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Institute
- Institut für Biochemie und Biologie (22)
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Mit der Liberalisierung des Strommarkts, den unsicheren Aussichten in der Klimapolitik und stark schwankenden Preisen bei Brennstoffen, Emissionsrechten und Kraftwerkskomponenten hat bei Kraftwerksinvestitionen das Risikomanagement an Bedeutung gewonnen. Dies äußert sich im vermehrten Einsatz probabilistischer Verfahren. Insbesondere bei regulativen Risiken liefert der klassische, häufigkeitsbasierte Wahrscheinlichkeitsbegriff aber keine Handhabe zur Risikoquantifizierung. In dieser Arbeit werden Kraftwerksinvestitionen und -portfolien in Deutschland mit Methoden des Bayes'schen Risikomanagements bewertet. Die Bayes'sche Denkschule begreift Wahrscheinlichkeit als persönliches Maß für Unsicherheit. Wahrscheinlichkeiten können auch ohne statistische Datenanalyse allein mit Expertenbefragungen gewonnen werden. Das Zusammenwirken unsicherer Werttreiber wurde mit einem probabilistischen DCF-Modell (Discounted Cash Flow-Modell) spezifiziert und in ein Einflussdiagramm mit etwa 1200 Objekten umgesetzt. Da der Überwälzungsgrad von Brennstoff- und CO2-Kosten und damit die Höhe der von den Kraftwerken erwirtschafteten Deckungsbeiträge im Wettbewerb bestimmt werden, reicht eine einzelwirtschaftliche Betrachtung der Kraftwerke nicht aus. Strompreise und Auslastungen werden mit Heuristiken anhand der individuellen Position der Kraftwerke in der Merit Order bestimmt, d.h. anhand der nach kurzfristigen Grenzkosten gestaffelten Einsatzreihenfolge. Dazu wurden 113 thermische Großkraftwerke aus Deutschland in einer Merit Order vereinigt. Das Modell liefert Wahrscheinlichkeitsverteilungen für zentrale Größen wie Kapitalwerte von Bestandsportfolien sowie Stromgestehungskosten und Kapitalwerte von Einzelinvestitionen (Steinkohle- und Braunkohlekraftwerke mit und ohne CO2-Abscheidung sowie GuD-Kraftwerke). Der Wert der Bestandsportfolien von RWE, E.ON, EnBW und Vattenfall wird primär durch die Beiträge der Braunkohle- und Atomkraftwerke bestimmt. Erstaunlicherweise schlägt sich der Emissionshandel nicht in Verlusten nieder. Dies liegt einerseits an den Zusatzgewinnen der Atomkraftwerke, andererseits an den bis 2012 gratis zugeteilten Emissionsrechten, welche hohe Windfall-Profite generieren. Dadurch erweist sich der Emissionshandel in seiner konkreten Ausgestaltung insgesamt als gewinnbringendes Geschäft. Über die Restlaufzeit der Bestandskraftwerke resultiert ab 2008 aus der Einführung des Emissionshandels ein Barwertvorteil von insgesamt 8,6 Mrd. €. In ähnlicher Dimension liegen die Barwertvorteile aus der 2009 von der Bundesregierung in Aussicht gestellten Laufzeitverlängerung für Atomkraftwerke. Bei einer achtjährigen Laufzeitverlängerung ergäben sich je nach CO2-Preisniveau Barwertvorteile von 8 bis 15 Mrd. €. Mit höheren CO2-Preisen und Laufzeitverlängerungen von bis zu 28 Jahren würden 25 Mrd. € oder mehr zusätzlich anfallen. Langfristig erscheint fraglich, ob unter dem gegenwärtigen Marktdesign noch Anreize für Investitionen in fossile Kraftwerke gegeben sind. Zu Beginn der NAP 2-Periode noch rentable Investitionen in Braunkohle- und GuD-Kraftwerke werden mit der auslaufenden Gratiszuteilung von Emissionsrechten zunehmend unrentabler. Die Rentabilität wird durch Strommarkteffekte der erneuerbaren Energien und ausscheidender alter Gas- und Ölkraftwerke stetig weiter untergraben. Steinkohlekraftwerke erweisen sich selbst mit anfänglicher Gratiszuteilung als riskante Investition. Die festgestellten Anreizprobleme für Neuinvestitionen sollten jedoch nicht dem Emissionshandel zugeschrieben werden, sondern resultieren aus den an Grenzkosten orientierten Strompreisen. Das Anreizproblem ist allerdings bei moderaten CO2-Preisen am größten. Es gilt auch für Kraftwerke mit CO2-Abscheidung: Obwohl die erwarteten Vermeidungskosten für CCS-Kraftwerke gegenüber konventionellen Kohlekraftwerken im Jahr 2025 auf 25 €/t CO2 (Braunkohle) bzw. 38,5 €/t CO2 (Steinkohle) geschätzt werden, wird ihr Bau erst ab CO2-Preisen von 50 bzw. 77 €/t CO2 rentabel. Ob und welche Kraftwerksinvestitionen sich langfristig rechnen, wird letztlich aber politisch entschieden und ist selbst unter stark idealisierten Bedingungen kaum vorhersagbar.
Die gewaltigen Strukturveränderungen im Bereich des Gesundheitswesens, die in den letzten Jahren bereits erfolgten und die, die noch bevorstehen, zwingen Unternehmen, mit geplanten und gesteuerten Veränderungsprozessen die Voraussetzungen für eine kontinuierliche Anpassung an die neuen Gegebenheiten zu schaffen und somit ihre Zukunftsfähigkeit sicherzustellen. Vor diesem Hintergrund wird gezeigt, wie das Excellence-Modell der EFQM als Instrument für Veränderungsprozesse eingesetzt werden kann und es geeignet ist, Veränderungsziele zu definieren und die Zielerreichung zu bewerten. Referenzobjekt der Fallstudienanalyse, die einen Zeitraum von 13 Jahren umfasst, ist der Medizinische Dienst der Krankenversicherung Rheinland-Pfalz. Neben der Analyse und Darstellung von theoretischen Grundlagen wird an einem Unternehmen des Gesundheitswesens beispielhaft gezeigt, wie die Umsetzung in der Praxis unter Einsatz des EFQM-Modells erfolgen kann. Da das EFQM-Modell mit seiner Systematik unternehmensunabhängig eingesetzt werden kann, sind Lern- und Übertragungsmöglichkeiten strukturiert möglich. Es wird der Nachweis erbracht, dass sich das EFQM-Modell im Rahmen eines Management- und Qualitätssteue-rungsmodells als Universalmethode nutzen lässt, sofern das Management über die Kompe-tenz branchenspezifischer Anpassung verfügt. Auf dem Weg zu organisatorischer Excel-lence wird gezielt an Planungs- und Prognosetechniken des strategischen Managements (SWOT, Szenario-Analyse, Portfolio-Analyse) angeknüpft und auf das VRIO-Paradigma des Resource-based View Bezug genommen. Das EFQM-Modell wird dem Stresstest des ressourcenstrategischen Ansatzes unterzogen, um so zu zeigen, dass es sich beim EFQM-Modell um ein einzigartiges, schwer imitierbares, kaum zu substituierendes, organisatorisch verankertes und kundennutzen-stiftendes Er-folgspotenzial handeln kann. Die Arbeit liefert Impulse und konkrete Anregungen, die zu einem hohen managementprakti-schen Erkenntniszuwachs für den erfolgreichen Umgang mit dem EFQM-Modell und dem Einsatz von Qualitätsmanagementsystemen führen können.
The aim of this thesis is the quantum dynamical study of two examples of scanning tunneling microscope (STM)-controllable, Si(100)(2x1) surface-mounted switches of atomic and molecular scale. The first example considers the switching of single H-atoms between two dangling-bond chemisorption sites on a Si-dimer of the Si(100) surface (Grey et al., 1996). The second system examines the conformational switching of single 1,5-cyclooctadiene molecules chemisorbed on the Si(100) surface (Nacci et al., 2008). The temporal dynamics are provided by the propagation of the density matrix in time via an according set of equations of motion (EQM). The latter are based on the open-system density matrix theory in Lindblad form. First order perturbation theory is used to evaluate those transition rates between vibrational levels of the system part. In order to account for interactions with the surface phonons, two different dissipative models are used, namely the bilinear, harmonic and the Ohmic bath model. IET-induced vibrational transitions in the system are due to the dipole- and the resonance-mechanism. A single surface approach is used to study the influence of dipole scattering and resonance scattering in the below-threshold regime. Further, a second electronic surface was included to study the resonance-induced switching in the above-threshold regime. Static properties of the adsorbate, e.g., potentials and dipole function and potentials, are obtained from quantum chemistry and used within the established quantum dynamical models.
Taking advantage of ATRP and using functionalized initiators, different functionalities were introduced in both α and ω chain-ends of synthetic polymers. These functionalized polymers could then go through modular synthetic pathways such as click cycloaddition (copper-catalyzed or copper-free) or amidation to couple synthetic polymers to other synthetic polymers, biomolecules or silica monoliths. Using this general strategy and designing these co/polymers so that they are thermoresponsive, yet bioinert and biocompatible with adjustable cloud point values (as it is the case in the present thesis), the whole generated system becomes "smart" and potentially applicable in different branches. The applications which were considered in the present thesis were in polymer post-functionalization (in situ functionalization of micellar aggregates with low and high molecular weight molecules), hydrophilic/hydrophobic tuning, chromatography and bioconjugation (enzyme thermoprecipitation and recovery, improvement of enzyme activity). Different α-functionalized co/polymers containing cholesterol moiety, aldehyde, t-Boc protected amine, TMS-protected alkyne and NHS-activated ester were designed and synthesized in this work.
The underlying motivation for the work carried out for this thesis was the growing need for more sustainable technologies. The aim was to synthesize a “palette” of functional nanomaterials using the established technique of hydrothermal carbonization (HTC). The incredible diversity of HTC was demonstrated together with small but steady advances in how HTC can be manipulated to tailor material properties for specific applications. Two main strategies were used to modify the materials obtained by HTC of glucose, a model precursor representing biomass. The first approach was the introduction of heteroatoms, or “doping” of the carbon framework. Sulfur was for the first time introduced as a dopant in hydrothermal carbon. The synthesis of sulfur and sulfur/nitrogen doped microspheres was presented whereby it was shown that the binding state of sulfur could be influenced by varying the type of sulfur source. Pyrolysis may additionally be used to tune the heteroatom binding states which move to more stable motifs with increasing pyrolysis temperature. Importantly, the presence of aromatic binding states in the as synthesized hydrothermal carbon allows for higher heteroatom retention levels after pyrolysis and hence more efficient use of dopant sources. In this regard, HTC may be considered as an “intermediate” step in the formation of conductive heteroatom doped carbon. To assess the novel hydrothermal carbons in terms of their potential for electrochemical applications, materials with defined nano-architectures and high surface areas were synthesized via templated, as well as template-free routes. Sulfur and/or nitrogen doped carbon hollow spheres (CHS) were synthesized using a polystyrene hard templating approach and doped carbon aerogels (CA) were synthesized using either the albumin directed or borax-mediated hydrothermal carbonization of glucose. Electrochemical testing showed that S/N dual doped CHS and aerogels derived via the albumin approach exhibited superior catalytic performance compared to solely nitrogen or sulfur doped counterparts in the oxygen reduction reaction (ORR) relevant to fuel cells. Using the borax mediated aerogel formation, nitrogen content and surface area could be tuned and a carbon aerogel was engineered to maximize electrochemical performance. The obtained sample exhibited drastically improved current densities compared to a platinum catalyst (but lower onset potential), as well as excellent long term stability. In the second approach HTC was carried out at elevated temperatures (550 °C) and pressure (50 bar), corresponding to the superheated vapor regime (htHTC). It was demonstrated that the carbon materials obtained via htHTC are distinct from those obtained via ltHTC and subsequent pyrolysis at 550 °C. No difference in htHTC-derived material properties could be observed between pentoses and hexoses. The material obtained from a polysaccharide exhibited a slightly lower degree of carbonization but was otherwise similar to the monosaccharide derived samples. It was shown that in addition to thermally induced carbonization at 550 °C, the SHV environment exhibits a catalytic effect on the carbonization process. The resulting materials are chemically inert (i.e. they contain a negligible amount of reactive functional groups) and possess low surface area and electronic conductivity which distinguishes them from carbon obtained from pyrolysis. Compared to the materials presented in the previous chapters on chemical modifications of hydrothermal carbon, this makes them ill-suited candidates for electronic applications like lithium ion batteries or electrocatalysts. However, htHTC derived materials could be interesting for applications that require chemical inertness but do not require specific electronic properties. The final section of this thesis therefore revisited the latex hard templating approach to synthesize carbon hollow spheres using htHTC. However, by using htHTC it was possible to carry out template removal in situ because the second heating step at 550 °C was above the polystyrene latex decomposition temperature. Preliminary tests showed that the CHS could be dispersed in an aqueous polystyrene latex without monomer penetrating into the hollow sphere voids. This leaves the stagnant air inside the CHS intact which in turn is promising for their application in heat and sound insulating coatings. Overall the work carried out in this thesis represents a noteworthy development in demonstrating the great potential of sustainable carbon materials.
In den letzten 20 Jahren sind Evaluationen Schritt für Schritt zu einem festen und gleichzeitig kontrovers diskutierten Bestandteil politischer Förderung geworden. Auf der Basis langjähriger Beobachtungen der Evaluationspraxis des Förderprogramms „Soziale Stadt“ zeigt dieses Buch zunächst, dass Evaluationstätigkeiten in Ministerien, Kommunalverwaltungen und Planungsbüros mit ganz unterschiedlichen Erwartungen, Herausforderungen, Widersprüchen und Irritationen verknüpft werden. Evaluationen werden dabei sowohl als Hoffnungsträger, als auch als Schreckgespenst gesehen. Der Autor nimmt diese Beobachtungen zum Anlass, den Umgang mit Evaluationen in politischen Organisationen kritisch zu hinterfragen und systematisch zu erklären. Reduziert auf die Frage „Wozu Evaluation?“ wird auf der Basis eines systemtheoretischen Zugangs erklärt, welche unterschiedlichen Funktionen Evaluationen in Organisationen erfüllen können. Vertiefend wird dabei auf organisationales Lernen, auf politische Steuerungslogik und auf die Notwendigkeit von Symbolisierungen eingegangen.
Agriculture is one of the most important human activities providing food and more agricultural goods for seven billion people around the world and is of special importance in sub-Saharan Africa. The majority of people depends on the agricultural sector for their livelihoods and will suffer from negative climate change impacts on agriculture until the middle and end of the 21st century, even more if weak governments, economic crises or violent conflicts endanger the countries’ food security. The impact of temperature increases and changing precipitation patterns on agricultural vegetation motivated this thesis in the first place. Analyzing the potentials of reducing negative climate change impacts by adapting crop management to changing climate is a second objective of the thesis. As a precondition for simulating climate change impacts on agricultural crops with a global crop model first the timing of sowing in the tropics was improved and validated as this is an important factor determining the length and timing of the crops´ development phases, the occurrence of water stress and final crop yield. Crop yields are projected to decline in most regions which is evident from the results of this thesis, but the uncertainties that exist in climate projections and in the efficiency of adaptation options because of political, economical or institutional obstacles have to be considered. The effect of temperature increases and changing precipitation patterns on crop yields can be analyzed separately and varies in space across the continent. Southern Africa is clearly the region most susceptible to climate change, especially to precipitation changes. The Sahel north of 13° N and parts of Eastern Africa with short growing seasons below 120 days and limited wet season precipitation of less than 500 mm are also vulnerable to precipitation changes while in most other part of East and Central Africa, in contrast, the effect of temperature increase on crops overbalances the precipitation effect and is most pronounced in a band stretching from Angola to Ethiopia in the 2060s. The results of this thesis confirm the findings from previous studies on the magnitude of climate change impact on crops in sub-Saharan Africa but beyond that helps to understand the drivers of these changes and the potential of certain management strategies for adaptation in more detail. Crop yield changes depend on the initial growing conditions, on the magnitude of climate change, and on the crop, cropping system and adaptive capacity of African farmers which is only now evident from this comprehensive study for sub-Saharan Africa. Furthermore this study improves the representation of tropical cropping systems in a global crop model and considers the major food crops cultivated in sub-Saharan Africa and climate change impacts throughout the continent.
Bad governance causes economic, social, developmental and environmental problems in many developing countries. Developing countries have adopted a number of reforms that have assisted in achieving good governance. The success of governance reform depends on the starting point of each country – what institutional arrangements exist at the out-set and who the people implementing reforms within the existing institutional framework are. This dissertation focuses on how formal institutions (laws and regulations) and informal institutions (culture, habit and conception) impact on good governance. Three characteristics central to good governance - transparency, participation and accountability are studied in the research.
A number of key findings were: Good governance in Hanoi and Berlin represent the two extremes of the scale, while governance in Berlin is almost at the top of the scale, governance in Hanoi is at the bottom. Good governance in Hanoi is still far from achieved. In Berlin, information about public policies, administrative services and public finance is available, reliable and understandable. People do not encounter any problems accessing public information. In Hanoi, however, public information is not easy to access. There are big differences between Hanoi and Berlin in the three forms of participation. While voting in Hanoi to elect local deputies is formal and forced, elections in Berlin are fair and free. The candidates in local elections in Berlin come from different parties, whereas the candidacy of local deputies in Hanoi is thoroughly controlled by the Fatherland Front. Even though the turnout of voters in local deputy elections is close to 90 percent in Hanoi, the legitimacy of both the elections and the process of representation is non-existent because the local deputy candidates are decided by the Communist Party.
The involvement of people in solving local problems is encouraged by the government in Berlin. The different initiatives include citizenry budget, citizen activity, citizen initiatives, etc. Individual citizens are free to participate either individually or through an association.
Lacking transparency and participation, the quality of public service in Hanoi is poor. Citizens seldom get their services on time as required by the regulations. Citizens who want to receive public services can bribe officials directly, use the power of relationships, or pay a third person – the mediator ("Cò" - in Vietnamese).
In contrast, public service delivery in Berlin follows the customer-orientated principle. The quality of service is high in relation to time and cost. Paying speed money, bribery and using relationships to gain preferential public service do not exist in Berlin.
