Schülerinnen und Schüler in der öffentlichen Wahrnehmung häufig mit „(Hoch-)Begabten“ identifiziert werden, geht die Arbeit über die traditionelle Begabungsforschung, die eine generelle Intelligenz als Grundlage für Leistungsfähigkeit von Schülerinnen und Schülern begreift und beforscht, hinaus. Stattdessen lässt sich eher in den Bereich der Talentforschung einordnen, die den Fokus weg von allgemeinen Begabungen auf spezifische Prädiktoren und Outcomes im individuellen Entwicklungsverlauf legt. Der Fokus der Arbeit liegt daher nicht auf Intelligenz als Potenzial, sondern auf der aktuellen schulischen Leistung, die als Ergebnis und Ausgangspunkt von Entwicklungsprozessen in einer Leistungsdomäne doppelte Bedeutung erhält.
Die Arbeit erkennt die Vielgestaltigkeit des Leistungsbegriffs an und ist bestrebt, neue Anlässe zu schaffen, über den Leistungsbegriff und seine Operationalisierung in der Forschung zu diskutieren. Hierfür wird im ersten Teil ein systematisches Review zur Operationalisierung von Leistungsstärke durchgeführt (Artikel I). Es werden Faktoren herausgearbeitet, auf welchen sich die Operationalisierungen unterscheiden können. Weiterhin wird ein Überblick gegeben, wie Studien zu Leistungsstarken sich seit dem Jahr 2000 auf diesen Dimensionen verorten lassen. Es zeigt sich, dass eindeutige Konventionen zur Definition schulischer Leistungsstärke noch nicht existieren, woraus folgt, dass Ergebnisse aus Studien, die sich mit leistungsstarken Schülerinnen und Schülern beschäftigen, nur bedingt miteinander vergleichbar sind. Im zweiten Teil der Arbeit wird im Rahmen zwei weiterer Artikel, welche sich mit der Leistungsentwicklung (Artikel II) und der sozialen Einbindung (Artikel III) von leistungsstarken Schülerinnen und Schülern befassen, darauf aufbauend der Ansatz verfolgt, die Variabilität von Ergebnissen über verschiedene Operationalisierungen von Leistungsstärke deutlich zu machen. Damit wird unter anderem auch die künftige Vergleichbarkeit mit anderen Studien erleichtert. Genutzt wird dabei das Konzept der Multiversumsanalyse (Steegen et al., 2016), bei welcher viele parallele Spezifikationen, die zugleich sinnvolle Alternativen für die Operationalisierung darstellen, nebeneinandergestellt und in ihrem Effekt verglichen werden (Jansen et al., 2021). Die Multiversumsanalyse knüpft konzeptuell an das bereits vor längerem entwickelte Forschungsprogramm des kritischen Multiplismus an (Patry, 2013; Shadish, 1986, 1993), erhält aber als spezifische Methode aktuell im Rahmen der Replizierbarkeitskrise in der Psychologie eine besondere Bedeutung. Dabei stützt sich die vorliegende Arbeit auf die Sekundäranalyse großangelegter Schulleistungsstudien, welche den Vorteil besitzen, dass eine große Zahl an Datenpunkten (Variablen und Personen) zur Verfügung steht, um Effekte unterschiedlicher Operationalisierungen zu vergleichen.
