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Der Bittergeschmack warnt den Organismus vor potentiell verdorbener oder giftiger Nahrung und ist somit ein wichtiger Kontrollmechanismus. Die initiale Detektion der zahlreich vorkommenden Bitterstoffe erfolgt bei der Maus durch 35 Bitterrezeptoren (Tas2rs), die sich im Zungengewebe befinden. Die Geschmacksinformation wird anschließend von der Zunge über das periphere (PNS) ins zentrale Nervensystem (ZNS) geleitet, wo deren Verarbeitung stattfindet. Die Verarbeitung der Geschmacksinformation konnte bislang nicht gänzlich aufgeklärt werden. Neue Studien deuten auf eine Expression von Tas2rs auch im PNS und ZNS entlang der Geschmacksbahn hin. Über Vorkommen und Aufgaben dieser Rezeptoren bzw. Rezeptorzellen im Nervensystem ist bislang wenig bekannt.
Im Rahmen dieser Arbeit wurde die Tas2r-Expression in verschiedenen Mausmodellen untersucht, Tas2r-exprimierende Zellen identifiziert und deren Funktionen bei der Übertragung der Geschmacksinformationen analysiert. Im Zuge der Expressionsanalysen mittels qRT-PCR konnte die Expression von 25 der 35 bekannten Bittergeschmacksrezeptoren im zentralen Nervensystem der Maus nachgewiesen werden. Die Expressionsmuster im PNS sowie im ZNS lassen darüber hinaus Vermutungen zu Funktionen in verschiedenen Bereichen des Nervensystems zu. Basierend auf den Ergebnissen der Expressionsanalysen war es möglich, stark exprimierte Tas2rs mittels In-situ-Hybridisierung in verschiedenen Zelltypen zu visualisieren. Des Weiteren konnten immunhistochemische Färbungen unter Verwendung eines genetisch modifizierten Mausmodells die Ergebnisse der Expressionsanalysen bestätigen. Sie zeigten eine Expression von Tas2rs, am Beispiel des Tas2r131-Rezeptors, in cholinergen, dopaminergen, GABAergen, noradrenergen und glycinerg-angesteuerten Projektionsneuronen sowie in Interneuronen. Die Ergebnisse der vorliegenden Arbeit zeigen daher erstmals das Vorkommen von Tas2rs in verschiedenen neuronalen Zelltypen in weiten Teilen des ZNS. Dies lässt den Schluss zu, dass Tas2r-exprimierende Zellen potentiell multiple Funktionen innehaben. Anhand von Verhaltensexperimenten in genetisch modifizierten Mäusen wurde die mögliche Funktion von Tas2r131-exprimierenden Neuronen (Tas2r131-Neurone) bei der Geschmackswahrnehmung untersucht. Die Ergebnisse weisen auf eine Beteiligung von Tas2r131-Neuronen an der Signalweiterleitung bzw. -verarbeitung der Geschmacksinformation für eine Auswahl von Bittersubstanzen hin. Die Analysen zeigen darüber hinaus, dass Tas2r131-Neuronen nicht an der Geschmackswahrnehmung anderer Bitterstoffe sowie Geschmacksstimuli anderer Qualitäten (süß, umami, sauer, salzig), beteiligt sind. Eine spezifische „Tas2r131-Bittergeschmacksbahn“, die mit anderen potentiellen „Bitterbahnen“ teils unabhängige, teils überlappende Signalwege bzw. Verarbeitungsbereiche besitzt, bildet eine mögliche zelluläre Grundlage zur Unterscheidung von Bitterstoffen. Die im Rahmen dieser Arbeit entstandene Hypothese einer potentiellen Diskriminierung von Bitterstoffen soll daher in weiterführenden Studien durch die Etablierung eines Verhaltenstest mit Mäusen geprüft werden.
Z,E-Diene sind ein häufig auftretendes Strukturmerkmal in Naturstoffen. Aus diesem Grund ist die einfache Darstellung dieser Struktureinheit von großen Interesse in der organischen Chemie.
Das erste Ziel der vorliegenden Arbeit war daher die Weiterentwicklung der Ringschlussmetathese-/ baseninduzierten Ringöffnungs-/ Veresterungssequenz (RBRV-Sequenz) zur Synthese von (2Z,4E)-Diencarbonsäureethylestern ausgehend von Butenoaten. Dazu wurde zunächst die RBRV-Sequenz optimiert. Diese aus drei Schritten bestehende Sequenz konnte in einem Eintopf-Verfahren angewendet werden. Die Ringschlussmetathese gelang mit einer Katalysatorbeladung von 1 mol% des GRUBBS-Katalysators der zweiten Generation in Dichlormethan. Für die baseninduzierte Ringöffnung des β,γ-ungesättigten δ Valerolactons wurde NaHMDS verwendet. Die Alkylierung der Carboxylatspezies gelang mit dem MEERWEIN-Reagenz. Die Anwendbarkeit der Sequenz wurde für verschiedene Substrate demonstriert.
