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The central motivation of the thesis was to provide possible solutions and concepts to improve the performance (e.g. activity and selectivity) of electrochemical N2 reduction reaction (NRR). Given that porous carbon-based materials usually exhibit a broad range of structural properties, they could be promising NRR catalysts. Therefore, the advanced design of novel porous carbon-based materials and the investigation of their application in electrocatalytic NRR including the particular reaction mechanisms are the most crucial points to be addressed. In this regard, three main topics were investigated. All of them are related to the functionalization of porous carbon for electrochemical NRR or other electrocatalytic reactions.
In chapter 3, a novel C-TixOy/C nanocomposite has been described that has been obtained via simple pyrolysis of MIL-125(Ti). A novel mode for N2 activation is achieved by doping carbon atoms from nearby porous carbon into the anion lattice of TixOy. By comparing the NRR performance of M-Ts and by carrying out DFT calculations, it is found that the existence of (O-)Ti-C bonds in C-doped TixOy can largely improve the ability to activate and reduce N2 as compared to unoccupied OVs in TiO2. The strategy of rationally doping heteroatoms into the anion lattice of transition metal oxides to create active centers may open many new opportunities beyond the use of noble metal-based catalysts also for other reactions that require the activation of small molecules as well.
In chapter 4, a novel catalyst construction composed of Au single atoms decorated on the surface of NDPCs was reported. The introduction of Au single atoms leads to active reaction sites, which are stabilized by the N species present in NDPCs. Thus, the interaction within as-prepared AuSAs-NDPCs catalysts enabled promising performance for electrochemical NRR. For the reaction mechanism, Au single sites and N or C species can act as Frustrated Lewis pairs (FLPs) to enhance the electron donation and back-donation process to activate N2 molecules. This work provides new opportunities for catalyst design in order to achieve efficient N2 fixation at ambient conditions by utilizing recycled electric energy.
The last topic described in chapter 5 mainly focused on the synthesis of dual heteroatom-doped porous carbon from simple precursors. The introduction of N and B heteroatoms leads to the construction of N-B motives and Frustrated Lewis pairs in a microporous architecture which is also rich in point defects. This can improve the strength of adsorption of different reactants (N2 and HMF) and thus their activation. As a result, BNC-2 exhibits a desirable electrochemical NRR and HMF oxidation performance. Gas adsorption experiments have been used as a simple tool to elucidate the relationship between the structure and catalytic activity. This work provides novel and deep insights into the rational design and the origin of activity in metal-free electrocatalysts and enables a physically viable discussion of the active motives, as well as the search for their further applications.
Throughout this thesis, the ubiquitous problems of low selectivity and activity of electrochemical NRR are tackled by designing porous carbon-based catalysts with high efficiency and exploring their catalytic mechanisms. The structure-performance relationships and mechanisms of activation of the relatively inert N2 molecules are revealed by either experimental results or DFT calculations. These fundamental understandings pave way for a future optimal design and targeted promotion of NRR catalysts with porous carbon-based structure, as well as study of new N2 activation modes.
Objeto de esta investigación es el auge y caída de una legitimación teológica de la poesía que tuvo lugar en el virreinato del Perú entre fines del siglo XVI y la segunda mitad del siglo XVII. Su punto cúlmine está marcado por el surgimiento de una “Academia Antártica” en las primeras décadas del siglo XVII, mientras que su fin, se aprecia a fines del mismo siglo, cuando eruditos de las órdenes religiosas, especialmente Juan de Espinosa y Medrano en sus textos en defensa de la poesía y las ciencias, negaron a la poesía cualquier estatuto teológico, sirviéndose sin embargo de ella para escribir sus sermones y textos. A partir del auge y caída de esta legitimación teológica en el virreinato del Perú, este estudio muestra la existencia de dos movimientos que forman un quiasmo entre una teologización de la poesía y una poetización de la teología, en cuyo centro velado se encuentra en disputa el saber teórico y práctico de la poesía. Lo que está en disputa en este sentido no es la poesía, entendida como una cumbre de las bellas letras, sino la posesión legítima de un modo de lectura analógico y tipológico del orden del universo, fundado en las Sagradas Escrituras y en la historia de la salvación, y un modo poético para doctrinar a todos los miembros de la sociedad virreinal en concordancia con aquel modo de lectura.
Ficción herética
(2019)
La metáfora de la «isla» en la narrativa cubana contemporánea engloba toda una serie de complejidades simbólicas dependientes de la vivencia del espacio y el tiempo. Su potencial visual se manifiesta u oculta las propias vivencias insulares de los escritores cubanos. En los últimos 30 años en Cuba, los fenómenos políticos económicos y sociales han modificado categóricamente la percepción y la configuración del plano social e individual frente a las exigencias globales (Fornet 2006, Rojas 1999, 2002, 2006). Se ha confirmado una sensación de acinesia e ingravidez (Casamayor 2013) y se ha presentado una actitud «herética» por parte de los narradores cubanos, quienes se confrontan con las ideas de la postmodernidad, lo postsoviético o postutópico, reafirmando así una sensibilidad presentista (Guerrero 2016). Estos autores presentan resonancias y reivindicaciones de los imaginarios insulares de autores y de tradiciones estéticas dentro y fuera de la isla como José Lezama Lima, Virgilio Piñera, Guillermo Cabrera Infante, Reinaldo Arenas y Severo Sarduy). El análisis de las écfrasis insulares permite examinar las dinámicas de representación y de sentido: disimulación: la disimulación, la anamorfosis y la trompe l’oeil (Sarduy 1981). La novela Tuyo es el reino (1998) de Abilio Estévez es un modelo desde el que se localizará las relaciones de sentido entre canon literario y los referentes socioculturales de las variaciones somatopológicas de la isla en la narrativa cubana actual: Ena Lucía Portela, Atilio Caballero, Antonio José Ponte, Daniel Díaz Mantilla, Emerio Medina, Orlando Luis Pardo, Anisley Negrin y Ahmel Echeverría, entre otros.
Modern health care systems are characterized by pronounced prevention and cost-optimized treatments. This dissertation offers novel empirical evidence on how useful such measures can be. The first chapter analyzes how radiation, a main pollutant in health care, can negatively affect cognitive health. The second chapter focuses on the effect of Low Emission Zones on public heath, as air quality is the major external source of health problems. Both chapters point out potentials for preventive measures. Finally, chapter three studies how changes in treatment prices affect the reallocation of hospital resources. In the following, I briefly summarize each chapter and discuss implications for health care systems as well as other policy areas. Based on the National Educational Panel Study that is linked to data on radiation, chapter one shows that radiation can have negative long-term effects on cognitive skills, even at subclinical doses. Exploiting arguably exogenous variation in soil contamination in Germany due to the Chernobyl disaster in 1986, the findings show that people exposed to higher radiation perform significantly worse in cognitive tests 25 years later. Identification is ensured by abnormal rainfall within a critical period of ten days. The results show that the effect is stronger among older cohorts than younger cohorts, which is consistent with radiation accelerating cognitive decline as people get older. On average, a one-standarddeviation increase in the initial level of CS137 (around 30 chest x-rays) is associated with a decrease in the cognitive skills by 4.1 percent of a standard deviation (around 0.05 school years). Chapter one shows that sub-clinical levels of radiation can have negative consequences even after early childhood. This is of particular importance because most of the literature focuses on exposure very early in life, often during pregnancy. However, population exposed after birth is over 100 times larger. These results point to substantial external human capital costs of radiation which can be reduced by choices of medical procedures. There is a large potential for reductions because about one-third of all CT scans are assumed to be not medically justified (Brenner and Hall, 2007). If people receive unnecessary CT scans because of economic incentives, this chapter points to additional external costs of health care policies. Furthermore, the results can inform the cost-benefit trade-off for medically indicated procedures. Chapter two provides evidence about the effectiveness of Low Emission Zones. Low Emission Zones are typically justified by improvements in population health. However, there is little evidence about the potential health benefits from policy interventions aiming at improving air quality in inner-cities. The chapter ask how the coverage of Low Emission Zones air pollution and hospitalization, by exploiting variation in the roll out of Low Emission Zones in Germany. It combines information on the geographic coverage of Low Emission Zones with rich panel data on the universe of German hospitals over the period from 2006 to 2016 with precise information on hospital locations and the annual frequency of detailed diagnoses. In order to establish that our estimates of Low Emission Zones’ health impacts can indeed be attributed to improvements in local air quality, we use data from Germany’s official air pollution monitoring system and assign monitor locations to Low Emission Zones and test whether measures of air pollution are affected by the coverage of a Low Emission Zone. Results in chapter two confirm former results showing that the introduction of Low Emission Zones improved air quality significantly by reducing NO2 and PM10 concentrations. Furthermore, the chapter shows that hospitals which catchment areas are covered by a Low Emission Zone, diagnose significantly less air pollution related diseases, in particular by reducing the incidents of chronic diseases of the circulatory and the respiratory system. The effect is stronger before 2012, which is consistent with a general improvement in the vehicle fleet’s emission standards. Depending on the disease, a one-standard-deviation increase in the coverage of a hospitals catchment area covered by a Low Emission Zone reduces the yearly number of diagnoses up to 5 percent. These findings have strong implications for policy makers. In 2015, overall costs for health care in Germany were around 340 billion euros, of which 46 billion euros for diseases of the circulatory system, making it the most expensive type of disease caused by 2.9 million cases (Statistisches Bundesamt, 2017b). Hence, reductions in the incidence of diseases of the circulatory system may directly reduce society’s health care costs. Whereas chapter one and two study the demand-side in health care markets and thus preventive potential, chapter three analyzes the supply-side. By exploiting the same hospital panel data set as in chapter two, chapter three studies the effect of treatment price shocks on the reallocation of hospital resources in Germany. Starting in 2005, the implementation of the German-DRG-System led to general idiosyncratic treatment price shocks for individual hospitals. Thus far there is little evidence of the impact of general price shocks on the reallocation of hospital resources. Additionally, I add to the exiting literature by showing that price shocks can have persistent effects on hospital resources even when these shocks vanish. However, simple OLS regressions would underestimate the true effect, due to endogenous treatment price shocks. I implement a novel instrument variable strategy that exploits the exogenous variation in the number of days of snow in hospital catchment areas. A peculiarity of the reform allowed variation in days of snow to have a persistent impact on treatment prices. I find that treatment price increases lead to increases in input factors such as nursing staff, physicians and the range of treatments offered but to decreases in the treatment volume. This indicates supplier-induced demand. Furthermore, the probability of hospital mergers and privatization decreases. Structural differences in pre-treatment characteristics between hospitals enhance these effects. For instance, private and larger hospitals are more affected. IV estimates reveal that OLS results are biased towards zero in almost all dimensions because structural hospital differences are correlated with the reallocation of hospital resources. These results are important for several reasons. The G-DRG-Reform led to a persistent polarization of hospital resources, as some hospitals were exposed to treatment price increases, while others experienced reductions. If hospitals increase the treatment volume as a response to price reductions by offering unnecessary therapies, it has a negative impact on population wellbeing and public spending. However, results show a decrease in the range of treatments if prices decrease. Hospitals might specialize more, thus attracting more patients. From a policy perspective it is important to evaluate if such changes in the range of treatments jeopardize an adequate nationwide provision of treatments. Furthermore, the results show a decrease in the number of nurses and physicians if prices decrease. This could partly explain the nursing crisis in German hospitals. However, since hospitals specialize more they might be able to realize efficiency gains which justify reductions in input factors without loses in quality. Further research is necessary to provide evidence for the impact of the G-DRG-Reform on health care quality. Another important aspect are changes in the organizational structure. Many public hospitals have been privatized or merged. The findings show that this is at least partly driven by the G-DRG-Reform. This can again lead to a lack in services offered in some regions if merged hospitals specialize more or if hospitals are taken over by ecclesiastical organizations which do not provide all treatments due to moral conviction. Overall, this dissertation reveals large potential for preventive health care measures and helps to explain reallocation processes in the hospital sector if treatment prices change. Furthermore, its findings have potentially relevant implications for other areas of public policy. Chapter one identifies an effect of low dose radiation on cognitive health. As mankind is searching for new energy sources, nuclear power is becoming popular again. However, results of chapter one point to substantial costs of nuclear energy which have not been accounted yet. Chapter two finds strong evidence that air quality improvements by Low Emission Zones translate into health improvements, even at relatively low levels of air pollution. These findings may, for instance, be of relevance to design further policies targeted at air pollution such as diesel bans. As pointed out in chapter three, the implementation of DRG-Systems may have unintended side-effects on the reallocation of hospital resources. This may also apply to other providers in the health care sector such as resident doctors.
Force plays a fundamental role in the regulation of biological processes. Cells can sense the mechanical properties of the extracellular matrix (ECM) by applying forces and transmitting mechanical signals. They further use mechanical information for regulating a wide range of cellular functions, including adhesion, migration, proliferation, as well as differentiation and apoptosis. Even though it is well understood that mechanical signals play a crucial role in directing cell fate, surprisingly little is known about the range of forces that define cell-ECM interactions at the molecular level.
Recently, synthetic molecular force sensor (MFS) designs have been established for measuring the molecular forces acting at the cell-ECM interface. MFSs detect the traction forces generated by cells and convert this mechanical input into an optical readout. They are composed of calibrated mechanoresponsive building blocks and are usually equipped with a fluorescence reporter system. Up to date, many different MFS designs have been introduced and successfully used for measuring forces involved in the adhesion of mammalian cells. These MFSs utilize different molecular building blocks, such as double-stranded deoxyribonucleic acid (dsDNA) molecules, DNA hairpins and synthetic polymers like polyethylene glycol (PEG). These currently available MFS designs lack ECM mimicking properties.
In this work, I introduce a new MFS building block for cell biology applications, derived from the natural ECM. It combines mechanical tunability with the ability to mimic the native cellular microenvironment. Inspired by structural ECM proteins with load bearing function, this new MFS design utilizes coiled coil (CC)-forming peptides. CCs are involved in structural and mechanical tasks in the cellular microenvironment and many of the key protein components of the cytoskeleton and the ECM contain CC structures. The well-known folding motif of CC structures, an easy synthesis via solid phase methods and the many roles CCs play in biological processes have inspired studies to use CCs as tunable model systems for protein design and assembly. All these properties make CCs ideal candidates as building blocks for MFSs. In this work, a series of heterodimeric CCs were designed, characterized and further used as molecular building blocks for establishing a novel, next-generation MFS prototype.
A mechanistic molecular understanding of their structural response to mechanical load is essential for revealing the sequence-structure-mechanics relationships of CCs. Here, synthetic heterodimeric CCs of different length were loaded in shear geometry and their mechanical response was investigated using a combination of atomic force microscope (AFM)-based single-molecule force spectroscopy (SMFS) and steered molecular dynamics (SMD) simulations. SMFS showed that the rupture forces of short heterodimeric CCs (3-5 heptads) lie in the range of 20-50 pN, depending on CC length, pulling geometry and the applied loading rate (dF/dt). Upon shearing, an initial rise in the force, followed by a force plateau and ultimately strand separation was observed in SMD simulations. A detailed structural analysis revealed that CC response to shear load depends on the loading rate and involves helix uncoiling, uncoiling-assisted sliding in the direction of the applied force and uncoiling-assisted dissociation perpendicular to the force axis.
The application potential of these mechanically characterized CCs as building blocks for MFSs has been tested in 2D cell culture applications with the goal of determining the threshold force for cell adhesion. Fully calibrated, 4- to 5-heptad long, CC motifs (CC-A4B4 and CC-A5B5) were used for functionalizing glass surfaces with MFSs. 3T3 fibroblasts and endothelial cells carrying mutations in a signaling pathway linked to cell adhesion and mechanotransduction processes were used as model systems for time-dependent adhesion experiments. A5B5-MFS efficiently supported cell attachment to the functionalized surfaces for both cell types, while A4B4-MFS failed to maintain attachment of 3T3 fibroblasts after the first 2 hours of initial cell adhesion. This difference in cell adhesion behavior demonstrates that the magnitude of cell-ECM forces varies depending on the cell type and further supports the application potential of CCs as mechanoresponsive and tunable molecular building blocks for the development of next-generation protein-based MFSs.This novel CC-based MFS design is expected to provide a powerful new tool for observing cellular mechanosensing processes at the molecular level and to deliver new insights into the mechanisms and forces involved. This MFS design, utilizing mechanically tunable CC building blocks, will not only allow for measuring the molecular forces acting at the cell-ECM interface, but also yield a new platform for the development of mechanically controlled materials for a large number of biological and medical applications.
In this work we investigated ultrafast demagnetization in a Heusler-alloy. This material belongs to the halfmetal and exists in a ferromagnetic phase. A special feature of investigated alloy is a structure of electronic bands. The last leads to the specific density of the states. Majority electrons form a metallic like structure while minority electrons form a gap near the Fermi-level, like in semiconductor. This particularity offers a good possibility to use this material as model-like structure and to make some proof of principles concerning demagnetization. Using pump-probe experiments we carried out time-resolved measurements to figure out the times of demagnetization. For the pumping we used ultrashort laser pulses with duration around 100 fs. Simultaneously we used two excitation regimes with two different wavelengths namely 400 nm and 1240 nm. Decreasing the energy of photons to the gap size of the minority electrons we explored the effect of the gap on the demagnetization dynamics. During this work we used for the first time OPA (Optical Parametrical Amplifier) for the generation of the laser irradiation in a long-wave regime. We tested it on the FETOSPEX-beamline in BASSYII electron storage ring. With this new technique we measured wavelength dependent demagnetization dynamics. We estimated that the demagnetization time is in a correlation with photon energy of the excitation pulse. Higher photon energy leads to the faster demagnetization in our material. We associate this result with the existence of the energy-gap for minority electrons and explained it with Elliot-Yaffet-scattering events. Additionally we applied new probe-method for magnetization state in this work and verified their effectivity. It is about the well-known XMCD (X-ray magnetic circular dichroism) which we adopted for the measurements in reflection geometry. Static experiments confirmed that the pure electronic dynamics can be separated from the magnetic one. We used photon energy fixed on the L3 of the corresponding elements with circular polarization. Appropriate incidence angel was estimated from static measurements. Using this probe method in dynamic measurements we explored electronic and magnetic dynamics in this alloy.