Inhaltlich greifen Artikel II und III Themen auf, die in der wissenschaftlichen und gesellschaftlichen Diskussion zu Leistungsstarken und ihrer Wahrnehmung in der Öffentlichkeit immer wieder aufscheinen: In Artikel II wird zunächst die Frage gestellt, ob Leistungsstarke bereits im aktuellen Regelunterricht einen kumulativen Vorteil gegenüber ihren weniger leistungsstarken Mitschülerinnen und Mitschülern haben (Matthäus-Effekt). Die Ergebnisse zeigen, dass an Gymnasien keineswegs von sich vergrößernden Unterschieden gesprochen werden kann. Im Gegenteil, es verringerte sich im Laufe der Sekundarstufe der Abstand zwischen den Gruppen, indem die Lernraten bei leistungsschwächeren Schülerinnen und Schülern höher waren. Artikel III hingegen betrifft die soziale Wahrnehmung von leistungsstarken Schülerinnen und Schülern. Auch hier hält sich in der öffentlichen Diskussion die Annahme, dass höhere Leistungen mit Nachteilen in der sozialen Integration einhergehen könnten, was sich auch in Studien widerspiegelt, die sich mit Geschlechterstereotypen Jugendlicher in Bezug auf Schulleistung beschäftigen. In Artikel III wird unter anderem erneut das Potenzial der Multiversumsanalyse genutzt, um die Variation des Zusammenhangs über Operationalisierungen von Leistungsstärke zu beschreiben. Es zeigt sich unter unterschiedlichen Operationalisierungen von Leistungsstärke und über verschiedene Facetten sozialer Integration hinweg, dass die Zusammenhänge zwischen Leistung und sozialer Integration insgesamt leicht positiv ausfallen. Annahmen, die auf differenzielle Effekte für Jungen und Mädchen oder für unterschiedliche Fächer abzielen, finden in diesen Analysen keine Bestätigung.
Die Dissertation zeigt, dass der Vergleich unterschiedlicher Ansätze zur Operationalisierung von Leistungsstärke — eingesetzt im Rahmen eines kritischen Multiplismus — das Verständnis von Phänomenen vertiefen kann und auch das Potenzial hat, Theorieentwicklung voranzubringen.
Hydraulic-driven fractures play a key role in subsurface energy technologies across several scales. By injecting fluid at high hydraulic pressure into rock with intrinsic low permeability, in-situ stress field and fracture development pattern can be characterised as well as rock permeability can be enhanced. Hydraulic fracturing is a commercial standard procedure for enhanced oil and gas production of rock reservoirs with low permeability in petroleum industry. However, in EGS utilization, a major geological concern is the unsolicited generation of earthquakes due to fault reactivation, referred to as induced seismicity, with a magnitude large enough to be felt on the surface or to damage facilities and buildings. Furthermore, reliable interpretation of hydraulic fracturing tests for stress measurement is a great challenge for the energy technologies. Therefore, in this cumulative doctoral thesis the following research questions are investigated. (1): How do hydraulic fractures grow in hard rock at various scales?; (2): Which parameters control hydraulic fracturing and hydro-mechanical coupling?; and (3): How can hydraulic fracturing in hard rock be modelled?
In the laboratory scale study, several laboratory hydraulic fracturing experiments are investigated numerically using Irazu2D that were performed on intact cubic Pocheon granite samples from South Korea applying different injection protocols. The goal of the laboratory experiments is to test the concept of cyclic soft stimulation which may enable sustainable permeability enhancement (Publication 1).
In the borehole scale study, hydraulic fracturing tests are reported that were performed in boreholes located in central Hungary to determine the in-situ stress for a geological site investigation. At depth of about 540 m, the recorded pressure versus time curves in mica schist with low dip angle foliation show atypical evolution. In order to provide explanation for this observation, a series of discrete element computations using Particle Flow Code 2D are performed (Publication 2).
In the reservoir scale study, the hydro-mechanical behaviour of fractured crystalline rock due to one of the five hydraulic stimulations at the Pohang Enhanced Geothermal site in South Korea is studied. Fluid pressure perturbation at faults of several hundred-meter lengths during hydraulic stimulation is simulated using FracMan (Publication 3).
The doctoral research shows that the resulting hydraulic fracturing geometry will depend “locally”, i.e. at the length scale of representative elementary volume (REV) and below that (sub-REV), on the geometry and strength of natural fractures, and “globally”, i.e. at super-REV domain volume, on far-field stresses. Regarding hydro-mechanical coupling, it is suggested to define separate coupling relationship for intact rock mass and natural fractures. Furthermore, the relative importance of parameters affecting the magnitude of formation breakdown pressure, a parameter characterising hydro-mechanical coupling, is defined. It can be also concluded that there is a clear gap between the capacity of the simulation software and the complexity of the studied problems. Therefore, the computational time of the simulation of complex hydraulic fracture geometries must be reduced while maintaining high fidelity simulation results. This can be achieved either by extending the computational resources via parallelization techniques or using time scaling techniques. The ongoing development of used numerical models focuses on tackling these methodological challenges.