Die Erweiterung der Methode auf α-substituierte Butenoate unterlag starken Einschränkungen. So konnte der Zugang für α Hydroxyderivate realisiert werden. Bei der Anwendung der RBRV-Sequenz auf die α-substituierten Butenoate wurde festgestellt, dass diese sich nur in moderaten Ausbeuten umsetzen ließen und zudem nicht selektiv zu den (2E,4E)-konfigurierten α-substituierten-Dienestern reagierten.
Der Einsatz von Eninen unter den Standardbedingungen der RBRV-Sequenz gelang nicht. Erst nach Modifizierung der Sequenz (höhere Katalysatorbeladung, Wechsel des Lösungsmittels) konnten die [3]Dendralen-Produkte in geringen Ausbeuten erhalten werden.
Im zweiten Teil der Arbeit wurde der Einsatz von (2Z,4E)-Diencarbonsäureethylestern in der Totalsynthese von Naturstoffen untersucht. Dazu wurden zunächst die Transformationsmöglichkeiten der Ester geprüft. Es konnte gezeigt werden, dass sich (2Z,4E)-Diencarbonsäureethylester insbesondere zur Synthese von (2Z,4E)-Aldehyden sowie zum Aufbau der (3Z,5E)-Dien-1-in-Struktur eignen.
Anhand dieser Ergebnisse wurde im Anschluss die RBRV-Sequenz in der Totalsynthese eingesetzt. Dazu wurde zunächst der (2Z,4E)-Dienester Microsphaerodiolin in seiner ersten Totalsynthese auf drei verschiedene Routen hergestellt. Im Anschluss wurden sechs verschiedene Polyacetylene mit einer (3Z,5E)-Dien-1-in-Einheit hergestellt. Schlüsselschritte in ihrer Synthese waren immer die RBRV-Sequenz zum Aufbau der Z,E-Dien-Einheit, die Transformation des Esters in ein terminales Alkin sowie die CADIOT-CHODKIEWICZ-Kupplung zum Aufbau unsymmetrischer Polyine. Alle sechs Polyacetylene wurden zum ersten Mal in einer Totalsynthese synthetisiert. Drei Polyacetylene wurden ausgehend von (S)-Butantriol enantiomerenrein dargestellt. Anhand ihrer Drehwerte konnte eine Revision der von YAO und Mitarbeitern vorgenommen Zuordnung der Absolutkonfiguration der Naturstoffe vorgenommen werden.
In this thesis sentence processing was investigated using a psychophysiological measure known as pupillometry as well as Event-Related Potentials (ERP). The scope of the the- sis was broad, investigating the processing of several different movement constructions with native speakers of English and second language learners of English, as well as word order and case marking in German speaking adults and children. Pupillometry and ERP allowed us to test competing linguistic theories and use novel methodologies to investigate the processing of word order. In doing so we also aimed to establish pupillometry as an effective way to investigate the processing of word order thus broadening the methodological spectrum.
Ziel der vorliegenden Arbeit ist es, belohnungsabhängiges (instrumentelles) Lernen und Entscheidungsfindungsprozesse auf Verhaltens- und neuronaler Ebene in Abhängigkeit von chronischem Stresserleben (erfasst über den Lifetime Stress Inventory, Holmes und Rahe 1962) und kognitiven Variablen (eingeteilt in eine fluide und eine kristalline Intelligenzkomponente) an gesunden Probanden zu untersuchen. Dabei steht zu Beginn die Sicherung der Konstruktvalidität zwischen den bislang oft synonym verwendeten Begriffen modellfrei ~ habituell, bzw. modellbasiert ~ zielgerichtet im Fokus. Darauf aufbauend soll dann insbesondere der differentielle und interaktionelle Einfluss von chronischem Stresserleben und kognitiven Variablen auf Entscheidungsprozesse (instrumentelles Lernen) und deren neuronales Korrelat im VS untersucht und dargestellt werden. Abschließend wird die Relevanz der untersuchten belohnungsabhängigen Lernprozesse für die Entstehung und Aufrechterhaltung der Alkoholabhängigkeit zusammen mit weiteren Einflussvariablen in einem Übersichtspapier diskutiert.
Die vorliegende Arbeit untersucht die Politik der Zentralbankunabhängigkeit (ZBU) am Beispiel der Türkei. Im Mittelpunkt der Arbeit stehen theoretische und empirische Fragen und Probleme, die sich im Zusammenhang mit der ZBU stellen und anhand der türkischen Geldpolitik diskutiert werden. Ein zentrales Ziel der Arbeit besteht darin, zu untersuchen, ob und inwiefern die türkische Zentralbank nach Erlangung der de jure institutionellen Unabhängigkeit tatsächlich als unabhängig und entpolitisiert eingestuft werden kann. Um diese Forschungsfrage zu beantworten, werden die institutionellen Bedingungen, die Ziele und die Regeln, nach denen sich die türkische Geldpolitik richtet, geklärt. Anschließend wird empirisch überprüft, ob die geldpolitische Praxis der CBRT sich an dem offiziell vorgegebenen Regelwerk orientiert. Die Hauptthese dieser Arbeit lautet, dass die formelle Unabhängigkeit der CBRT und die regelorientierte Geldpolitik nicht mit einer Entpolitisierung der Geldpolitik in der Türkei gleichzusetzen ist. Als Alternative schlägt die vorliegende Studie vor, den institutionellen Status der CBRT als einen der relativen Autonomie zu untersuchen. Auch eine de jure unabhängige Zentralbank kann sich nicht von politischen Eingriffen abkoppeln, wie das Fallbeispiel Türkei zeigen wird.