Membrane adhesion is a fundamental biological process in which membranes are attached to neighboring membranes or surfaces. Membrane adhesion emerges from a complex interplay between the binding of membrane-anchored receptors/ligands and the membrane properties. In this work, we study membrane adhesion mediated by lipid-anchored saccharides using microsecond-long full-atomistic molecular dynamics simulations. Motivated by neutron scattering experiments on membrane adhesion via lipid-anchored saccharides, we investigate the role of LeX, Lac1, and Lac2 saccharides and membrane fluctuations in membrane adhesion.
We study the binding of saccharides in three different systems: for saccharides in water, for saccharides anchored to essentially planar membranes at fixed separations, and for saccharides anchored to apposing fluctuating membranes. Our simulations of two saccharides in water indicate that the saccharides engage in weak interactions to form dimers. We find that the binding occurs in a continuum of bound states instead of a certain number of well-defined bound structures, which we term as "diffuse binding".
The binding of saccharides anchored to essentially planar membranes strongly depends on separation of the membranes, which is fixed in our simulation system. We show that the binding constants for trans-interactions of two lipid-anchored saccharides monotonically decrease with increasing separation. Saccharides anchored to the same membrane leaflet engage in cis-interactions with binding constants comparable to the trans-binding constants at the smallest membrane separations. The interplay of cis- and trans-binding can be investigated in simulation systems with many lipid-anchored saccharides. For Lac2, our simulation results indicate a positive cooperativity of trans- and cis-binding. In this cooperative binding the trans-binding constant is enhanced by the cis-interactions. For LeX, in contrast, we observe no cooperativity between trans- and cis-binding. In addition, we determine the forces generated by trans-binding of lipid-anchored saccharides in planar membranes from the binding-induced deviations of the lipid-anchors. We find that the forces acting on trans-bound saccharides increase with increasing membrane separation to values of the order of 10 pN.
The binding of saccharides anchored to the fluctuating membranes results from an interplay between the binding properties of the lipid-anchored saccharides and membrane fluctuations. Our simulations, which have the same average separation of the membranes as obtained from the neutron scattering experiments, yield a binding constant larger than in planar membranes with the same separation. This result demonstrates that membrane fluctuations play an important role at average membrane separations which are seemingly too large for effective binding. We further show that the probability distribution of the local separation can be well approximated by a Gaussian distribution. We calculate the relative membrane roughness and show that our results are in good agreement with the roughness values reported from the neutron scattering experiments.
Die vorliegende Dissertation zielt generell darauf ab, die Anwendung der dialektischen Methodologie auf den Bereich der Sprachphilosophie zu rechtfertigen und eine systematische Bearbeitung eines begrenzten Teils der Sprachphilosophie mithilfe der Dialektik durchzuführen. Um diese Herangehensweise, die in der Forschung kaum oder gar nicht vertreten ist, aufzuklären und festzustellen, werde ich zuerst auf die philosophischen Überlegungen von zwei Autoren zurückgreifen: Hegel und Wittgenstein.
Hegel und Wittgenstein sind, auf den ersten Blick, Autoren, die kaum Gemeinsamkeiten haben, außer dass sie sich beide mit der Philosophie als Fach beschäftigt und unvermeidlich ein gemeinschaftliches Thema, die Sprache, behandelt haben, wobei jedoch weder eine inhaltliche noch eine methodologische Verbindung hervorgehoben werden könnte. Die erste Voraussetzung dieser Dissertation, in Bezug auf die Geschichte der Idee, besteht darin, darauf hinzudeuten, dass der hegelsche Geistesbegriff und Wittgensteins Lebensform zwei Ansätze und Resultat einer philosophischen Bemühung sind, die gemeinsam die notwendige Auflösung bzw. Überwindung skeptischer Argumentation vornehmen. Tatsächlich hat Wittgenstein in seinen Philosophischen Untersuchungen eine Argumentation entwickelt, die als „Paradox des Regelfolgens“ bezeichnet und in der sekundären Literatur (hauptsächlich bei Kripke) als eine Art skeptische Argumentation betrachtet wurde. Demnach wird Wittgensteins Theorie der Sprache entweder als eine Auflösung dieses Skeptizismus oder einfach als ein skeptischer Text selbst ausgelegt (Brandom). Das erste Ziel meiner Dissertation besteht darin, zu zeigen, dass dieses Paradox als skeptische Argumentation allerdings unvollständig geblieben ist dass dieses Paradox als der erster entscheidender Moment zu der höchsten Form der skeptischen Herausforderung, der Antinomie, betrachtet werden kann. Eine vollständige skeptische Argumentation heißt, dass die alleinige Auflösung des Paradoxes, der Dispositionalismus und die Negation dieser Theorie, beide beweisbar sind. Ich werde also versuchen, aus der in den PU dargestellten Auflösung des Paradoxes des Regelfolgens die Vervollständigung einer Antinomie des Begriffes der Normativität in Bezug auf die Sprachregeln festzulegen, ähnlich der von Kant entwickelten kosmologischen Antinomie (Thesis cum Antithesis). Das zweite Ziel meiner Dissertation besteht folglich darin, zu zeigen, 1. dass die kantische Auflösung der Antinomie unwirksam bezüglich der Antinomie der Normativität ist, 2. dass diese Antinomie eine notwendige Auseinandersetzung mit einem radikalen Skeptizismus bedeutet und dass wir logisch gezwungen sind, nicht nur irgendeine Theorie der Sprachphilosophie neu zu bestimmen, sondern unsere Methodologie – das heißt die Anwendung der üblichen Normen der Rationalität – selbst grundsätzlich tiefer gehend in Frage zu stellen, und 3. dass die hegelsche Dialektik sich als die methodologische Auflösung einer solchen radikalen skeptischen Herausforderung bzw. als die Auflösung einer Antinomie überhaupt ergibt. Anlässlich dieser methodologischen Revidierung wird auf die hegelsche Dialektik zurückgegriffen.
Dennoch begrenzt sich der Zweck dieser Dissertation nicht darauf, eine Interpretation von Hegels Dialektik oder eine Überwindung von Wittgensteins Lebensform darzustellen, vielmehr geht es darum, auf die Problematik und die Grundsätze des Begriffs der Lebensform bzw. des theoretischen Geistes zurückzugreifen und kraft Hegels Dialektik darüber hinauszuführen, um den Platz und die Funktion der Sprache besser zu verstehen. Diese Arbeit erfolgt vielmehr im Rahmen eines wissenschaftlichen Projekts, oder anders gesagt, sie nutzt die methodologischen Resultate von zwei Autoren der Philosophie, um ein wissenschaftliches Programm vorzustellen. Der Anspruch dieser Arbeit ist dementsprechend, durch das Zurückgreifen auf Hegels Dialektik eine neue Erkenntnis über die Sprache zu gewinnen, wobei die beiden kontradiktorischen Momente der Kognition – die Normativität, die durch das Bewusstsein erfolgt und diejenige, die durch Dispositionen erfolgt –, konstruktiv verbinden sind. Der konkrete Gewinn dieser Methodologie ist es demnach, eine Sprachphilosophie überhaupt als System festlegen zu können, ein System, das es ermöglicht, sprachliche Phänomene in all ihren Aspekten in kohärenter Weise zu fassen. Inhaltlich betrachtet zielt dieses Programm darauf ab, die allgemeine Stufe des Begriffs der Sprache als Moment des Begriffs des Geistes dialektisch abzuleiten, d. h. den richtigen Sinn der Sprache festzulegen. Eine vollständige Bearbeitung der Sprachphilosophie mithilfe der Dialektik konnte ich allerdings nicht durchführen, und der Umfang der mithilfe der Dialektik hergeleiteten Sprachkategorien begrenzt sich auf die Lehre der Einbildungskraft, die die Lehre der allgemeinen Semiologie und der Grammatik einschließt.
Light-switchable proteins are being used increasingly to understand and manipulate complex molecular systems. The success of this approach has fueled the development of tailored photo-switchable proteins, to enable targeted molecular events to be studied using light. The development of novel photo-switchable tools has to date largely relied on rational design. Complementing this approach with directed evolution would be expected to facilitate these efforts. Directed evolution, however, has been relatively infrequently used to develop photo-switchable proteins due to the challenge presented by high-throughput evaluation of switchable protein activity. This thesis describes the development of two genetic circuits that can be used to evaluate libraries of switchable proteins, enabling optimization of both the on- and off-states. A screening system is described, which permits detection of DNA-binding activity based on conditional expression of a fluorescent protein. In addition, a tunable selection system is presented, which allows for the targeted selection of protein-protein interactions of a desired affinity range. This thesis additionally describes the development and characterization of a synthetic protein that was designed to investigate chromophore reconstitution in photoactive yellow protein (PYP), a promising scaffold for engineering photo-controlled protein tools.
Skarn deposits are found on every continents and were formed at different times from Precambrian to Tertiary. Typically, the formation of a skarn is induced by a granitic intrusion in carbonates-rich sedimentary rocks. During contact metamorphism, fluids derived from the granite interact with the sedimentary host rocks, which results in the formation of calc-silicate minerals at the expense of carbonates. Those newly formed minerals generally develop in a metamorphic zoned aureole with garnet in the proximal and pyroxene in the distal zone. Ore elements contained in magmatic fluids are precipitated due to the change in fluid composition. The temperature decrease of the entire system, due to the cooling of magmatic fluids and the entering of meteoric water, allows retrogression of some prograde minerals.
The Hämmerlein skarn deposit has a multi-stage history with a skarn formation during regional metamorphism and a retrogression of primary skarn minerals during the granitic intrusion. Tin was mobilized during both events. The 340 Ma old tin-bearing skarn minerals show that tin was present in sediments before the granite intrusion, and that the first Sn enrichment occurred during the skarn formation by regional metamorphism fluids. In a second step at ca. 320 Ma, tin-bearing fluids were produced with the intrusion of the Eibenstock granite. Tin, which has been added by the granite and remobilized from skarn calc-silicates, precipitated as cassiterite.
Compared to clay or marl, the skarn is enriched in Sn, W, In, Zn, and Cu. These metals have been supplied during both regional metamorphism and granite emplacement. In addition, the several isotopic and chemical data of skarn samples show that the granite selectively added elements such as Sn, and that there was no visible granitic contribution to the sedimentary signature of the skarn
The example of Hämmerlein shows that it is possible to form a tin-rich skarn without associated granite when tin has already been transported from tin-bearing sediments during regional metamorphism by aqueous metamorphic fluids. These skarns are economically not interesting if tin is only contained in the skarn minerals. Later alteration of the skarn (the heat and fluid source is not necessarily a granite), however, can lead to the formation of secondary cassiterite (SnO2), with which the skarn can become economically highly interesting.
Geomagnetic paleosecular variations (PSVs) are an expression of geodynamo processes inside the Earth’s liquid outer core. These paleomagnetic time series provide insights into the properties of the Earth’s magnetic field, from normal behavior with a dominating dipolar geometry, over field crises, such as pronounced intensity lows and geomagnetic excursions with a distorted field geometry, to the complete reversal of the dominating dipole contribution. Particularly, long-term high-resolution and high-quality PSV time series are needed for properly reconstructing the higher frequency components in the spectrum of geomagnetic field variations and for a better understanding of the effects of smoothing during the recording of such paleomagnetic records by sedimentary archives.
In this doctorate study, full vector paleomagnetic records were derived from 16 sediment cores recovered from the southeastern Black Sea. Age models are based on radiocarbon dating and correlations of warming/cooling cycles monitored by high-resolution X-ray fluorescence (XRF) elementary ratios as well as ice-rafted debris (IRD) in Black Sea sediments to the sequence of ‘Dansgaard-Oeschger’ (DO) events defined from Greenland ice core oxygen isotope stratigraphy.
In order to identify the carriers of magnetization in Black Sea sediments, core MSM33-55-1 recovered from the southeast Black Sea was subjected to detailed rock magnetic and electron microscopy investigations. The younger part of core MSM33-55-1 was continuously deposited since 41 ka. Before 17.5 ka, the magnetic minerals were dominated by a mixture of greigite (Fe3S4) and titanomagnetite (Fe3-xTixO4) in samples with SIRM/κLF >10 kAm-1, or exclusively by titanomagnetite in samples with SIRM/κLF ≤10 kAm-1. It was found that greigite is generally present as crustal aggregates in locally reducing micro-environments. From 17.5 ka to 8.3 ka, the dominant magnetic mineral in this transition phase was changing from greigite (17.5 – ~10.0 ka) to probably silicate-hosted titanomagnetite (~10.0 – 8.3 ka). After 8.3 ka, the anoxic Black Sea was a favorable environment for the formation of non-magnetic pyrite (FeS2) framboids.
Aiming to avoid compromising of paleomagnetic data by erroneous directions carried by greigite, paleomagnetic data from samples with SIRM/κLF >10 kAm-1, shown to contain greigite by various methods, were removed from obtained records. Consequently, full vector paleomagnetic records, comprising directional data and relative paleointensity (rPI), were derived only from samples with SIRM/κLF ≤10 kAm-1 from 16 Black Sea sediment cores. The obtained data sets were used to create a stack covering the time window between 68.9 and 14.5 ka with temporal resolution between 40 and 100 years, depending on sedimentation rates.
At 64.5 ka, according to obtained results from Black Sea sediments, the second deepest minimum in relative paleointensity during the past 69 ka occurred. The field minimum during MIS 4 is associated with large declination swings beginning about 3 ka before the minimum. While a swing to 50°E is associated with steep inclinations (50-60°) according to the coring site at 42°N, the subsequent declination swing to 30°W is associated with shallow inclinations of down to 40°. Nevertheless, these large deviations from the direction of a geocentric axial dipole field (I=61°, D=0°) still can not yet be termed as 'excursional', since latitudes of corresponding VGPs only reach down to 51.5°N (120°E) and 61.5°N (75°W), respectively. However, these VGP positions at opposite sides of the globe are linked with VGP drift rates of up to 0.2° per year in between. These extreme secular variations might be the mid-latitude expression of the Norwegian–Greenland Sea excursion found at several sites much further North in Arctic marine sediments between 69°N and 81°N.
At about 34.5 ka, the Mono Lake excursion is evidenced in the stacked Black Sea PSV record by both a rPI minimum and directional shifts. Associated VGPs from stacked Black Sea data migrated from Alaska, via central Asia and the Tibetan Plateau, to Greenland, performing a clockwise loop. This agrees with data recorded in the Wilson Creek Formation, USA., and Arctic sediment core PS2644-5 from the Iceland Sea, suggesting a dominant dipole field. On the other hand, the Auckland lava flows, New Zealand, the Summer Lake, USA., and Arctic sediment core from ODP Site-919 yield distinct VGPs located in the central Pacific Ocean due to a presumably non-dipole (multi-pole) field configuration.
A directional anomaly at 18.5 ka, associated with pronounced swings in inclination and declination, as well as a low in rPI, is probably contemporaneous with the Hilina Pali excursion, originally reported from Hawaiian lava flows. However, virtual geomagnetic poles (VGPs) calculated from Black Sea sediments are not located at latitudes lower than 60° N, which denotes normal, though pronounced secular variations. During the postulated Hilina Pali excursion, the VGPs calculated from Black Sea data migrated clockwise only along the coasts of the Arctic Ocean from NE Canada (20.0 ka), via Alaska (18.6 ka) and NE Siberia (18.0 ka) to Svalbard (17.0 ka), then looping clockwise through the Eastern Arctic Ocean.
In addition to the Mono Lake and the Norwegian–Greenland Sea excursions, the Laschamp excursion was evidenced in the Black Sea PSV record with the lowest paleointensities at about 41.6 ka and a short-term (~500 years) full reversal centered at 41 ka. These excursions are further evidenced by an abnormal PSV index, though only the Laschamp and the Mono Lake excursions exhibit excursional VGP positions. The stacked Black Sea paleomagnetic record was also converted into one component parallel to the direction expected from a geocentric axial dipole (GAD) and two components perpendicular to it, representing only non-GAD components of the geomagnetic field. The Laschamp and the Norwegian–Greenland Sea excursions are characterized by extremely low GAD components, while the Mono Lake excursion is marked by large non-GAD contributions. Notably, negative values of the GAD component, indicating a fully reversed geomagnetic field, are observed only during the Laschamp excursion.