Using the examples of Berlin and Hanoi, it is clear to see how transparency, participation and accountability are interconnected and influence each other. Without a free and fair election as well as participation of non-governmental organisations, civil organisations, and the media in political decision-making and public actions, it is hard to hold the Hanoi local government accountable.
The key differences in formal institutions (regulative and cognitive) between Berlin and Hanoi reflect the three main principles: rule of law vs. rule by law, pluralism vs. monopoly Party in politics and social market economy vs. market economy with socialist orientation.
In Berlin the logic of appropriateness and codes of conduct are respect for laws, respect of individual freedom and ideas and awareness of community development. People in Berlin take for granted that public services are delivered to them fairly. Ideas such as using money or relationships to shorten public administrative procedures do not exist in the mind of either public officials or citizens.
In Hanoi, under a weak formal framework of good governance, new values and norms (prosperity, achievement) generated in the economic transition interact with the habits of the centrally-planned economy (lying, dependence, passivity) and traditional values (hierarchy, harmony, family, collectivism) influence behaviours of those involved.
In Hanoi “doing the right thing” such as compliance with law doesn’t become “the way it is”.
The unintended consequence of the deliberate reform actions of the Party is the prevalence of corruption. The socialist orientation seems not to have been achieved as the gap between the rich and the poor has widened.
Good governance is not achievable if citizens and officials are concerned only with their self-interest. State and society depend on each other. Theoretically to achieve good governance in Hanoi, institutions (formal and informal) able to create good citizens, officials and deputies should be generated. Good citizens are good by habit rather than by nature.
The rule of law principle is necessary for the professional performance of local administrations and People’s Councils. When the rule of law is applied consistently, the room for informal institutions to function will be reduced.
Promoting good governance in Hanoi is dependent on the need and desire to change the government and people themselves. Good governance in Berlin can be seen to be the result of the efforts of the local government and citizens after a long period of development and continuous adjustment.
Institutional transformation is always a long and complicated process because the change in formal regulations as well as in the way they are implemented may meet strong resistance from the established practice. This study has attempted to point out the weaknesses of the institutions of Hanoi and has identified factors affecting future development towards good governance. But it is not easy to determine how long it will take to change the institutional setting of Hanoi in order to achieve good governance.
Eye movements are a powerful tool to examine cognitive processes. However, in most paradigms little is known about the dynamics present in sequences of saccades and fixations. In particular, the control of fixation durations has been widely neglected in most tasks. As a notable exception, both spatial and temporal aspects of eye-movement control have been thoroughly investigated during reading. There, the scientific discourse was dominated by three controversies, (i), the role of oculomotor vs. cognitive processing on eye-movement control, (ii) the serial vs. parallel processing of words, and, (iii), the control of fixation durations. The main purpose of this thesis was to investigate eye movements in tasks that require sequences of fixations and saccades. While reading phenomena served as a starting point, we examined eye guidance in non-reading tasks with the aim to identify general principles of eye-movement control. In addition, the investigation of eye movements in non-reading tasks helped refine our knowledge about eye-movement control during reading. Our approach included the investigation of eye movements in non-reading experiments as well as the evaluation and development of computational models. I present three main results : First, oculomotor phenomena during reading can also be observed in non-reading tasks (Chapter 2 & 4). Oculomotor processes determine the fixation position within an object. The fixation position, in turn, modulates both the next saccade target and the current fixation duration. Second, predicitions of eye-movement models based on sequential attention shifts were falsified (Chapter 3). In fact, our results suggest that distributed processing of multiple objects forms the basis of eye-movement control. Third, fixation durations are under asymmetric control (Chapter 4). While increasing processing demands immediately prolong fixation durations, decreasing processing demands reduce fixation durations only with a temporal delay. We propose a computational model ICAT to account for asymmetric control. In this model, an autonomous timer initiates saccades after random time intervals independent of ongoing processing. However, processing demands that are higher than expected inhibit the execution of the next saccade and, thereby, prolong the current fixation. On the other hand, lower processing demands will not affect the duration before the next saccade is executed. Since the autonomous timer adjusts to expected processing demands from fixation to fixation, a decrease in processing demands may lead to a temporally delayed reduction of fixation durations. In an extended version of ICAT, we evaluated its performance while simulating both temporal and spatial aspects of eye-movement control. The eye-movement phenomena investigated in this thesis have now been observed in a number of different tasks, which suggests that they represent general principles of eye guidance. I propose that distributed processing of the visual input forms the basis of eye-movement control, while fixation durations are controlled by the principles outlined in ICAT. In addition, oculomotor control contributes considerably to the variability observed in eye movements. Interpretations for the relation between eye movements and cognition strongly benefit from a precise understanding of this interplay.
Chemische und physikalische Eigenschaften von Polymeren können verschiedene Zelltypen unterschiedlich, z. B. hinsichtlich Adhärenz oder Funktionalität, beeinflussen. Die Elastizität eines Polymers beeinflusst vor allem, welche Zugkräfte eine Zelle gegenüber ihrem Substrat entwickeln kann. Das Zellverhalten wird dann über intrazelluläre Rückkopplungsmechanismen reguliert. Die Oberflächenladung und/oder Hydrophilie eines Polymers beeinflusst zunächst die Adsorption von Ionen, Proteinen und anderen Molekülen. Vor allem über die Zusammensetzung, Dichte und Konformation der adsorbierten Komponenten werden anschließend die Wechselwirkungen mit den Zellen vermittelt. Des Weiteren können verschiedene Zelltypen unterschiedliche membranassoziierte Proteine, Zucker und Lipide aufweisen, so dass Polymereigenschaften zellspezifische Effekte bewirken können. Für biotechnologische Anwendungen und für den Einsatz in der regenerativen Medizin gewinnen Polymere, die spezifische Zellreaktionen regulieren können, immer weiter an Bedeutung. Die Isolierung und Kultur von primären Keratinozyten ist noch immer anspruchsvoll und die adäquate Heilung von Hautwunden stellt eine fortwährende medizinische Herausforderung dar. Ein Polymer, das eine bevorzugte Adhärenz von Keratinozyten bei gleichzeitig verminderter Anheftung dermaler Fibroblasten ermöglicht, würde erhebliche Vorteile für den Einsatz in der Keratinozyten-Zellkultur und als Wundauflage bieten. Um den potentiell spezifischen Einfluss bestimmter Polymereigenschaften auf primäre humane Keratinozyten und dermale Fibroblasten zu untersuchen, wurde in der vorliegenden Arbeit ein Zellkultursystem für die Mono- und Cokultur beider Zelltypen entwickelt. Das Testsystem wurde als Screening konzipiert, um den Einfluss unterschiedlicher Polymereigenschaften in mehreren Abstufungen auf die Zellen zu untersuchen. Folgende Parameter wurden untersucht: 1. Vitalität und Dichte adhärenter und nicht-adhärierter Zellen, 2. Schädigung der Zellmembran, 3. selektive Adhärenz von Keratinozyten in Cokultur durch die spezifische immunzytochemische Färbung von Keratin14 und Vimentin. Für die Polymere mit variabler Elastizität wurden zusätzlich die Ablagerung extrazellulärer Matrixkomponenten und die Sekretion löslicher Faktoren durch die Zellen untersucht. Als Modellpolymere für die Variation der Elastizität wurden vernetzte Poly(n-butylacrylate) (cPnBA) verwendet, da deren Elastizität durch den Anteil des Vernetzers eingestellt werden kann. Auf dem weniger elastischen cPnBA zeigte sich in der Cokultur ein doppelt so hohes Verhältnis von Keratinozyten zu Fibroblasten wie auf dem elastischeren cPnBA, so dass ein leichter zellselektiver Effekt angenommen werden kann. Acrylnitril-basierte Copolymere wurden als Modellpolymere für die Variation der Oberflächenladung und Hydrophilie verwendet, da die Eigenschaften durch Art und molaren Anteil des Comonomers eingestellt werden können. Durch Variation des molaren Anteils der Comonomere mit positiver bzw. negativer Ladung, Methacrylsäure-2-aminoethylester-hydrochhlorid (AEMA) und N-3-Aminopropyl-methacrylamid-hydro-chlorid (APMA) bzw. Natriumsalz der 2-Methyl-2-propen-1-sulfonsäure (NaMAS), wurde der Anteil der positiven bzw. negativen Ladung im Copolymer variiert. Durch die Erhöhung des molaren Anteils des hydrophilen Comonomers N-Vinylpyrrolidon (NVP) wurde die Hydrophilie des Copolymers gesteigert. Die Erhöhung des molaren Anteils an positiv geladenem Comonomer AEMA im Copolymer führte tendenziell zu einer höheren Keratinozytendichte, wobei die Fibroblastendichte unverändert blieb. Durch die Erhöhung des molaren Anteils des positiv geladenen Comonomers APMA ergaben sich keine deutlichen Unterschiede in Dichte, Vitalität oder Selektivität der Zellen. Durch die stufenweise Erhöhung des molaren Anteils des negativ geladenen Comonomers NaMAS konnte, wie im Falle von AEMA, eine Tendenz zur verbesserten Keratinozytenadhärenz beobachtet werden. Die Steigerung der Hydrophilie der Copolymere führte sowohl für Keratinozyten als auch für Fibroblasten zu einer reduzierten Adhärenz und Vitalität. In der vorliegenden Doktorarbeit wurde ein Testverfahren etabliert, das die Untersuchung von primären humanen Keratinozyten und primären humanen Fibroblasten in Monokultur und Cokultur auf verschiedenen Polymeren ermöglicht. Die bisherigen Ergebnisse zeigen, dass sich durch die gezielte Modifizierung verschiedener Polymereigenschaften die Adhärenz und Vitalität beider Zelltypen beeinflussen lässt. Die Reduktion der Elastizität sowie die Erhöhung des molaren Anteils geladener Comonomere führten zu einer Zunahme der Keratinozytenadhärenz. Da die Fibroblasten unbeeinflusst blieben, zeigte sich für einige der untersuchten Polymere eine leichte Zellselektivität. Diese könnte durch die weitere Erhöhung der Steifigkeit oder des Anteils geladener Comonomere möglicherweise weiter gesteigert werden.
Die Entwicklung neuer Verfahren für die Rückführung von Palladium aus Altmaterialien, wie gebrauchten Autoabgaskatalysatoren, in den Stoffstromkreislauf ist sowohl aus ökologischer als auch ökonomischer Sicht erstrebenswert. In dieser Arbeit wurden neue Flüssig-Flüssig- und Fest-Flüssig-Extraktionsmittel entwickelt, mit denen Palladium(II) aus einer oxidierenden, salzsauren Laugungslösung, die neben Palladium auch Platin und Rhodium sowie zahlreiche unedle Metalle enthält, zurückgewonnen werden kann. Die neuen Extraktionsmittel ungesättigte monomere 1,2-Dithioether und oligomere Ligandenmischungen mit vicinalen Dithioether-Einheiten – sind im Gegensatz zu vielen in der Literatur aufgeführten Extraktionsmitteln hochselektiv. Aufgrund ihrer geometrischen und elektronischen Präorganisation bilden sie mit Palladium(II) stabile quadratisch-planare Chelatkomplexe. Für die Entwicklung des Flüssig-Flüssig-Extraktionsmittels wurde eine Reihe von ungesättigten 1,2-Dithioetherliganden dargestellt, welche auf einer starren 1,2-Dithioethen-Einheit, die in ein variierendes elektronenziehendes Grundgerüst eingebettet ist, basieren und polare Seitenketten besitzen. Neben der Bestimmung der Kristallstrukturen der Liganden und ihrer Palladiumdichlorid-Komplexe wurden die elektro- und photochemischen Eigenschaften, die Komplexstabilität und das Verhalten in Lösung untersucht. In Flüssig-Flüssig-Extraktionsuntersuchungen konnte gezeigt werden, dass einige der neuen Liganden industriell genutzten Extraktionsmitteln durch eine schnellere Einstellung des Extraktionsgleichgewichts überlegen sind. Anhand von Kriterien, die für eine industrielle Nutzbarkeit entscheidend sind, wie: guter Oxidationsbeständigkeit, einer hohen Extraktionsausbeute (auch bei hohen Salzsäurekonzentrationen der Speiselösung), schneller Extraktionskinetik und einer hohen Selektivität für Palladium(II) wurde aus der Reihe der sechs Liganden ein geeignetes Flüssig-Flüssig-Extraktionsmittel ausgewählt: 1,2-Bis(2-methoxyethylthio)benzen. Mit diesem wurde ein praxisnahes Flüssig-Flüssig-Extraktionssystem entwickelt. Nach der schrittweisen Adaption der wässrigen Phase von einer Modelllösung hin zu der oxidierenden, salzsauren Laugungslösung erfolgte die Auswahl eines geeigneten großtechnisch, einsetzbaren Lösemittels (1,2-Dichlorbenzen) und eines effizienten Reextraktionsmittels (0,5 M Thioharnstoff in 0,1 M HCl). Die hohe Palladium(II)-Selektivität dieses Flüssig-Flüssig-Extraktionssystems konnte verifiziert und seine Wiederverwendbarkeit und Praxistauglichkeit unter Beweis gestellt werden. Weiterhin wurde gezeigt, dass sich beim Kontakt mit oxidierenden Medien aus dem Dithioether 1,2-Bis(2-methoxyethylthio)benzen geringe Mengen des Thioethersulfoxids 1-(2-Methoxyethylsulfinyl)-2-(2-methoxyethylthio)benzen bilden. Dieses wird im sauren Milieu protoniert und beschleunigt die Extraktion wie ein Phasentransferkatalysator, ohne jedoch die Palladium(II)-Selektivität herabzusetzen. Die Kristallstruktur des Palladiumdichlorid-Komplexes des Tioethersulfoxids zeigt, dass der unprotonierte Ligand Palladium(II), analog zum Dithioether, über die chelatisierenden Schwefelatome koordiniert. Verschiedene Mischungen von Oligo(dithioether)-Liganden und der monomere Ligand 1,2-Bis(2-methoxyethylthio)benzen dienten als Extraktionsmittel für Fest-Flüssig-Extraktionsversuche mit SIRs (solvent impregnated resins) und wurden zu diesem Zweck auf hydrophilem Kieselgel und organophilem Amberlite® XAD 2 adsorbiert. Die Oligo(dithioether)-Liganden basieren auf 1,2-Dithiobenzen oder 1,2-Dithiomaleonitril-Einheiten, welche über Tris(oxyethylen)ethylen- oder Trimethylen-Brücken miteinander verknüpft sind. Mit Hilfe von Batch-Versuchen konnte gezeigt werden, dass sich strukturelle Unterschiede - wie die Art der chelatisierenden Einheit, die Art der verbrückenden Ketten und das Trägermaterial - auf die Extraktionsausbeuten, die Extraktionskinetik und die Beladungskapazität auswirken. Die kieselgelhaltigen SIRs stellen das Extraktionsgleichgewicht viel schneller ein als die Amberlite® XAD 2-haltigen. Jedoch bleiben die Extraktionsmittel auf Amberlite® XAD 2, im Gegensatz zu Kieselgel, dauerhaft haften. Im salzsauren Milieu sind die 1,2-Dithiobenzen-derivate besser als Extraktionsmittel geeignet als die 1,2-Dithiomaleonitrilderivate. In Säulenversuchen mit der oxidierenden, salzsauren Laugungslösung und wiederverwendbaren, mit 1,2-Dithiobenzenderivaten imprägnierten, Amberlite® XAD 2-haltigen SIRs zeigte sich, dass für die Realisierung hoher Beladungskapazitäten sehr geringe Pumpraten benötigt werden. Trotzdem konnte die gute Palladium(II)-Selektivität dieser Festphasenmaterialien demonstriert werden. Allerdings wurden in den Eluaten im Gegensatz zu den Eluaten, die aus Flüssig-Flüssig-Extraktion resultierten neben dem Palladium auch geringe Mengen an Platin, Aluminium, Eisen und Blei gefunden.
Aufstiege aus der Mittelschicht : soziale Aufstiegsmobilität von Haushalten zwischen 1984 und 2010
(2012)
Die Dissertation widmet sich den intragenerationalen Aufstiegsprozessen von Haushalten aus der Mittelschicht zu den Wohlhabenden. Intragenerationale Mobilitätsforschung wird bislang vor allem als arbeitsmarktbezogene Inidivualmobilität angesehen. Diese Dissertation erweitert den Ansatz auf die Ebene des Haushaltes. Dem liegt der Gedanke zugrunde, dass die soziale Position eines Individuums nicht allein durch sein Erwerbseinkommen determiniert wird. Ebenso entscheidend ist der Kontext des Haushaltes. Dieser bestimmt darüber, wie viele Personen zum Einkommen beitragen können und wie viele daran partizipieren. Weiterhin kommt der Haushaltsebene in Paar-Haushalten die Rolle des Aushandlungsortes zu. Hier wird über Familienplanung, Kinderwunsch und damit in Zusammenhang stehend auch über die Erwerbsbeteiligung der Partner entscheiden. Die vorliegende Dissertation untersucht diese Annahmen mithilfe von Daten des Sozioökonomischen Panels (SOEP) der Jahre 1984 bis 2010. Der Fokus liegt auf der Erwerbsbeteiligung und dem Bildungsniveau des Haushaltes, seiner Struktur, sowie dem Beruf des Haushaltsvorstandes. Es wird davon ausgegangen, dass dies die Hauptfaktoren sind, die über die finanziellen Möglichkeiten eines Haushaltes entscheiden. Ein weiterer Schwerpunkt der Arbeit liegt in der Berücksichtigung des historischen Kontextes, da anzunehmen ist, dass die oben benannten Faktoren sich und ihren Einfluss auf die Aufstiegsmöglichkeiten von Haushalten im historischen Verlauf verändert haben.