La siguiente investigación aborda la relación entre mito y modernidad en la obra literaria (poemas, cuentos, novelas y crónicas) del autor chileno Rosamel del Valle (Curacaví, 1901 – Santiago de Chile, 1965). En sus distintos textos existe una tensión entre un proyecto poético basado en una visión mítica del mundo y un contexto histórico que privilegia posturas más racionalistas, relegando lo poético y lo mítico. Ya en el siglo XIX la modernidad y los fenómenos asociados de la modernización producen el desplazamiento de la poesía como discurso y del poeta como persona a una situación deficitaria dentro de la sociedad, lo que se extiende en el siglo XX. Debido a este conflicto Rosamel del Valle cuestiona en su obra los alcances de sus propios postulados, tanto estéticos como vitales. Esto conlleva una vacilación entre la reafirmación de su proyecto poético-vital y la consciencia del fracaso. Es por esto que la obra del poeta chileno contiene un Lebenswissen, que concibe a la poesía como una forma privilegiada de vida. Sin embargo, debido a las dificultades de las condiciones históricas es posible entender este Lebenswissen también como un ÜberLebenswissen (Ette).
En la primera parte del texto se estudia la concepción mítica de la poesía de del Valle y se analiza los distintos niveles en los que aparece el mito en su obra literaria: como pensamiento, como lenguaje y como narración tradicional. La identificación de la poesía como mito muestra las principales características de la poética de del Valle: una concepción ontológica que diferencia entre una dimensión visible y otra invisible de la realidad; la tendencia mística de la poesía; una concepción cíclica del tiempo que funda una relación con los discursos de la memoria y de la muerte, así como la idea de un pasado utópico que por medio de la poesía podría revivir en el presente; además de la figura de la mujer cómo símbolo del amor y de la poesía.
En la segunda parte se investiga la relación y las consecuencias de esta “poesía mítica” en el contexto de la modernidad. Se aborda especialmente el efecto en la poética de Rosamel del Valle de la Entzauberung der Welt (Weber), como experiencia específica de la época. Para esto se destaca ante todo sus impresiones sobre Nueva York. Esta ciudad en la que vivió y trabajó entre 1946 y 1963, se transforma en sus textos en un lugar en el que sería posible el “habitar poético del hombre” en la modernidad.
Dynamics of mantle plumes
(2016)
Mantle plumes are a link between different scales in the Earth’s mantle: They are an important part of large-scale mantle convection, transporting material and heat from the core-mantle boundary to the surface, but also affect processes on a smaller scale, such as melt generation and transport and surface magmatism. When they reach the base of the lithosphere, they cause massive magmatism associated with the generation of large igneous provinces, and they can be related to mass extinction events (Wignall, 2001) and continental breakup (White and McKenzie, 1989).
Thus, mantle plumes have been the subject of many previous numerical modelling studies (e.g. Farnetani and Richards, 1995; d’Acremont et al., 2003; Lin and van Keken, 2005; Sobolev et al., 2011; Ballmer et al., 2013). However, complex mechanisms, such as the development and implications of chemical heterogeneities in plumes, their interaction with mid-ocean ridges and global mantle flow, and melt ascent from the source region to the surface are still not very well understood; and disagreements between observations and the predictions of classical plume models have led to a challenge of the plume concept in general (Czamanske et al., 1998; Anderson, 2000; Foulger, 2011). Hence, there is a need for more sophisticated models that can explain the underlying physics, assess which properties and processes are important, explain how they cause the observations visible at the Earth’s surface and provide a link between the different scales.
In this work, integrated plume models are developed that investigate the effect of dense recycled oceanic crust on the development of mantle plumes, plume–ridge interaction under the influence of global mantle flow and melting and melt migration in form of two-phase flow.
The presented analysis of these models leads to a new, updated picture of mantle plumes: Models considering a realistic depth-dependent density of recycled oceanic crust and peridotitic mantle material show that plumes with excess temperatures of up to 300 K can transport up to 15% of recycled oceanic crust through the whole mantle. However, due to the high density of recycled crust, plumes can only advance to the base of the lithosphere directly if they have high excess temperatures, high plume volumes and the lowermost mantle is subadiabatic, or plumes rise from the top or edges of thermo-chemical piles. They might only cause minor surface uplift, and instead of the classical head–tail structure, these low-buoyancy plumes are predicted to be broad features in the lower mantle with much less pronounced plume heads. They can form a variety of shapes and regimes, including primary plumes directly advancing to the base of the lithosphere, stagnating plumes, secondary plumes rising from the core–mantle boundary or a pool of eclogitic material in the upper mantle and failing plumes. In the upper mantle, plumes are tilted and deflected by global mantle flow, and the shape, size and stability of the melting region is influenced by the distance from nearby plate boundaries, the speed of the overlying plate and the movement of the plume tail arriving from the lower mantle. Furthermore, the structure of the lithosphere controls where hot material is accumulated and melt is generated. In addition to melting in the plume tail at the plume arrival position, hot plume material flows upwards towards opening rifts, towards mid-ocean ridges and towards other regions of thinner lithosphere, where it produces additional melt due to decompression. This leads to the generation of either broad ridges of thickened magmatic crust or the separation into multiple thinner lines of sea mount chains at the surface. Once melt is generated within the plume, it influences its dynamics, lowering the viscosity and density, and while it rises the melt volume is increased up to 20% due to decompression. Melt has the tendency to accumulate at the top of the plume head, forming diapirs and initiating small-scale convection when the plume reaches the base of the lithosphere. Together with the introduced unstable, high-density material produced by freezing of melt, this provides an efficient mechanism to thin the lithosphere above plume heads.