The NAC transcription factor (TF) JUNGBRUNNEN1 (JUB1) is an important negative regulator of plant senescence, as well as of gibberellic acid (GA) and brassinosteroid (BR) biosynthesis in Arabidopsis thaliana. Overexpression of JUB1 promotes longevity and enhances tolerance to drought and other abiotic stresses. A similar role of JUB1 has been observed in other plant species, including tomato and banana. Our data show that JUB1 overexpressors (JUB1-OXs) accumulate higher levels of proline than WT plants under control conditions, during the onset of drought stress, and thereafter. We identified that overexpression of JUB1 induces key proline biosynthesis and suppresses key proline degradation genes. Furthermore, bZIP63, the transcription factor involved in proline metabolism, was identified as a novel downstream target of JUB1 by Yeast One-Hybrid (Y1H) analysis and Chromatin immunoprecipitation (ChIP). However, based on Electrophoretic Mobility Shift Assay (EMSA), direct binding of JUB1 to bZIP63 could not be confirmed. Our data indicate that JUB1-OX plants exhibit reduced stomatal conductance under control conditions. However, selective overexpression of JUB1 in guard cells did not improve drought stress tolerance in Arabidopsis. Moreover, the drought-tolerant phenotype of JUB1 overexpressors does not solely depend on the transcriptional control of the DREB2A gene. Thus, our data suggest that JUB1 confers tolerance to drought stress by regulating multiple components. Until today, none of the previous studies on JUB1´s regulatory network focused on identifying protein-protein interactions. We, therefore, performed a yeast two-hybrid screen (Y2H) which identified several protein interactors of JUB1, two of which are the calcium-binding proteins CaM1 and CaM4. Both proteins interact with JUB1 in the nucleus of Arabidopsis protoplasts. Moreover, JUB1 is expressed with CaM1 and CaM4 under the same conditions. Since CaM1.1 and CaM4.1 encode proteins with identical amino acid sequences, all further experiments were performed with constructs involving the CaM4 coding sequence. Our data show that JUB1 harbors multiple CaM-binding sites, which are localized in both the N-terminal and C-terminal regions of the protein. One of the CaM-binding sites, localized in the DNA-binding domain of JUB1, was identified as a functional CaM-binding site since its mutation strongly reduced the binding of CaM4 to JUB1. Furthermore, JUB1 transactivates expression of the stress-related gene DREB2A in mesophyll cells; this effect is significantly reduced when the calcium-binding protein CaM4 is expressed as well. Overexpression of both genes in Arabidopsis results in early senescence observed through lower chlorophyll content and an enhanced expression of senescence-associated genes (SAGs) when compared with single JUB1 overexpressors. Our data also show that JUB1 and CaM4 proteins interact in senescent leaves, which have increased Ca2+ levels when compared to young leaves. Collectively, our data indicate that JUB1 activity towards its downstream targets is fine-tuned by calcium-binding proteins during leaf senescence.
Stimuli-promoted in situ formation of hydrogels with thiol/thioester containing peptide precursors
(2022)
Hydrogels are potential synthetic ECM-like substitutes since they provide functional and structural similarities compared to soft tissues. They can be prepared by crosslinking of macromolecules or by polymerizing suitable precursors. The crosslinks are not necessarily covalent bonds, but could also be formed by physical interactions such as π-π interactions, hydrophobic interactions, or H-bonding. On demand in situ forming hydrogels have garnered increased interest especially for biomedical applications over preformed gels due to the relative ease of in vivo delivery and filling of cavities. The thiol-Michael addition reaction provides a straightforward and robust strategy for in situ gel formation with its fast reaction kinetics and ability to proceed under physiological conditions. The incorporation of a trigger function into a crosslinking system becomes even more interesting since gelling can be controlled with stimulus of choice. The use of small molar mass crosslinker precursors with active groups orthogonal to thiol-Michael reaction type electrophile provides the opportunity to implement an on-demand in situ crosslinking without compromising the fast reaction kinetics.