In summary, this doctoral thesis reconstructed high-resolution and high-fidelity PSV records from SE Black Sea sediments. The obtained record comprises three geomagnetic excursions, the Norwegian–Greenland Sea excursion, the Laschamp excursion, and the Mono Lake excursion. They are characterized by abnormal secular variations of different amplitudes centered at about 64.5 ka, 41.0 ka and 34.5 ka, respectively. In addition, the obtained PSV record from the Black Sea do not provide evidence for the postulated 'Hilina Pali excursion' at about 18.5 ka. Anyway, the obtained Black Sea paleomagnetic record, covering field fluctuations from normal secular variations, over excursions, to a short but full reversal, points to a geomagnetic field characterized by a large dynamic range in intensity and a highly variable superposition of dipole and non-dipole contributions from the geodynamo during the past 68.9 to 14.5 ka.
In this thesis we introduce the concept of the degree of formality. It is directed against a dualistic point of view, which only distinguishes between formal and informal proofs. This dualistic attitude does not respect the differences between the argumentations classified as informal and it is unproductive because the individual potential of the respective argumentation styles cannot be appreciated and remains untapped.
This thesis has two parts. In the first of them we analyse the concept of the degree of formality (including a discussion about the respective benefits for each degree) while in the second we demonstrate its usefulness in three case studies. In the first case study we will repair Haskell B. Curry's view of mathematics, which incidentally is of great importance in the first part of this thesis, in light of the different degrees of formality. In the second case study we delineate how awareness of the different degrees of formality can be used to help students to learn how to prove. Third, we will show how the advantages of proofs of different degrees of formality can be combined by the development of so called tactics having a medium degree of formality. Together the three case studies show that the degrees of formality provide a convincing solution to the problem of untapped potential.
Carbonate-rich silicate and carbonate melts play a crucial role in deep Earth magmatic processes and their melt structure is a key parameter, as it controls physical and chemical properties. Carbonate-rich melts can be strongly enriched in geochemically important trace elements. The structural incorporation mechanisms of these elements are difficult to study because such melts generally cannot be quenched to glasses, which are usually employed for structural investigations. This thesis investigates the influence of CO2 on the local environments of trace elements contained in silicate glasses with variable CO2 concentrations as well as in silicate and carbonate melts. The compositions studied include sodium-rich peralkaline silicate melts and glasses and carbonate melts similar to those occurring naturally at Oldoinyo Lengai volcano, Tanzania.
The local environments of the three elements yttrium (Y), lanthanum (La) and strontium (Sr) were investigated in synthesized glasses and melts using X-ray absorption fine structure (XAFS) spectroscopy. Especially extended X-ray absorption fine structure spectroscopy (EXAFS) provides element specific information on local structure, such as bond lengths, coordination numbers and the degree of disorder. To cope with the enhanced structural disorder present in glasses and melts, EXAFS analysis was based on fitting approaches using an asymmetric distribution function as well as a correlation model according to bond valence theory. Firstly, silicate glasses quenched from high pressure/temperature melts with up to 7.6 wt % CO2 were investigated. In strongly and extremely peralkaline glasses the local structure of Y is unaffected by the CO2 content (with oxygen bond lengths of ~ 2.29 Å). Contrary, the bond lengths for Sr-O and La-O increase with increasing CO2 content in the strongly peralkaline glasses from ~ 2.53 to ~ 2.57 Å and from ~ 2.52 to ~ 2.54 Å, respectively, while they remain constant in extremely peralkaline glasses (at ~ 2.55 Å and 2.54 Å, respectively). Furthermore, silicate and unquenchable carbonate melts were investigated in-situ at high pressure/temperature conditions (2.2 to 2.6 GPa, 1200 to 1500 °C) using a Paris-Edinburgh press. A novel design of the pressure medium assembly for this press was developed, which features increased mechanical stability as well as enhanced transmittance at relevant energies to allow for low content element EXAFS in transmission. Compared to glasses the bond lengths of Y-O, La-O and Sr-O are elongated by up to + 3 % in the melt and exhibit higher asymmetric pair distributions. For all investigated silicate melt compositions Y-O bond lengths were found constant at ~ 2.37 Å, while in the carbonate melt the Y-O length increases slightly to 2.41 Å. The La-O bond lengths in turn, increase systematically over the whole silicate – carbonate melt joint from 2.55 to 2.60 Å. Sr-O bond lengths in melts increase from ~ 2.60 to 2.64 Å from pure silicate to silicate-bearing carbonate composition with constant elevated bond length within the carbonate region.
For comparison and deeper insight, glass and melt structures of Y and Sr bearing sodium-rich silicate to carbonate compositions were simulated in an explorative ab initio molecular dynamics (MD) study. The simulations confirm observed patterns of CO2-dependent local changes around Y and Sr and additionally provide further insights into detailed incorporation mechanisms of the trace elements and CO2. Principle findings include that in sodium-rich silicate compositions carbon either is mainly incorporated as a free carbonate-group or shares one oxygen with a network former (Si or [4]Al) to form a non-bridging carbonate. Of minor importance are bridging carbonates between two network formers. Here, a clear preference for two [4]Al as adjacent network formers occurs, compared to what a statistical distribution would suggest. In C-bearing silicate melts minor amounts of molecular CO2 are present, which is almost totally dissolved as carbonate in the quenched glasses.
The combination of experiment and simulation provides extraordinary insights into glass and melt structures. The new data is interpreted on the basis of bond valence theory and is used to deduce potential mechanisms for structural incorporation of investigated elements, which allow for prediction on their partitioning behavior in natural melts. Furthermore, it provides unique insights into the dissolution mechanisms of CO2 in silicate melts and into the carbonate melt structure. For the latter, a structural model is suggested, which is based on planar CO3-groups linking 7- to 9-fold cation polyhedra, in accordance to structural units as found in the Na-Ca carbonate nyerereite. Ultimately, the outcome of this study contributes to rationalize the unique physical properties and geological phenomena related to carbonated silicate-carbonate melts.
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.
Synchronization – the adjustment of rhythms among coupled self-oscillatory systems – is a fascinating dynamical phenomenon found in many biological, social, and technical systems.
The present thesis deals with synchronization in finite ensembles of weakly coupled self-sustained oscillators with distributed frequencies.
The standard model for the description of this collective phenomenon is the Kuramoto model – partly due to its analytical tractability in the thermodynamic limit of infinitely many oscillators. Similar to a phase transition in the thermodynamic limit, an order parameter indicates the transition from incoherence to a partially synchronized state. In the latter, a part of the oscillators rotates at a common frequency. In the finite case, fluctuations occur, originating from the quenched noise of the finite natural frequency sample.
We study intermediate ensembles of a few hundred oscillators in which fluctuations are comparably strong but which also allow for a comparison to frequency distributions in the infinite limit.
First, we define an alternative order parameter for the indication of a collective mode in the finite case. Then we test the dependence of the degree of synchronization and the mean rotation frequency of the collective mode on different characteristics for different coupling strengths.
We find, first numerically, that the degree of synchronization depends strongly on the form (quantified by kurtosis) of the natural frequency sample and the rotation frequency of the collective mode depends on the asymmetry (quantified by skewness) of the sample. Both findings are verified in the infinite limit.
With these findings, we better understand and generalize observations of other authors. A bit aside of the general line of thoughts, we find an analytical expression for the volume contraction in phase space.
The second part of this thesis concentrates on an ordering effect of the finite-size fluctuations. In the infinite limit, the oscillators are separated into coherent and incoherent thus ordered and disordered oscillators. In finite ensembles, finite-size fluctuations can generate additional order among the asynchronous oscillators. The basic principle – noise-induced synchronization – is known from several recent papers. Among coupled oscillators, phases are pushed together by the order parameter fluctuations, as we on the one hand show directly and on the other hand quantify with a synchronization measure from directed statistics between pairs of passive oscillators.
We determine the dependence of this synchronization measure from the ratio of pairwise natural frequency difference and variance of the order parameter fluctuations. We find a good agreement with a simple analytical model, in which we replace the deterministic fluctuations of the order parameter by white noise.
Oscillatory systems under weak coupling can be described by the Kuramoto model of phase oscillators. Kuramoto phase oscillators have diverse applications ranging from phenomena such as communication between neurons and collective influences of political opinions, to engineered systems such as Josephson Junctions and synchronized electric power grids. This thesis includes the author's contribution to the theoretical framework of coupled Kuramoto oscillators and to the understanding of non-trivial N-body dynamical systems via their reduced mean-field dynamics.
The main content of this thesis is composed of four parts. First, a partially integrable theory of globally coupled identical Kuramoto oscillators is extended to include pure higher-mode coupling. The extended theory is then applied to a non-trivial higher-mode coupled model, which has been found to exhibit asymmetric clustering. Using the developed theory, we could predict a number of features of the asymmetric clustering with only information of the initial state provided.
The second part consists of an iterated discrete-map approach to simulate phase dynamics. The proposed map --- a Moebius map --- not only provides fast computation of phase synchronization, it also precisely reflects the underlying group structure of the dynamics. We then compare the iterated-map dynamics and various analogous continuous-time dynamics. We are able to replicate known phenomena such as the synchronization transition of the Kuramoto-Sakaguchi model of oscillators with distributed natural frequencies, and chimera states for identical oscillators under non-local coupling.
The third part entails a particular model of repulsively coupled identical Kuramoto-Sakaguchi oscillators under common random forcing, which can be shown to be partially integrable. Via both numerical simulations and theoretical analysis, we determine that such a model cannot exhibit stationary multi-cluster states, contrary to the numerical findings in previous literature. Through further investigation, we find that the multi-clustering states reported previously occur due to the accumulation of discretization errors inherent in the integration algorithms, which introduce higher-mode couplings into the model. As a result, the partial integrability condition is violated.
Lastly, we derive the microscopic cross-correlation of globally coupled non-identical Kuramoto oscillators under common fluctuating forcing. The effect of correlation arises naturally in finite populations, due to the non-trivial fluctuations of the meanfield. In an idealized model, we approximate the finite-sized fluctuation by a Gaussian white noise. The analytical approximation qualitatively matches the measurements in numerical experiments, however, due to other periodic components inherent in the fluctuations of the mean-field there still exist significant inconsistencies.
Simulating the impact of herbicide drift exposure on non-target terrestrial plant communities
(2019)
In Europe, almost half of the terrestrial landscape is used for agriculture. Thus, semi-natural habitats such as field margins are substantial for maintaining diversity in intensively managed farmlands. However, plants located at field margins are threatened by agricultural practices such as the application of pesticides within the fields. Pesticides are chemicals developed to control for undesired species within agricultural fields to enhance yields. The use of pesticides implies, however, effects on non-target organisms within and outside of the agricultural fields. Non-target organisms are organisms not intended to be sprayed or controlled for. For example, plants occurring in field margins are not intended to be sprayed, however, can be impaired due to herbicide drift exposure. The authorization of plant protection products such as herbicides requires risk assessments to ensure that the application of the product has no unacceptable effects on the environment. For non-target terrestrial plants (NTTPs), the risk assessment is based on standardized greenhouse studies on plant individual level. To account for the protection of plant populations and communities under realistic field conditions, i.e. extrapolating from greenhouse studies to field conditions and from individual-level to community-level, assessment factors are applied. However, recent studies question the current risk assessment scheme to meet the specific protection goals for non-target terrestrial plants as suggested by the European Food Safety Authority (EFSA). There is a need to clarify the gaps of the current risk assessment and to include suitable higher tier options in the upcoming guidance document for non-target terrestrial plants.
In my thesis, I studied the impact of herbicide drift exposure on NTTP communities using a mechanistic modelling approach. I addressed main gaps and uncertainties of the current risk assessment and finally suggested this modelling approach as a novel higher tier option in future risk assessments. Specifically, I extended the plant community model IBC-grass (Individual-based community model for grasslands) to reflect herbicide impacts on plant individuals. In the first study, I compared model predictions of short-term herbicide impacts on artificial plant communities with empirical data. I demonstrated the capability of the model to realistically reflect herbicide impacts. In the second study, I addressed the research question whether or not reproductive endpoints need to be included in future risk assessments to protect plant populations and communities. I compared the consequences of theoretical herbicide impacts on different plant attributes for long-term plant population dynamics in the community context. I concluded that reproductive endpoints only need to be considered if the herbicide effect is assumed to be very high. The endpoints measured in the current vegetative vigour and seedling emergence studies had high impacts for the dynamic of plant populations and communities already at lower effect intensities. Finally, the third study analysed long-term impacts of herbicide application for three different plant communities. This study highlighted the suitability of the modelling approach to simulate different communities and thus detecting sensitive environmental conditions.
Overall, my thesis demonstrates the suitability of mechanistic modelling approaches to be used as higher tier options for risk assessments. Specifically, IBC-grass can incorporate available individual-level effect data of standardized greenhouse experiments to extrapolate to community-level under various environmental conditions. Thus, future risk assessments can be improved by detecting sensitive scenarios and including worst-case impacts on non-target plant communities.
The individual’s mental lexicon comprises all known words as well related infor-mation on semantics, orthography and phonology. Moreover, entries connect due to simi-larities in these language domains building a large network structure. The access to lexical information is crucial for processing of words and sentences. Thus, a lack of information in-hibits the retrieval and can cause language processing difficulties. Hence, the composition of the mental lexicon is essential for language skills and its assessment is a central topic of lin-guistic and educational research.
In early childhood, measurement of the mental lexicon is uncomplicated, for example through parental questionnaires or the analysis of speech samples. However, with growing content the measurement becomes more challenging: With more and more words in the mental lexicon, the inclusion of all possible known words into a test or questionnaire be-comes impossible. That is why there is a lack of methods to assess the mental lexicon for school children and adults. For the same reason, there are only few findings on the courses of lexical development during school years as well as its specific effect on other language skills. This dissertation is supposed to close this gap by pursuing two major goals: First, I wanted to develop a method to assess lexical features, namely lexicon size and lexical struc-ture, for children of different age groups. Second, I aimed to describe the results of this method in terms of lexical development of size and structure. Findings were intended to help understanding mechanisms of lexical acquisition and inform theories on vocabulary growth.
The approach is based on the dictionary method where a sample of words out of a dictionary is tested and results are projected on the whole dictionary to determine an indi-vidual’s lexicon size. In the present study, the childLex corpus, a written language corpus for children in German, served as the basis for lexicon size estimation. The corpus is assumed to comprise all words children attending primary school could know. Testing a sample of words out of the corpus enables projection of the results on the whole corpus. For this purpose, a vocabulary test based on the corpus was developed. Afterwards, test performance of virtual participants was simulated by drawing different lexicon sizes from the corpus and comparing whether the test items were included in the lexicon or not. This allowed determination of the relation between test performance and total lexicon size and thus could be transferred to a sample of real participants. Besides lexicon size, lexical content could be approximated with this approach and analyzed in terms of lexical structure.
To pursue the presented aims and establish the sampling method, I conducted three consecutive studies. Study 1 includes the development of a vocabulary test based on the childLex corpus. The testing was based on the yes/no format and included three versions for different age groups. The validation grounded on the Rasch Model shows that it is a valid instrument to measure vocabulary for primary school children in German. In Study 2, I estab-lished the method to estimate lexicon sizes and present results on lexical development dur-ing primary school. Plausible results demonstrate that lexical growth follows a quadratic function starting with about 6,000 words at the beginning of school and about 73,000 words on average for young adults. Moreover, the study revealed large interindividual differences. Study 3 focused on the analysis of network structures and their development in the mental lexicon due to orthographic similarities. It demonstrates that networks possess small-word characteristics and decrease in interconnectivity with age.
Taken together, this dissertation provides an innovative approach for the assessment and description of the development of the mental lexicon from primary school onwards. The studies determine recent results on lexical acquisition in different age groups that were miss-ing before. They impressively show the importance of this period and display the existence of extensive interindividual differences in lexical development. One central aim of future research needs to address the causes and prevention of these differences. In addition, the application of the method for further research (e.g. the adaptation for other target groups) and teaching purposes (e.g. adaptation of texts for different target groups) appears to be promising.
Optimization is a core part of technological advancement and is usually heavily aided by computers. However, since many optimization problems are hard, it is unrealistic to expect an optimal solution within reasonable time. Hence, heuristics are employed, that is, computer programs that try to produce solutions of high quality quickly. One special class are estimation-of-distribution algorithms (EDAs), which are characterized by maintaining a probabilistic model over the problem domain, which they evolve over time. In an iterative fashion, an EDA uses its model in order to generate a set of solutions, which it then uses to refine the model such that the probability of producing good solutions is increased.
In this thesis, we theoretically analyze the class of univariate EDAs over the Boolean domain, that is, over the space of all length-n bit strings. In this setting, the probabilistic model of a univariate EDA consists of an n-dimensional probability vector where each component denotes the probability to sample a 1 for that position in order to generate a bit string.
My contribution follows two main directions: first, we analyze general inherent properties of univariate EDAs. Second, we determine the expected run times of specific EDAs on benchmark functions from theory. In the first part, we characterize when EDAs are unbiased with respect to the problem encoding. We then consider a setting where all solutions look equally good to an EDA, and we show that the probabilistic model of an EDA quickly evolves into an incorrect model if it is always updated such that it does not change in expectation.
In the second part, we first show that the algorithms cGA and MMAS-fp are able to efficiently optimize a noisy version of the classical benchmark function OneMax. We perturb the function by adding Gaussian noise with a variance of σ², and we prove that the algorithms are able to generate the true optimum in a time polynomial in σ² and the problem size n. For the MMAS-fp, we generalize this result to linear functions. Further, we prove a run time of Ω(n log(n)) for the algorithm UMDA on (unnoisy) OneMax. Last, we introduce a new algorithm that is able to optimize the benchmark functions OneMax and LeadingOnes both in O(n log(n)), which is a novelty for heuristics in the domain we consider.