In summary, this thesis shows that mantle plumes are more complex than previously considered, and linking the scales and coupling the physics of different processes occurring in mantle plumes can provide insights into how mantle plumes are influenced by chemical heterogeneities, interact with the lithosphere and global mantle flow, and are affected by melting and melt migration. Including these complexities in geodynamic models shows that plumes can also have broad plume tails, might produce only negligible surface uplift, can generate one or several volcanic island chains in interaction with a mid–ocean ridge, and can magmatically thin the lithosphere.
Mujeres de apocalipsis
(2016)
Mujeres del Apocalipsis propone nuevas lecturas de género en relación a las mujeres piadosas que habitaron Nueva España en el siglo XVIII. El estudio sebasa en un corpus de los archivos de sus procesos inquisitoriales, mucho de ellos aún indéditos. Estas mujeres ganaron libertad y accedieon a una parcial autonomía en el mundo colonial. A través de su lectura, se descubren las estrategías tácticas a través de las cuales las beatas pactaron una nueva forma de se mujer en aquella era.
Die vorliegende Arbeit befasst sich mit Führungsverhalten im öffentlichen Sektor sowie mit Einflussfaktoren auf dieses Führungsverhalten. Hierzu wurde eine Taxonomie, bestehend aus sechs Metakategorien von Führungsverhalten, entwickelt. Die Metakategorien umfassen Aufgaben-, Beziehungs-, Veränderungs-, Außen-, Ethik- und Sachbearbeitungsorientierung. Eine Analyse von Umfragedaten, die für diese Arbeit bei Mitarbeitern und unteren Führungskräften dreier Behörden erhoben wurden, zeigt, dass diese Taxonomie sehr gut geeignet ist, die Führungsrealität in der öffentlichen Verwaltung abzubilden.
Eine deskriptive Auswertung der Daten zeigt außerdem, dass es eine relativ große Differenz zwischen der Selbsteinschätzung der Führungskräfte und der Fremdeinschätzung durch ihre Mitarbeiter gibt. Diese Differenz ist bei der Beziehungs- und Veränderungsorientierung besonders hoch.
Der deskriptiven Auswertung schließt sich eine Analyse von Einflussfaktoren auf das Führungsverhalten an. Die Einflussfaktoren können den vier Kategorien "Charakteristika und Eigenschaften der Führungskräfte", "Erwartungen und Interesse von Vorgesetzten", "Charakteristika und Einstellungen von Geführten" und "Managementinstrumente und -rahmenbedingungen" zugeordnet werden.
Eine Analyse mit Hilfe von hierarchischen linearen Modellen zeigt, dass vor allem die Führungsmotivation und die Managementorientierung der Führungskräfte, die Gemeinwohlorientierung und die Art der Aufgabe der Geführten sowie die strategische Führungskräfteauswahl und die Leistungsmessung durch die Führungskräfte anhand konkreter Ziele einen Einfluss auf das Führungsverhalten haben.
Die Ergebnisse dieser Arbeit ergänzen die Literatur zu Führungsverhalten im öffentlichen Sektor um die Perspektive der Einflussfaktoren auf das Führungsverhalten und leisten zusätzlich mit Hilfe der verwendeten Taxonomie einen Beitrag zur theoretischen Diskussion von Führungsverhalten in der Public-Management-Forschung. Darüber hinaus bieten die gewonnenen Erkenntnisse der Verwaltungspraxis Hinweise zu relevanten Einflussfaktoren auf das Führungsverhalten sowie auf beachtliche Differenzen zwischen Selbst- und Fremdwahrnehmung des Führungsverhaltens.
In recent years, entire industries and their participants have been affected by disruptive technologies, resulting in dramatic market changes and challenges to firm’s business logic and thus their business models (BMs). Firms from mature industries are increasingly realizing that BMs that worked successfully for years have become insufficient to stay on track in today’s “move fast and break things” economy. Firms must scrutinize the core logic that informs how they do business, which means exploring novel ways to engage customers and get them to pay. This can lead to a complete renewal of existing BMs or innovating completely new BMs.