It was postulated that short peptide sequences due to the broad range structural-function relations available with the different constituent amino acids, can be exploited for the realisation of stimuli-promoted in situ covalent crosslinking and gelation applications. The advantages of this system over conventional polymer-polymer hydrogel systems are the ability tune and predict material property at the molecular level.
The main aim of this work was to develop a simplified and biologically-friendly stimuli-promoted in situ crosslinking and hydrogelation system using peptide mimetics as latent crosslinkers. The approach aims at using a single thiodepsipeptide sequence to achieve separate pH- and enzyme-promoted gelation systems with little modification to the thiodepsipeptide sequence. The realization of this aim required the completion of three milestones.
In the first place, after deciding on the thiol-Michael reaction as an effective in situ crosslinking strategy, a thiodepsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) with expected propensity towards pH-dependent thiol-thioester exchange (TTE) activation, was proposed as a suitable crosslinker precursor for pH-promoted gelation system. Prior to the synthesis of the proposed peptide-mimetic, knowledge of the thiol-Michael reactivity of the would-be activated thiol moiety SH-Leu, which is internally embedded in the thiodepsipeptide was required. In line with pKa requirements for a successful TTE, the reactivity of a more acidic thiol, SH-Phe was also investigated to aid the selection of the best thiol to be incorporated in the thioester bearing peptide based crosslinker precursor. Using ‘pseudo’ 2D-NMR investigations, it was found that only reactions involving SH-Leu yielded the expected thiol-Michael product, an observation that was attributed to the steric hindrance of the bulkier nature of SH-Phe. The fast reaction rates and complete acrylate/maleimide conversion obtained with SH-Leu at pH 7.2 and higher aided the direct elimination of SH-Phe as a potential thiol for the synthesis of the peptide mimetic.
Based on the initial studies, for the pH-promoted gelation system, the proposed Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH was kept unmodified. The subtle difference in pKa values between SH-Leu (thioester thiol) and the terminal cysteamine thiol from theoretical conditions should be enough to effect a ‘pseudo’ intramolecular TTE. In polar protic solvents and under basic aqueous conditions, TDP successfully undergoes a ‘pseudo’ intramolecular TTE reaction to yield an α,ω-dithiol tripeptide, HSLeu-Leu-Gly-NEtSH. The pH dependence of thiolate ion generation by the cysteamine thiol aided the incorporation of the needed stimulus (pH) for the overall success of TTE (activation step) – thiol-Michael addition (crosslinking) strategy.
Secondly, with potential biomedical applications in focus, the susceptibility of TDP, like other thioesters, to intermolecular TTE reaction was probed with a group of thiols of varying thiol pKa values, since biological milieu characteristically contain peptide/protein thiols. L-cysteine, which is a biologically relevant thiol, and a small molecular weight thiol, methylthioglycolate both with relatively similar thiol pKa, values, led to an increase concentration of the dithiol crosslinker when reacted with TDP. In the presence of acidic thiols (p-NTP and 4MBA), a decrease in the dithiol concentration was observed, an observation that can be attributed to the inability of the TTE tetrahedral intermediate to dissociate into exchange products and is in line with pKa requirements for successful TTE reaction. These results additionally makes TDP more attractive and the potentially the first crosslinker precursor for applications in biologically relevant media.
Finally, the ability of TDP to promote pH-sensitive in situ gel formation was probed with maleimide functionalized 4-arm polyethylene glycol polymers in tris-buffered media of varying pHs. When a 1:1 thiol: maleimide molar ratio was used, TDP-PEG4MAL hydrogels formed within 3, 12 and 24 hours at pH values of 8.5, 8.0 and 7.5 respectively. However, gelation times of 3, 5 and 30 mins were observed for the same pH trend when the thiol: maleimide molar was increased to 2:1.