Cellulose derived polymers
(2019)
Plastics, such as polyethylene, polypropylene, and polyethylene terephthalate are part of our everyday lives in the form of packaging, household goods, electrical insulation, etc. These polymers are non-degradable and create many environmental problems and public health concerns. Additionally, these polymers are produced from finite fossils resources. With the continuous utilization of these limited resources, it is important to look towards renewable sources along with biodegradation of the produced polymers, ideally. Although many bio-based polymers are known, such as polylactic acid, polybutylene succinate adipate or polybutylene succinate, none have yet shown the promise of replacing conventional polymers like polyethylene, polypropylene and polyethylene terephthalate. Cellulose is one of the most abundant renewable resources produced in nature. It can be transformed into various small molecules, such as sugars, furans, and levoglucosenone. The aim of this research is to use the cellulose derived molecules for the synthesis of polymers.
Acid-treated cellulose was subjected to thermal pyrolysis to obtain levoglucosenone, which was reduced to levoglucosenol. Levoglucosenol was polymerized, for the first time, by ring-opening metathesis polymerization (ROMP) yielding high molar mass polymers of up to ~150 kg/mol. The poly(levoglucosenol) is thermally stable up to ~220 ℃, amorphous, and is exhibiting a relatively high glass transition temperature of ~100 ℃. The poly(levoglucosenol) can be converted to a transparent film, resembling common plastic, and was found to degrade in a moist acidic environment. This means that poly(levoglucosenol) may find its use as an alternative to conventional plastic, for instance, polystyrene.
Levoglucosenol was also converted into levoglucosenyl methyl ether, which was polymerized by cationic ring-opening metathesis polymerization (CROP). Polymers were obtained with molar masses up to ~36 kg/mol. These polymers are thermally stable up to ~220 ℃ and are semi-crystalline thermoplastics, having a glass transition temperature of ~35 ℃ and melting transition of 70-100 ℃. Additionally, the polymers underwent cross-linking, hydrogenation and thiol-ene click chemistry.
Predators can have numerical and behavioral effects on prey animals. While numerical effects are well explored, the impact of behavioral effects is unclear. Furthermore, behavioral effects are generally either analyzed with a focus on single individuals or with a focus on consequences for other trophic levels. Thereby, the impact of fear on the level of prey communities is overlooked, despite potential consequences for conservation and nature management. In order to improve our understanding of predator-prey interactions, an assessment of the consequences of fear in shaping prey community structures is crucial.
In this thesis, I evaluated how fear alters prey space use, community structure and composition, focusing on terrestrial mammals. By integrating landscapes of fear in an existing individual-based and spatially-explicit model, I simulated community assembly of prey animals via individual home range formation. The model comprises multiple hierarchical levels from individual home range behavior to patterns of prey community structure and composition. The mechanistic approach of the model allowed for the identification of underlying mechanism driving prey community responses under fear.
My results show that fear modified prey space use and community patterns. Under fear, prey animals shifted their home ranges towards safer areas of the landscape. Furthermore, fear decreased the total biomass and the diversity of the prey community and reinforced shifts in community composition towards smaller animals. These effects could be mediated by an increasing availability of refuges in the landscape. Under landscape changes, such as habitat loss and fragmentation, fear intensified negative effects on prey communities. Prey communities in risky environments were subject to a non-proportional diversity loss of up to 30% if fear was taken into account. Regarding habitat properties, I found that well-connected, large safe patches can reduce the negative consequences of habitat loss and fragmentation on prey communities. Including variation in risk perception between prey animals had consequences on prey space use. Animals with a high risk perception predominantly used safe areas of the landscape, while animals with a low risk perception preferred areas with a high food availability. On the community level, prey diversity was higher in heterogeneous landscapes of fear if individuals varied in their risk perception compared to scenarios in which all individuals had the same risk perception.
Overall, my findings give a first, comprehensive assessment of the role of fear in shaping prey communities. The linkage between individual home range behavior and patterns at the community level allows for a mechanistic understanding of the underlying processes. My results underline the importance of the structure of the landscape of fear as a key driver of prey community responses, especially if the habitat is threatened by landscape changes. Furthermore, I show that individual landscapes of fear can improve our understanding of the consequences of trait variation on community structures. Regarding conservation and nature management, my results support calls for modern conservation approaches that go beyond single species and address the protection of biotic interactions.
Der Porenraum eines Karbonatgesteins ist zumeist aus einer spezifischen Vergesellschaftung verschiedenster Porentypen aufgebaut, die eine unterschiedliche Herkunft aufweisen und zusätzlich in ihrer Form und Größe stark variieren können (e.g., Melim et al., 2001; Lee et al., 2009; He et al., 2014; Dernaika & Sinclair, 2017; Zhang et al., 2017). Diese für Karbonate typischen multimodalen Porensysteme entstehen sowohl durch primäre Ablagerungsprozesse, als auch durch mehrmalige Modifikation des Porenraumes nach Ablagerung des Sediments. Dies führt zu einer ungleichen Verteilung der Porenraumeigenschaften auf engstem Raum und das zeitgleiche Auftreten von effektiven und ineffektiven Poren. Diese immanenten Unterschiede in der Effektivität einzelner Porentypen sind der Hauptgrund für die häufig sehr niedrige Korellation zwischen Porosität und Permeabilität in Karbonaten (e.g., Mazzullo 2004; Ehrenberg & Nadeau, 2005; Hollis et al., 2010; He et al., 2014; Rashid et al., 2015; Dernaika & Sinclair, 2017). Durch die Extraktion von miteinander verbundenen und somit effektiven Porentypen jedoch kann das Verständnis und die Vorhersage der Permeabilität für einen gegeben Porositätswert stark verbessert werden (e.g., Melim et al., 2001; Zhang et al., 2017). Dazu wird in dieser Arbeit eine auf der digitalen Bildanalyse (DIA) beruhende Methode vorgestellt, mit der schrittweise die Effektivität von Poren aus den analysierten mittelmiozänen lakustrinen Karbonaten des Nördlinger Ries Kratersees (Süddeutschland) berechnet werden kann. Mithilfe des Porenformfaktors (sensu Anselmetti et al., 1998), der als Parameter zur Quantifizierung der Interkonnektivität zwischen Poren dient, wird der potentiellen Beitrag an Permeabilität jedes Porentyps zur Gesamtpermeabilität bestimmt. Somit können die effektivsten Porentypen innerhalb der analysierten Karbonate identifiziert werden. Desweiteren wird die digitale Bildanalyse dazu benutzt, zementierte Porenräume zu extrahieren, um den Einfluss der Zementation auf die Porenraumeigenschaften zu quantifizieren. Durch eine unabhängige Methode (Fluid-Flow-Simulation), deren Ergebnisse wiederum mit der digitalen Bildanalyse ausgewertet werden, können die vorherigen Erkentnisse bestätigt werden: Interpeloidale Poren und Lösungsporen sind die beiden effektivsten Porentypen im Porenraum der Riesseekarbonate. Die Extraktion des miteinander verbundenen (d.h. effektiven) Porennetzwerkes führt schließlich zu einer erheblich verbesserten Korrelation zwischen Porosität und Permeabilität in den analysierten Karbonaten. Die in dieser Arbeit beschriebene Methode bietet ein quantitatives petrographisches Werkzeug, mit dessen Hilfe die effektive Porosität eines Porenraumes extrahiert werden kann. Dies führt zu einem besseren Verständnis darüber, wie Porensysteme von Karbonaten Permeabilität erzeugen. Diese Dissertation zeigt auch, dass die Formkomplexität von Poren einer der wichtigsten Parameter ist, der die Interkonnektivität zwischen einzelnen Poren und somit die Entstehung von effektiver Porosität steuert. Außerdem erweist sich die digitale Bildanalyse als ausgezeichnetes Werkzeug um die Porosität und Permeabilität direkt an ihren gemeinsamen Ursprung zu knüpfen: die Gesteinstextur und die damit assoziierte Porenstruktur.
On a planetary scale human populations need to adapt to both socio-economic and environmental problems amidst rapid global change. This holds true for coupled human-environment (socio-ecological) systems in rural and urban settings alike. Two examples are drylands and urban coasts. Such socio-ecological systems have a global distribution. Therefore, advancing the knowledge base for identifying socio-ecological adaptation needs with local vulnerability assessments alone is infeasible: The systems cover vast areas, while funding, time, and human resources for local assessments are limited. They are lacking in low an middle-income countries (LICs and MICs) in particular.
But places in a specific socio-ecological system are not only unique and complex – they also exhibit similarities. A global patchwork of local rural drylands vulnerability assessments of human populations to socio-ecological and environmental problems has already been reduced to a limited number of problem structures, which typically cause vulnerability. However, the question arises whether this is also possible in urban socio-ecological systems. The question also arises whether these typologies provide added value in research beyond global change. Finally, the methodology employed for drylands needs refining and standardizing to increase its uptake in the scientific community. In this dissertation, I set out to fill these three gaps in research.
The geographical focus in my dissertation is on LICs and MICs, which generally have lower capacities to adapt, and greater adaptation needs, regarding rapid global change. Using a spatially explicit indicator-based methodology, I combine geospatial and clustering methods to identify typical configurations of key factors in case studies causing vulnerability to human populations in two specific socio-ecological systems. Then I use statistical and analytical methods to interpret and appraise both the typical configurations and the global typologies they constitute.
First, I improve the indicator-based methodology and then reanalyze typical global problem structures of socio-ecological drylands vulnerability with seven indicator datasets. The reanalysis confirms the key tenets and produces a more realistic and nuanced typology of eight spatially explicit problem structures, or vulnerability profiles: Two new profiles with typically high natural resource endowment emerge, in which overpopulation has led to medium or high soil erosion. Second, I determine whether the new drylands typology and its socio-ecological vulnerability concept advance a thematically linked scientific debate in human security studies: what drives violent conflict in drylands? The typology is a much better predictor for conflict distribution and incidence in drylands than regression models typically used in peace research. Third, I analyze global problem structures typically causing vulnerability in an urban socio-ecological system - the rapidly urbanizing coastal fringe (RUCF) – with eleven indicator datasets. The RUCF also shows a robust typology, and its seven profiles show huge asymmetries in vulnerability and adaptive capacity. The fastest population increase, lowest income, most ineffective governments, most prevalent poverty, and lowest adaptive capacity are all typically stacked in two profiles in LICs. This shows that beyond local case studies tropical cyclones and/or coastal flooding are neither stalling rapid population growth, nor urban expansion, in the RUCF. I propose entry points for scaling up successful vulnerability reduction strategies in coastal cities within the same vulnerability profile.
This dissertation shows that patchworks of local vulnerability assessments can be generalized to structure global socio-ecological vulnerabilities in both rural and urban socio-ecological systems according to typical problems. In terms of climate-related extreme events in the RUCF, conflicting problem structures and means to deal with them are threatening to widen the development gap between LICs and high-income countries unless successful vulnerability reduction measures are comprehensively scaled up. The explanatory power for human security in drylands warrants further applications of the methodology beyond global environmental change research in the future. Thus, analyzing spatially explicit global typologies of socio-ecological vulnerability is a useful complement to local assessments: The typologies provide entry points for where to consider which generic measures to reduce typical problem structures – including the countless places without local assessments. This can save limited time and financial resources for adaptation under rapid global change.
Interactions and feedbacks between tectonics, climate, and upper plate architecture control basin geometry, relief, and depositional systems. The Andes is part of a longlived continental margin characterized by multiple tectonic cycles which have strongly modified the Andean upper plate architecture. In the Andean retroarc, spatiotemporal variations in the structure of the upper plate and tectonic regimes have resulted in marked along-strike variations in basin geometry, stratigraphy, deformational style, and mountain belt morphology. These along-strike variations include high-elevation plateaus (Altiplano and Puna) associated with a thin-skin fold-and-thrust-belt and thick-skin deformation in broken foreland basins such as the Santa Barbara system and the Sierras Pampeanas. At the confluence of the Puna Plateau, the Santa Barbara system and the Sierras Pampeanas, major along-strike changes in upper plate architecture, mountain belt morphology, basement exhumation, and deformation style can be recognized. I have used a source to sink approach to unravel the spatiotemporal tectonic evolution of the Andean retroarc between 26 and 28°S. I obtained a large low-temperature thermochronology data set from basement units which includes apatite fission track, apatite U-Th-Sm/He, and zircon U-Th/He (ZHe) cooling ages. Stratigraphic descriptions of Miocene units were temporally constrained by U-Pb LA-ICP-MS zircon ages from interbedded pyroclastic material.
Modeled ZHe ages suggest that the basement of the study area was exhumed during the Famatinian orogeny (550-450 Ma), followed by a period of relative tectonic quiescence during the Paleozoic and the Triassic. The basement experienced horst exhumation during the Cretaceous development of the Salta rift. After initial exhumation, deposition of thick Cretaceous syn-rift strata caused reheating of several basement blocks within the Santa Barbara system. During the Eocene-Oligocene, the Andean compressional setting was responsible for the exhumation of several disconnected basement blocks. These exhumed blocks were separated by areas of low relief, in which humid climate and low erosion rates facilitated the development of etchplains on the crystalline basement. The exhumed basement blocks formed an Eocene to Oligocene broken foreland basin in the back-bulge depozone of the Andean foreland. During the Early Miocene, foreland basin strata filled up the preexisting Paleogene topography. The basement blocks in lower relief positions were reheated; associated geothermal gradients were higher than 25°C/km. Miocene volcanism was responsible for lateral variations on the amount of reheating along the Campo-Arenal basin. Around 12 Ma, a new deformational phase modified the drainage network and fragmented the lacustrine system. As deformation and rock uplift continued, the easily eroded sedimentary cover was efficiently removed and reworked by an ephemeral fluvial system, preventing the development of significant relief. After ~6 Ma, the low erodibility of the basement blocks which began to be exposed caused relief increase, leading to the development of stable fluvial systems. Progressive relief development modified atmospheric circulation, creating a rainfall gradient. After 3 Ma, orographic rainfall and high relief lead to the development of proximal fluvial-gravitational depositional systems in the surrounding basins.
Aluminum oxide is an Earth-abundant geological material, and its interaction with water is of crucial importance for geochemical and environmental processes. Some aluminum oxide surfaces are also known to be useful in heterogeneous catalysis, while the surface chemistry of aqueous oxide interfaces determines the corrosion, growth and dissolution of such materials. In this doctoral work, we looked mainly at the (0001) surface of α-Al 2 O 3 and its reactivity towards water. In particular, a great focus of this work is dedicated to simulate and address the vibrational spectra of water adsorbed on the α-alumina(0001) surface in various conditions and at different coverages. In fact, the main source of comparison and inspiration for this work comes from the collaboration with the “Interfacial Molecular Spectroscopy” group led by Dr. R. Kramer Campen at the Fritz-Haber Institute of the MPG in Berlin. The expertise of our project partners in surface-sensitive Vibrational Sum Frequency (VSF) generation spectroscopy was crucial to develop and adapt specific simulation schemes used in this work. Methodologically, the main approach employed in this thesis is Ab Initio Molecular Dynamics (AIMD) based on periodic Density Functional Theory (DFT) using the PBE functional with D2 dispersion correction. The analysis of vibrational frequencies from both a static and a dynamic, finite-temperature perspective offers the ability to investigate the water / aluminum oxide interface in close connection to experiment.
The first project presented in this work considers the characterization of dissociatively adsorbed deuterated water on the Al-terminated (0001) surface. This particular structure is known from both experiment and theory to be the thermodynamically most stable surface termination of α-alumina in Ultra-High Vacuum (UHV) conditions. Based on experiments performed by our colleagues at FHI, different adsorption sites and products have been proposed and identified for D 2 O. While previous theoretical investigations only looked at vibrational frequencies of dissociated OD groups by staticNormal Modes Analysis (NMA), we rather employed a more sophisticated approach to directly assess vibrational spectra (like IR and VSF) at finite temperature from AIMD. In this work, we have employed a recent implementation which makes use of velocity-velocity autocorrelation functions to simulate such spectral responses of O-H(D) bonds. This approach allows for an efficient and qualitatively accurate estimation of Vibrational Densities of States (VDOS) as well as IR and VSF spectra, which are then tested against experimental spectra from our collaborators.
In order to extend previous work on unimolecularly dissociated water on α-Al 2 O 3 , we then considered a different system, namely, a fully hydroxylated (0001) surface, which results from the reconstruction of the UHV-stable Al-terminated surface at high water contents. This model is then further extended by considering a hydroxylated surface with additional water molecules, forming a two-dimensional layer which serves as a potential template to simulate an aqueous interface in environmental conditions. Again, employing finite-temperature AIMD trajectories at the PBE+D2 level, we investigated the behaviour of both hydroxylated surface (HS) and the water-covered structure derived from it (known as HS+2ML). A full range of spectra, from VDOS to IR and VSF, is then calculated using the same methodology, as described above. This is the main focus of the second project, reported in Chapter 5. In this case, comparison between theoretical spectra and experimental data is definitely good. In particular, we underline the nature of high-frequency resonances observed above 3700 cm −1 in VSF experiments to be associated with surface OH-groups, known as “aluminols” which are a key fingerprint of the fully hydroxylated surface.