BMs have emerged as a popular object of research within the last decade. Despite the popularity of the BM, the theoretical and empirical foundation underlying the concept is still weak. In particular, the innovation process for BMs has been developed and implemented in firms, but understanding of the mechanisms behind it is still lacking. Business model innovation (BMI) is a complex and challenging management task that requires more than just novel ideas. Systematic studies to generate a better understanding of BMI and support incumbents with appropriate concepts to improve BMI development are in short supply. Further, there is a lack of knowledge about appropriate research practices for studying BMI and generating valid data sets in order to meet expectations in both practice and academia.
This paper-based dissertation aims to contribute to research practice in the field of BM and BMI and foster better understanding of the BM concept and BMI processes in incumbent firms from mature industries. The overall dissertation presents three main results. The first result is a new perspective, or the systems thinking view, on the BM and BMI. With the systems thinking view, the fuzzy BM concept is clearly structured and a BMI framework is proposed. The second result is a new research strategy for studying BMI. After analyzing current research practice in the areas of BMs and BMI, it is obvious that there is a need for better research on BMs and BMI in terms of accuracy, transparency, and practical orientation. Thus, the action case study approach combined with abductive methodology is proposed and proven in the research setting of this thesis. The third result stems from three action case studies in incumbent firms from mature industries employed to study how BMI occurs in practice. The new insights and knowledge gained from the action case studies help to explain BMI in such industries and increase understanding of the core of these processes.
By studying these issues, the articles complied in this thesis contribute conceptually and empirically to the recently consolidated but still increasing literature on the BM and BMI. The conclusions and implications made are intended to foster further research and improve managerial practices for achieving BMI in a dramatically changing business environment.
In the past, floods were basically managed by flood control mechanisms. The focus was set on the reduction of flood hazard. The potential consequences were of minor interest. Nowadays river flooding is increasingly seen from the risk perspective, including possible consequences. Moreover, the large-scale picture of flood risk became increasingly important for disaster management planning, national risk developments and the (re-) insurance industry. Therefore, it is widely accepted that risk-orientated flood management ap-proaches at the basin-scale are needed. However, large-scale flood risk assessment methods for areas of several 10,000 km² are still in early stages. Traditional flood risk assessments are performed reach wise, assuming constant probabilities for the entire reach or basin. This might be helpful on a local basis, but where large-scale patterns are important this approach is of limited use. Assuming a T-year flood (e.g. 100 years) for the entire river network is unrealistic and would lead to an overestimation of flood risk at the large scale. Due to the lack of damage data, additionally, the probability of peak discharge or rainfall is usually used as proxy for damage probability to derive flood risk. With a continuous and long term simulation of the entire flood risk chain, the spatial variability of probabilities could be consider and flood risk could be directly derived from damage data in a consistent way.
The objective of this study is the development and application of a full flood risk chain, appropriate for the large scale and based on long term and continuous simulation. The novel approach of ‘derived flood risk based on continuous simulations’ is introduced, where the synthetic discharge time series is used as input into flood impact models and flood risk is directly derived from the resulting synthetic damage time series.
The bottleneck at this scale is the hydrodynamic simu-lation. To find suitable hydrodynamic approaches for the large-scale a benchmark study with simplified 2D hydrodynamic models was performed. A raster-based approach with inertia formulation and a relatively high resolution of 100 m in combination with a fast 1D channel routing model was chosen.
To investigate the suitability of the continuous simulation of a full flood risk chain for the large scale, all model parts were integrated into a new framework, the Regional Flood Model (RFM). RFM consists of the hydrological model SWIM, a 1D hydrodynamic river network model, a 2D raster based inundation model and the flood loss model FELMOps+r. Subsequently, the model chain was applied to the Elbe catchment, one of the largest catchments in Germany. For the proof-of-concept, a continuous simulation was per-formed for the period of 1990-2003. Results were evaluated / validated as far as possible with available observed data in this period. Although each model part introduced its own uncertainties, results and runtime were generally found to be adequate for the purpose of continuous simulation at the large catchment scale.
Finally, RFM was applied to a meso-scale catchment in the east of Germany to firstly perform a flood risk assessment with the novel approach of ‘derived flood risk assessment based on continuous simulations’. Therefore, RFM was driven by long term synthetic meteorological input data generated by a weather generator. Thereby, a virtual time series of climate data of 100 x 100 years was generated and served as input to RFM providing subsequent 100 x 100 years of spatially consistent river discharge series, inundation patterns and damage values. On this basis, flood risk curves and expected annual damage could be derived directly from damage data, providing a large-scale picture of flood risk. In contrast to traditional flood risk analysis, where homogenous return periods are assumed for the entire basin, the presented approach provides a coherent large-scale picture of flood risk. The spatial variability of occurrence probability is respected. Additionally, data and methods are consistent. Catchment and floodplain processes are repre-sented in a holistic way. Antecedent catchment conditions are implicitly taken into account, as well as physical processes like storage effects, flood attenuation or channel–floodplain interactions and related damage influencing effects. Finally, the simulation of a virtual period of 100 x 100 years and consequently large data set on flood loss events enabled the calculation of flood risk directly from damage distributions. Problems associated with the transfer of probabilities in rainfall or peak runoff to probabilities in damage, as often used in traditional approaches, are bypassed.