The potential increase in frequency and magnitude of extreme floods is currently discussed in terms of global warming and the intensification of the hydrological cycle. The profound knowledge of past natural variability of floods is of utmost importance in order to assess flood risk for the future. Since instrumental flood series cover only the last ~150 years, other approaches to reconstruct historical and pre-historical flood events are needed. Annually laminated (varved) lake sediments are meaningful natural geoarchives because they provide continuous records of environmental changes > 10000 years down to a seasonal resolution. Since lake basins additionally act as natural sediment traps, the riverine sediment supply, which is preserved as detrital event layers in the lake sediments, can be used as a proxy for extreme discharge events. Within my thesis I examined a ~ 8.50 m long sedimentary record from the pre-Alpine Lake Mondsee (Northeast European Alps), which covered the last 7000 years. This sediment record consists of calcite varves and intercalated detrital layers, which range in thickness from 0.05 to 32 mm. Detrital layer deposition was analysed by a combined method of microfacies analysis via thin sections, Scanning Electron Microscopy (SEM), μX-ray fluorescence (μXRF) scanning and magnetic susceptibility. This approach allows characterizing individual detrital event layers and assigning a corresponding input mechanism and catchment. Based on varve counting and controlled by 14C age dates, the main goals of this thesis are (i) to identify seasonal runoff processes, which lead to significant sediment supply from the catchment into the lake basin and (ii) to investigate flood frequency under changing climate boundary conditions. This thesis follows a line of different time slices, presenting an integrative approach linking instrumental and historical flood data from Lake Mondsee in order to evaluate the flood record inferred from Lake Mondsee sediments. The investigation of eleven short cores covering the last 100 years reveals the abundance of 12 detrital layers. Therein, two types of detrital layers are distinguished by grain size, geochemical composition and distribution pattern within the lake basin. Detrital layers, which are enriched in siliciclastic and dolomitic material, reveal sediment supply from the Flysch sediments and Northern Calcareous Alps into the lake basin. These layers are thicker in the northern lake basin (0.1-3.9 mm) and thinner in the southern lake basin (0.05-1.6 mm). Detrital layers, which are enriched in dolomitic components forming graded detrital layers (turbidites), indicate the provenance from the Northern Calcareous Alps. These layers are generally thicker (0.65-32 mm) and are solely recorded within the southern lake basin. In comparison with instrumental data, thicker graded layers result from local debris flow events in summer, whereas thin layers are deposited during regional flood events in spring/summer. Extreme summer floods as reported from flood layer deposition are principally caused by cyclonic activity from the Mediterranean Sea, e.g. July 1954, July 1997 and August 2002. During the last two millennia, Lake Mondsee sediments reveal two significant flood intervals with decadal-scale flood episodes, during the Dark Ages Cold Period (DACP) and the transition from the Medieval Climate Anomaly (MCA) into the Little Ice Age (LIA) suggesting a linkage of transition to climate cooling and summer flood recurrences in the Northeastern Alps. In contrast, intermediate or decreased flood episodes appeared during the MWP and the LIA. This indicates a non-straightforward relationship between temperature and flood recurrence, suggesting higher cyclonic activity during climate transition in the Northeast Alps. The 7000-year flood chronology reveals 47 debris flows and 269 floods, with increased flood activity shifting around 3500 and 1500 varve yr BP (varve yr BP = varve years before present, before present = AD 1950). This significant increase in flood activity shows a coincidence with millennial-scale climate cooling that is reported from main Alpine glacier advances and lower tree lines in the European Alps since about 3300 cal. yr BP (calibrated years before present). Despite relatively low flood occurrence prior to 1500 varve yr BP, floods at Lake Mondsee could have also influenced human life in early Neolithic lake dwellings (5750-4750 cal. yr BP). While the first lake dwellings were constructed on wetlands, the later lake dwellings were built on piles in the water suggesting an early flood risk adaptation of humans and/or a general change of the Late Neolithic Culture of lake-dwellers because of socio-economic reasons. However, a direct relationship between the final abandonment of the lake dwellings and higher flood frequencies is not evidenced.
Nowadays, model-driven engineering (MDE) promises to ease software development by decreasing the inherent complexity of classical software development. In order to deliver on this promise, MDE increases the level of abstraction and automation, through a consideration of domain-specific models (DSMs) and model operations (e.g. model transformations or code generations). DSMs conform to domain-specific modeling languages (DSMLs), which increase the level of abstraction, and model operations are first-class entities of software development because they increase the level of automation. Nevertheless, MDE has to deal with at least two new dimensions of complexity, which are basically caused by the increased linguistic and technological heterogeneity. The first dimension of complexity is setting up an MDE environment, an activity comprised of the implementation or selection of DSMLs and model operations. Setting up an MDE environment is both time-consuming and error-prone because of the implementation or adaptation of model operations. The second dimension of complexity is concerned with applying MDE for actual software development. Applying MDE is challenging because a collection of DSMs, which conform to potentially heterogeneous DSMLs, are required to completely specify a complex software system. A single DSML can only be used to describe a specific aspect of a software system at a certain level of abstraction and from a certain perspective. Additionally, DSMs are usually not independent but instead have inherent interdependencies, reflecting (partial) similar aspects of a software system at different levels of abstraction or from different perspectives. A subset of these dependencies are applications of various model operations, which are necessary to keep the degree of automation high. This becomes even worse when addressing the first dimension of complexity. Due to continuous changes, all kinds of dependencies, including the applications of model operations, must also be managed continuously. This comprises maintaining the existence of these dependencies and the appropriate (re-)application of model operations. The contribution of this thesis is an approach that combines traceability and model management to address the aforementioned challenges of configuring and applying MDE for software development. The approach is considered as a traceability approach because it supports capturing and automatically maintaining dependencies between DSMs. The approach is considered as a model management approach because it supports managing the automated (re-)application of heterogeneous model operations. In addition, the approach is considered as a comprehensive model management. Since the decomposition of model operations is encouraged to alleviate the first dimension of complexity, the subsequent composition of model operations is required to counteract their fragmentation. A significant portion of this thesis concerns itself with providing a method for the specification of decoupled yet still highly cohesive complex compositions of heterogeneous model operations. The approach supports two different kinds of compositions - data-flow compositions and context compositions. Data-flow composition is used to define a network of heterogeneous model operations coupled by sharing input and output DSMs alone. Context composition is related to a concept used in declarative model transformation approaches to compose individual model transformation rules (units) at any level of detail. In this thesis, context composition provides the ability to use a collection of dependencies as context for the composition of other dependencies, including model operations. In addition, the actual implementation of model operations, which are going to be composed, do not need to implement any composition concerns. The approach is realized by means of a formalism called an executable and dynamic hierarchical megamodel, based on the original idea of megamodels. This formalism supports specifying compositions of dependencies (traceability and model operations). On top of this formalism, traceability is realized by means of a localization concept, and model management by means of an execution concept.
This thesis is focussed on the electronic properties of the new material class named topological insulators. Spin and angle resolved photoelectron spectroscopy have been applied to reveal several unique properties of the surface state of these materials. The first part of this thesis introduces the methodical background of these quite established experimental techniques.
In the following chapter, the theoretical concept of topological insulators is introduced. Starting from the prominent example of the quantum Hall effect, the application of topological invariants to classify material systems is illuminated. It is explained how, in presence of time reversal symmetry, which is broken in the quantum Hall phase, strong spin orbit coupling can drive a system into a topologically non trivial phase. The prediction of the spin quantum Hall effect in two dimensional insulators an the generalization to the three dimensional case of topological insulators is reviewed together with the first experimental realization of a three dimensional topological insulator in the Bi1-xSbx alloys given in the literature.
The experimental part starts with the introduction of the Bi2X3 (X=Se, Te) family of materials. Recent theoretical predictions and experimental findings on the bulk and surface electronic structure of these materials are introduced in close discussion to our own experimental results. Furthermore, it is revealed, that the topological surface state of Bi2Te3 shares its orbital symmetry with the bulk valence band and the observation of a temperature induced shift of the chemical potential is to a high probability unmasked as a doping effect due to residual gas adsorption.
The surface state of Bi2Te3 is found to be highly spin polarized with a polarization value of about 70% in a macroscopic area, while in Bi2Se3 the polarization appears reduced, not exceeding 50%. We, however, argue that the polarization is most likely only extrinsically limited in terms of the finite angular resolution and the lacking detectability of the out of plane component of the electron spin. A further argument is based on the reduced surface quality of the single crystals after cleavage and, for Bi2Se3 a sensitivity of the electronic structure to photon exposure.
We probe the robustness of the topological surface state in Bi2X3 against surface impurities in Chapter 5. This robustness is provided through the protection by the time reversal symmetry. Silver, deposited on the (111) surface of Bi2Se3 leads to a strong electron doping but the surface state is observed up to a deposited Ag mass equivalent to one atomic monolayer. The opposite sign of doping, i.e., hole-like, is observed by exposing oxygen to Bi2Te3. But while the n-type shift of Ag on Bi2Se3 appears to be more or less rigid, O2 is lifting the Dirac point of the topological surface state in Bi2Te3 out of the valence band minimum at $\Gamma$. After increasing the oxygen dose further, it is possible to shift the Dirac point to the Fermi level, while the valence band stays well beyond. The effect is found reversible, by warming up the samples which is interpreted in terms of physisorption of O2.
For magnetic impurities, i.e., Fe, we find a similar behavior as for the case of Ag in both Bi2Se3 and Bi2Te3. However, in that case the robustness is unexpected, since magnetic impurities are capable to break time reversal symmetry which should introduce a gap in the surface state at the Dirac point which in turn removes the protection. We argue, that the fact that the surface state shows no gap must be attributed to a missing magnetization of the Fe overlayer. In Bi2Te3 we are able to observe the surface state for deposited iron mass equivalents in the monolayer regime. Furthermore, we gain control over the sign of doping through the sample temperature during deposition.
Chapter6 is devoted to the lifetime broadening of the photoemission signal from the topological surface states of Bi2Se3 and Bi2Te3. It is revealed that the hexagonal warping of the surface state in Bi2Te3 introduces an anisotropy for electrons traveling along the two distinct high symmetry directions of the surface Brillouin zone, i.e., $\Gamma$K and $\Gamma$M. We show that the phonon coupling strength to the surface electrons in Bi2Te3 is in nice agreement with the theoretical prediction but, nevertheless, higher than one may expect. We argue that the electron-phonon coupling is one of the main contributions to the decay of photoholes but the relatively small size of the Fermi surface limits the number of phonon modes that may scatter off electrons. This effect is manifested in the energy dependence of the imaginary part of the electron self energy of the surface state which shows a decay to higher binding energies in contrast to the monotonic increase proportional to E$^2$ in the Fermi liquid theory due to electron-electron interaction.
Furthermore, the effect of the surface impurities of Chapter 5 on the quasiparticle life- times is investigated. We find that Fe impurities have a much stronger influence on the lifetimes as compared to Ag. Moreover, we find that the influence is stronger independently of the sign of the doping. We argue that this observation suggests a minor contribution of the warping on increased scattering rates in contrast to current belief. This is additionally confirmed by the observation that the scattering rates increase further with increasing silver amount while the doping stays constant and by the fact that clean Bi2Se3 and Bi2Te3 show very similar scattering rates regardless of the much stronger warping in Bi2Te3.
In the last chapter we report on a strong circular dichroism in the angle distribution of the photoemission signal of the surface state of Bi2Te3. We show that the color pattern obtained by calculating the difference between photoemission intensities measured with opposite photon helicity reflects the pattern expected for the spin polarization. However, we find a strong influence on strength and even sign of the effect when varying the photon energy. The sign change is qualitatively confirmed by means of one-step photoemission calculations conducted by our collaborators from the LMU München, while the calculated spin polarization is found to be independent of the excitation energy. Experiment and theory together unambiguously uncover the dichroism in these systems as a final state effect and the question in the title of the chapter has to be negated: Circular dichroism in the angle distribution is not a new spin sensitive technique.
In einer quasiexperimentellen Längsschnittstudie mit 380 Lehramtsstudierenden wurde das Interventionsprogramm „Gestärkt für den Lehrerberuf“, welches Elemente eines Self-Assessments der berufsrelevanten Kompetenzen mit konkreten Beratungsmöglichkeiten und einem Zieleffektivitätstraining (Dargel, 2006) zur Entwicklung individueller berufsbezogener Kompetenzen verbindet, auf seine Wirksamkeit (Reflexionskompetenz, Lehrerselbstwirksamkeit, berufsbezogene Kompetenzen, Beanspruchungserleben, Widerstandsfähigkeit) und den Wirkungsprozess (Zielbindung, Zielrealisierbarkeit, Zieleffektivität) hin überprüft. In dem Prä-Post-Follow-up-Test-Vergleichsgruppen-Design wurden eine Interventionsgruppe, deren Treatment auf dem Stärkenansatz basiert (1), eine defizitorientierte Interventionsgruppe (2), sowie eine kombinierte Interventionsgruppe, bei der der Stärkenansatz durch den Defizitansatz ergänzt wird (3), einer unbehandelten Kontrollgruppe sowie einer alternativ behandelten Kontrollgruppe, die ausschließlich in ihren sozial-kommunikativer Kompetenzen geschult wurde, gegenübergestellt. Es gelang zum Post- und Follow-up-Test, sowohl die individuellen beruflichen Kompetenzen als auch die Reflexionskompetenz von Teilnehmern der Interventionsgruppen im Vergleich zur unbehandelten Kontrollgruppe zu fördern. Die Teilnehmer der kombinierten Intervention profitierten im Vergleich zu den Teilnehmern der anderen beiden Interventionsgruppen stärker im Bereich Lehrerselbstwirksamkeit, Widerstandsfähigkeit und Zieleffektivität. Gegenüber der alternativen Kontrollgruppe zeigten sie ebenfalls einen stärkeren Zuwachs in der Entwicklung ihrer berufsrelevanten Kompetenzen und in ihrer Widerstandsfähigkeit. Die Studie liefert erste Hinweise darauf, dass ein Ansatz, welcher Stärkenfokussierung und Defizitorientierung integriert, besonders effektiv wirkt.
Immune genes of the major histocompatibility complex (MHC) constitute a central component of the adaptive immune system and play an essential role in parasite resistance and associated life-history strategies. In addition to pathogen-mediated selection also sexual selection mechanisms have been identified as the main drivers of the typically-observed high levels of polymorphism in functionally important parts of the MHC. The recognition of the individual MHC constitution is presumed to be mediated through olfactory cues. Indeed, MHC genes are in physical linkage with olfactory receptor genes and alter the individual body odour. Moreover, they are expressed on sperm and trophoplast cells. Thus, MHC-mediated sexual selection processes might not only act in direct mate choice decisions, but also through cryptic processes during reproduction. Bats (Chiroptera) represent the second largest mammalian order and have been identified as important vectors of newly emerging infectious diseases affecting humans and wildlife. In addition, they are interesting study subjects in evolutionary ecology in the context of olfactory communication, mate choice and associated fitness benefits. Thus, it is surprising that Chiroptera belong to the least studied mammalian taxa in terms of their MHC evolution. In my doctoral thesis I aimed to gain insights in the evolution and diversity pattern of functional MHC genes in some of the major New World bat families by establishing species-specific primers through genome-walking into unknown flanking parts of familiar sites. Further, I took a free-ranging population of the lesser bulldog bat (Noctilio albiventris) in Panama as an example to understand the functional importance of the individual MHC constitution in parasite resistance and reproduction as well as the possible underlying selective forces shaping the observed diversity. My studies indicated that the typical MHC characteristics observed in other mammalian orders, like evidence for balancing and positive selection as well as recombination and gene conversion events, are also present in bats shaping their MHC diversity. I found a wide range of copy number variation of expressed DRB loci in the investigated species. In Saccopteryx bilineata, a species with a highly developed olfactory communication system, I found an exceptionally high number of MHC loci duplications generating high levels of variability at the individual level, which has never been described for any other mammalian species so far. My studies included for the first time phylogenetic relationships of MHC genes in bats and I found signs for a family-specific independent mode of evolution of duplicated genes, regardless whether the highly variable exon 2 (coding for the antigen binding region of the molecule) or more conserved exons (3, 4; encoding protein stabilizing parts) were considered indicating a monophyletic origin of duplicated loci within families. This result questions the general assumed pattern of MHC evolution in mammals where duplicated genes of different families usually cluster together suggesting that duplication occurred before speciation took place, which implies a trans-species mode of evolution. However, I found a trans-species mode of evolution within genera (Noctilio, Myotis) based on exon 2 signified by an intermingled clustering of DRB alleles. The gained knowledge on MHC sequence evolution in major New World bat families will facilitate future MHC investigations in this order. In the N. albiventris study population, the single expressed MHC class II DRB gene showed high sequence polymorphism, moderate allelic variability and high levels of population-wide heterozygosity. Whereas demographic processes had minor relevance in shaping the diversity pattern, I found clear evidence for parasite-mediated selection. This was evident by historical positive Darwinian selection maintaining diversity in the functionally important antigen binding sites, and by specific MHC alleles which were associated with low and high ectoparasite burden according to predictions of the ‘frequency dependent selection hypothesis’. Parasite resistance has been suggested to play an important role in mediating costly life history trade-offs leading to e.g. MHC- mediated benefits in sexual selection. The ‘good genes model’ predicts that males with a genetically well-adapted immune system in defending harmful parasites have the ability to allocate more resources to reproductive effort. I found support for this prediction since non-reproductive adult N. albiventris males carried more often an allele associated with high parasite loads, which differentiated them genetically from reproductively active males as well as from subadults, indicating a reduced transmission of this allele in subsequent generations. In addition, they suffered from increased ectoparasite burden which presumably reduced resources to invest in reproduction. Another sign for sexual selection was the observation of gender-specific difference in heterozygosity, with females showing lower levels of heterozygosity than males. This signifies that the sexes differ in their selection pressures, presumably through MHC-mediated molecular processes during reproduction resulting in a male specific heterozygosity advantage. My data make clear that parasite-mediated selection and sexual selection are interactive and operate together to form diversity at the MHC. Furthermore, my thesis is one of the rare studies contributing to fill the gap between MHC-mediated effects on co-evolutionary processes in parasite-host-interactions and on aspects of life-history evolution.