In the third and last project, which is presented in Chapter 6, the extension of VSF spectroscopy experiments to the time-resolved regime offered us the opportunity to investigate vibrational energy relaxation at the α-alumina / water interface. Specifically, using again DFT-based AIMD simulations, we simulated vibrational lifetimes for surface aluminols as experimentally detected via pump-probe VSF. We considered the water-covered HS model as a potential candidate to address this problem. The vibrational (IR) excitation and subsequent relaxation is performed by means of a non-equilibrium molecular dynamics scheme. In such a scheme, we specifically looked at the O-H stretching mode of surface aluminols. Afterwards, the analysis of non-equilibrium trajectories allows for an estimation of relaxation times in the order of 2-4 ps which are in overall agreement with measured ones.
The aim of this work has been to provide, within a consistent theoretical framework, a better understanding of vibrational spectroscopy and dynamics for water on the α-alumina(0001) surface,ranging from very low water coverage (similar to the UHV case) up to medium-high coverages, resembling the hydroxylated oxide in environmental moist conditions.
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.
The growing energy demand of the modern economies leads to the increased consumption of fossil fuels in form of coal, oil, and natural gases, as the mains sources. The combustion of these carbon-based fossil fuels is inevitably producing greenhouse gases, especially CO2. Approaches to tackle the CO2 problem are to capture it from the combustion sources or directly from air, as well as to avoid CO2 production in energy consuming sources (e.g., in the refrigeration sector). In the former, relatively low CO2 concentrations and competitive adsorption of other gases is often leading to low CO2 capacities and selectivities. In both approaches, the interaction of gas molecules with porous materials plays a key role. Porous carbon materials possess unique properties including electric conductivity, tunable porosity, as well as thermal and chemical stability. Nevertheless, pristine carbon materials offer weak polarity and thus low CO2 affinity. This can be overcome by nitrogen doping, which enhances the affinity of carbon materials towards acidic or polar guest molecules (e.g., CO2, H2O, or NH3). In contrast to heteroatom-free materials, such carbon materials are in most cases “noble”, that is, they oxidize other matter rather than being oxidized due to the very positive working potential of their electrons. The challenging task here is to achieve homogenous distribution of significant nitrogen content with similar bonding motives throughout the carbon framework and a uniform pore size/distribution to maximize host-guest interactions. The aim of this thesis is the development of novel synthesis pathways towards nitrogen-doped nanoporous noble carbon materials with precise design on a molecular level and understanding of their structure-related performance in energy and environmental applications, namely gas adsorption and electrochemical energy storage.
A template-free synthesis approach towards nitrogen-doped noble microporous carbon materials with high pyrazinic nitrogen content and C2N-type stoichiometry was established via thermal condensation of a hexaazatriphenylene derivative. The materials exhibited high uptake of guest molecules, such as H2O and CO2 at low concentrations, as well as moderate CO2/N2 selectivities. In the following step, the CO2/N2 selectivity was enhanced towards molecular sieving of CO2 via kinetic size exclusion of N2. The precise control over the condensation degree, and thus, atomic construction and porosity of the resulting materials led to remarkable CO2/N2 selectivities, CO2 capacities, and heat of CO2 adsorption. The ultrahydrophilic nature of the pore walls and the narrow microporosity of these carbon materials served as ideal basis for the investigation of interface effects with more polar guest molecules than CO2, namely H2O and NH3.
H2O vapor physisorption measurements, as well as NH3-temperature programmed desorption and thermal response measurements showed exceptionally high affinity towards H2O vapor and NH3 gas. Another series of nitrogen-doped carbon materials was synthesized by direct condensation of a pyrazine-fused conjugated microporous polymer and their structure-related performance in electrochemical energy storage, namely as anode materials for sodium-ion battery, was investigated.
All in all, the findings in this thesis exemplify the value of molecularly designed nitrogen-doped carbon materials with remarkable heteroatom content implemented as well-defined structure motives. The simultaneous adjustment of the porosity renders these materials suitable candidates for fundamental studies about the interactions between nitrogen-doped carbon materials and different guest species.
Im Rahmen dieser Arbeit wird anhand von neuartigen Materialien das Potential der Europium-Lumineszenz für die strukturelle Analyse dargestellt. Bei diesen Materialien handelt es sich zum einen um Nanopartikel mit Matrizes aus mehreren Metall-Mischoxiden und Dotierungen durch die Sonde Europium und zum anderen um Metallorganische Netzwerke (MOFs), die mit Neodym , Samarium- und Europium-Ionen beladen sind.
Die Synthese der aus der Kombination von Metalloxiden enthaltenen Nanopartikel ist unter milden Bedingungen mithilfe von speziell dafür hergestellten Reagenzien erfolgt und hat zu sehr kleinen, amorphen Nanopartikeln geführt. Durch eine nachfolgende Temperaturbehandlung hat sich die Kristallinität erhöht. Damit verbunden haben sich auch die Kristallstruktur sowie die Position des Dotanden Europium verändert.
Während die etablierte Methode der Röntgendiffraktometrie einen Blick auf das Kristallgitter als Gesamtes ermöglicht, so trifft die Lumineszenz des Europiums durch die Sichtbarkeit einzelner Stark-Aufspaltungen Aussagen über dessen lokale Symmetrien. Die Symmetrie wird durch Sauerstofffehlstellen verändert, welche die Sauerstoffleitfähigkeit der Nanopartikel beeinflussen. Diese ist für die Anwendung als Katalysatoren in industriellen Prozessen und ebenso als Sensoren und Therapeutika in biologischen Systemen von Bedeutung.
Zur ersten katalytischen Charakterisierung werden die Proben mittels Temperatur-programmierter Reduktion untersucht. Des Weiteren werden die Mischoxid-Nanopartikel auch hinsichtlich ihrer Verwendbarkeit als Matrix in Aufkonversionsprozessen untersucht.
Die Metallorganischen Netzwerke eignen sich aufgrund ihrer mikroporösen Struktur für Anwendungen in der Speicherung gleichermaßen von Nutzgasen wie auch von Schadstoffen. Ebenfalls ist eine biologische Anwendung denkbar, die insbesondere den Bereich der drug delivery-Reagenzien betrifft.
Erfolgt in die mikroporösen Strukturen der Metallorganischen Netzwerke die Einlagerung von Lanthanoid-Ionen, so können diese bei der entsprechenden Kombination als Weißlicht-Emittierer fungieren. Dabei ist neben den Verhältnissen zwischen den Lanthanoid-Ionen auch die genaue Position innerhalb des Netzwerks sowie die Distanz zu anderen Ionen von Interesse. Zur Untersuchung dieser Fragestellungen wird die Umgebungssensitivität der Europium-Lumineszenz ausgenutzt. Die auf diese Weise festgestellte Formiat-Bildung hängt von zahlreichen Parametern ab.
Insgesamt stellt sich die im Rahmen dieser Arbeit verwendete Methodik des Einsatzes von Europium als strukturelle Sonde in höchstem Maße vielseitig dar und zeigt seine größte Stärke in der Kombination mit weiteren Methoden der Strukturanalytik. Die auf diese Weise genauestens charakterisierten neuartigen Materialien können nun gezielt und anwendungsfokussiert weiterentwickelt werden.
Electrets are dielectrics with quasi-permanent electric charge and/or dipoles, sometimes can be regarded as an electric analogy to a magnet. Since the discovery of the excellent charge retention capacity of poly(tetrafluoro ethylene) and the invention of the electret microphone, electrets have grown out of a scientific curiosity to an important application both in science and technology. The history of electret research goes hand in hand with the quest for new materials with better capacity at charge and/or dipole retention. To be useful, electrets normally have to be charged/poled to render them electro-active. This process involves electric-charge deposition and/or electric dipole orientation within the dielectrics ` surfaces and bulk. Knowledge of the spatial distribution of electric charge and/or dipole polarization after their deposition and subsequent decay is crucial in the task to improve their stability in the dielectrics.
Likewise, for dielectrics used in electrical insulation applications, there are also needs for accumulated space-charge and polarization spatial profiling. Traditionally, space-charge accumulation and large dipole polarization within insulating dielectrics is considered undesirable and harmful to the insulating dielectrics as they might cause dielectric loss and could lead to internal electric field distortion and local field enhancement. High local electric field could trigger several aging processes and reduce the insulating dielectrics' lifetime. However, with the advent of high-voltage DC transmission and high-voltage capacitor for energy storage, these are no longer the case. There are some overlapped between the two fields of electrets and electric insulation. While quasi-permanently trapped electric-charge and/or large remanent dipole polarization are the requisites for electret operation, stably trapped electric charge in electric insulation helps reduce electric charge transport and overall reduced electric conductivity. Controlled charge trapping can help in preventing further charge injection and accumulation as well as serving as field grading purpose in insulating dielectrics whereas large dipole polarization can be utilized in energy storage applications.
In this thesis, the Piezoelectrically-generated Pressure Steps (PPSs) were employed as a nondestructive method to probe the electric-charge and dipole polarization distribution in a range of thin film (several hundred micron) polymer-based materials, namely polypropylene (PP), low-density polyethylene/magnesium oxide (LDPE/MgO) nanocomposites and poly(vinylidene fluoride-co- trifluoro ethylene) (P(VDF-TrFE)) copolymer. PP film surface-treated with phosphoric acid to introduce surfacial isolated nanostructures serves as example of 2-dimensional nano-composites whereas LDPE/MgO serves as the case of 3-dimensional nano-composites with MgO nano-particles dispersed in LDPE polymer matrix. It is evidenced that the nanoparticles on the surface of acid-treated PP and in the bulk of LDPE/MgO nanocomposites improve charge trapping capacity of the respective material and prevent further charge injection and transport and that the enhanced charge trapping capacity makes PP and LDPE/MgO nanocomposites potential materials for both electret and electrical insulation applications. As for PVDF and VDF-based copolymers, the remanent spatial polarization distribution depends critically on poling method as well as specific parameters used in the respective poling method. In this work, homogeneous polarization poling of P(VDF-TrFE) copolymers with different VDF-contents have been attempted with hysteresis cyclical poling. The behaviour of remanent polarization growth and spatial polarization distribution are reported and discussed. The Piezoelectrically-generated Pressure Steps (PPSs) method has proven as a powerful method for the charge storage and transport characterization of a wide range of polymer material from nonpolar, to polar, to polymer nanocomposites category.
The identification of vulnerabilities in IT infrastructures is a crucial problem in enhancing the security, because many incidents resulted from already known vulnerabilities, which could have been resolved. Thus, the initial identification of vulnerabilities has to be used to directly resolve the related weaknesses and mitigate attack possibilities. The nature of vulnerability information requires a collection and normalization of the information prior to any utilization, because the information is widely distributed in different sources with their unique formats. Therefore, the comprehensive vulnerability model was defined and different sources have been integrated into one database. Furthermore, different analytic approaches have been designed and implemented into the HPI-VDB, which directly benefit from the comprehensive vulnerability model and especially from the logical preconditions and postconditions.
Firstly, different approaches to detect vulnerabilities in both IT systems of average users and corporate networks of large companies are presented. Therefore, the approaches mainly focus on the identification of all installed applications, since it is a fundamental step in the detection. This detection is realized differently depending on the target use-case. Thus, the experience of the user, as well as the layout and possibilities of the target infrastructure are considered. Furthermore, a passive lightweight detection approach was invented that utilizes existing information on corporate networks to identify applications.
In addition, two different approaches to represent the results using attack graphs are illustrated in the comparison between traditional attack graphs and a simplistic graph version, which was integrated into the database as well. The implementation of those use-cases for vulnerability information especially considers the usability. Beside the analytic approaches, the high data quality of the vulnerability information had to be achieved and guaranteed. The different problems of receiving incomplete or unreliable information for the vulnerabilities are addressed with different correction mechanisms. The corrections can be carried out with correlation or lookup mechanisms in reliable sources or identifier dictionaries. Furthermore, a machine learning based verification procedure was presented that allows an automatic derivation of important characteristics from the textual description of the vulnerabilities.
Risiken für Cyberressourcen können durch unbeabsichtigte oder absichtliche Bedrohungen entstehen. Dazu gehören Insider-Bedrohungen von unzufriedenen oder nachlässigen Mitarbeitern und Partnern, eskalierende und aufkommende Bedrohungen aus aller Welt, die stetige Weiterentwicklung der Angriffstechnologien und die Entstehung neuer und zerstörerischer Angriffe. Informationstechnik spielt mittlerweile in allen Bereichen des Lebens eine entscheidende Rolle, u. a. auch im Bereich des Militärs. Ein ineffektiver Schutz von Cyberressourcen kann hier Sicherheitsvorfälle und Cyberattacken erleichtern, welche die kritischen Vorgänge stören, zu unangemessenem Zugriff, Offenlegung, Änderung oder Zerstörung sensibler Informationen führen und somit die nationale Sicherheit, das wirtschaftliche Wohlergehen sowie die öffentliche Gesundheit und Sicherheit gefährden. Oftmals ist allerdings nicht klar, welche Bedrohungen konkret vorhanden sind und welche der kritischen Systemressourcen besonders gefährdet ist.
In dieser Dissertation werden verschiedene Analyseverfahren für Bedrohungen in militärischer Informationstechnik vorgeschlagen und in realen Umgebungen getestet. Dies bezieht sich auf Infrastrukturen, IT-Systeme, Netze und Anwendungen, welche Verschlusssachen (VS)/Staatsgeheimnisse verarbeiten, wie zum Beispiel bei militärischen oder Regierungsorganisationen. Die Besonderheit an diesen Organisationen ist das Konzept der Informationsräume, in denen verschiedene Datenelemente, wie z. B. Papierdokumente und Computerdateien, entsprechend ihrer Sicherheitsempfindlichkeit eingestuft werden, z. B. „STRENG GEHEIM“, „GEHEIM“, „VS-VERTRAULICH“, „VS-NUR-FÜR-DEN-DIENSTGEBRAUCH“ oder „OFFEN“.
Die Besonderheit dieser Arbeit ist der Zugang zu eingestuften Informationen aus verschiedenen Informationsräumen und der Prozess der Freigabe dieser. Jede in der Arbeit entstandene Veröffentlichung wurde mit Angehörigen in der Organisation besprochen, gegengelesen und freigegeben, so dass keine eingestuften Informationen an die Öffentlichkeit gelangen.
Die Dissertation beschreibt zunächst Bedrohungsklassifikationsschemen und Angreiferstrategien, um daraus ein ganzheitliches, strategiebasiertes Bedrohungsmodell für Organisationen abzuleiten. Im weiteren Verlauf wird die Erstellung und Analyse eines Sicherheitsdatenflussdiagramms definiert, welches genutzt wird, um in eingestuften Informationsräumen operationelle Netzknoten zu identifizieren, die aufgrund der Bedrohungen besonders gefährdet sind. Die spezielle, neuartige Darstellung ermöglicht es, erlaubte und verbotene Informationsflüsse innerhalb und zwischen diesen Informationsräumen zu verstehen.
Aufbauend auf der Bedrohungsanalyse werden im weiteren Verlauf die Nachrichtenflüsse der operationellen Netzknoten auf Verstöße gegen Sicherheitsrichtlinien analysiert und die Ergebnisse mit Hilfe des Sicherheitsdatenflussdiagramms anonymisiert dargestellt. Durch Anonymisierung der Sicherheitsdatenflussdiagramme ist ein Austausch mit externen Experten zur Diskussion von Sicherheitsproblematiken möglich.
Der dritte Teil der Arbeit zeigt, wie umfangreiche Protokolldaten der Nachrichtenflüsse dahingehend untersucht werden können, ob eine Reduzierung der Menge an Daten möglich ist. Dazu wird die Theorie der groben Mengen aus der Unsicherheitstheorie genutzt. Dieser Ansatz wird in einer Fallstudie, auch unter Berücksichtigung von möglichen auftretenden Anomalien getestet und ermittelt, welche Attribute in Protokolldaten am ehesten redundant sind.
Medical imaging plays an important role in disease diagnosis, treatment planning, and clinical monitoring. One of the major challenges in medical image analysis is imbalanced training data, in which the class of interest is much rarer than the other classes. Canonical machine learning algorithms suppose that the number of samples from different classes in the training dataset is roughly similar or balance. Training a machine learning model on an imbalanced dataset can introduce unique challenges to the learning problem.
A model learned from imbalanced training data is biased towards the high-frequency samples. The predicted results of such networks have low sensitivity and high precision. In medical applications, the cost of misclassification of the minority class could be more than the cost of misclassification of the majority class. For example, the risk of not detecting a tumor could be much higher than referring to a healthy subject to a doctor. The current Ph.D. thesis introduces several deep learning-based approaches for handling class imbalanced problems for learning multi-task such as disease classification and semantic segmentation.
At the data-level, the objective is to balance the data distribution through re-sampling the data space: we propose novel approaches to correct internal bias towards fewer frequency samples. These approaches include patient-wise batch sampling, complimentary labels, supervised and unsupervised minority oversampling using generative adversarial networks for all.
On the other hand, at algorithm-level, we modify the learning algorithm to alleviate the bias towards majority classes. In this regard, we propose different generative adversarial networks for cost-sensitive learning, ensemble learning, and mutual learning to deal with highly imbalanced imaging data.
We show evidence that the proposed approaches are applicable to different types of medical images of varied sizes on different applications of routine clinical tasks, such as disease classification and semantic segmentation. Our various implemented algorithms have shown outstanding results on different medical imaging challenges.