RFM and the ‘derived flood risk approach based on continuous simulations’ has the potential to provide flood risk statements for national planning, re-insurance aspects or other questions where spatially consistent, large-scale assessments are required.
In this dissertation, an electric field-assisted method was developed and applied to achieve immobilization and alignment of biomolecules on metal electrodes in a simple one-step experiment. Neither modifications of the biomolecule nor of the electrodes were needed. The two major electrokinetic effects that lead to molecule motion in the chosen electrode configurations used were identified as dielectrophoresis and AC electroosmotic flow. To minimize AC electroosmotic flow, a new 3D electrode configuration was designed. Thus, the influence of experimental parameters on the dielectrophoretic force and the associated molecule movement could be studied. Permanent immobilization of proteins was examined and quantified absolutely using an atomic force microscope. By measuring the volumes of the immobilized protein deposits, a maximal number of proteins contained therein was calculated. This was possible since the proteins adhered to the tungsten electrodes even after switching off the electric field. The permanent immobilization of functional proteins on surfaces or electrodes is one crucial prerequisite for the fabrication of biosensors.
Furthermore, the biofunctionality of the proteins must be retained after immobilization. Due to the chemical or physical modifications on the proteins caused by immobilization, their biofunctionality is sometimes hampered. The activity of dielectrophoretically immobilized proteins, however, was proven here for an enzyme for the first time. The enzyme horseradish peroxidase was used exemplarily, and its activity was demonstrated with the oxidation of dihydrorhodamine 123, a non-fluorescent precursor of the fluorescence dye rhodamine 123.
Molecular alignment and immobilization - reversible and permanent - was achieved under the influence of inhomogeneous AC electric fields. For orientational investigations, a fluorescence microscope setup, a reliable experimental procedure and an evaluation protocol were developed and validated using self-made control samples of aligned acridine orange molecules in a liquid crystal.
Lambda-DNA strands were stretched and aligned temporarily between adjacent interdigitated electrodes, and the orientation of PicoGreen molecules, which intercalate into the DNA strands, was determined. Similarly, the aligned immobilization of enhanced Green Fluorescent Protein was demonstrated exploiting the protein's fluorescence and structural properties. For this protein, the angle of the chromophore with respect to the protein's geometrical axis was determined in good agreement with X-ray crystallographic data. Permanent immobilization with simultaneous alignment of the proteins was achieved along the edges, tips and on the surface of interdigitated electrodes. This was the first demonstration of aligned immobilization of proteins by electric fields.
Thus, the presented electric field-assisted immobilization method is promising with regard to enhanced antibody binding capacities and enzymatic activities, which is a requirement for industrial biosensor production, as well as for general interaction studies of proteins.
In many statistical applications, the aim is to model the relationship between covariates and some outcomes. A choice of the appropriate model depends on the outcome and the research objectives, such as linear models for continuous outcomes, logistic models for binary outcomes and the Cox model for time-to-event data. In epidemiological, medical, biological, societal and economic studies, the logistic regression is widely used to describe the relationship between a response variable as binary outcome and explanatory variables as a set of covariates. However, epidemiologic cohort studies are quite expensive regarding data management since following up a large number of individuals takes long time. Therefore, the case-cohort design is applied to reduce cost and time for data collection. The case-cohort sampling collects a small random sample from the entire cohort, which is called subcohort. The advantage of this design is that the covariate and follow-up data are recorded only on the subcohort and all cases (all members of the cohort who develop the event of interest during the follow-up process).
In this thesis, we investigate the estimation in the logistic model for case-cohort design. First, a model with a binary response and a binary covariate is considered. The maximum likelihood estimator (MLE) is described and its asymptotic properties are established. An estimator for the asymptotic variance of the estimator based on the maximum likelihood approach is proposed; this estimator differs slightly from the estimator introduced by Prentice (1986). Simulation results for several proportions of the subcohort show that the proposed estimator gives lower empirical bias and empirical variance than Prentice's estimator.
Then the MLE in the logistic regression with discrete covariate under case-cohort design is studied. Here the approach of the binary covariate model is extended. Proving asymptotic normality of estimators, standard errors for the estimators can be derived. The simulation study demonstrates the estimation procedure of the logistic regression model with a one-dimensional discrete covariate. Simulation results for several proportions of the subcohort and different choices of the underlying parameters indicate that the estimator developed here performs reasonably well. Moreover, the comparison between theoretical values and simulation results of the asymptotic variance of estimator is presented.
Clearly, the logistic regression is sufficient for the binary outcome refers to be available for all subjects and for a fixed time interval. Nevertheless, in practice, the observations in clinical trials are frequently collected for different time periods and subjects may drop out or relapse from other causes during follow-up. Hence, the logistic regression is not appropriate for incomplete follow-up data; for example, an individual drops out of the study before the end of data collection or an individual has not occurred the event of interest for the duration of the study. These observations are called censored observations. The survival analysis is necessary to solve these problems. Moreover, the time to the occurence of the event of interest is taken into account. The Cox model has been widely used in survival analysis, which can effectively handle the censored data. Cox (1972) proposed the model which is focused on the hazard function. The Cox model is assumed to be
λ(t|x) = λ0(t) exp(β^Tx)
where λ0(t) is an unspecified baseline hazard at time t and X is the vector of covariates, β is a p-dimensional vector of coefficient.