A direct correlation of thiol content with G’ of the gels at each pH could also be drawn by comparing gels with thiol: maleimide ratios of 1:1 to those with 2:1 thiol: maleimide mole ratios. This is supported by the fact that the storage modulus (G') is linearly dependent on the crosslinking density of the polymer. The values of initial G′ for all gels ranged between (200 – 5000 Pa), which falls in the range of elasticities of certain tissue microenvironments for example brain tissue 200 – 1000 Pa and adipose tissue (2500 – 3500 Pa).
Knowledge so far gained from the study on the ability to design and tune the exchange reaction of thioester containing peptide mimetic will give those working in the field further insight into the development of new sequences tailored towards specific applications.
TTE substrate design using peptide mimetic as presented in this work has revealed interesting new insights considering the state-of-the-art. Using the results obtained as reference, the strategy provides a possibility to extend the concept to the controlled delivery of active molecules needed for other robust and high yielding crosslinking reactions for biomedical applications. Application for this sequentially coupled functional system could be seen e.g. in the treatment of inflamed tissues associated with urinary tract like bladder infections for which pH levels above 7 were reported. By the inclusion of cell adhesion peptide motifs, the hydrogel network formed at this pH could act as a new support layer for the healing of damage epithelium as shown in interfacial gel formation experiments using TDP and PEG4MAL droplets.
The versatility of the thiodepsipeptide sequence, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-(TDPo) was extended for the design and synthesis of a MMP-sensitive 4-arm PEG-TDPo conjugate. The purported cleavage of TDPo at the Gly-SLeu bond yields active thiol units for subsequent reaction of orthogonal Michael acceptor moieties. One of the advantages of stimuli-promoted in situ crosslinking systems using short peptides should be the ease of design of required peptide molecules due to the predictability of peptide functions their sequence structure. Consequently the functionalisation of a 4-arm PEG core with the collagenase active TDPo sequence yielded an MMP-sensitive 4-arm thiodepsipeptide-PEG conjugate (PEG4TDPo) substrate.
Cleavage studies using thiol flourometric assay in the presence of MMPs -2 and -9 confirmed the susceptibility of PEG4TDPo towards these enzymes. The resulting time-dependent increase in fluorescence intensity in the presence of thiol assay signifies the successful cleavage of TDPo at the Gly-SLeu bond as expected. It was observed that the cleavage studies with thiol flourometric assay introduces a sigmoid non-Michaelis-Menten type kinetic profile, hence making it difficult to accurately determine the enzyme cycling parameters, kcat and KM .
Gelation studies with PEG4MAL at 10 % wt. concentrations revealed faster gelation with MMP-2 than MMP-9 with 28 and 40 min gelation times respectively. Possible contributions by hydrolytic cleavage of PEG4TDPo has resulted in the gelation of PEG4MAL blank samples but only after 60 minutes of reaction. From theoretical considerations, the simultaneous gelation reaction would be expected to more negatively impact the enzymatic than hydrolytic cleavage. The exact contributions from hydrolytic cleavage of PEG4TDPo would however require additional studies.
In summary this new and simplified in situ crosslinking system using peptide-based crosslinker precursors with tuneable properties exhibited in situ crosslinking gelation kinetics on similar levels with already active dithiols reported. The advantageous on-demand functionality associated with its pH-sensitivity and physiological compatibility makes it a strong candidate worth further research as biomedical applications in general and on-demand material synthesis is concerned.
Results from MMP-promoted gelation system unveils a simple but unexplored approach for in situ synthesis of covalently crosslinked soft materials, that could lead to the development of an alternative pathway in addressing cancer metastasis by making use of MMP overexpression as a trigger. This goal has so far not being reach with MMP inhibitors despite the extensive work this regard.