It sometimes happens that we finish reading a passage of text just to realize that we have no idea what we just read. During these episodes of mindless reading our mind is elsewhere yet the eyes still move across the text. The phenomenon of mindless reading is common and seems to be widely recognized in lay psychology. However, the scientific investigation of mindless reading has long been underdeveloped. Recent progress in research on mindless reading has been based on self-report measures and on treating it as an all-or-none phenomenon (dichotomy-hypothesis). Here, we introduce the levels-of-inattention hypothesis proposing that mindless reading is graded and occurs at different levels of cognitive processing. Moreover, we introduce two new behavioral paradigms to study mindless reading at different levels in the eye-tracking laboratory. First (Chapter 2), we introduce shuffled text reading as a paradigm to approximate states of weak mindless reading experimentally and compare it to reading of normal text. Results from statistical analyses of eye movements that subjects perform in this task qualitatively support the ‘mindless’ hypothesis that cognitive influences on eye movements are reduced and the ‘foveal load’ hypothesis that the response of the zoom lens of attention to local text difficulty is enhanced when reading shuffled text. We introduce and validate an advanced version of the SWIFT model (SWIFT 3) incorporating the zoom lens of attention (Chapter 3) and use it to explain eye movements during shuffled text reading. Simulations of the SWIFT 3 model provide fully quantitative support for the ‘mindless’ and the ‘foveal load’ hypothesis. They moreover demonstrate that the zoom lens is an important concept to explain eye movements across reading and mindless reading tasks. Second (Chapter 4), we introduce the sustained attention to stimulus task (SAST) to catch episodes when external attention spontaneously lapses (i.e., attentional decoupling or mind wandering) via the overlooking of errors in the text and via signal detection analyses of error detection. Analyses of eye movements in the SAST revealed reduced influences from cognitive text processing during mindless reading. Based on these findings, we demonstrate that it is possible to predict states of mindless reading from eye movement recordings online. That cognition is not always needed to move the eyes supports autonomous mechanisms for saccade initiation. Results from analyses of error detection and eye movements provide support to our levels-of-inattention hypothesis that errors at different levels of the text assess different levels of decoupling. Analyses of pupil size in the SAST (Chapter 5) provide further support to the levels of inattention hypothesis and to the decoupling hypothesis that off-line thought is a distinct mode of cognitive functioning that demands cognitive resources and is associated with deep levels of decoupling. The present work demonstrates that the elusive phenomenon of mindless reading can be vigorously investigated in the cognitive laboratory and further incorporated in the theoretical framework of cognitive science.
The field of machine learning studies algorithms that infer predictive models from data. Predictive models are applicable for many practical tasks such as spam filtering, face and handwritten digit recognition, and personalized product recommendation. In general, they are used to predict a target label for a given data instance. In order to make an informed decision about the deployment of a predictive model, it is crucial to know the model’s approximate performance. To evaluate performance, a set of labeled test instances is required that is drawn from the distribution the model will be exposed to at application time. In many practical scenarios, unlabeled test instances are readily available, but the process of labeling them can be a time- and cost-intensive task and may involve a human expert. This thesis addresses the problem of evaluating a given predictive model accurately with minimal labeling effort. We study an active model evaluation process that selects certain instances of the data according to an instrumental sampling distribution and queries their labels. We derive sampling distributions that minimize estimation error with respect to different performance measures such as error rate, mean squared error, and F-measures. An analysis of the distribution that governs the estimator leads to confidence intervals, which indicate how precise the error estimation is. Labeling costs may vary across different instances depending on certain characteristics of the data. For instance, documents differ in their length, comprehensibility, and technical requirements; these attributes affect the time a human labeler needs to judge relevance or to assign topics. To address this, the sampling distribution is extended to incorporate instance-specific costs. We empirically study conditions under which the active evaluation processes are more accurate than a standard estimate that draws equally many instances from the test distribution. We also address the problem of comparing the risks of two predictive models. The standard approach would be to draw instances according to the test distribution, label the selected instances, and apply statistical tests to identify significant differences. Drawing instances according to an instrumental distribution affects the power of a statistical test. We derive a sampling procedure that maximizes test power when used to select instances, and thereby minimizes the likelihood of choosing the inferior model. Furthermore, we investigate the task of comparing several alternative models; the objective of an evaluation could be to rank the models according to the risk that they incur or to identify the model with lowest risk. An experimental study shows that the active procedure leads to higher test power than the standard test in many application domains. Finally, we study the problem of evaluating the performance of ranking functions, which are used for example for web search. In practice, ranking performance is estimated by applying a given ranking model to a representative set of test queries and manually assessing the relevance of all retrieved items for each query. We apply the concepts of active evaluation and active comparison to ranking functions and derive optimal sampling distributions for the commonly used performance measures Discounted Cumulative Gain and Expected Reciprocal Rank. Experiments on web search engine data illustrate significant reductions in labeling costs.
Die Fähigkeit, mit anderen Zellen zu kommunizieren, ist eine grundlegende Eigenschaft aller lebenden Zellen und essentiell für die normale Funktionsweise vielzelliger Organismen. Die Speicheldrüsen der Schmeißfliege Calliphora vicina bilden ein ausgezeichnetes physiologisches Modellsystem um zelluläre Signaltransduktionsprozesse an einem intakten Organ zu untersuchen. Die Speichelsekretion wird dabei hormonell durch das biogene Amin Serotonin (5-Hydroxytryptamin; 5-HT) reguliert. 5-HT aktiviert in den sekretorischen Zellen der Drüsen über die Bindung an mindestens zwei membranständige G-Protein gekoppelte Rezeptoren (GPCR) zwei separate Signalwege, den IP3/Ca2+- und den cAMP-Signalweg. Zur Identifizierung und Charakterisierung der 5-HT-Rezeptoren in den Speicheldrüsen von Calliphora wurden unter Anwendung verschiedener Klonierungsstrategien zwei cDNAs (Cv5-ht2α und Cv5-ht7) isoliert, die große Ähnlichkeit zu 5-HT2- und 5-HT7-Rezeptoren aus Säugetieren aufweisen. Die Hydropathieprofile der abgeleiteten Aminosäuresequenzen postulieren die für GPCRs charakteristische heptahelikale Architektur. Alle Aminosäuremotive, die für die Ligandenbindung, die Rezeptoraktivierung und die Kopplung an G-Proteine essentiell sind, liegen konserviert vor. Interessanterweise wurde für den Cv5-HT7-Rezeptor eine zusätzliche hydrophobe Domäne im N Terminus vorhergesagt. Die Cv5-HT2α-mRNA liegt in zwei alternativ gespleißten Varianten vor. Mittels RT-PCR-Experimenten konnte die Expression beider Rezeptoren in Gehirn und Speicheldrüsen adulter Fliegen nachgewiesen werden. Ein Antiserum gegen den Cv5-HT7 Rezeptor markiert in den Speicheldrüsen die basolaterale Plasmamembran. Die Expression der Rezeptoren in einem heterologen System (HEK 293-Zellen) bestätigte diese als funktionelle 5-HT Rezeptoren. So führte die Stimulation mit Serotonin für den Cv5-HT2α zu einer dosis-abhängigen Erhöhung der intrazellulären Ca2+ Konzentration ([Ca2+]i, EC50 = 24 nM). In Cv5-HT7-exprimierenden Zellen löste 5-HT dosisabhängig (EC50 = 4,1 nM) einen Anstieg der intrazellulären cAMP Konzentration ([cAMP]i) aus. Für beide heterolog exprimierten Rezeptoren wurden pharmakologische Profile erstellt. Liganden, die eine Rezeptorsubtyp-spezifische Wirkung vermuten ließen, wurden daraufhin auf ihre Wirkung auf das transepitheliale Potential (TEP) intakter Speicheldrüsenpräparate getestet. Drei 5-HT-Rezeptoragonisten: AS 19, R-(+)-Lisurid und 5-Carboxamidotryptamin führten zu einer cAMP-abhängigen Positivierung des TEP durch eine selektive Aktivierung der 5 HT7-Rezeptoren. Eine selektive Aktivierung des Ca2+-Signalweges durch den Cv5-HT2 Rezeptor ist mit Hilfe von 5-Methoxytryptamin möglich. Dagegen konnte Clozapin im TEP als selektiver Cv5-HT7-Rezeptorantagonist bestätigt werden. Die Kombination eines molekularen Ansatzes mit physiologischen Messungen ermöglichte somit die Identifikation selektiver Liganden für 5-HT2- bzw. 5-HT7-Rezeptoren aus Calliphora vicina. Dies ermöglicht zukünftig eine separate Aktivierung der 5-HT-gesteuerten Signalwege und erleichtert dadurch die weitere Erforschung der intrazellulären Signalwege und ihrer Wechselwirkungen.
Tensorial spacetime geometries carrying predictive, interpretable and quantizable matter dynamics
(2012)
Which tensor fields G on a smooth manifold M can serve as a spacetime structure? In the first part of this thesis, it is found that only a severely restricted class of tensor fields can provide classical spacetime geometries, namely those that can carry predictive, interpretable and quantizable matter dynamics. The obvious dependence of this characterization of admissible tensorial spacetime geometries on specific matter is not a weakness, but rather presents an insight: it was Maxwell theory that justified Einstein to promote Lorentzian manifolds to the status of a spacetime geometry. Any matter that does not mimick the structure of Maxwell theory, will force us to choose another geometry on which the matter dynamics of interest are predictive, interpretable and quantizable. These three physical conditions on matter impose three corresponding algebraic conditions on the totally symmetric contravariant coefficient tensor field P that determines the principal symbol of the matter field equations in terms of the geometric tensor G: the tensor field P must be hyperbolic, time-orientable and energy-distinguishing. Remarkably, these physically necessary conditions on the geometry are mathematically already sufficient to realize all kinematical constructions familiar from Lorentzian geometry, for precisely the same structural reasons. This we were able to show employing a subtle interplay of convex analysis, the theory of partial differential equations and real algebraic geometry. In the second part of this thesis, we then explore general properties of any hyperbolic, time-orientable and energy-distinguishing tensorial geometry. Physically most important are the construction of freely falling non-rotating laboratories, the appearance of admissible modified dispersion relations to particular observers, and the identification of a mechanism that explains why massive particles that are faster than some massless particles can radiate off energy until they are slower than all massless particles in any hyperbolic, time-orientable and energy-distinguishing geometry. In the third part of the thesis, we explore how tensorial spacetime geometries fare when one wants to quantize particles and fields on them. This study is motivated, in part, in order to provide the tools to calculate the rate at which superluminal particles radiate off energy to become infraluminal, as explained above. Remarkably, it is again the three geometric conditions of hyperbolicity, time-orientability and energy-distinguishability that allow the quantization of general linear electrodynamics on an area metric spacetime and the quantization of massive point particles obeying any admissible dispersion relation. We explore the issue of field equations of all possible derivative order in rather systematic fashion, and prove a practically most useful theorem that determines Dirac algebras allowing the reduction of derivative orders. The final part of the thesis presents the sketch of a truly remarkable result that was obtained building on the work of the present thesis. Particularly based on the subtle duality maps between momenta and velocities in general tensorial spacetimes, it could be shown that gravitational dynamics for hyperbolic, time-orientable and energy distinguishable geometries need not be postulated, but the formidable physical problem of their construction can be reduced to a mere mathematical task: the solution of a system of homogeneous linear partial differential equations. This far-reaching physical result on modified gravity theories is a direct, but difficult to derive, outcome of the findings in the present thesis. Throughout the thesis, the abstract theory is illustrated through instructive examples.
Die Mykorrhiza (griechisch: mýkēs für „Pilz”; rhiza für „Wurzel”) stellt eine Symbiose zwischen Pilzen und einem Großteil der Landpflanzen dar. Der Pilz verbessert durch die Symbiose die Versorgung der Pflanze mit Nährstoffen, während die Pflanze den Pilz mit Kohlenhydraten versorgt. Die arbuskuläre Mykorrhiza (AM) stellt dabei einen beson-dere Form der Mykorrhiza dar. Der AM-Pilz bildet dabei während der Symbiose die namensgebenden Arbuskeln innerhalb der Wurzelzellen als Ort des primären Nährstoff- austausches aus. Die AM-Symbiose (AMS) ist der Forschungsschwerpunkt dieser Arbeit. Als Modellorganismen wurden Medicago truncatula und Glomus intraradices verwendet. Es wurden Transkriptionsanalysen durchgeführt um u.a. AMS regulierte Transkriptions- faktoren (TFs) zu identifizieren. Die Aktivität der Promotoren von drei der so identifizier-ten AMS-regulierten TFs (MtOFTN, MtNTS, MtDES) wurde mit Hilfe eine Reportergens visualisiert. Der Bereich der größten Promotoraktivität waren in einem Fall nur die ar- buskelhaltigen Zellen (MtOFTN). Im zweiten Fall war der Promotor auch aktiv in nicht arbuskelhaltigen Zellen, jedoch am stärksten aktiv in den arbuskelhaltigen Zellen (MtNTS). Ein weiterer Promotor war in arbuskelhaltigen Zellen und den diesen benach-barten Zellen gleich aktiv (MtDES). Zusätzlich wurden weitere Gene als AMS-reguliert identifiziert und es wurde für drei dieser Gene (MtPPK, MtAmT, MtMDRL) ebenfalls eine Promotor::Reporter-Aktivitäts- studie durchgeführt. Die Promotoren der Kinase (MtPPK) und des Ammoniumtrans-porters (MtAmt) waren dabei ausschließlich in arbuskelhaltigen Zellen aktiv, während die Aktivität des ABC-Transporters (MtMDRL) keinem bestimmten Zelltyp zuzuordnen war. Für zwei weitere identifizierte Gene, ein Kupfertransporter (MtCoT) und ein Zucker- bzw. Inositoltransporter (MtSuT), wurden RNA-Interferenz (RNAi)-Untersuchungen durchgeführt. Dabei stellte sich in beiden Fällen heraus, dass, sobald ein RNAi-Effekt in den transformierten Wurzeln vorlag, diese in einem deutlich geringerem Ausmaß wie in der Wurzelkontrolle von G. intraradices kolonisiert worden sind. Im Falle von MtCoT könnte das aus dem selben Grund geschehen, wie im Falle von MtPt4. Welche Rolle MtSuT genau in der Ausbildung der AMS spielt und welche Rolle Inositol in der Aus- bildung der AMS spielt müsste durch weitere Untersuchungen am Protein untersucht werden. Weitere Untersuchen an den in dieser Arbeit als spezifisch für arbuskelhaltige Zellen gezeigten Genen MtAmT, MtPPK und MtOFTN könnten ebenfalls aufschlussreich für das weitere Verständnis der AMS sein. Dies trifft auch auf die TFs MtNTS und MtDES zu, die zwar nicht ausschließlich arbuskelspezifisch transkribiert werden, aber auch eine Rolle in der Regulation der AMS innerhalb von M. truncatula Wurzeln zu spielen scheinen.
Structuring process models
(2012)
One can fairly adopt the ideas of Donald E. Knuth to conclude that process modeling is both a science and an art. Process modeling does have an aesthetic sense. Similar to composing an opera or writing a novel, process modeling is carried out by humans who undergo creative practices when engineering a process model. Therefore, the very same process can be modeled in a myriad number of ways. Once modeled, processes can be analyzed by employing scientific methods. Usually, process models are formalized as directed graphs, with nodes representing tasks and decisions, and directed arcs describing temporal constraints between the nodes. Common process definition languages, such as Business Process Model and Notation (BPMN) and Event-driven Process Chain (EPC) allow process analysts to define models with arbitrary complex topologies. The absence of structural constraints supports creativity and productivity, as there is no need to force ideas into a limited amount of available structural patterns. Nevertheless, it is often preferable that models follow certain structural rules. A well-known structural property of process models is (well-)structuredness. A process model is (well-)structured if and only if every node with multiple outgoing arcs (a split) has a corresponding node with multiple incoming arcs (a join), and vice versa, such that the set of nodes between the split and the join induces a single-entry-single-exit (SESE) region; otherwise the process model is unstructured. The motivations for well-structured process models are manifold: (i) Well-structured process models are easier to layout for visual representation as their formalizations are planar graphs. (ii) Well-structured process models are easier to comprehend by humans. (iii) Well-structured process models tend to have fewer errors than unstructured ones and it is less probable to introduce new errors when modifying a well-structured process model. (iv) Well-structured process models are better suited for analysis with many existing formal techniques applicable only for well-structured process models. (v) Well-structured process models are better suited for efficient execution and optimization, e.g., when discovering independent regions of a process model that can be executed concurrently. Consequently, there are process modeling languages that encourage well-structured modeling, e.g., Business Process Execution Language (BPEL) and ADEPT. However, the well-structured process modeling implies some limitations: (i) There exist processes that cannot be formalized as well-structured process models. (ii) There exist processes that when formalized as well-structured process models require a considerable duplication of modeling constructs. Rather than expecting well-structured modeling from start, we advocate for the absence of structural constraints when modeling. Afterwards, automated methods can suggest, upon request and whenever possible, alternative formalizations that are "better" structured, preferably well-structured. In this thesis, we study the problem of automatically transforming process models into equivalent well-structured models. The developed transformations are performed under a strong notion of behavioral equivalence which preserves concurrency. The findings are implemented in a tool, which is publicly available.