In this thesis, the Cox model is considered under the view point of experimental design. The estimability of the parameter β0 in the Cox model, where β0 denotes the true value of β, and the choice of optimal covariates are investigated. We give new representations of the observed information matrix In(β) and extend results for the Cox model of Andersen and Gill (1982). In this way conditions for the estimability of β0 are formulated. Under some regularity conditions, ∑ is the inverse of the asymptotic variance matrix of the MPLE of β0 in the Cox model and then some properties of the asymptotic variance matrix of the MPLE are highlighted. Based on the results of asymptotic estimability, the calculation of local optimal covariates is considered and shown in examples. In a sensitivity analysis, the efficiency of given covariates is calculated. For neighborhoods of the exponential models, the efficiencies have then been found. It is appeared that for fixed parameters β0, the efficiencies do not change very much for different baseline hazard functions. Some proposals for applicable optimal covariates and a calculation procedure for finding optimal covariates are discussed.
Furthermore, the extension of the Cox model where time-dependent coefficient are allowed, is investigated. In this situation, the maximum local partial likelihood estimator for estimating the coefficient function β(·) is described. Based on this estimator, we formulate a new test procedure for testing, whether a one-dimensional coefficient function β(·) has a prespecified parametric form, say β(·; ϑ). The score function derived from the local constant partial likelihood function at d distinct grid points is considered. It is shown that the distribution of the properly standardized quadratic form of this d-dimensional vector under the null hypothesis tends to a Chi-squared distribution. Moreover, the limit statement remains true when replacing the unknown ϑ0 by the MPLE in the hypothetical model and an asymptotic α-test is given by the quantiles or p-values of the limiting Chi-squared distribution. Finally, we propose a bootstrap version of this test. The bootstrap test is only defined for the special case of testing whether the coefficient function is constant. A simulation study illustrates the behavior of the bootstrap test under the null hypothesis and a special alternative. It gives quite good results for the chosen underlying model.
References
P. K. Andersen and R. D. Gill. Cox's regression model for counting processes: a large samplestudy. Ann. Statist., 10(4):1100{1120, 1982.
D. R. Cox. Regression models and life-tables. J. Roy. Statist. Soc. Ser. B, 34:187{220, 1972.
R. L. Prentice. A case-cohort design for epidemiologic cohort studies and disease prevention trials. Biometrika, 73(1):1{11, 1986.
Exhaustivity
(2016)
The dissertation proposes an answer to the question of how to model exhaustive inferences and what the meaning of the linguistic material that triggers these inferences is. In particular, it deals with the semantics of exclusive particles, clefts, and progressive aspect in Ga, an under-researched language spoken in Ghana. Based on new data coming from the author’s original fieldwork in Accra, the thesis points to a previously unattested variation in the semantics of exclusives in a cross-linguistic perspective, analyzes the connections between exhaustive interpretation triggered by clefts and the aspectual interpretation of the sentence, and identifies a cross-categorial definite determiner. By that it sheds new light on several exhaustivity-related phenomena in both the nominal and the verbal domain and shows that both domains are closely connected.
Im Verlauf dieser Arbeit sind Blockcopolymere verschiedener Ladung auf Basis von PEO mit hohen Molekulargewichten durch lebendende freie radikalische Polymerisation hergestellt worden. Die Polymere sind einfach im Grammmaßstab herstellbar. Sie zeigen sowohl einen großen Einfluss auf die Nukleation als auch auf die Auflösung von Calciumphosphat. Gleichwohl scheint das Vorhandensein von positiven Gruppen (Kationen, Ampholyten und Betainen) keinen dramatischen Einfluss auf die Nukleation zu haben.
So verursachen Polymere mit positiven Ladungen die gleiche Retentionwirkung wie solche, die ausschließlich anionische Gruppen enthalten. Aus der Verwendung der kationischen, ampholytischen und betainischen Copolymere resultiert allerdings eine andersartige Morphologie der Niederschläge, als aus der Verwendung der Anionischen hervorgeht. Bei der Stabilisierung einer HAP-Oberfläche setzt sich dieser Trend fort, das heißt, rein anionische Copolymere wirken stärker stabilisierend als solche, die positive Ladungen enthalten. Durch Inkubation von menschlichem Zahnschmelz mit anionischen Copolymeren konnte gezeigt werden, dass die Biofilmbildung verglichen mit einer unbehandelten Zahnoberfläche eingeschränkt abläuft. All dies macht die Polymere zu interessanten Additiven für Zahnpflegeprodukte.
Zusätzlich konnten auf Basis dieser rein anionischen Copolymere Polymerbürsten, ebenfalls über lebendende freie radikalische Polymerisation, hergestellt werden. Diese zeichnen sich durch einen großen Einfluss auf die Kristallphase aus und bilden mit dem CHAP des AB-Types das Material, welches auch in Knochen und Zähnen vorkommt. Erste Cytotoxizitätstests lassen auf das große Potential dieser Polymerbürsten für Beschichtungen in der Medizintechnik schließen.