In the era of social networks, internet of things and location-based services, many online services produce a huge amount of data that have valuable objective information, such as geographic coordinates and date time. These characteristics (parameters) in the combination with a textual parameter bring the challenge for the discovery of geospatiotemporal knowledge. This challenge requires efficient methods for clustering and pattern mining in spatial, temporal and textual spaces.
In this thesis, we address the challenge of providing methods and frameworks for geospatiotemporal data analytics. As an initial step, we address the challenges of geospatial data processing: data gathering, normalization, geolocation, and storage. That initial step is the basement to tackle the next challenge -- geospatial clustering challenge. The first step of this challenge is to design the method for online clustering of georeferenced data. This algorithm can be used as a server-side clustering algorithm for online maps that visualize massive georeferenced data. As the second step, we develop the extension of this method that considers, additionally, the temporal aspect of data. For that, we propose the density and intensity-based geospatiotemporal clustering algorithm with fixed distance and time radius.
Each version of the clustering algorithm has its own use case that we show in the thesis.
In the next chapter of the thesis, we look at the spatiotemporal analytics from the perspective of the sequential rule mining challenge. We design and implement the framework that transfers data into textual geospatiotemporal data - data that contain geographic coordinates, time and textual parameters. By this way, we address the challenge of applying pattern/rule mining algorithms in geospatiotemporal space. As the applicable use case study, we propose spatiotemporal crime analytics -- discovery spatiotemporal patterns of crimes in publicly available crime data.
The second part of the thesis, we dedicate to the application part and use case studies. We design and implement the application that uses the proposed clustering algorithms to discover knowledge in data. Jointly with the application, we propose the use case studies for analysis of georeferenced data in terms of situational and public safety awareness.
Interlocutors typically link their utterances to the discourse environment and enrich communication by linguistic (e.g., information packaging) and extra-linguistic (e.g., eye gaze, gestures) means to optimize information transfer. Psycholinguistic studies underline that ‒for meaning computation‒ listeners profit from linguistic and visual cues that draw their focus of attention to salient information. This dissertation is the first work that examines how linguistic compared to visual salience cues influence sentence comprehension using the very same experimental paradigms and materials, that is, German subject-before-object (SO) and object-before-subject (OS) sentences, across the two cue modalities. Linguistic salience was induced by indicating a referent as the aboutness topic. Visual salience was induced by implicit (i.e., unconscious) or explicit (i.e., shared) manipulations of listeners’ attention to a depicted referent.
In Study 1, a selective, facilitative impact of linguistic salience on the context-sensitive OS word order was found using offline comprehensibility judgments. More precisely, during online sentence processing, this impact was characterized by a reduced sentence-initial Late positivity which reflects reduced processing costs for updating the current mental representation of discourse. This facilitative impact of linguistic salience was not replicated by means of an implicit visual cue (Study 2) shown to modulate word order preferences during sentence production. However, a gaze shift to a depicted referent as an indicator of shared attention eased sentence-initial processing similar to linguistic salience as revealed by reduced reading times (Study 3). Yet, this cue did not modulate the strong subject-antecedent preference during later pronoun resolution like linguistic salience. Taken together, these findings suggest a significant impact of linguistic and visual salience cues on sentence comprehension, which substantiates that both the information delivered via language and via the visual environment is integrated into the mental representation of the discourse; but, the way how salience is induced is crucial to its impact.
With the emergence of the Internet of things (IoT), plenty of battery-powered and energy-harvesting devices are being deployed to fulfill sensing and actuation tasks in a variety of application areas, such as smart homes, precision agriculture, smart cities, and industrial automation. In this context, a critical issue is that of denial-of-sleep attacks. Such attacks temporarily or permanently deprive battery-powered, energy-harvesting, or otherwise energy-constrained devices of entering energy-saving sleep modes, thereby draining their charge. At the very least, a successful denial-of-sleep attack causes a long outage of the victim device. Moreover, to put battery-powered devices back into operation, their batteries have to be replaced. This is tedious and may even be infeasible, e.g., if a battery-powered device is deployed at an inaccessible location. While the research community came up with numerous defenses against denial-of-sleep attacks, most present-day IoT protocols include no denial-of-sleep defenses at all, presumably due to a lack of awareness and unsolved integration problems. After all, despite there are many denial-of-sleep defenses, effective defenses against certain kinds of denial-of-sleep attacks are yet to be found.
The overall contribution of this dissertation is to propose a denial-of-sleep-resilient medium access control (MAC) layer for IoT devices that communicate over IEEE 802.15.4 links. Internally, our MAC layer comprises two main components. The first main component is a denial-of-sleep-resilient protocol for establishing session keys among neighboring IEEE 802.15.4 nodes. The established session keys serve the dual purpose of implementing (i) basic wireless security and (ii) complementary denial-of-sleep defenses that belong to the second main component. The second main component is a denial-of-sleep-resilient MAC protocol. Notably, this MAC protocol not only incorporates novel denial-of-sleep defenses, but also state-of-the-art mechanisms for achieving low energy consumption, high throughput, and high delivery ratios. Altogether, our MAC layer resists, or at least greatly mitigates, all denial-of-sleep attacks against it we are aware of. Furthermore, our MAC layer is self-contained and thus can act as a drop-in replacement for IEEE 802.15.4-compliant MAC layers. In fact, we implemented our MAC layer in the Contiki-NG operating system, where it seamlessly integrates into an existing protocol stack.
Carbonfasern haben sich in der Luft- und Raumfahrt etabliert und gewinnen in Alltagsanwendungen wie dem Automobilbereich, Windkraft- und Sportbereich durch ihre hohen Zugfestigkeiten, insbesondere ihrer hohen E-Moduli, und ihrer geringen Dichte immer mehr an Bedeutung. Auf Grund ihrer hohen Kosten, welche sich zur Hälfte aus der Precursorherstellung, inklusive seiner Synthese und seinem Verspinnprozess, dem Lösungsspinnverfahren, ergeben, erhalten zunehmend alternative und schmelzspinnbare Precursoren Interesse. Für die Carbonfaserherstellung wird fast ausschließlich Polyacrylnitril (PAN) verwendet, das vor dem Schmelzen irreversible exotherme Zyklisierungsreaktionen aufweist, welchen sich seine Zersetzung anschließt. Eine Möglichkeit der Reduzierung der Schmelztemperatur von Polymeren ist die Einbringung von Comonomeren zur Erhöhung des freien Volumens und die Reduzierung der intermolekularen Wechselwirkungen als interne Weichmacher. Wie am Fraunhofer IAP gezeigt wurde, kann mittels 2-Methoxyethylacrylat (MEA) die Schmelztemperatur zu neuartigen PAN-basierten Precursoren verringert werden. Um den PAN-co-MEA-Precursor für die nachfolgenden Prozessschritte der Carbonfaserherstellung zu verwenden, müssen die thermoplastischen Fasern in thermisch stabile Fasern ohne thermoplastisches Verhalten überführt werden. Es wurde ein neuer Prozessschritt (Prästabilisierung) eingeführt, welcher unter alkalischen Bedingungen zur Abspaltung der Comonomerseitenkette führt. Neben der Esterhydrolyse finden Reaktionen statt, welche an diesem Material noch nicht hinreichend untersucht wurden. Weiterhin stellt sich die Frage nach der Kinetik der Prästabilisierung und der Ermittlung einer geeigneten Prozessführung.
Hierzu wurde die Prästabilisierung in den Labormaßstab überführt und die möglichen Zusammensetzungen des aus DMSO und einer KOH-Lösung bestehenden Reaktionsmediums evaluiert. Weiterhin wurde die Behandlung bei verschiedenen Prästabilisierungszeiten von maximal 30 min und Temperaturen von 40, 50 und 60 °C durchgeführt, um primär mittels NMR-Spektroskopie die chemischen Strukturänderungen aufzuklären. Die Esterhydrolyse des Comonomers, welche zur Abspaltung des 2-Methoxyethanols führt, wurde mittels 1H-NMR-spektroskopischer Untersuchungen detektiert.
Es wurde ein Modell aufgestellt, das die chemisch-physikalischen Strukturänderungen während der Prästabilisierung aufzeigt. Die zuerst ablaufende Reaktion ist die Esterhydrolyse am Comonomer, welche vom Faserrand nach innen verläuft und durch die Präsenz des DMSO in Kombination mit der KOH-Lösung (Superbase) initiiert wird. Der zeitliche Reaktionsverlauf der Esterhydrolyse kann in drei Bereiche eingeteilt werden. Der erste Bereich ab dem Prästabilisierungsbeginn wird durch die Diffusion der basischen Anionen in die Faser, der zweite Bereich durch die Reaktion an der Estergruppe des Comonomers und der dritte Bereich durch letzte Reaktionen im Faserinneren und diffusiven Prozessen der Produkte und Edukte charakterisiert. Der zweite Bereich kann mit einer Reaktion pseudo 1. Ordnung abgebildet werden, da in diesem Bereich bereits eine ausreichende Diffusion der Edukte in die Faser stattgefunden hat. Bei 50 °C spielt die Diffusion im ersten Bereich im Vergleich zur Reaktion eine untergeordnete Rolle. Mit Erhöhung der Temperatur auf 60 °C kann eine im Verhältnis geringere Diffusions- als Reaktionsgeschwindigkeit beobachtet werden. Die Nebenreaktionen wurden mittels 13C-CP/MAS-NMR-spektroskopischen, elementaranlaytischen Untersuchungen sowie Doppelbrechungsmessungen charakterisiert. Während der alkalischen Esterhydrolyse beginnt die Reduzierung der Nitrilgruppen unter der Bildung von primären Carbonsäureamiden und Carbonsäuren. Zur Beschreibung dieser Umsetzung wurde eine Methode entwickelt, welche die Addition von 13C-CP/MAS-NMR-Spektren der Modellsubstanzen PAN, PAM und PAA beinhaltet. Weitere stattfindende Reaktionen sind die Bildung von konjugierten Doppelbindungen, welche insbesondere auf eine Zyklisierung der Nitrile hinweisen. Die nasschemisch initiierte Zyklisierung der Nitrilgruppen kann zu kürzeren Stabilisierungszeiten und einem besser kontrollierbaren Stabilisierungsprozess durch geringere Wärmefreisetzung und schlussendlich zu einer Kostenersparnis des gesamten Verfahrens führen. Die Umsetzung der Nitrilgruppen konnte mit einer Reaktion pseudo 1. Ordnung gut abgebildet werden. DMSO initiiert die Esterhydrolyse, wobei die KOH-Konzentration einen höheren Einfluss auf die Reaktionsgeschwindigkeit der Ester- und Nitrilhydrolyse als die DMSO-Konzentration besitzt. Beide Reaktionen zeigen eine vergleichbare Abhängigkeit von der Temperatur. Die Erhöhung der Prästabilisierungszeit und der KOH- bzw. DMSO-Konzentration führt zur Migration niedermolekularer Bestandteile des Fasermaterials an die Oberfläche und der Bildung punktueller Ablagerungen bis hin zu miteinander verbundenen Einzelfasern. Eine weitere Erhöhung der Prästabilisierungszeit bzw. der Konzentration führt zu einem steigenden Carbonsäureanteil und zur Quellung des Fasermaterials, wodurch die Ablagerungen in das Reaktionsmedium diffundieren. Die Ablagerungen enthalten Chlor, welches durch den Waschvorgang mit HCl in das Materialsystem gelangt ist und durch Parameteranpassungen reduziert wurde. Die schmelzbaren Fasern konnten durch die Prästabilisierung erfolgreich über eine Kern-Mantel-Struktur in nicht-thermoplastische Fasern überführt werden.
Zur Ermittlung eines geeigneten Prozessfensters für nachfolgende thermische Beanspruchungen der prästabilisierten Fasern wurden drei Kriterien identifiziert, anhand welcher die Evaluation erfolgte. Das erste Kriterium beinhaltet die Notwendigkeit der vollständigen Aufhebung der thermoplastischen Eigenschaft der Fasern. Als zweites Kriterium diente die Fasermorphologie. Anhand von REM-Aufnahmen wurden Faserbündel mit separierten Einzelfasern ohne Ablagerungen für die nachfolgende Stabilisierung ausgewählt. Das dritte Kriterium bezieht sich auf eine möglichst geringe Umsetzung der Nitrilgruppen, um Prästabilisierungsbedingungen mit Nebenreaktionen zu vermeiden.
Aus den Untersuchungen konnte eine Prästabilisierungstemperatur von 60 °C als geeignet identifiziert werden. Weiterhin führen hoch alkalische Zusammensetzungen des Reaktionsmediums mit KOH-Konzentrationen von 1, 1,5 und 2 M, vorzugsweise 1,5 M und 50 vol% DMSO mit Reaktionszeiten von unter 10 min zu geeigneten Fasern. Ein MEA-Anteil unterhalb von 2 mol% bewirkt eine Überführung in die Unschmelzbarkeit. Thermisch stabile und für die nachfolgende Stabilisierung geeignete Fasern besitzen weiterhin 68 – 80 mol% Nitrilgruppen, 20 – 25 mol% Carbonsäuren, bis zu 15 mol% primäre Carbonsäureamide und zyklisierte Strukturen.
Due to advances in science and technology towards smaller and more powerful processing units, the fabrication of micrometer sized machines for different tasks becomes more and more possible. Such micro-robots could revolutionize medical treatment of diseases and shall support to work on other small machines. Nevertheless, scaling down robots and other devices is a challenging task and will probably remain limited in near future. Over the past decade the concept of bio-hybrid systems has proved to be a promising approach in order to advance the further development of micro-robots. Bio-hybrid systems combine biological cells with artificial components, thereby benefiting from the functionality of living biological cells. Cell-driven micro-transport is one of the most prominent applications in the emerging field of these systems. So far, micrometer sized cargo has been successfully transported by means of swimming bacterial cells. The potential of motile adherent cells as transport systems has largely remained unexplored.
This thesis concentrates on the social amoeba Dictyostelium discoideum as a potential candidate for an amoeboid bio-hybrid transport system. The use of this model organism comes with several advantages. Due to the unspecific properties of Dictyostelium adhesion, a wide range of different cargo materials can be used for transport. As amoeboid cells exceed bacterial cells in size by one order of magnitude, also the size of an object carried by a single cell can also be much larger for an amoeba. Finally it is possible to guide the cell-driven transport based on the chemotactic behavior of the amoeba. Since cells undergo a developmentally induced chemotactic aggregation, cargo could be assembled in a self-organized manner into a cluster. It is also possible to impose an external chemical gradient to guide the amoeboid transport system to a desired location.
To establish Dictyostelium discoideum as a possible candidate for bio-hybrid transport systems, this thesis will first investigate the movement of single cells. Secondly, the interaction of cargo and cells will be studied. Eventually, a conceptional proof will be conducted, that the cheomtactic behavior can be exploited either to transport a cargo self-organized or through an external chemical source.
With the growth of information technology, patient attitudes are shifting – away from passively receiving care towards actively taking responsibility for their well- being. Handling doctor-patient relationships collaboratively and providing patients access to their health information are crucial steps in empowering patients. In mental healthcare, the implicit consensus amongst practitioners has been that sharing medical records with patients may have an unpredictable, harmful impact on clinical practice. In order to involve patients more actively in mental healthcare processes, Tele-Board MED (TBM) allows for digital collaborative documentation in therapist-patient sessions. The TBM software system offers a whiteboard-inspired graphical user interface that allows therapist and patient to jointly take notes during the treatment session. Furthermore, it provides features to automatically reuse the digital treatment session notes for the creation of treatment session summaries and clinical case reports. This thesis presents the development of the TBM system and evaluates its effects on 1) the fulfillment of the therapist’s duties of clinical case documentation, 2) patient engagement in care processes, and 3) the therapist-patient relationship. Following the design research methodology, TBM was developed and tested in multiple evaluation studies in the domains of cognitive behavioral psychotherapy and addiction care. The results show that therapists are likely to use TBM with patients if they have a technology-friendly attitude and when its use suits the treatment context. Support in carrying out documentation duties as well as fulfilling legal requirements contributes to therapist acceptance. Furthermore, therapists value TBM as a tool to provide a discussion framework and quick access to worksheets during treatment sessions. Therapists express skepticism, however, regarding technology use in patient sessions and towards complete record transparency in general. Patients expect TBM to improve the communication with their therapist and to offer a better recall of discussed topics when taking a copy of their notes home after the session. Patients are doubtful regarding a possible distraction of the therapist and usage in situations when relationship-building is crucial. When applied in a clinical environment, collaborative note-taking with TBM encourages patient engagement and a team feeling between therapist and patient. Furthermore, it increases the patient’s acceptance of their diagnosis, which in turn is an important predictor for therapy success. In summary, TBM has a high potential to deliver more than documentation support and record transparency for patients, but also to contribute to a collaborative doctor-patient relationship. This thesis provides design implications for the development of digital collaborative documentation systems in (mental) healthcare as well as recommendations for a successful implementation in clinical practice.
The foreland of the Andes in South America is characterised by distinct along strike changes in surface deformational styles. These styles are classified into two end-members, the thin-skinned and the thick-skinned style. The superficial expression of thin-skinned deformation is a succession of narrowly spaced hills and valleys, that form laterally continuous ranges on the foreland facing side of the orogen. Each of the hills is defined by a reverse fault that roots in a basal décollement surface within the sedimentary cover, and acted as thrusting ramp to stack the sedimentary pile. Thick-skinned deformation is morphologically characterised by spatially disparate, basement-cored mountain ranges. These mountain ranges are uplifted along reactivated high-angle crustal-scale discontinuities, such as suture zones between different tectonic terranes.