In this work, the synthesis of biopolymer-based hydrogel networks with defined architecture is presented. In order to obtain materials with defined properties, the chemoselective copper-catalyzed azide-alkyne cycloaddition (or Click Chemistry) was used for the synthesis of gelatin-based hydrogels. Alkyne-functionalized gelatin was reacted with four different diazide crosslinkers above its sol-gel transition to suppress the formation of triple helices. By variation of the crosslinking density and the crosslinker flexibility, the swelling (Q: 150-470 vol.-%;) and the Young’s and shear moduli (E: 50 kPa - 635 kPa, G’: 0.1 kPa - 16 kPa) could be tuned in the kPa range. In order to understand the network structure, a method based on the labelling of free functional groups within the hydrogel was developed. Gelatin-based hydrogels were incubated with alkyne-functionalized fluorescein to detect the free azide groups, resulting from the formation of dangling chains. Gelatin hydrogels were also incubated with azido-functionalized fluorescein to check the presence of alkyne groups available for the attachment of bioactive molecules. By using confocal laser scanning microscopy and fluorescence spectroscopy, the amount of crosslinking, grafting and free alkyne groups could be determined. Dangling chains were observed in samples prepared by using an excess of crosslinker and also when using equimolar amounts of alkyne:azide. In the latter case the amount of dangling chains was affected by the crosslinker structure. Specifically, 0.1% of dangling chains were found using 4,4’-diazido-2,2’-stilbene-disulfonic acid as cosslinker, 0.06% with 1,8-diazidooctane, 0.05% with 1,12-diazidododecane and 0.022 % with PEG-diazide. This observation could be explained considering the structure of the crosslinkers. During network formation, the movements of the gelatin chains are restricted due to the formation of covalent netpoints. A further crosslinking will be possible only in the case of crosslinker that are flexible and long enough to reach another chain. The method used to obtain defined gelatin-based hydrogels enabled also the synthesis of hyaluronic acid-based hydrogels with tailorable properties. Alkyne-functionalized hyaluronic acid was crosslinked with three different linkers having two terminal azide functionalities. By variation of the crosslinking density and crosslinker type, hydrogels with elastic moduli in the range of 0.5-3 kPa have been prepared. The variation of the crosslinking density and crosslinker type had furthermore an influence also on the hydrolytic and enzymatic degradation of gelatin-based hydrogels. Hydrogels with a low crosslinker amount experienced a faster decrease in mass loss and elastic modulus compared to hydrogels with higher crosslinker content. Moreover, the structure of the crosslinker had a strong influence on the enzymatic degradation. Hydrogels containing a crosslinker with a rigid structure were much more resistant to enzymatic degradation than hydrogels containing a flexible crosslinker. During hydrolytic degradation, the hydrogel became softer while maintaining the same outer dimensions. These observations are in agreement with a bulk degradation mechanism, while the decrease in size of the hydrogels during enzymatic degradation suggested a surface erosion mechanism. Because of the use of small amount of crosslinker (0.002 mol.% 0.02 mol.%) the networks synthesized can still be defined as biopolymer-based hydrogels. However, they contain a small percentage of synthetic residues. Alternatively, a possible method to obtain biopolymer-based telechelics, which could be used as crosslinkers, was investigated. Gelatin-based fragments with defined molecular weight were obtained by controlled degradation of gelatin with hydroxylamine, due to its specific action on asparaginyl-glycine bonds. The reaction of gelatin with hydroxylamine resulted in fragments with molecular weights of 15, 25, 37, and 50 kDa (determined by SDS-PAGE) independently of the reaction time and conditions. Each of these fragments could be potentially used for the synthesis of hydrogels in which all components are biopolymer-based materials.
Neben der Frequenz eines cues ist es dessen Zuverlässigkeit, die Kindern hilft, die an sie gerichtete Sprache zu segmentieren, Worteinheiten zu erkennen sowie diese syntaktisch zu kategorisieren. Im Deutschen weist die Subsilbe „Langvokal+Konsonant+/t/“ (z.B. in fehlt, wohnt) zuverlässig auf eine -t-flektierte Verbform hin. Die in kindgerichteter Sprache höher frequente Subsilbe „Kurzvokal+Konsonant+/t/“ (z.B. in Feld, Hemd, fällt, rund) gibt hingegen keinen derartig eindeutigen Hinweis. Es wurde der Frage nachgegangen, inwiefern diese unterschiedlichen Zuverlässigkeiten und Frequenzen der Subsilben auf die Nomen-, Verb- und Verbflexionsverarbeitung einwirken. Drei Altersgruppen wurden untersucht: achtzehn Monate alte Kinder, drei- bis fünfjährige sprachunauffällige und -auffällige Kinder sowie erwachsene Sprecher. Einflüsse der unterschiedlichen Zuverlässigkeiten und Frequenzen der ausgewählten Subsilben konnten für alle Probandengruppen gefunden werden. Die Subsilbe stellt damit eine linguistische Größe dar, die in der frühen Sprachwahrnehmung als cue dienen sowie die Sprachverarbeitung Erwachsener lenken kann und auch für die Sprachdiagnostik und -therapie sprachauffälliger Kinder berücksichtigt werden sollte.
One of the most exciting predictions of Einstein's theory of gravitation that have not yet been proven experimentally by a direct detection are gravitational waves. These are tiny distortions of the spacetime itself, and a world-wide effort to directly measure them for the first time with a network of large-scale laser interferometers is currently ongoing and expected to provide positive results within this decade. One potential source of measurable gravitational waves is the inspiral and merger of two compact objects, such as binary black holes. Successfully finding their signature in the noise-dominated data of the detectors crucially relies on accurate predictions of what we are looking for. In this thesis, we present a detailed study of how the most complete waveform templates can be constructed by combining the results from (A) analytical expansions within the post-Newtonian framework and (B) numerical simulations of the full relativistic dynamics. We analyze various strategies to construct complete hybrid waveforms that consist of a post-Newtonian inspiral part matched to numerical-relativity data. We elaborate on exsisting approaches for nonspinning systems by extending the accessible parameter space and introducing an alternative scheme based in the Fourier domain. Our methods can now be readily applied to multiple spherical-harmonic modes and precessing systems. In addition to that, we analyze in detail the accuracy of hybrid waveforms with the goal to quantify how numerous sources of error in the approximation techniques affect the application of such templates in real gravitational-wave searches. This is of major importance for the future construction of improved models, but also for the correct interpretation of gravitational-wave observations that are made utilizing any complete waveform family. In particular, we comprehensively discuss how long the numerical-relativity contribution to the signal has to be in order to make the resulting hybrids accurate enough, and for currently feasible simulation lengths we assess the physics one can potentially do with template-based searches.
We investigate properties of quantum mechanical systems in the light of quantum information theory. We put an emphasize on systems with infinite-dimensional Hilbert spaces, so-called continuous-variable systems'', which are needed to describe quantum optics beyond the single photon regime and other Bosonic quantum systems. We present methods to obtain a description of such systems from a series of measurements in an efficient manner and demonstrate the performance in realistic situations by means of numerical simulations. We consider both unconditional quantum state tomography, which is applicable to arbitrary systems, and tomography of matrix product states. The latter allows for the tomography of many-body systems because the necessary number of measurements scales merely polynomially with the particle number, compared to an exponential scaling in the generic case. We also present a method to realize such a tomography scheme for a system of ultra-cold atoms in optical lattices. Furthermore, we discuss in detail the possibilities and limitations of using continuous-variable systems for measurement-based quantum computing. We will see that the distinction between Gaussian and non-Gaussian quantum states and measurements plays an crucial role. We also provide an algorithm to solve the large and interesting class of naturally occurring Hamiltonians, namely frustration free ones, efficiently and use this insight to obtain a simple approximation method for slightly frustrated systems. To achieve this goals, we make use of, among various other techniques, the well developed theory of matrix product states, tensor networks, semi-definite programming, and matrix analysis.
Actin is one of the most abundant and highly conserved proteins in eukaryotic cells. The globular protein assembles into long filaments, which form a variety of different networks within the cytoskeleton. The dynamic reorganization of these networks - which is pivotal for cell motility, cell adhesion, and cell division - is based on cycles of polymerization (assembly) and depolymerization (disassembly) of actin filaments. Actin binds ATP and within the filament, actin-bound ATP is hydrolyzed into ADP on a time scale of a few minutes. As ADP-actin dissociates faster from the filament ends than ATP-actin, the filament becomes less stable as it grows older. Recent single filament experiments, where abrupt dynamical changes during filament depolymerization have been observed, suggest the opposite behavior, however, namely that the actin filaments become increasingly stable with time. Several mechanisms for this stabilization have been proposed, ranging from structural transitions of the whole filament to surface attachment of the filament ends. The key issue of this thesis is to elucidate the unexpected interruptions of depolymerization by a combination of experimental and theoretical studies. In new depolymerization experiments on single filaments, we confirm that filaments cease to shrink in an abrupt manner and determine the time from the initiation of depolymerization until the occurrence of the first interruption. This duration differs from filament to filament and represents a stochastic variable. We consider various hypothetical mechanisms that may cause the observed interruptions. These mechanisms cannot be distinguished directly, but they give rise to distinct distributions of the time until the first interruption, which we compute by modeling the underlying stochastic processes. A comparison with the measured distribution reveals that the sudden truncation of the shrinkage process neither arises from blocking of the ends nor from a collective transition of the whole filament. Instead, we predict a local transition process occurring at random sites within the filament. The combination of additional experimental findings and our theoretical approach confirms the notion of a local transition mechanism and identifies the transition as the photo-induced formation of an actin dimer within the filaments. Unlabeled actin filaments do not exhibit pauses, which implies that, in vivo, older filaments become destabilized by ATP hydrolysis. This destabilization can be identified with an acceleration of the depolymerization prior to the interruption. In the final part of this thesis, we theoretically analyze this acceleration to infer the mechanism of ATP hydrolysis. We show that the rate of ATP hydrolysis is constant within the filament, corresponding to a random as opposed to a vectorial hydrolysis mechanism.
A point process is a mechanism, which realizes randomly locally finite point measures. One of the main results of this thesis is an existence theorem for a new class of point processes with a so called signed Levy pseudo measure L, which is an extension of the class of infinitely divisible point processes. The construction approach is a combination of the classical point process theory, as developed by Kerstan, Matthes and Mecke, with the method of cluster expansions from statistical mechanics. Here the starting point is a family of signed Radon measures, which defines on the one hand the Levy pseudo measure L, and on the other hand locally the point process. The relation between L and the process is the following: this point process solves the integral cluster equation determined by L. We show that the results from the classical theory of infinitely divisible point processes carry over in a natural way to the larger class of point processes with a signed Levy pseudo measure. In this way we obtain e.g. a criterium for simplicity and a characterization through the cluster equation, interpreted as an integration by parts formula, for such point processes. Our main result in chapter 3 is a representation theorem for the factorial moment measures of the above point processes. With its help we will identify the permanental respective determinantal point processes, which belong to the classes of Boson respective Fermion processes. As a by-product we obtain a representation of the (reduced) Palm kernels of infinitely divisible point processes. In chapter 4 we see how the existence theorem enables us to construct (infinitely extended) Gibbs, quantum-Bose and polymer processes. The so called polymer processes seem to be constructed here for the first time. In the last part of this thesis we prove that the family of cluster equations has certain stability properties with respect to the transformation of its solutions. At first this will be used to show how large the class of solutions of such equations is, and secondly to establish the cluster theorem of Kerstan, Matthes and Mecke in our setting. With its help we are able to enlarge the class of Polya processes to the so called branching Polya processes. The last sections of this work are about thinning and splitting of point processes. One main result is that the classes of Boson and Fermion processes remain closed under thinning. We use the results on thinning to identify a subclass of point processes with a signed Levy pseudo measure as doubly stochastic Poisson processes. We also pose the following question: Assume you observe a realization of a thinned point process. What is the distribution of deleted points? Surprisingly, the Papangelou kernel of the thinning, besides a constant factor, is given by the intensity measure of this conditional probability, called splitting kernel.
This work is concerned with the characterization of certain classes of stochastic processes via duality formulae. In particular we consider reciprocal processes with jumps, a subject up to now neglected in the literature. In the first part we introduce a new formulation of a characterization of processes with independent increments. This characterization is based on a duality formula satisfied by processes with infinitely divisible increments, in particular Lévy processes, which is well known in Malliavin calculus. We obtain two new methods to prove this duality formula, which are not based on the chaos decomposition of the space of square-integrable function- als. One of these methods uses a formula of partial integration that characterizes infinitely divisible random vectors. In this context, our characterization is a generalization of Stein’s lemma for Gaussian random variables and Chen’s lemma for Poisson random variables. The generality of our approach permits us to derive a characterization of infinitely divisible random measures. The second part of this work focuses on the study of the reciprocal classes of Markov processes with and without jumps and their characterization. We start with a resume of already existing results concerning the reciprocal classes of Brownian diffusions as solutions of duality formulae. As a new contribution, we show that the duality formula satisfied by elements of the reciprocal class of a Brownian diffusion has a physical interpretation as a stochastic Newton equation of motion. Thus we are able to connect the results of characterizations via duality formulae with the theory of stochastic mechanics by our interpretation, and to stochastic optimal control theory by the mathematical approach. As an application we are able to prove an invariance property of the reciprocal class of a Brownian diffusion under time reversal. In the context of pure jump processes we derive the following new results. We describe the reciprocal classes of Markov counting processes, also called unit jump processes, and obtain a characterization of the associated reciprocal class via a duality formula. This formula contains as key terms a stochastic derivative, a compensated stochastic integral and an invariant of the reciprocal class. Moreover we present an interpretation of the characterization of a reciprocal class in the context of stochastic optimal control of unit jump processes. As a further application we show that the reciprocal class of a Markov counting process has an invariance property under time reversal. Some of these results are extendable to the setting of pure jump processes, that is, we admit different jump-sizes. In particular, we show that the reciprocal classes of Markov jump processes can be compared using reciprocal invariants. A characterization of the reciprocal class of compound Poisson processes via a duality formula is possible under the assumption that the jump-sizes of the process are incommensurable.
This work investigates diffusion in nonlinear Hamiltonian systems. The diffusion, more precisely subdiffusion, in such systems is induced by the intrinsic chaotic behavior of trajectories and thus is called chaotic diffusion''. Its properties are studied on the example of one- or two-dimensional lattices of harmonic or nonlinear oscillators with nearest neighbor couplings. The fundamental observation is the spreading of energy for localized initial conditions. Methods of quantifying this spreading behavior are presented, including a new quantity called excitation time. This new quantity allows for a more precise analysis of the spreading than traditional methods. Furthermore, the nonlinear diffusion equation is introduced as a phenomenologic description of the spreading process and a number of predictions on the density dependence of the spreading are drawn from this equation. Two mathematical techniques for analyzing nonlinear Hamiltonian systems are introduced. The first one is based on a scaling analysis of the Hamiltonian equations and the results are related to similar scaling properties of the NDE. From this relation, exact spreading predictions are deduced. Secondly, the microscopic dynamics at the edge of spreading states are thoroughly analyzed, which again suggests a scaling behavior that can be related to the NDE. Such a microscopic treatment of chaotically spreading states in nonlinear Hamiltonian systems has not been done before and the results present a new technique of connecting microscopic dynamics with macroscopic descriptions like the nonlinear diffusion equation. All theoretical results are supported by heavy numerical simulations, partly obtained on one of Europe's fastest supercomputers located in Bologna, Italy. In the end, the highly interesting case of harmonic oscillators with random frequencies and nonlinear coupling is studied, which resembles to some extent the famous Discrete Anderson Nonlinear Schroedinger Equation. For this model, a deviation from the widely believed power-law spreading is observed in numerical experiments. Some ideas on a theoretical explanation for this deviation are presented, but a conclusive theory could not be found due to the complicated phase space structure in this case. Nevertheless, it is hoped that the techniques and results presented in this work will help to eventually understand this controversely discussed case as well.
Der Förster-Resonanzenergietransfer (FRET) liefert einen wichtigen Beitrag bei der Untersuchung kleinskaliger biologischer Systeme und Prozesse. Möglich wird dies durch die r-6-Abhängigkeit des FRET, die es erlaubt Abstände und strukturelle Änderungen weit unterhalb der Beugungsgrenze des Lichts mit hoher Sensitivität und geringem Aufwand zu bestimmen. Die besonderen photophysikalischen Eigenschaften von Terbiumkomplexen (LTC) und Quantenpunkten (QD) machen sie zu geeigneten Kandidaten für hochsensitive und störungsarme Multiplex-Abstandsmessungen in biologischen Systemen und Prozessen. Die Abstandsbestimmungen setzen jedoch eine genaueste Kenntnis des Mechanismus des Energietransfers von LTC auf QD ebenso voraus, wie das Wissen um Größe und Gestalt letzterer. Quantenpunkte haben im Vergleich zu biologischen Strukturen ähnliche Dimensionen und können nicht als punktförmig betrachtet werden, wie es bei einfacheren Farbstoffen möglich ist. Durch ihre Form kommt es zu einer Abstandsverteilung innerhalb des Donor-Akzeptorsystems. Dies beeinflusst den Energietransfer und damit die experimentellen Ergebnisse. In dieser Arbeit wurde der Energietransfer von LTC auf QD untersucht, um zu einer Aussage hinsichtlich des Mechanismus der Energieübertragung und der dabei zu berücksichtigenden photophysikalischen und strukturellen Parameter von LTC und QD zu gelangen. Mit der Annahme einer Abstandsverteilung sollten die Größen der Quantenpunkte bestimmt und der Einfluss von Form und Gestalt auf den Energietransfer betrachtet werden. Die notwendigen theoretischen und praktischen Grundlagen wurden eingangs dargestellt. Daran schlossen sich Messungen zur photophysikalischen Charakterisierung der Donoren und Akzeptoren an, die Grundlage der Berechnung der FRET-Parameter waren. Die Förster-Radien zeigten die für den FRET von LTC auf QD typischen extrem hohen Werte von bis zu 11 nm. Zeitaufgelöste Messungen der FRET-induzierten Lumineszenz der Donoren und Akzeptoren in den beiden biomolekularen Modellsystemen Zink-Histidin und Biotin-Streptavidin beschlossen den praktischen Teil. Als Donor wurde Lumi4Tb gebunden an ein Peptid bzw. Streptavidin genutzt, Akzeptoren waren fünf verschiedene, kommerziell erhältliche Quantenpunkte mit Carboxyl- bzw. Biotinfunktionalisierung. Bei allen Donor-Akzeptor-Paarungen konnte FRET beobachtet und ausgewertet werden. Es konnte gezeigt werden, dass die gesamte Emission des Terbiums zum Energietransfer beiträgt und der Orientierungsfaktor ² den Wert 2/3 annimmt. Die Charakterisierung der Bindungsverhältnisse innerhalb der FRET-Paare von LTC und QD über Verteilungsfunktionen bietet über die Form der Verteilungskurve die Möglichkeit Aussagen über die Gestalt der FRET-Partner zu treffen. So war es möglich, die mittlere Form der Quantenpunkte als Sphäre zu bestimmen. Dies entsprach, insbesondere bei den in z-Richtung des Kristallgitters elongierten Quantenpunkten, nicht den Erwartungen. Dieser Befund ermöglicht daher bei zukünftigen Messungen eine Verbesserung der Genauigkeit bei Abstandsbestimmungen mit Quantenpunkten. Neben der Ermittlung der die FRET-Verteilung bestimmenden Gestalt der Quantenpunkte konnte im Rahmen dieser Arbeit anhand vergleichender Messungen die Dicke der Polymerhülle der QD bestimmt und so gezeigt werden, dass FRET-Paare aus lumineszenten Terbiumkomplexen und Quantenpunkten in der Lage sind, Abstände im Nano- bis Sub-Nanometerbereich aufzulösen.