The aim of this work is the evaluation of the geothermal potential of Luxembourg. The approach consists in a joint interpretation of different types of information necessary for a first rather qualitative assessment of deep geothermal reservoirs in Luxembourg and the adjoining regions in the surrounding countries of Belgium, France and Germany. For the identification of geothermal reservoirs by exploration, geological, thermal, hydrogeological and structural data are necessary. Until recently, however, reliable information about the thermal field and the regional geology, and thus about potential geothermal reservoirs, was lacking. Before a proper evaluation of the geothermal potential can be performed, a comprehensive survey of the geology and an assessment of the thermal field are required.
As a first step, the geology and basin structure of the Mesozoic Trier–Luxembourg Basin (TLB) is reviewed and updated using recently published information on the geology and structures as well as borehole data available in Luxembourg and the adjoining regions. A Bouguer map is used to get insight in the depth, morphology and structures in the Variscan basement buried beneath the Trier–Luxembourg Basin. The geological section of the old Cessange borehole is reinterpreted and provides, in combination with the available borehole data, consistent information for the production of isopach maps. The latter visualize the synsedimentary evolution of the Trier–Luxembourg Basin. Complementary, basin-wide cross sections illustrate the evolution and structure of the Trier–Luxembourg Basin. The knowledge gained does not support the old concept of the Weilerbach Mulde. The basin-wide cross sections, as well as the structural and sedimentological observations in the Trier–Luxembourg Basin suggest that the latter probably formed above a zone of weakness related to a buried Rotliegend graben. The inferred graben structure designated by SE-Luxembourg Graben (SELG) is located in direct southwestern continuation of the Wittlicher Rotliegend-Senke.
The lack of deep boreholes and subsurface temperature prognosis at depth is circumnavigated by using thermal modelling for inferring the geothermal resource at depth. For this approach, profound structural, geological and petrophysical input data are required. Conceptual geological cross sections encompassing the entire crust are constructed and further simplified and extended to lithospheric scale for their utilization as thermal models. The 2-D steady state and conductive models are parameterized by means of measured petrophysical properties including thermal conductivity, radiogenic heat production and density. A surface heat flow of 75 ∓ 7 (2δ) mW m–2 for verification of the thermal models could be determined in the area. The models are further constrained by the geophysically-estimated depth of the lithosphere–asthenosphere boundary (LAB) defined by the 1300 °C isotherm. A LAB depth of 100 km, as seismically derived for the Ardennes, provides the best fit with the measured surface heat flow. The resulting mantle heat flow amounts to ∼40 mW m–2. Modelled temperatures are in the range of 120–125 °C at 5 km depth and of 600–650 °C at the crust/mantle discontinuity (Moho). Possible thermal consequences of the 10–20 Ma old Eifel plume, which apparently caused upwelling of the asthenospheric mantle to 50–60 km depth, were modelled in a steady-state thermal scenario resulting in a surface heat flow of at least 91 mW m–2 (for the plume top at 60 km) in the Eifel region. Available surface heat-flow values are significantly lower (65–80 mW m–2) and indicate that the plume-related heating has not yet entirely reached the surface.
Once conceptual geological models are established and the thermal regime is assessed, the geothermal potential of Luxembourg and the surrounding areas is evaluated by additional consideration of the hydrogeology, the stress field and tectonically active regions. On the one hand, low-enthalpy hydrothermal reservoirs in Mesozoic reservoirs in the Trier–Luxembourg Embayment (TLE) are considered. On the other hand, petrothermal reservoirs in the Lower Devonian basement of the Ardennes and Eifel regions are considered for exploitation by Enhanced/Engineered Geothermal Systems (EGS). Among the Mesozoic aquifers, the Buntsandstein aquifer characterized by temperatures of up to 50 °C is a suitable hydrothermal reservoir that may be exploited by means of heat pumps or provide direct heat for various applications. The most promising area is the zone of the SE–Luxembourg Graben. The aquifer is warmest underneath the upper Alzette River valley and the limestone plateau in Lorraine, where the Buntsandstein aquifer lies below a thick Mesozoic cover. At the base of an inferred Rotliegend graben in the same area, temperatures of up to 75 °C are expected. However, geological and hydraulic conditions are uncertain. In the Lower Devonian basement, thick sandstone-/quartzite-rich formations with temperatures >90 °C are expected at depths >3.5 km and likely offer the possibility of direct heat use. The setting of the Südeifel (South Eifel) region, including the Müllerthal region near Echternach, as a tectonically active zone may offer the possibility of deep hydrothermal reservoirs in the fractured Lower Devonian basement. Based on the recent findings about the structure of the Trier–Luxembourg Basin, the new concept presents the Müllerthal–Südeifel Depression (MSD) as a Cenozoic structure that remains tectonically active and subsiding, and therefore is relevant for geothermal exploration. Beyond direct use of geothermal heat, the expected modest temperatures at 5 km depth (about 120 °C) and increased permeability by EGS in the quartzite-rich Lochkovian could prospectively enable combined geothermal heat production and power generation in Luxembourg and the western realm of the Eifel region.