Amongst proposed causes for the observed variation are variations in the dip angle of the Nazca plate, variation in sediment thickness, lithospheric thickening, volcanism or compositional differences. The proposed mechanisms are predominantly based on geological observations or numerical thermomechanical modelling, but there has been no attempt to understand the mechanisms from a point of data-integrative 3D modelling. The aim of this dissertation is therefore to understand how lithospheric structure controls the deformational behaviour. The integration of independent data into a consistent model of the lithosphere allows to obtain additional evidence that helps to understand the causes for the different deformational styles. Northern Argentina encompasses the transition from the thin-skinned fold-and-thrust belt in Bolivia, to the thick-skinned Sierras Pampeanas province, which makes this area a well suited location for such a study. The general workflow followed in this study first involves data-constrained structural- and density-modelling in order to obtain a model of the study area. This model was then used to predict the steady-state thermal field, which was then used to assess the present-day rheological state in northern Argentina.
The structural configuration of the lithosphere in northern Argentina was determined by means of data-integrative, 3D density modelling verified by Bouguer gravity. The model delineates the first-order density contrasts in the lithosphere in the uppermost 200 km, and discriminates bodies for the sediments, the crystalline crust, the lithospheric mantle and the subducting Nazca plate. To obtain the intra-crustal density structure, an automated inversion approach was developed and applied to a starting structural model that assumed a homogeneously dense crust. The resulting final structural model indicates that the crustal structure can be represented by an upper crust with a density of 2800 kg/m³, and a lower crust of 3100 kg/m³. The Transbrazilian Lineament, which separates the Pampia terrane from the Río de la Plata craton, is expressed as a zone of low average crustal densities.
In an excursion, we demonstrate in another study, that the gravity inversion method developed to obtain intra-crustal density structures, is also applicable to obtain density variations in the uppermost lithospheric mantle. Densities in such sub-crustal depths are difficult to constrain from seismic tomographic models due to smearing of crustal velocities. With the application to the uppermost lithospheric mantle in the north Atlantic, we demonstrate in Tan et al. (2018) that lateral density trends of at least 125\,km width are robustly recovered by the inversion method, thereby providing an important tool for the delineation of subcrustal density trends.
Due to the genetic link between subduction, orogenesis and retroarc foreland basins the question rises whether the steady-state assumption is valid in such a dynamic setting. To answer this question, I analysed (i) the impact of subduction on the conductive thermal field of the overlying continental plate, (ii) the differences between the transient and steady-state thermal fields of a geodynamic coupled model. Both studies indicate that the assumption of a thermal steady-state is applicable in most parts of the study area. Within the orogenic wedge, where the assumption cannot be applied, I estimated the transient thermal field based on the results of the conducted analyses.
Accordingly, the structural model that had been obtained in the first step, could be used to obtain a 3D conductive steady-state thermal field. The rheological assessment based on this thermal field indicates that the lithosphere of the thin-skinned Subandean ranges is characterised by a relatively strong crust and a weak mantle. Contrarily, the adjacent foreland basin consists of a fully coupled, very strong lithosphere. Thus, shortening in northern Argentina can only be accommodated within the weak lithosphere of the orogen and the Subandean ranges. The analysis suggests that the décollements of the fold-and-thrust belt are the shallow continuation of shear zones that reside in the ductile sections of the orogenic crust. Furthermore, the localisation of the faults that provide strain transfer between the deeper ductile crust and the shallower décollement is strongly influenced by crustal weak zones such as foliation. In contrast to the northern foreland, the lithosphere of the thick-skinned Sierras Pampeanas is fully coupled and characterised by a strong crust and mantle. The high overall strength prevents the generation of crustal-scale faults by tectonic stresses. Even inherited crustal-scale discontinuities, such as sutures, cannot sufficiently reduce the strength of the lithosphere in order to be reactivated. Therefore, magmatism that had been identified to be a precursor of basement uplift in the Sierras Pampeanas, is the key factor that leads to the broken foreland of this province. Due to thermal weakening, and potentially lubrication of the inherited discontinuities, the lithosphere is locally weakened such that tectonic stresses can uplift the basement blocks. This hypothesis explains both the spatially disparate character of the broken foreland, as well as the observed temporal delay between volcanism and basement block uplift.
This dissertation provides for the first time a data-driven 3D model that is consistent with geophysical data and geological observations, and that is able to causally link the thermo-rheological structure of the lithosphere to the observed variation of surface deformation styles in the retroarc foreland of northern Argentina.
Untersuchungen an neuartigen sauerstoffsubstituierten Donoren und Akzeptoren für Singulettsauerstoff
(2019)
Im Verlauf dieser Arbeit wurden Aromaten wie Naphthaline und Anthracene mit Singulettsauerstoff, einer reaktiven Form des gewöhnlichen Sauerstoffs, zu sogenannten Endoperoxiden umgesetzt. Die hier eingesetzten Systeme wurden mit funktionellen Gruppen modifiziert, die über eine Sauerstoffbrücke mit dem Aromaten verknüpft sind. Die daraus entstandenen Endoperoxide sind meist besonders labil und konnten in dieser Arbeit isoliert und umfassend untersucht werden.
Hierbei wurde zum einen das Reaktionsverhalten untersucht. Es konnte gezeigt werden, dass die Aromaten in Abhängigkeit ihrer funktionellen Gruppen unterschiedlich schnell mit Singulettsauerstoff reagieren. Die so ermittelten Reaktivitäten wurden zusätzlich durch theoretische Berechnungen gestützt.
Die resultierenden Endoperoxide wurden unter verschiedenen Bedingungen wie erhöhter Temperatur oder einem sauren bzw. basischen Milieu auf ihre Stabilität hin untersucht. Dabei konnte gezeigt werden, dass die auf Naphthalinen basierenden Endoperoxiden den gebundenen Singulettsauerstoff in guten Ausbeuten oft schon bei sehr niedrigen Temperaturen (−40 bis 0 °C) freisetzen. Diese Verbindungen können daher als milde Quellen dieser reaktiven Sauerstoffspezies eingesetzt werden. Weiterhin konnten bei den Anthracenendoperoxiden Zerfallsmechanismen aufgeklärt und andere reaktive Sauerstoffspezies wie Wasserstoffperoxid oder Persäuren nachgewiesen werden.
Zu den Modifikationen der Aromaten gehören auch Glucosereste. Dadurch könnten sich die hier hergestellten Endoperoxide als vielversprechende Verbindungen in der Krebstherapie herausstellen, da Krebszellen deutlich stärker als gesunde Zellen kohlenhydratreiche Verbindungen für ihren Stoffwechsel benötigen. Bei der Spaltung von Endoperoxiden mit Glucosesubstituenten werden ebenfalls reaktive Sauerstoffspezies frei, die so zum Zelltod führen könnten.
Partial melting is a first order process for the chemical differentiation of the crust (Vielzeuf et al., 1990). Redistribution of chemical elements during melt generation crucially influences the composition of the lower and upper crust and provides a mechanism to concentrate and transport chemical elements that may also be of economic interest. Understanding of the diverse processes and their controlling factors is therefore not only of scientific interest but also of high economic importance to cover the demand for rare metals.
The redistribution of major and trace elements during partial melting represents a central step for the understanding how granite-bound mineralization develops (Hedenquist and Lowenstern, 1994). The partial melt generation and mobilization of ore elements (e.g. Sn, W, Nb, Ta) into the melt depends on the composition of the sedimentary source and melting conditions. Distinct source rocks have different compositions reflecting their deposition and alteration histories. This specific chemical “memory” results in different mineral assemblages and melting reactions for different protolith compositions during prograde metamorphism (Brown and Fyfe, 1970; Thompson, 1982; Vielzeuf and Holloway, 1988). These factors do not only exert an important influence on the distribution of chemical elements during melt generation, they also influence the volume of melt that is produced, extraction of the melt from its source, and its ascent through the crust (Le Breton and Thompson, 1988). On a larger scale, protolith distribution and chemical alteration (weathering), prograde metamorphism with partial melting, melt extraction, and granite emplacement are ultimately depending on a (plate-)tectonic control (Romer and Kroner, 2016). Comprehension of the individual stages and their interaction is crucial in understanding how granite-related mineralization forms, thereby allowing estimation of the mineralization potential of certain areas. Partial melting also influences the isotope systematics of melt and restite. Radiogenic and stable isotopes of magmatic rocks are commonly used to trace back the source of intrusions or to quantify mixing of magmas from different sources with distinct isotopic signatures (DePaolo and Wasserburg, 1979; Lesher, 1990; Chappell, 1996). These applications are based on the fundamental requirement that the isotopic signature in the melt reflects that of the bulk source from which it is derived. Different minerals in a protolith may have isotopic compositions of radiogenic isotopes that deviate from their whole rock signature (Ayres and Harris, 1997; Knesel and Davidson, 2002). In particular, old minerals with a distinct parent-to-daughter (P/D) ratio are expected to have a specific radiogenic isotope signature. As the partial melting reaction only involves selective phases in a protolith, the isotopic signature of the melt reflects that of the minerals involved in the melting reaction and, therefore, should be different from the bulk source signature. Similar considerations hold true for stable isotopes.
A reliable inference of networks from data is of key interest in many scientific fields. Several methods have been suggested in the literature to reliably determine links in a network. These techniques rely on statistical methods, typically controlling the number of false positive links, but not considering false negative links. In this thesis new methodologies to improve network inference are suggested. Initial analyses demonstrate the impact of falsepositive and false negative conclusions about the presence or absence of links on the resulting inferred network. Consequently, revealing the importance of making well-considered choices leads to suggest new approaches to enhance existing network reconstruction methods.
A simulation study, presented in Chapter 3, shows that different values to balance false positive and false negative conclusions about links should be used in order to reliably estimate network characteristics. The existence of type I and type II errors in the reconstructed network, also called biased network, is accepted. Consequently, an analytic method that describes the influence of these two errors on the network structure is explored. As a result of this analysis, an analytic formula of the density of the biased vertex degree distribution is found (Chapter 4).
In the inverse problem, the vertex degree distribution of the true underlying network is analytically reconstructed, assuming the probabilities of type I and type II errors. Chapters 4-5 show that the method is robust to incorrect estimates of α and β within reasonable limits. In Chapter 6, an iterative procedure to enhance this method is presented in the case of large errors on the estimates of α and β.
The investigations presented so far focus on the influence of false positive and false negative links on the network characteristics. In Chapter 7, the analysis is reversed - the study focuses on the influence of network characteristics on the probability of type I and type II errors, in the case of networks of coupled oscillators. The probabilities of α and β are influenced by the shortest path length and the detour degree, respectively. These results have been used to improve the network reconstruction, when the true underlying network is not known a priori, introducing a novel and advanced concept of threshold.
Einleitung
Die Implantation einer Knie- oder Hüft-Totalendoprothese (TEP) ist eine der häufigsten operativen Eingriffe. Im Anschluss an die Operation und die postoperative Rehabilitation stellt die Bewegungstherapie einen wesentlichen Bestandteil der Behandlung zur Verbesserung der Gelenkfunktion und der Lebensqualität dar. In strukturschwachen Gebieten werden entsprechende Angebote nur in unzureichender Dichte vorgehalten. Zudem zeichnet sich ein flächendeckender Fachkräftemangel im Bereich der Physiotherapie ab. Die Tele-Nachsorge bietet daher einen innovativen Ansatz für die postrehabilitative Versorgung der Patienten. Das Ziel der vorliegenden Untersuchung war die Überprüfung der Wirksamkeit einer interaktiven Tele-Nachsorgeintervention für Patienten mit Knie- oder Hüft-TEP im Vergleich zur herkömmlichen Versorgung (usual care). Dazu wurden die Funktionalität und die berufliche Wiedereingliederung untersucht.
Methode
Zwischen August 2016 und August 2017 wurden 111 Patienten (54,9 ± 6,8 Jahre, 54,3 % weiblich) zu Beginn ihrer stationären Anschlussheilbehandlung nach Implantation einer Knie- oder Hüft-TEP in diese randomisiert, kontrolliert, multizentrische Studie eingeschlossen. Nach Entlassung aus der orthopädischen Anschlussrehabilitation (Baseline) führte die Interventionsgruppe (IG) ein dreimonatiges interaktives Training über ein Telerehabilitationssystem durch. Hierfür erstellte ein betreuender Physiotherapeut einen individuellen Trainingsplan aus 38 Übungen zur Verbesserung der Kraft sowie der posturalen Kontrolle. Zur Anpassung des Trainingsplans übermittelte das System dem Physiotherapeuten Daten zur Quantität sowie zur Qualität des Trainings. Die Kontrollgruppe (KG) konnte die herkömmlichen Versorgungsangebote nutzen. Zur Beurteilung der Wirksamkeit der Intervention wurde die Differenz der Verbesserung im 6MWT zwischen der IG und der KG nach drei Monaten als primärer Endpunkt definiert. Als sekundäre Endpunkte wurden die Return-to-Work-Rate sowie die funktionelle Mobilität mittels des Stair Ascend Tests, des Five-Times-Sit-to-Stand Test und des Timed Up and Go Tests untersucht. Weiterhin wurden die gesundheitsbezogene Lebensqualität mit dem Short-Form 36 (SF-36) und die gelenkbezogenen Einschränkungen mit dem Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) evaluiert. Der primäre und die sekundären Endpunkte wurden anhand von baseline-adjustierten Kovarianzanalysen im intention-to-treat-Ansatz ausgewertet. Zusätzlich wurde die Teilnahme an Nachsorgeangeboten und die Adhärenz der Interventionsgruppe an der Tele-Nachsorge erfasst und evaluiert.
Ergebnisse
Zum Ende der Intervention wiesen beide Gruppen einen statistisch signifikanten Anstieg ihrer 6MWT Strecke auf (p < 0,001). Zu diesem Zeitpunkt legten die Teilnehmer der IG im Mittel 530,8 ± 79,7 m, die der KG 514,2 ± 71,2 m zurück. Dabei betrug die Differenz der Verbesserung der Gehstrecke in der IG 88,3 ± 57,7 m und in der KG 79,6 ± 48,7 m. Damit zeigt der primäre Endpunkt keine signifikanten Gruppenunterschiede (p = 0,951). Bezüglich der beruflichen Wiedereingliederung konnte jedoch eine signifikant höhere Rate in der IG (64,6 % versus 46,2 %; p = 0,014) festgestellt werden. Für die sekundären Endpunkte der funktionellen Mobilität, der Lebensqualität und der gelenkbezogenen Beschwerden belegen die Ergebnisse eine Gleichwertigkeit beider Gruppen zum Ende der Intervention.
Schlussfolgerung
Die telemedizinisch assistierte Bewegungstherapie für Knie- oder Hüft-TEP Patienten ist der herkömmlichen Versorgung zur Nachsorge hinsichtlich der erzielten Verbesserungen der funktionellen Mobilität, der gesundheitsbezogenen Lebensqualität und der gelenkbezogenen Beschwerden gleichwertig. In dieser Patientenpopulation ließen sich klinisch relevante Verbesserungen unabhängig von der Form der Bewegungstherapie erzielen. Im Hinblick auf die berufliche Wiedereingliederung zeigte sich eine signifikant höhere Rate in der Interventionsgruppe. Die telemedizinisch assistierte Bewegungstherapie scheint eine geeignete Versorgungsform der Nachsorge zu sein, die orts- und zeitunabhängig durchgeführt werden kann und somit den Bedürfnissen berufstätiger Patienten entgegenkommt und in den Alltag der Patienten integriert werden kann. Die Tele-Nachsorge sollte daher als optionale und komplementäre Form der postrehabilitativen Nachsorge angeboten werden. Auch im Hinblick auf den zunehmenden Fachkräftemangel im Bereich der Physiotherapie und bestehende Versorgungslücken in strukturschwachen Gebieten kann der Einsatz der Tele-Nachsorge innovative und bedarfsgerechte Lösungsansätze bieten.
The goal of this thesis is to broaden the empirical basis for a better, comprehensive understanding
of massive star evolution, star formation and feedback at low metallicity. Low metallicity massive stars are a key to understand the early universe. Quantitative information on metal-poor massive stars was sparse before. The quantitative spectroscopic studies of massive star populations associated with large-scale ISM structures were not performed at low metallicity before, but are important to investigate star-formation histories and feedback in detail. Much of this work relies on spectroscopic observations with VLT-FLAMES of ~500 OB stars in the Magellanic Clouds. When available, the optical spectroscopy was complemented by UV spectra from the HST, IUE, and FUSE archives. The two representative young stellar populations that have been studied are associated with the superbubble N 206 in the Large Magellanic Cloud (LMC) and with the supergiant shell SMC-SGS 1 in the Wing of the Small Magellanic Cloud (SMC), respectively. We performed spectroscopic analyses of the massive stars using the nonLTE Potsdam Wolf-Rayet (PoWR) model atmosphere code. We estimated the stellar, wind, and feedback parameters of the individual massive stars and established their statistical distributions.