Current climate warming is affecting arctic regions at a faster rate than the rest of the world. This has profound effects on permafrost that underlies most of the arctic land area. Permafrost thawing can lead to the liberation of considerable amounts of greenhouse gases as well as to significant changes in the geomorphology, hydrology, and ecology of the corresponding landscapes, which may in turn act as a positive feedback to the climate system. Vast areas of the east Siberian lowlands, which are underlain by permafrost of the Yedoma-type Ice Complex, are particularly sensitive to climate warming because of the high ice content of these permafrost deposits. Thermokarst and thermal erosion are two major types of permafrost degradation in periglacial landscapes. The associated landforms are prominent indicators of climate-induced environmental variations on the regional scale. Thermokarst lakes and basins (alasses) as well as thermo-erosional valleys are widely distributed in the coastal lowlands adjacent to the Laptev Sea. This thesis investigates the spatial distribution and morphometric properties of these degradational features to reconstruct their evolutionary conditions during the Holocene and to deduce information on the potential impact of future permafrost degradation under the projected climate warming. The methodological approach is a combination of remote sensing, geoinformation, and field investigations, which integrates analyses on local to regional spatial scales. Thermokarst and thermal erosion have affected the study region to a great extent. In the Ice Complex area of the Lena River Delta, thermokarst basins cover a much larger area than do present thermokarst lakes on Yedoma uplands (20.0 and 2.2 %, respectively), which indicates that the conditions for large-area thermokarst development were more suitable in the past. This is supported by the reconstruction of the development of an individual alas in the Lena River Delta, which reveals a prolonged phase of high thermokarst activity since the Pleistocene/Holocene transition that created a large and deep basin. After the drainage of the primary thermokarst lake during the mid-Holocene, permafrost aggradation and degradation have occurred in parallel and in shorter alternating stages within the alas, resulting in a complex thermokarst landscape. Though more dynamic than during the first phase, late Holocene thermokarst activity in the alas was not capable of degrading large portions of Pleistocene Ice Complex deposits and substantially altering the Yedoma relief. Further thermokarst development in existing alasses is restricted to thin layers of Holocene ice-rich alas sediments, because the Ice Complex deposits underneath the large primary thermokarst lakes have thawed completely and the underlying deposits are ice-poor fluvial sands. Thermokarst processes on undisturbed Yedoma uplands have the highest impact on the alteration of Ice Complex deposits, but will be limited to smaller areal extents in the future because of the reduced availability of large undisturbed upland surfaces with poor drainage. On Kurungnakh Island in the central Lena River Delta, the area of Yedoma uplands available for future thermokarst development amounts to only 33.7 %. The increasing proximity of newly developing thermokarst lakes on Yedoma uplands to existing degradational features and other topographic lows decreases the possibility for thermokarst lakes to reach large sizes before drainage occurs. Drainage of thermokarst lakes due to thermal erosion is common in the study region, but thermo-erosional valleys also provide water to thermokarst lakes and alasses. Besides these direct hydrological interactions between thermokarst and thermal erosion on the local scale, an interdependence between both processes exists on the regional scale. A regional analysis of extensive networks of thermo-erosional valleys in three lowland regions of the Laptev Sea with a total study area of 5,800 km² found that these features are more common in areas with higher slopes and relief gradients, whereas thermokarst development is more pronounced in flat lowlands with lower relief gradients. The combined results of this thesis highlight the need for comprehensive analyses of both, thermokarst and thermal erosion, in order to assess past and future impacts and feedbacks of the degradation of ice-rich permafrost on hydrology and climate of a certain region.
Ein viel diskutiertes Thema unserer Zeit ist die Zukunft der Energiegewinnung und Speicherung. Dabei nimmt die Nanowissenschaft eine bedeutende Rolle ein; sie führt zu einer Effizienzsteigerung bei der Speicherung und Gewinnung durch bereits bekannte Materialien und durch neue Materialien. In diesem Zusammenhang ist die Chemie Wegbereiter für Nanomaterialien. Allerdings führen bisher die meisten bekannten Synthesen von Nanopartikeln zu undefinierten Partikeln. Eine einfache, kostengünstige und sichere Synthese würde die Möglichkeit einer breiten Anwendung und Skalierbarkeit bieten. In dieser Arbeit soll daher die Darstellung der einfachen Synthese von Mangannitrid-, Aluminiumnitrid-, Lithiummangansilicat-, Zirkonium-oxinitrid- und Mangancarbonatnanopartikel betrachtet werden. Dabei werden die sogenannte Harnstoff-Glas-Route als eine Festphasensynthese und die Solvothermalsynthese als typische Flüssigphasensynthese eingesetzt. Beide Synthesewege führen zu definierten Partikelgrößen und interessanten Morphologien und ermöglichen eine Einflussnahme auf die Produkte. Im Falle der Synthese der Mangannitridnanopartikel mithilfe der Harnstoff-Glas-Route führt diese zu Nanopartikeln mit Kern-Hülle-Struktur, deren Einsatz als Konversionsmaterial erstmalig vorgestellt wird. Mit dem Ziel einer leichteren Anwendung von Nanopartikeln wird eine einfache Beschichtung von Oberflächen mit Nanopartikeln mithilfe der Rotationsbeschichtung beschrieben. Es entstand ein Gemisch aus MnN0,43/MnO-Nanopartikeln, eingebettet in einem Kohlenstofffilm, dessen Untersuchung als Konversionsmaterial hohe spezifische Kapazitäten (811 mAh/g) zeigt, die die von dem konventionellen Anodenmaterial Graphit (372 mAh/g) übersteigt. Neben der Synthese des Anodenmaterials wurde ebenfalls die des Kathodenmaterials Li2MnSiO4-Nanopartikeln mithilfe der Harnstoff-Glas-Route vorgestellt. Mithilfe der Synthese von Zirkoniumoxinitridnanopartikeln Zr2ON2 kann eine einfache Einflussnahme auf das gewünschte Produkt durch die Variation derReaktionsbedingungen, wie Harnstoffmenge oder Reaktionstemperatur, bei der Harnstoff-Glas-Route demonstriert werden. Der Zusatz von kleinsten Mengen an Ammoniumchlorid vermeidet, dass sich Kohlenstoff im Endprodukt bildet und führt so zu gelben Zr2ON2-Nanopartikeln mit einer Größe d = 8 nm, die Halbleitereigen-schaften besitzen. Die Synthese von Aluminiumnitridnanopartikeln führt zu kristallinen Nanopartikeln, die in eine amorphe Matrix eingebettet sind. Die Solvothermalsynthese von Mangancarbonatnanopartikel lässt neue Morphologien in Form von Nanostäbchen entstehen, die zu schuppenartigen sphärischen Überstrukturen agglomeriert sind.
This work describes the synthesis and characterization of stimuli-responsive polymers made by reversible addition-fragmentation chain transfer (RAFT) polymerization and the investigation of their self-assembly into “smart” hydrogels. In particular the hydrogels were designed to swell at low temperature and could be reversibly switched to a collapsed hydrophobic state by rising the temperature. Starting from two constituents, a short permanently hydrophobic polystyrene (PS) block and a thermo-responsive poly(methoxy diethylene glycol acrylate) (PMDEGA) block, various gelation behaviors and switching temperatures were achieved. New RAFT agents bearing tert-butyl benzoate or benzoic acid groups, were developed for the synthesis of diblock, symmetrical triblock and 3-arm star block copolymers. Thus, specific end groups were attached to the polymers that facilitate efficient macromolecular characterization, e.g by routine 1H-NMR spectroscopy. Further, the carboxyl end-groups allowed functionalizing the various polymers by a fluorophore. Because reports on PMDEGA have been extremely rare, at first, the thermo-responsive behavior of the polymer was investigated and the influence of factors such as molar mass, nature of the end-groups, and architecture, was studied. The use of special RAFT agents enabled the design of polymer with specific hydrophobic and hydrophilic end-groups. Cloud points (CP) of the polymers proved to be sensitive to all molecular variables studied, namely molar mass, nature and number of the end-groups, up to relatively high molar masses. Thus, by changing molecular parameters, CPs of the PMDEGA could be easily adjusted within the physiological interesting range of 20 to 40°C. A second responsivity, namely to light, was added to the PMDEGA system via random copolymerization of MDEGA with a specifically designed photo-switchable azobenzene acrylate. The composition of the copolymers was varied in order to determine the optimal conditions for an isothermal cloud point variation triggered by light. Though reversible light-induced solubility changes were achieved, the differences between the cloud points before and after the irradiation were small. Remarkably, the response to light differed from common observations for azobenzene-based systems, as CPs decreased after UV-irradiation, i.e with increasing content of cis-azobenzene units. The viscosifying and gelling abilities of the various block copolymers made from PS and PMDEGA blocks were studied by rheology. Important differences were observed between diblock copolymers, containing one hydrophobic PS block only, the telechelic symmetrical triblock copolymers made of two associating PS termini, and the star block copolymers having three associating end blocks. Regardless of their hydrophilic block length, diblock copolymers PS11 PMDEGAn were freely flowing even at concentrations as high as 40 wt. %. In contrast, all studied symmetrical triblock copolymers PS8-PMDEGAn-PS8 formed gels at low temperatures and at concentrations as low as 3.5 wt. % at best. When heated, these gels underwent a gel-sol transition at intermediate temperatures, well below the cloud point where phase separation occurs. The gel-sol transition shifted to markedly higher transition temperatures with increasing length of the hydrophilic inner block. This effect increased also with the number of arms, and with the length of the hydrophobic end blocks. The mechanical properties of the gels were significantly altered at the cloud point and liquid-like dispersions were formed. These could be reversibly transformed into hydrogels by cooling. This thesis demonstrates that high molar mass PMDEGA is an easily accessible, presumably also biocompatible and at ambient temperature well water-soluble, non-ionic thermo-responsive polymer. PMDEGA can be easily molecularly engineered via the RAFT method, implementing defined end-groups, and producing different, also complex, architectures, such as amphiphilic triblock and star block copolymers, having an analogous structure to associative telechelics. With appropriate design, such amphiphilic copolymers give way to efficient, “smart” viscosifiers and gelators displaying tunable gelling and mechanical properties.
Entwicklung multi-stimuli sensitiver Materialien auf der Basis von flüssigkristallinen Elastomeren
(2012)
Aufgrund der zunehmenden technischen Ansprüche der Gesellschaft sind sich aktiv bewegende Polymere in den Mittelpunkt aktueller Forschung gerückt. Diese spielen bei Anwen-dungen im Bereich von künstlichen Muskeln und Implantaten für die minimal invasive Chirurgie eine wichtige Rolle. Vor allem Formänderungs- und Formgedächtnispolymere stehen dabei im wissenschaftlichen Fokus. Während die kontaktlose Deformation einer permanenten Form in eine temporäre metastabile Form, charakteristisch für Formände-rungspolymere ist, kann bei Formgedächtnis-Materialien die temporäre Form, aufgrund der Ausbildung reversibler, temporärer Netzpunkte, fixiert werden. Ein Polymermaterial, das eine Kombination beider Funktionen aufweist würde zu einem Material führen welches kontaktlos in eine temporäre Form deformiert und in dieser fixiert werden kann. Zusätzlich würde aufgrund der kontaktlosen Deformation die Reversibilität dieser Funktion gewähr-leistet sein. Ein solches Material ist bislang noch nicht beschrieben worden. In dieser Arbeit wird untersucht, ob durch die Kopplung zweier separat schaltbarer, be-kannter Funktionen eine neue schaltbare Funktion erzielt werden kann. Daher wurden multi-stimuli sensitive Materialien entwickelt die eine Kopplung des Formänderungs- und des Formgedächtniseffektes aufweisen. Dazu wurden zwei Konzepte entwickelt, die sich hinsichtlich der Reihenfolge der verwendeten Stimuli unterscheiden. Im ersten Konzept wurden flüssigkristalline Elastomere basie-rend auf Azobenzenderivaten aufgebaut und hinsichtlich der Kombination des licht-induzierten Formänderungseffektes mit dem thermisch-induzierten Formgedächtniseffekt untersucht. Diese orientierten Netzwerke weisen oberhalb der Glasübergangstemperatur (Tg) eine kontaktlose Verformung (Biegung) durch Bestrahlung mit UV-Licht des geeigneten Wellenlängenbereichs auf, wodurch eine temporäre Form erhalten wurde. Hierbei spielt der Vernetzungsgrad eine entscheidende Rolle bezüglich der Ausprägung dieser Biegung. Eine fixierte, temporäre Form konnte durch gleichzeitiges Abkühlen des Materials unterhalb von Tg während der Bestrahlung mit UV-Licht erhalten werden. Nach erneutem Aufheizen über Tg konnte die Originalform wiederhergestellt werden. Dieser Vorgang konnte reversibel durchgeführt werden. Damit wurde gezeigt, dass eine neue schaltbare Funktion erzielt wurde, die auf der Kopplung des lichtinduzierten Formänderungs- mit dem thermisch-induzierten Formgedächtniseffekt basiert. Die Abstimmung der einzelnen Funktion wird in diesem Konzept über die Morphologie des Systems gewährleistet. Diese neue Funktion ermöglicht eine kontaktlose Deformation des Materials in eine temporäre Form, welche fixiert werden kann. Im zweiten Konzept wurde eine Kopplung des thermisch induzierten Formänderungs- mit dem licht-induzierten Formgedächtniseffekt angestrebt. Um dies zu realisieren wurden nematisch, flüssigkristalline Hauptkettenelastomere (NMC-LCE) entwickelt, die eine nied-rige Übergangstemperatur der nematischen in die isotrope Phase (TNI), als auch einen aus-geprägten thermisch induzierten Formänderungseffekt aufweisen. Zusätzlich wurde eine photosensitive Schicht aufgebaut, die Cinnamylidenessigsäuregruppen in der Seitenkette eines Polysiloxanrückgrates aufweist. Die Reversibilität der photoinduzierten [2+2]-Cycloaddition konnte für dieses photosensitive Polymer beobachtet werden, wodurch die-ses Polymersystem in der Lage ist reversible temporäre Netzpunkte, aufgrund der Bestrah-lung mit UV-Licht, auszubilden. Die kovalente Anbindung der photosensitiven Schicht an die Oberfläche des flüssigkristallinen Kerns wurde erfolgreich durchgeführt, wodurch ein Multi-Komponenten-System aufgebaut wurde. Die Kombination des thermisch-induzierten Formänderungs- mit dem licht-induzierten Formgedächtniseffektes wurde anhand dieses Systems untersucht. Während die Einzelkomponenten die erforderliche Funktion zeigten, ist hier noch Arbeit in der Abstimmung beider Strukturen zu leisten. Insbesondere die Variation der Schichtdicken beider Komponenten steht im Fokus zukünftiger Arbeiten. In dieser Arbeit wurde durch die Kopplung von zwei separat schaltbaren, bekannten Funktionen eine neue schaltbare Funktion erzielt. Dies setzt voraus, dass die Einzelkomponenten hinsichtlich einer Funktion schaltbar sind und in einem Material integriert werden können. Des Weiteren müssen die beiden Funktionen mit unterschiedlichen Stimuli geschaltet werden. Ein wichtiger Schritt bei der Kopplung der Funktionen, ist die Abstimmung der beiden Komponenten. Dies kann über die Variation der Morphologie oder der Struktur erzielt werden. Anhand der Vielzahl der vorhandenen stimuli-sensitiven Materialien sind verschiedene Kopplungsmöglichkeiten vorhanden. Demnach wird erwartet, dass auf diesem Gebiet weitere neue Funktionen erzielt werden können.
Leaf senescence is an active process required for plant survival, and it is flexibly controlled, allowing plant adaptation to environmental conditions. Although senescence is largely an age-dependent process, it can be triggered by environmental signals and stresses. Leaf senescence coordinates the breakdown and turnover of many cellular components, allowing a massive remobilization and recycling of nutrients from senescing tissues to other organs (e.g., young leaves, roots, and seeds), thus enhancing the fitness of the plant. Such metabolic coordination requires a tight regulation of gene expression. One important mechanism for the regulation of gene expression is at the transcriptional level via transcription factors (TFs). The NAC TF family (NAM, ATAF, CUC) includes various members that show elevated expression during senescence, including ORE1 (ANAC092/AtNAC2) among others. ORE1 was first reported in a screen for mutants with delayed senescence (oresara1, 2, 3, and 11). It was named after the Korean word “oresara,” meaning “long-living,” and abbreviated to ORE1, 2, 3, and 11, respectively. Although the pivotal role of ORE1 in controlling leaf senescence has recently been demonstrated, the underlying molecular mechanisms and the pathways it regulates are still poorly understood. To unravel the signaling cascade through which ORE1 exerts its function, we analyzed particular features of regulatory pathways up-stream and down-stream of ORE1. We identified characteristic spatial and temporal expression patterns of ORE1 that are conserved in Arabidopsis thaliana and Nicotiana tabacum and that link ORE1 expression to senescence as well as to salt stress. We proved that ORE1 positively regulates natural and dark-induced senescence. Molecular characterization of the ORE1 promoter in silico and experimentally suggested a role of the 5’UTR in mediating ORE1 expression. ORE1 is a putative substrate of a calcium-dependent protein kinase named CKOR (unpublished data). Promising data revealed a positive regulation of putative ORE1 targets by CKOR, suggesting the phosphorylation of ORE1 as a requirement for its regulation. Additionally, as part of the ORE1 up-stream regulatory pathway, we identified the NAC TF ATAF1 which was able to transactivate the ORE1 promoter in vivo. Expression studies using chemically inducible ORE1 overexpression lines and transactivation assays employing leaf mesophyll cell protoplasts provided information on target genes whose expression was rapidly induced upon ORE1 induction. First, a set of target genes was established and referred to as early responding in the ORE1 regulatory network. The consensus binding site (BS) of ORE1 was characterized. Analysis of some putative targets revealed the presence of ORE1 BSs in their promoters and the in vitro and in vivo binding of ORE1 to their promoters. Among these putative target genes, BIFUNCTIONAL NUCLEASE I (BFN1) and VND-Interacting2 (VNI2) were further characterized. The expression of BFN1 was found to be dependent on the presence of ORE1. Our results provide convincing data which support a role for BFN1 as a direct target of ORE1. Characterization of VNI2 in age-dependent and stress-induced senescence revealed ORE1 as a key up-stream regulator since it can bind and activate VNI2 expression in vivo and in vitro. Furthermore, VNI2 was able to promote or delay senescence depending on the presence of an activation domain located in its C-terminal region. The plasticity of this gene might include alternative splicing (AS) to regulate its function in different organs and at different developmental stages, particularly during senescence. A model is proposed on the molecular mechanism governing the dual role of VNI2 during senescence.
This thesis contains several theoretical studies on optomechanical systems, i.e. physical devices where mechanical degrees of freedom are coupled with optical cavity modes. This optomechanical interaction, mediated by radiation pressure, can be exploited for cooling and controlling mechanical resonators in a quantum regime. The goal of this thesis is to propose several new ideas for preparing meso- scopic mechanical systems (of the order of 10^15 atoms) into highly non-classical states. In particular we have shown new methods for preparing optomechani-cal pure states, squeezed states and entangled states. At the same time, proce-dures for experimentally detecting these quantum effects have been proposed. In particular, a quantitative measure of non classicality has been defined in terms of the negativity of phase space quasi-distributions. An operational al- gorithm for experimentally estimating the non-classicality of quantum states has been proposed and successfully applied in a quantum optics experiment. The research has been performed with relatively advanced mathematical tools related to differential equations with periodic coefficients, classical and quantum Bochner’s theorems and semidefinite programming. Nevertheless the physics of the problems and the experimental feasibility of the results have been the main priorities.
Estimation of the self-similarity exponent has attracted growing interest in recent decades and became a research subject in various fields and disciplines. Real-world data exhibiting self-similar behavior and/or parametrized by self-similarity exponent (in particular Hurst exponent) have been collected in different fields ranging from finance and human sciencies to hydrologic and traffic networks. Such rich classes of possible applications obligates researchers to investigate qualitatively new methods for estimation of the self-similarity exponent as well as identification of long-range dependencies (or long memory). In this thesis I present the Bayesian estimation of the Hurst exponent. In contrast to previous methods, the Bayesian approach allows the possibility to calculate the point estimator and confidence intervals at the same time, bringing significant advantages in data-analysis as discussed in this thesis. Moreover, it is also applicable to short data and unevenly sampled data, thus broadening the range of systems where the estimation of the Hurst exponent is possible. Taking into account that one of the substantial classes of great interest in modeling is the class of Gaussian self-similar processes, this thesis considers the realizations of the processes of fractional Brownian motion and fractional Gaussian noise. Additionally, applications to real-world data, such as the data of water level of the Nile River and fixational eye movements are also discussed.
The constantly growing capacity of reconfigurable devices allows simultaneous execution of complex applications on those devices. The mere diversity of applications deems it impossible to design an interconnection network matching the requirements of every possible application perfectly, leading to suboptimal performance in many cases. However, the architecture of the interconnection network is not the only aspect affecting performance of communication. The resource manager places applications on the device and therefore influences latency between communicating partners and overall network load. Communication protocols affect performance by introducing data and processing overhead putting higher load on the network and increasing resource demand. Approaching communication holistically not only considers the architecture of the interconnect, but communication-aware resource management, communication protocols and resource usage just as well. Incorporation of different parts of a reconfigurable system during design- and runtime and optimizing them with respect to communication demand results in more resource efficient communication. Extensive evaluation shows enhanced performance and flexibility, if communication on reconfigurable devices is regarded in a holistic fashion.
Üblicherweise vermeiden deutsche Parteien Kampfkandidaturen um den Vorsitz. Dennoch kam es auf dem Mannheimer SPD-Parteitag 1995 zu einer unerwarteten offenen Konkurrenz um das Spitzenamt. Das unbeabsichtigte Scheitern der Inszenierung der „Geschlossenheit“ der Partei führte zum Ausbruch der bis dahin unterdrückten Kämpfe um den Parteivorsitz. Der Mannheimer Parteitag steht exemplarisch für den Zusammenhang zwischen Inszenierung, Disziplin und den informellen Regeln innerparteilicher Machtkonstruktion. Am Beispiel dieses Parteitages zeigt die vorliegende Arbeit, wie umstrittenen Parteivorsitzenden sich gegen Widerstände im Amt behaupten können bzw. woran diese Strategie scheitern kann. Aus figurationstheoretischer Perspektive wird die Inszenierung als Notwendigkeit medienvermittelter Parteienkonkurrenz um Wählerstimmen gefasst. Inszenierung erfordert Selbstdisziplin und das koordinierte Handeln der Parteimitglieder. Innerparteilich wird so wechselseitige Abhängigkeit erzeugt. Diese wird gesteigert durch die Medien-Konzentration auf wenige Spitzenpolitiker. Die Mehrheit der Mandatsträger und Funktionäre ist angewiesen auf das medienwirksame Auftreten der Führung. Für den Medienerfolg braucht die Führung ihrerseits die Unterstützung der Mitglieder. Diese wechselseitige Abhängigkeit erzeugt sowohl typische Relevanzen als auch Möglichkeiten, die jeweils andere Interessengruppe unter Zugzwang zu setzen. Imageprobleme des Vorsitzenden sind als verletzte Erwartungen Anlass für innerparteiliche Machtkämpfe, in denen die Parteiführung insbesondere die Inszenierung der „Geschlossenheit“ nutzen kann, um offene Personaldiskussionen zu verhindern. Da Handlungsoptionen und -grenzen durch das Handeln der Akteure immer wieder neu geschaffen werden, besteht stets das Risiko des Scheiterns innerparteilicher Disziplinierung. Mit dem Nachvollzug von Disziplinierung und den Gründen ihrer Kontingenz versteht sich die vorliegende Arbeit als Beitrag zu einer Theorie informeller Machtregeln in Organisationen mit schwach ausgeprägten Herrschaftsstrukturen. Im ersten Teil der Arbeit wird der Zusammenhang zwischen Inszenierung und Macht durch die Konzepte Theatralität und Figuration entwickelt. Im zweiten Teil werden typische Konstellationen der gegenwärtigen parlamentarischen Demokratie auf typische beziehungsvermittelte Situationsdeutungen, Handlungsmöglichkeiten und -grenzen untersucht. Im dritten Teil wird der kontingente Prozess des innerparteilichen Machtkampfes am Beispiel des Mannheimer Parteitages 1995 nachvollzogen.
Sustainable management of semi-arid African savannas under environmental and political change
(2012)
Drylands cover about 40% of the earth’s land surface and provide the basis for the livelihoods of 38% of the global human population. Worldwide, these ecosystems are prone to heavy degradation. Increasing levels of dryland degradation result a strong decline of ecosystem services. In addition, in highly variable semi-arid environments changing future environmental conditions will potentially have severe consequences for productivity and ecosystem dynamics. Hence, global efforts have to be made to understand the particular causes and consequences of dryland degradation and to promote sustainable management options for semi-arid and arid ecosystems in a changing world. Here I particularly address the problem of semi-arid savanna degradation, which mostly occurs in form of woody plant encroachment. At this, I aim at finding viable sustainable management strategies and improving the general understanding of semi-arid savanna vegetation dynamics under conditions of extensive livestock production. Moreover, the influence of external forces, i.e. environmental change and land reform, on the use of savanna vegetation and on the ecosystem response to this land use is assessed. Based on this I identify conditions and strategies that facilitate a sustainable use of semi-arid savanna rangelands in a changing world. I extended an eco-hydrological model to simulate rangeland vegetation dynamics for a typical semi-arid savanna in eastern Namibia. In particular, I identified the response of semi-arid savanna vegetation to different land use strategies (including fire management) also with regard to different predicted precipitation, temperature and CO2 regimes. Not only environmental but also economic and political constraints like e.g. land reform programmes are shaping rangeland management strategies. Hence, I aimed at understanding the effects of the ongoing process of land reform in southern Africa on land use and the semi-arid savanna vegetation. Therefore, I developed and implemented an agent-based ecological-economic modelling tool for interactive role plays with land users. This tool was applied in an interdisciplinary empirical study to identify general patterns of management decisions and the between-farm cooperation of land reform beneficiaries in eastern Namibia. The eco-hydrological simulations revealed that the future dynamics of semi-arid savanna vegetation strongly depend on the respective climate change scenario. In particular, I found that the capacity of the system to sustain domestic livestock production will strongly depend on changes in the amount and temporal distribution of precipitation. In addition, my simulations revealed that shrub encroachment will become less likely under future climatic conditions although positive effects of CO2 on woody plant growth and transpiration have been considered. While earlier studies predicted a further increase in shrub encroachment due to increased levels of atmospheric CO2, my contrary finding is based on the negative impacts of temperature increase on the drought sensitive seedling germination and establishment of woody plant species. Further simulation experiments revealed that prescribed fires are an efficient tool for semi-arid rangeland management, since they suppress woody plant seedling establishment. The strategies tested have increased the long term productivity of the savanna in terms of livestock production and decreased the risk for shrub encroachment (i.e. savanna degradation). This finding refutes the views promoted by existing studies, which state that fires are of minor importance for the vegetation dynamics of semi-arid and arid savannas. Again, the difference in predictions is related to the bottleneck at the seedling establishment stage of woody plants, which has not been sufficiently considered in earlier studies. The ecological-economic role plays with Namibian land reform beneficiaries showed that the farmers made their decisions with regard to herd size adjustments according to economic but not according to environmental variables. Hence, they do not manage opportunistically by tracking grass biomass availability but rather apply conservative management strategies with low stocking rates. This implies that under the given circumstances the management of these farmers will not per se cause (or further worsen) the problem of savanna degradation and shrub encroachment due to overgrazing. However, as my results indicate that this management strategy is rather based on high financial pressure, it is not an indicator for successful rangeland management. Rather, farmers struggle hard to make any positive revenue from their farming business and the success of the Namibian land reform is currently disputable. The role-plays also revealed that cooperation between farmers is difficult even though obligatory due to the often small farm sizes. I thus propose that cooperation needs to be facilitated to improve the success of land reform beneficiaries.
Mikroorganismen in geothermischen Aquiferen : Einfluss mikrobieller Prozesse auf den Anlagenbetrieb
(2012)
In Fluid-, Filter- und Sedimentproben von vier geothermischen Anlagen des Norddeutschen Beckens wurden mit molekulargenetischen Verfahren unterschiedliche mikrobielle Gemeinschaften nachgewiesen. Die mikrobielle Zusammensetzung in den Prozesswässern wurde dabei durch die Aquiferteufe, die Salinität, die Temperatur und den verfügbaren Elektronendonatoren und -akzeptoren beeinflusst. Die in den anoxischen Prozesswässern identifizierten Organismen zeichneten sich durch einen chemoheterotrophen oder chemoautotrophen Stoffwechsel aus, wobei Nitrat, Sulfat, Eisen (III) oder Bikarbonat als terminale Elektronenakzeptoren fungierten. Mikroorganismen beeinflussten den Betrieb von zwei Anlagen negativ. So reduzierten im Prozesswasser des Kältespeichers am Berliner Reichstag vorhandene Eisenoxidierer, nahe verwandt zu der Gattung Gallionella, die Injektivität der Bohrungen durch Eisenhydroxidausfällungen in den Filterschlitzen. Biofilme, die von schwefeloxidierenden Bakterien der Gattung Thiothrix in den Filtern der obertägigen Anlage gebildet wurden, führten ebenfalls zu Betriebsstörungen, indem sie die Injektion des Fluids in den Aquifer behinderten. Beim Wärmespeicher in Neubrandenburg waren Sulfatreduzierer vermutlich an der Bildung von Eisensulfidausfällungen in den obertägigen Filtern und im bohrlochnahen Bereich beteiligt und verstärkten Korrosionsprozesse an der Pumpe im Bohrloch der kalten Aquiferseite. Organische Säuren in den Fluiden sowie mineralische Ausfällungen in den Filtern der obertägigen Anlagen waren Belege für die Aktivität der in den verschiedenen Anlagen vorhandenen Mikroorganismen. Es wurde zudem deutlich, dass Mikroorganismen auf Grund der hohen Durchflussraten in den Anlagen chemische Veränderungen in den Prozesswässern deutlich sensitiver anzeigen als chemische Analyseverfahren. So deuteten Änderungen in der Zusammensetzung der mikrobiellen Biozönosen und speziell die Identifikation von Indikatororganismen wie Eisen- und Schwefeloxidierern, fermentativen Bakterien und Sulfatreduzierern auf eine erhöhte Verfügbarkeit von Elektronendonatoren oder akzeptoren in den Prozesswässern hin. Die Ursachen für die an den Geothermieanlagen auftretenden Betriebsstörungen konnten dadurch erkannt werden.
The present work is devoted to establishing of a new generation of self-healing anti-corrosion coatings for protection of metals. The concept of self-healing anticorrosion coatings is based on the combination of the passive part, represented by the matrix of conventional coating, and the active part, represented by micron-sized capsules loaded with corrosion inhibitor. Polymers were chosen as the class of compounds most suitable for the capsule preparation. The morphology of capsules made of crosslinked polymers, however, was found to be dependent on the nature of the encapsulated liquid. Therefore, a systematic analysis of the morphology of capsules consisting of a crosslinked polymer and a solvent was performed. Three classes of polymers such as polyurethane, polyurea and polyamide were chosen. Capsules made of these polymers and eight solvents of different polarity were synthesized via interfacial polymerization. It was shown that the morphology of the resulting capsules is specific for every polymer-solvent pair. Formation of capsules with three general types of morphology, such as core-shell, compact and multicompartment, was demonstrated by means of Scanning Electron Microscopy. Compact morphology was assumed to be a result of the specific polymer-solvent interactions and be analogues to the process of swelling. In order to verify the hypothesis, pure polyurethane, polyurea and polyamide were synthesized; their swelling behavior in the solvents used as the encapsulated material was investigated. It was shown that the swelling behavior of the polymers in most cases correlates with the capsules morphology. Different morphologies (compact, core-shell and multicompartment) were therefore attributed to the specific polymer-solvent interactions and discussed in terms of “good” and “poor” solvent. Capsules with core-shell morphology are formed when the encapsulated liquid is a “poor” solvent for the chosen polymer while compact morphologies are formed when the solvent is “good”. Multicompartment morphology is explained by the formation of infinite networks or gelation of crosslinked polymers. If gelation occurs after the phase separation in the system is achieved, core-shell morphology is present. If gelation of the polymer occurs far before crosslinking is accomplished, further condensation of the polymer due to the crosslinking may lead to the formation of porous or multicompartment morphologies. It was concluded that in general, the morphology of capsules consisting of certain polymer-solvent pairs can be predicted on the basis of polymer-solvent behavior. In some cases, the swelling behavior and morphology may not match. The reasons for that are discussed in detail in the thesis. The discussed approach is only capable of predicting capsule morphology for certain polymer-solvent pairs. In practice, the design of the capsules assumes the trial of a great number of polymer-solvent combinations; more complex systems consisting of three, four or even more components are often used. Evaluation of the swelling behavior of each component pair of such systems becomes unreasonable. Therefore, exploitation of the solubility parameter approach was found to be more useful. The latter allows consideration of the properties of each single component instead of the pair of components. In such a manner, the Hansen Solubility Parameter (HSP) approach was used for further analysis. Solubility spheres were constructed for polyurethane, polyurea and polyamide. For this a three-dimensional graph is plotted with dispersion, polar and hydrogen bonding components of solubility parameter, obtained from literature, as the orthogonal axes. The HSP of the solvents are used as the coordinates for the points on the HSP graph. Then a sphere with a certain radius is located on a graph, and the “good” solvents would be located inside the sphere, while the “poor” ones are located outside. Both the location of the sphere center and the sphere radius should be fitted according to the information on polymer swelling behavior in a number of solvents. According to the existing correlation between the capsule morphology and swelling behavior of polymers, the solvents located inside the solubility sphere of a polymer give capsules with compact morphologies. The solvents located outside the solubility sphere of the solvent give either core-shell or multicompartment capsules in combination with the chosen polymer. Once the solubility sphere of a polymer is found, the solubility/swelling behavior is approximated to all possible substances. HSP theory allows therefore prediction of polymer solubility/swelling behavior and consequently the capsule morphology for any given substance with known HSP parameters on the basis of limited data. The latter makes the theory so attractive for application in chemistry and technology, since the choice of the system components is usually performed on the basis of a large number of different parameters that should mutually match. Even slight change of the technology sometimes leads to the necessity to find the analogue of this or that solvent in a sense of solvency but carrying different chemistry. Usage of the HSP approach in this case is indispensable. In the second part of the work examples of the HSP application for the fabrication of capsules with on-demand-morphology are presented. Capsules with compact or core-shell morphology containing corrosion inhibitors were synthesized. Thus, alkoxysilanes possessing long hydrophobic tail, combining passivating and water-repelling properties, were encapsulated in polyurethane shell. The mechanism of action of the active material required core-shell morphology of the capsules. The new hybrid corrosion inhibitor, cerium diethylhexyl phosphate, was encapsulated in polyamide shells in order to facilitate the dispersion of the substance and improve its adhesion to the coating matrix. The encapsulation of commercially available antifouling agents in polyurethane shells was carried out in order to control its release behavior and colloidal stability. Capsules with compact morphology made of polyurea containing the liquid corrosion inhibitor 2-methyl benzothiazole were synthesized in order to improve the colloidal stability of the substance. Capsules with compact morphology allow slower release of the liquid encapsulated material compared to the core-shell ones. If the “in-situ” encapsulation is not possible due to the reaction of the oil-soluble monomer with the encapsulated material, a solution was proposed: loading of the capsules should be performed after monomer deactivation due to the accomplishment of the polymerization reaction. Capsules of desired morphologies should be preformed followed by the loading step. In this way, compact polyurea capsules containing the highly effective but chemically active corrosion inhibitors 8-hydroxyquinoline and benzotriazole were fabricated. All the resulting capsules were successfully introduced into model coatings. The efficiency of the resulting “smart” self-healing anticorrosion coatings on steel and aluminium alloy of the AA-2024 series was evaluated using characterization techniques such as Scanning Vibrating Electron Spectroscopy, Electrochemical Impedance Spectroscopy and salt-spray chamber tests.