The mass-loss rates of N206 OB stars are consistent with theoretical expectations for LMC metallicity. The most massive and youngest stars show nitrogen enrichment at their surface and are found to be slower rotators than the rest of the sample. The N 206 complex has undergone star formation episodes since more than 30 Myr, with a current star formation rate higher than average in the LMC. The spatial age distribution of stars across the complex possibly indicates triggered star formation due to the expansion of the superbubble. Three very massive, young Of stars in the region dominate the ionizing and mechanical feedback among hundreds of other OB stars in the sample. The current stellar wind feedback rate from the two WR stars in the complex is comparable to that released by the whole OB sample. We see only a minor fraction of this stellar wind feedback converted into X-ray emission. In this LMC complex, stellar winds and supernovae equally contribute to the total energy feedback, which eventually powered the central superbubble. However, the total energy input accumulated over the time scale of the superbubble significantly exceeds the observed energy content of the complex. The lack of energy along with the morphology of the complex suggests a leakage of hot gas from the superbubble.
With a detailed spectroscopic study of massive stars in SMC-SGS 1, we provide the stellar and wind parameters of a large sample of OB stars at low metallicity, including those in the lower mass-range. The stellar rotation velocities show a broad, tentatively bimodal distribution, with Be stars being among the fastest. A few very luminous O stars are found close to the main sequence, while all other, slightly evolved stars obey a strict luminosity limit. Considering additional massive stars in evolved stages, with published parameters and located all over the SMC, essentially confirms this picture. The comparison with single-star evolutionary tracks suggests a dichotomy in the fate of massive stars in the SMC. Only stars with an initial mass below 30 solar masses seem to evolve from the main sequence to the cool side of the HRD to become a red supergiant and to explode as type II-P supernova. In contrast, more massive stars appear to stay always hot and might evolve quasi chemically homogeneously, finally collapsing to relatively massive black holes. However, we find no indication that chemical mixing is correlated with rapid rotation. We measured the key parameters of stellar feedback and established the links between the rates of star formation and supernovae. Our study demonstrates that in metal-poor environments stellar feedback is dominated by core-collapse supernovae in combination with winds and ionizing radiation supplied by a few of the most massive stars. We found indications of the stochastic mode of star formation, where the resulting stellar population is fully capable of producing large-scale structures such as the supergiant shell SMC-SGS 1 in the Wing. The low level of feedback in metal-poor stellar populations allows star formation episodes to persist over long timescales.
Our study showcases the importance of quantitative spectroscopy of massive stars with adequate stellar-atmosphere models in order to understand star-formation, evolution, and feedback. The stellar population analyses in the LMC and SMC make us understand that massive stars and their impact can be very different depending on their environment. Obviously, due to their different metallicity, the massive stars in the LMC and the SMC follow different evolutionary paths. Their winds differ significantly, and the key feedback agents are different. As a consequence, the star formation can proceed in different modes.
C-Arylglykoside und Chalkone
(2019)
Im bis heute andauernden Zeitalter der wissenschaftlichen Medizin, konnte ein breites Spektrum von Wirkstoffen zur Behandlung diverser Krankheiten zusammengetragen werden. Dennoch hat es sich die organische Synthesechemie zur Aufgabe gemacht, dieses Spektrum auf neuen oder bekannten Wegen und aus verschiedenen Gründen zu erweitern. Zum einen ist das Vorkommen bestimmter Verbindungen in der Natur häufig limitiert, sodass synthetische Methoden immer öfter an Stelle eines weniger nachhaltigen Abbaus treten. Zum anderen kann durch Derivatisierung und Wirkstoffanpassung die physiologische Wirkung oder die Bioverfügbarkeit eines Wirkstoffes erhöht werden. In dieser Arbeit konnten einige Vertreter der bekannten Wirkstoffklassen C-Arylglykoside und Chalkone durch den Schlüsselschritt der Palladium-katalysierten MATSUDA-HECK-Reaktion synthetisiert werden.
Dazu wurden im Fall der C-Arylglykoside zunächst ungesättigte Kohlenhydrate (Glykale) über eine Ruthenium-katalysierte Zyklisierungsreaktion dargestellt. Diese wurden im Anschluss mit unterschiedlich substituierten Diazoniumsalzen in der oben erwähnten Palladium-katalysierten Kupplungsreaktion zur Reaktion gebracht. Bei der Auswertung der analytischen Daten konnte festgestellt werden, dass stets die trans-Diastereomere gebildet wurden. Im Anschluss konnte gezeigt werden, dass die Doppelbindungen dieser Verbindungen durch Hydrierung, Dihydroxylierung oder Epoxidierung funktionalisiert werden können. Auf diesem Wege konnte u. a. eine dem Diabetesmedikament Dapagliflozin ähnliche Verbindung hergestellt werden.
Im zweiten Teil der Arbeit wurden Arylallylchromanone durch die MATSUDA-HECK-Reaktion von verschiedenen 8-Allylchromanonen mit Diazoniumsalzen dargestellt. Dabei konnte beobachtet werden, dass eine MOM-Schutzgruppe in 7-Position der Moleküle die Darstellung von Produktgemischen unterdrückt und jeweils nur eine der möglichen Verbindungen gebildet wird. Die Lage der Doppelbindung konnte mittels 2D-NMR-Untersuchungen lokalisiert werden. In Kooperation mit der theoretischen Chemie sollte durch Berechnungen untersucht werden, wie die beobachteten Verbindungen entstehen. Durch eine auftretende Wechselwirkung innerhalb des Moleküls konnte allerdings keine explizite Aussage getroffen werden.
Im Anschluss sollten die erhaltenen Verbindungen in einer allylischen Oxidation zu Chalkonen umgesetzt werden. Die Ruthenium-katalysierten Methoden zeigten u. a. keine Eignung. Es konnte allerdings eine metallfreie, Mikrowellen-unterstützte Methode erfolgreich erprobt werden, sodass die Darstellung einiger Vertreter dieser physiologisch aktiven Stoffklasse gelang.
Das Preußische Erbrecht in der Judikatur des Berliner Obertribunals in den Jahren 1836 bis 1865
(2019)
Die Dissertation befasst sich mit dem Allgemeinen Preußischen Landrecht von 1794 und der hierzu ergangenen Rechtsprechung des Berliner Obertribunals. Im Fokus der Untersuchung stehen die erbrechtlichen Regelungen des Landrechts und deren Anwendung sowie Auslegung in der Judikatur des höchsten preußischen Gerichts. Der Forschungsgegenstand ergibt sich aus dem im Landrecht kodifizierten speziellen Gesetzesverständnisses. Nach diesem sollte die Gesetzesauslegung durch die Rechtsprechung auf ein Minimum, nämlich die Auslegung allein anhand des Wortlauts der Regelung reduziert werden, um dem absolutistischen Regierungsanspruch der preußischen Monarchen, namentlich Friedrich des Großen, hinreichend Rechnung zu tragen. In diesem Kontext wird der Frage nachgegangen, inwieweit das preußische Obertribunal das im Landrecht statuierte „Auslegungsverbot“ beachtet hat und in welchen Fällen sich das Gericht von der Vorgabe emanzipierte und weitere Auslegungsmethoden anwendete und sich so eine unabhängige Rechtsprechung entwickeln konnte.
Die Arbeit gliedert sich in drei Hauptabschnitte. Im Anschluss an die Einleitung, in der zunächst die rechtshistorische Bedeutung des Landrechts und des Erbrechts sowie der Untersuchungsgegenstand umrissen werden, folgt die Darstellung der Entstehungsgeschichte des Landrechts und des Berliner Obertribunals.
Hieran schließt sich in einem dritten Abschnitt eine Analyse der erbrechtlichen Vorschriften des Landrechts an. In dieser wird auf die Entstehungsgeschichte der verschiedenen erbrechtlichen Institute wie beispielsweise der gesetzlichen und gewillkürten Erbfolge, dem Pflichtteilsrecht etc., unter Berücksichtigung des zeitgenössischen wissenschaftlichen Diskurses eingegangen.
Im vierten Abschnitt geht es um die Judikate des Berliner Obertribunals aus den Jahren 1836-1865 in denen die zuvor dargestellten erbrechtlichen Regelungen entscheidungserheblich waren. Dabei wird der Forschungsfrage, inwieweit das Obertribunal das im Landrecht statuierte Auslegungsverbot beachtet hat und in welchen Fällen es von diesem abwich bzw. weitere Auslegungsmethoden anwendete, konkret nachgegangen wird. Insgesamt werden 26 Entscheidungen des Obertribunals unter dem Aspekt der Auslegungspraxis, der Kontinuität und der Beschleunigung der Rechtsprechung analysiert und ausgewertet.
Vom Monomer zum Glykopolymer
(2019)
Glykopolymere sind synthetische und natürlich vorkommende Polymere, die eine Glykaneinheit in der Seitenkette des Polymers tragen. Glykane sind durch die Glykan-Protein-Wechselwirkung verantwortlich für viele biologische Prozesse. Die Beteiligung der Glykanen in diesen biologischen Prozessen ermöglicht das Imitieren und Analysieren der Wechselwirkungen durch geeignete Modellverbindungen, z.B. der Glykopolymere. Dieses System der Glykan-Protein-Wechselwirkung soll durch die Glykopolymere untersucht und studiert werden, um die spezifische und selektive Bindung der Proteine an die Glykopolymere nachzuweisen. Die Proteine, die in der Lage sind, Kohlenhydratstrukturen selektiv zu binden, werden Lektine genannt.
In dieser Dissertationsarbeit wurden verschiedene Glykopolymere synthetisiert. Dabei sollte auf einen effizienten und kostengünstigen Syntheseweg geachtet werden.
Verschiedene Glykopolymere wurden durch funktionalisierte Monomere mit verschiedenen Zuckern, wie z.B. Mannose, Laktose, Galaktose oder N-Acetyl-Glukosamin als funktionelle Gruppe, hergestellt. Aus diesen funktionalisierten Glykomonomeren wurden über ATRP und RAFT-Polymerisation Glykopolymere synthetisiert.
Die erhaltenen Glykopolymere wurden in Diblockcopolymeren als hydrophiler Block angewendet und die Selbstassemblierung in wässriger Lösung untersucht. Die Polymere formten in wässriger Lösung Mizellen, bei denen der Zuckerblock an der Oberfläche der Mizellen sitzt. Die Mizellen wurden mit einem hydrophoben Fluoreszenzfarbstoff beladen, wodurch die CMC der Mizellenbildung bestimmt werden konnte.
Außerdem wurden die Glykopolymere als Oberflächenbeschichtung über „Grafting from“ mit SI-ATRP oder über „Grafting to“ auf verschiedene Oberflächen gebunden. Durch die glykopolymerbschichteten Oberflächen konnte die Glykan Protein Wechselwirkung über spektroskopische Messmethoden, wie SPR- und Mikroring Resonatoren untersucht werden. Hierbei wurde die spezifische und selektive Bindung der Lektine an die Glykopolymere nachgewiesen und die Bindungsstärke untersucht.
Die synthetisierten Glykopolymere könnten durch Austausch der Glykaneinheit für andere Lektine adressierbar werden und damit ein weites Feld an anderen Proteinen erschließen. Die bioverträglichen Glykopolymere wären alternativen für den Einsatz in biologischen Prozessen als Transporter von Medikamenten oder Farbstoffe in den Körper. Außerdem könnten die funktionalisierten Oberflächen in der Diagnostik zum Erkennen von Lektinen eingesetzt werden. Die Glykane, die keine selektive und spezifische Bindung zu Proteinen eingehen, könnten als antiadsorptive Oberflächenbeschichtung z.B. in der Zellbiologie eingesetzt werden.
Seit 2003 hat sich das politische Bild des Irak stark verändert. Dadurch begann der Prozess der Neugestaltung der irakischen Rechtsordnung. Die irakische Verfassung von 2005 legt erstmalig in der Geschichte des Irak den Islam und die Demokratie als zwei nebeneinander zu beachtende Grundprinzipien bei der Gesetzgebung fest. Trotz dieser signifikanten Veränderung im irakischen Rechtssystem und erheblicher Entwicklungen im internationalen Privat- und Zivilverfahrensrecht (IPR/IZVR) im internationalen Vergleich gilt die hauptsächlich im irakischen Zivilgesetzbuch (ZGB) von 1951 enthaltene gesetzliche Regelung des IPR/IZVR im Irak weiterhin. Deshalb entstand diese Arbeit für eine Reformierung des irakischen IPR/IZVR.
Die Arbeit gilt als erste umfassende wissenschaftliche Untersuchung, die sich mit dem jetzigen Inhalt und der zukünftigen Reformierung des irakischen internationalen Privatrecht- und Zivilverfahrensrechts (IPR/IZVR) beschäftigt.
Die Verfasserin vermittelt einen Gesamtüberblick über das jetzt geltende irakische internationale Privat- und Zivilverfahrensrecht mit gelegentlicher punktueller und stichwortartiger Heranziehung des deutschen, islamischen, türkischen und tunesischen Rechts, zeigt dessen Schwachstellen auf und unterbreitet entsprechende Reformvorschläge.
Wegen der besonderen Bedeutung des internationalen Vertragsrechts für die Wirtschaft im Irak und auch zum Teil für Deutschland gibt die Verfasserin einen genaueren Überblick über das irakische internationale Vertragsrecht und bekräftigt gleichzeitig dessen Reformbedürftigkeit.
Die Darstellung der wichtigen Entwicklungen im deutsch-europäischen, im traditionellen islamischen Recht und im türkischen und tunesischen internationalen Privat- und Zivilverfahrensrecht im zweiten Kapitel dienen als Grundlage, auf die bei der Reformierung des irakischen IPR/ IZVR zurück gegriffen werden kann. Da die Kenntnisse des islamischen Rechts nicht zwingend zum Rechtsstudium gehören, wird das islamische Recht dazu in Bezug auf seine Entstehung und die Rechtsquellen dargestellt.
Am Ende der Arbeit wird ein Entwurf eines föderalen Gesetzes zum internationalen Privatrecht im Irak katalogisiert, der sich im Rahmen der irakischen Verfassung gleichzeitig mit dem Islam und der Demokratie vereinbaren lässt.
Die Anfechtbarkeit und die Feststellbarkeit der Mutterschaft de lege lata und de lege ferenda
(2019)
Der althergebrachte Grundsatz, wonach das Kind von der Frau abstammt, welche es geboren hat, ist durch die moderne Fortpflanzungsmedizin ins Wanken geraten. Dennoch ordnet § 1591 BGB das Kind unanfechtbar der Geburtsmutter zu. Rechtliche und genetische Mutterschaft fallen deshalb dauerhaft auseinander, wenn das Kind im Wege der Leihmutterschaft oder nach einer Eizell- bzw. Embryospende zur Welt kommt. Die auf diese Methoden der artifiziellen Reproduktion bezogenen, im Inland bestehenden Verbote halten Paare mit Kinderwunsch nicht davon ab, auf entsprechende Angebote im Ausland zurückzugreifen. Daraus resultierende kollisions- und verfassungsrechtliche Probleme sind Gegenstand der vorliegenden Arbeit.
Für den Bereich der Leihmutterschaft wird der Frage nachgegangen, ob die mit dem Anfechtungsausschluss verfolgten Ziele des Gesetzgebers die damit einhergehenden Beeinträchtigungen grundrechtlich geschützter Rechtspositionen von genetischer Mutter und Kind rechtfertigen können. Besonderes Augenmerk liegt auf dem von Art. 6 Abs. 2 S. 1 GG geschützten Interesse von leiblichen Eltern und Kindern, die verfahrensrechtliche Möglichkeit zu erhalten, rechtlich einander zugeordnet zu werden. Dieses Interesse wird den Zielen des Gesetzgebers, der mit dem Anfechtungsausschluss die Rechte von Leihmüttern und Kindern zu schützen beabsichtigt, im Rahmen einer umfassenden Verhältnismäßigkeitsprüfung gegenübergestellt.
In den Konstellationen der Eizell- und Embryospende tritt schwerpunktmäßig das Recht des Kindes auf Kenntnis der eigenen Abstammung in den Vordergrund und mit ihm die Frage, ob sich daraus eine Verpflichtung des Gesetzgebers ableiten lässt, den Tatbestand von § 1598a BGB so zu erweitern, dass die vermuteten genetischen Eltern für den Bereich der artifiziellen Reproduktion in den Kreis der Klärungsverpflichteten aufgenommen werden.
Neben diesen Schwerpunkten werden viele weitere Probleme angesprochen. Im Ergebnis mündet die Arbeit in einen Vorschlag für die Legislative.
Der historische Spielfilm zählt zu den populärsten Formen geschichtskultureller Artikulation. Als solche ist er Gegenstand kontroverser Diskussionen über einen angemessenen didaktischen Umgang. Vor diesem Hintergrund ist es das Ziel der vorliegenden Arbeit, ein integratives, theoretisch und empirisch abgesichertes Analysemodell zu entwickeln, das nach den Tiefenstrukturen historischen Erzählens im Medium des Spielfilms fragt und dabei unterschiedliche Erscheinungsformen historischer Spielfilme berücksichtigt. Die Überlegungen bewegen sich deshalb in einem interdisziplinären Spannungsfeld von Theorien zum historischen Erzählen und Konzepten der Literatur- und Filmwissenschaft. Die Diskussion und Synthese dieser unterschiedlichen Konzepte geht dabei – auf der Grundlage einer großen Materialbasis – vom Gegenstand aus und ist induktiv angelegt. Als Orientierung für die praktische Arbeit werden am Ende der einzelnen Kapitel Toolkits entwickelt, die zu einer vertieften Auseinandersetzung mit historischen Spielfilmen anregen sollen.