In industrialized economies such as the European countries unemployment rates are very responsive to the business cycle and significant shares stay unemployed for more than one year. To fight cyclical and long-term unemployment countries spend significant shares of their budget on Active Labor Market Policies (ALMP). To improve the allocation and design of ALMP it is essential for policy makers to have reliable evidence on the effectiveness of such programs available. Although the number of studies has been increased during the last decades, policy makers still lack evidence on innovative programs and for specific subgroups of the labor market. Using Germany as a case study, the dissertation aims at contributing in this way by providing new evidence on start-up subsidies, marginal employment and programs for youth unemployed. The idea behind start-up subsidies is to encourage unemployed individuals to exit unemployment by starting their own business. Those programs have compared to traditional programs of ALMP the advantage that not only the participant escapes unemployment but also might generate additional jobs for other individuals. Considering two distinct start-up subsidy programs, the dissertation adds three substantial aspects to the literature: First, the programs are effective in improving the employment and income situation of participants compared to non-participants in the long-run. Second, the analysis on effect heterogeneity reveals that the programs are particularly effective for disadvantaged groups in the labor market like low educated or low qualified individuals, and in regions with unfavorable economic conditions. Third, the analysis considers the effectiveness of start-up programs for women. Due to higher preferences for flexible working hours and limited part-time jobs, unemployed women often face more difficulties to integrate in dependent employment. It can be shown that start-up subsidy programs are very promising as unemployed women become self-employed which gives them more flexibility to reconcile work and family. Overall, the results suggest that the promotion of self-employment among the unemployed is a sensible strategy to fight unemployment by abolishing labor market barriers for disadvantaged groups and sustainably integrating those into the labor market. The next chapter of the dissertation considers the impact of marginal employment on labor market outcomes of the unemployed. Unemployed individuals in Germany are allowed to earn additional income during unemployment without suffering a reduction in their unemployment benefits. Those additional earnings are usually earned by taking up so-called marginal employment that is employment below a certain income level subject to reduced payroll taxes (also known as “mini-job”). The dissertation provides an empirical evaluation of the impact of marginal employment on unemployment duration and subsequent job quality. The results suggest that being marginal employed during unemployment has no significant effect on unemployment duration but extends employment duration. Moreover, it can be shown that taking up marginal employment is particularly effective for long-term unemployed, leading to higher job-finding probabilities and stronger job stability. It seems that mini-jobs can be an effective instrument to help long-term unemployed individuals to find (stable) jobs which is particularly interesting given the persistently high shares of long-term unemployed in European countries. Finally, the dissertation provides an empirical evaluation of the effectiveness of ALMP programs to improve labor market prospects of unemployed youth. Youth are generally considered a population at risk as they have lower search skills and little work experience compared to adults. This results in above-average turnover rates between jobs and unemployment for youth which is particularly sensitive to economic fluctuations. Therefore, countries spend significant resources on ALMP programs to fight youth unemployment. However, so far only little is known about the effectiveness of ALMP for unemployed youth and with respect to Germany no comprehensive quantitative analysis exists at all. Considering seven different ALMP programs, the results show an overall positive picture with respect to post-treatment employment probabilities for all measures under scrutiny except for job creation schemes. With respect to effect heterogeneity, it can be shown that almost all programs particularly improve the labor market prospects of youths with high levels of pretreatment schooling. Furthermore, youths who are assigned to the most successful employment measures have much better characteristics in terms of their pre-treatment employment chances compared to non-participants. Therefore, the program assignment process seems to favor individuals for whom the measures are most beneficial, indicating a lack of ALMP alternatives that could benefit low-educated youths.
Growing populations, continued economic development, and limited natural resources are critical factors affecting sustainable development. These factors are particularly pertinent in developing countries in which large parts of the population live at a subsistence level and options for sustainable development are limited. Therefore, addressing sustainable land use strategies in such contexts requires that decision makers have access to evidence-based impact assessment tools that can help in policy design and implementation. Ex-ante impact assessment is an emerging field poised at the science-policy interface and is used to assess the potential impacts of policy while also exploring trade-offs between economic, social and environmental sustainability targets. The objective of this study was to operationalise the impact assessment of land use scenarios in the context of developing countries that are characterised by limited data availability and quality. The Framework for Participatory Impact Assessment (FoPIA) was selected for this study because it allows for the integration of various sustainability dimensions, the handling of complexity, and the incorporation of local stakeholder perceptions. FoPIA, which was originally developed for the European context, was adapted to the conditions of developing countries, and its implementation was demonstrated in five selected case studies. In each case study, different land use options were assessed, including (i) alternative spatial planning policies aimed at the controlled expansion of rural-urban development in the Yogyakarta region (Indonesia), (ii) the expansion of soil and water conservation measures in the Oum Zessar watershed (Tunisia), (iii) the use of land conversion and the afforestation of agricultural areas to reduce soil erosion in Guyuan district (China), (iv) agricultural intensification and the potential for organic agriculture in Bijapur district (India), and (v) land division and privatisation in Narok district (Kenya). The FoPIA method was effectively adapted by dividing the assessment into three conceptual steps: (i) scenario development; (ii) specification of the sustainability context; and (iii) scenario impact assessment. A new methodological approach was developed for communicating alternative land use scenarios to local stakeholders and experts and for identifying recommendations for future land use strategies. Stakeholder and expert knowledge was used as the main sources of information for the impact assessment and was complemented by available quantitative data. Based on the findings from the five case studies, FoPIA was found to be suitable for implementing the impact assessment at case study level while ensuring a high level of transparency. FoPIA supports the identification of causal relationships underlying regional land use problems, facilitates communication among stakeholders and illustrates the effects of alternative decision options with respect to all three dimensions of sustainable development. Overall, FoPIA is an appropriate tool for performing preliminary assessments but cannot replace a comprehensive quantitative impact assessment, and FoPIA should, whenever possible, be accompanied by evidence from monitoring data or analytical tools. When using FoPIA for a policy oriented impact assessment, it is recommended that the process should follow an integrated, complementary approach that combines quantitative models, scenario techniques, and participatory methods.
Charakterisierung der neuen centrosomalen Proteine CP148 und CP55 in Dictyostelium discoideum
(2012)
Das im Cytosol liegende Dictyostelium Centrosom ist aus einer geschichteten Core-Region aufgebaut, die von einer Mikrotubuli-nukleierenden Corona umgeben ist. Zudem ist es über eine spezifische Verbindung eng an den Kern geknüpft und durch die Kernmembran hindurch mit den geclusterten Centromeren verbunden. Beim G2/M Übergang dissoziiert die Corona vom Centrosom und der Core verdoppelt sich so dass zwei Spindelpole entstehen. CP55 und CP148 wurden in einer Proteom-Analyse des Centrosoms identifiziert. CP148 ist ein neues coiled-coil Protein der centrosomalen Corona. Es zeigt eine zellzyklusabhängige An- und Abwesenheit am Centrosom, die mit der Dissoziation der Corona in der Prophase und ihrer Neubildung in der Telophase korreliert. Während der Telophase erschienen in GFP-CP148 exprimierenden Zellen viele, kleine GFP-CP148-Foci im Cytoplasma, die zum Teil miteinander fusionierten und zum Centrosom wanderten. Daraus resultierte eine hypertrophe Corona in Zellen mit starker GFP-CP148 Überexpression. Ein Knockdown von CP148 durch RNAi führte zu einem Verlust der Corona und einem ungeordneten Interphase Mikrotubuli-Cytoskelett. Die Bildung der mitotischen Spindel und der astralen Mikrotubuli blieb davon unbeeinflusst. Das bedeutet, dass die Mikrotubuli-Nukleationskomplexe während der Interphase und Mitose über verschiedene Wege mit dem Core assoziiert sind. Des Weiteren bewirkte der Knockdown eine Dispersion der Centromere sowie eine veränderte Sun1 Lokalisation in der Kernhülle. Somit spielt CP148 ebenso eine Rolle in der Centrosomen-Centromer-Verbindung. Zusammengefasst ist CP148 ein essentielles Protein für die Bildung und Organisation der Corona, welche wiederum für die Centrosom/Centromer Verbindung benötigt wird. CP55 wurde als Protein der Core-Region identifiziert und verbleibt während des Zellzyklus am Centrosom. Dort besitzt es strukturelle Aufgaben, da die Mehrheit der GFP-CP55 Moleküle in der Interphase keine Mobilität zeigten. Die GFP-CP55 Überexpression führte zur Bildung von überzähligen Centrosomen mit der üblichen Ausstattung an Markerproteinen der Corona und des Cores. CP55 Knockout-Zellen waren durch eine erhöhte Ploidie, eine weniger strukturierte und leicht vergrößerte Corona sowie zusätzliche cytosolische Mikrotubuli-organisierende Zentren charakterisiert. Letztere entstanden in der Telophase und enthielten nur Corona- aber keine Core-Proteine. In CP55 k/o Zellen erfolgte die Rekrutierung des Corona-Organisators CP148 an den Spindelpol bereits in der frühen Metaphase anstatt, wie üblich, erst in der Telophase. Außerdem zeigten die Knockout-Zellen Wachstumsdefekte, deren Grund vermutlich Schwierigkeiten bei der Centrosomenverdopplung in der Prophase durch das Fehlen von CP55 waren. Darüber hinaus konnten die Knockout-Zellen phagozytiertes Material nicht verwerten, obwohl der Vorgang der Phagozytose nicht beeinträchtigt war. Dieser Defekt kann dem im CP55 k/o auftretenden dispergierten Golgi-Apparat zugeschrieben werden.
The dissertation examines the use of performance information by public managers. “Use” is conceptualized as purposeful utilization in order to steer, learn, and improve public services. The main research question is: Why do public managers use performance information? To answer this question, I systematically review the existing literature, identify research gaps and introduce the approach of my dissertation. The first part deals with manager-related variables that might affect performance information use but which have thus far been disregarded. The second part models performance data use by applying a theory from social psychology which is based on the assumption that this management behavior is conscious and reasoned. The third part examines the extent to which explanations of performance information use vary if we include others sources of “unsystematic” feedback in our analysis. The empirical results are based on survey data from 2011. I surveyed middle managers from eight selected divisions of all German cities with county status (n=954). To analyze the data, I used factor analysis, multiple regression analysis, and structural equation modeling. My research resulted in four major findings: 1) The use of performance information can be modeled as a reasoned behavior which is determined by the attitude of the managers and of their immediate peers. 2) Regular users of performance data surprisingly are not generally inclined to analyze abstract data but rather prefer gathering information through personal interaction. 3) Managers who take on ownership of performance information at an early stage in the measurement process are also more likely to use this data when it is reported to them. 4) Performance reports are only one source of information among many. Public managers prefer verbal feedback from insiders and feedback from external stakeholders over systematic performance reports. The dissertation explains these findings using a deductive approach and discusses their implications for theory and practice.
Essstörungen bei Jugendlichen im Hochleistungssport : eine Analyse sportbezogener Einflussfaktoren
(2012)
Essstörungen, wie Anorexia Nervosa oder Bulimia Nervorsa, gehen mit einer hohen psychischen Belastung einher und können gesundheitliche Schäden zur Folge haben. Bei Athleten mit einer Essstörung kann es darüber hinaus zu Einbußen in der Sportleistung kommen. Gerade für den Hochleistungssport ist es daher wichtig zu wissen, welches Risiko für Essstörungen besteht und wodurch das Risiko bedingt wird. Bisherige Studien zeigen deutliche Unterschiede zwischen den Sportarten. Eliteathleten aus ästhetischen Sportarten, wie rhythmische Sportgymnastik oder Eiskunstlauf, scheinen ein besonders hohes Essstörungsrisiko aufzuweisen. Deutlich geringere Prävalenzraten finden sich in Ballsportarten, wie Handball oder Basketball. Um zu verstehen, welche Aspekte der Sportart das Essstörungsrisiko beeinflussen, beschäftigt sich die vorliegende Arbeit mit der Rolle sportbezogener Variablen. In die Studien einbezogen wurden insgesamt 171 Athleten zwischen 11 und 18 Jahren (im Mittel 14.1 ± 1.8 Jahre) aus ästhetischen Sportarten und Ballsportarten, die einen Fragebogenpaket mit Instrumenten zu gestörtem Essverhalten, allgemeiner Körperunzufriedenheit, sozialem Druck im Sport, sportbezogener Körperunzufriedenheit, Schlankheitsstreben zur Leistungssteigerung und negativen Gefühle bei Trainingsausfall ausfüllten. Nach einem Jahr wieder befragt wurden 65 Athleten aus ästhetischen Sportarten. Nach Kontrolle von Alter, Geschlecht, BMI und allgemeiner Körperunzufriedenheit trugen sportbezogene Variablen signifikant zur weiteren Varianzaufklärung gestörten Essverhaltens bei. Die Längsschnittanalysen bestätigten einen Risikofaktorstatus für Schlankheitsstreben zur Leistungssteigerung. Zusammenhänge zwischen sportbezogenen Aspekten und gestörtem Essverhalten zeigten sich sowohl in Hochrisikosportarten für gestörtes Essverhalten (ästhetischen Sportarten), als auch in Niedrigrisikosportarten für gestörtes Essverhalten (Ballsportarten). Mit Ausnahme von negativen Gefühlen nach Trainingsausfall traten die sportbezogenen Variabeln häufiger in den ästhetischen Sportarten auf als in den Ballsportarten. Die eigenen Befunde verdeutlichen somit, dass der Einbezug potentieller sportbezogener Risikofaktoren − zusätzlich zu den allgemeinen Risikofaktoren − zum besseren Verständnis der Essstörungssymptomatik von Athleten beiträgt. Vor allem die Bedeutung von Gewicht für die Leistung beeinflusst das Essstörungsrisiko bei Athleten und ist stärker ausgeprägt in Hochrisikosportarten für Essstörungssymptomatik.
Der Einfluss unterschiedlich aggressiver Fusarium culmorum- und F. graminearum-Isolate auf die Schadbildausprägung bei Winterweizen sowie die Möglichkeit der Befallskontrolle mit Mykorrhiza Die durch Pilzarten der Gattung Fusarium spp. hervorgerufene partielle Taubährigkeit ist ein ernstes Problem im weltweiten Weizenanbau. Eine für die Schaderreger günstige feuchte Witterung zum Zeitpunkt der Weizenblüte in Kombination mit befallsfördernden agrotechnischen Maßnahmen löst immer wieder Epidemien aus. Hauptsächlich verursacht durch F. culmorum und F. graminearum führt eine Erkrankung zu Ertrags- und Qualitätseinbußen sowie zu einer Belastung des Ernteguts mit Mykotoxinen, die bereits in niedrigen Konzentrationen toxisch auf den tierischen und menschlichen Organismus wirken. Die am häufigsten vorkommenden Fusarium-Toxine in Weizen sind Deoxynivalenol (DON) und Zearalenon (ZEA). Isolate von F. graminearum- und F. culmorum können in ihrem DON- und ZEA-Bildungsvermögen und ihrem Potential, Nekrosen zu verursachen, stark variieren. In Laborversuchen (in vitro) wurden F. graminearum- und F. culmorum-Isolate hinsichtlich dieser Eigenschaften (hier als Aggressivität bezeichnet) charakterisiert und anschließend wurde im Feldversuch überprüft, ob die in vitro-ermittelte Aggressivität die Schadbildausprägung bei Weizenpflanzen beeinflusst. Nur im ersten Versuchsjahr, das durch hohe Niederschläge gekennzeichnet war, konnte ein Einfluss der Aggressivität und einer zusätzlichen Beregnung im Feldversuch nachgewiesen werden. Die als hoch-aggressiv eingestuften Fusarium-Isolate reduzierten unter dem Einfluss der Beregnung den Ertrag und das Tausendkorngewicht. Die Beregnung führte zu einer Erhöhung des Pilzwachstums und der DON- und ZEA-Produktion. Ein extrem trockener Sommer verhinderte die Infektion der Weizenpflanzen durch die beimpften Fusarium-Isolate und ein anschließendes Pilzwachstum in den Ähren im zweiten Versuchsjahr. Um den Befall von Weizenpflanzen mit Fusarium spp. vorzubeugen, stehen verschiedene pflanzenbauliche Maßnahmen zur Verfügung. Eine Möglichkeit stellen in diesem Zusammenhang die symbiotischen Mykorrhizapilze (MP) dar. Die Pilze sind in der Lage, Pflanzen zu stärken und antagonistisch auf pilzliche Schaderreger zu wirken. Um zu überprüfen, ob MP dazu beitragen könnten, den Befall von Weizenpflanzen mit Fusarium spp. niedrig zu halten, wurden Weizenpflanzen mit MP und Fusarium spp. beimpft und die Auswirkungen der Interaktionen auf die Weizenpflanzen in einem Klimakammer- und einem Feldversuch getestet. In der Klimakammer wurde eine Reduzierung des Fusarium-Befalls nachgewiesen. Die mykorrhizierten Weizenpflanzen wiesen außerdem höhere Photosyntheseraten, höhere Sprosstrockenmassen und mehr Ähren im Vergleich zu den nicht-mykorrhizierten und mit Fusarium-beimpften Weizenpflanzen auf. Insgesamt wurde durch die Mykorrhizierung der negative Einfluss von Fusarium spp. kompensiert. Im Freiland konnte kein Einfluss der MP auf Fusarium spp. beobachtet werden. Im ersten Versuchsjahr führte das Beimpfen der Weizenpflanzen mit MP zu höheren Wurzel- und Sprosstrockenmassen sowie zu höheren Tausendkorngewichten im Vergleich zu den mit Fusarium spp.-beimpften Weizenpflanzen. Im zweiten Versuchsjahr konnte dieses Ergebnis nicht wiederholt werden.