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Anhand einer inhaltlichen Untersuchung der französischen fünfbändigen Oktavausgabe seines Essai politique sur le royaume de la Nouvelle-Espagne (1811), unter besonderer Berücksichtigung der intertextuellen Bezüge, wird Alexander von Humboldt auf multiplen Ebenen als Denker zwischen Europa und Amerika ausgewiesen. In seinem Werk über Neuspanien durchbricht er die Inferiorisierung amerikanischer bzw. kreolischer Wissenschaftler und schafft ein Bewusstsein fernab eurozentrischer Denkmuster. Dies äußert sich unter anderem in Humboldts unvoreingenommener intertextueller Einbeziehung von Vertretern verschiedener Strömungen der Aufklärung, insbesondere des kreolischen aufklärerischen Denkens.
Delay
(2018)
Das Sinnbild »Diabolisches Spiel mit den Zeitmaschinen« spiegelt eine Sicht auf den Musikeffekt »Delay« und seine wechselseitige Beziehung zwischen Technik, Musikproduktion und Rezeption wider. Der durch die beabsichtigte Verzögerung eines akustischen Signals erzeugte und häufig als »Echo« beschriebene Effekt kann nicht nur als echoähnliche Verzögerung, sondern auch in anderen Weisen eingesetzt und vernommen werden. Dies zeigt die Dub-Musik, in der das Delay von der ersten Stunde bis in seine gegenwärtige Ausprägung zum Stilmerkmal wurde. Lee »Scratch« Perry ist Zeitzeuge und Exponent dieser Entwicklung. Sein Schaffen bildet den geeigneten Anlass, den Zeitgeist des Delay und seine Wahrnehmung als psychoakustischen Effekt zu erforschen. Damit führt dieses Buch von einer allgemeinen Beschreibung und Neuverortung des Delays in den prominenten Verwendungskontext der Dub-Musik und die Erkundung eines vielschichtigen Bezugskosmos aus Natur, Technik, Religion, Okkultismus und (Musik-)Kultur.
Synchrotron-based angle-resolved time-of-flight electron spectroscopy for dynamics in dichalogenides
(2018)
Der Anspruch der Biologie, Leben zum Hauptgegenstand zu haben, provoziert Fragen in Anbetracht von Methoden wie der Mikroskopie. Die vorliegende Bild- und Medientheorie der Mikroskopie rekonstruiert und reflektiert biologische Praktiken der Licht- und Elektronenmikroskopie.Dabei geht sie systematisch von der Auswahl der Objekte über die Präparation und Beobachtung bis hin zur Aufzeichnung des Sichtbargemachten in Form von Zeichnung, Fotografie oder Datenbild unter Einbeziehung von historischem Material vor. Die umfassende Untersuchung des Bildgebungsprozesses, seiner medialen Bedingungen sowie technischen und methodologischen Grundlagen zeigt, dass die mikroskopische Beobachtung kein passiver oder rein rezeptiver Vorgang, sondern von Beginn an in die Darstellung des Beobachteten involviert ist – bis zu einem Grad, in dem sich Beobachtung als schädigender Eingriff erweisen kann. Das Buch wirft somit zugleich epistemologische wie wissenschaftstheoretische Fragen auf.
Samarium hexaboride
(2018)
Im historischen Zentrum der mittelalterlichen Stadt Capua hat sich mit den drei Kirchen S. Salvatore „Maggiore“ a Corte, S. Giovanni a Corte und S. Michele a Corte eine Gruppe von Sakralbauten erhalten, die nicht nur durch ihre übereinstimmende namentliche Attribution einen Zusammenhang mit dem langobardischen Fürstenhof der Stadt offenbaren, sondern auch durch die räumliche Disposition im urbanistischen Gefüge. Im vorliegenden Buch wird die überkommene Bausubstanz einer grundlegenden Analyse unterzogen, um herauszuarbeiten, welche Bestandteile den ältesten Bauphasen zuzuordnen sind und somit als langobardenzeitlich angesprochen werden können. Eine ausführliche Untersuchung der zugehörigen Bauplastik ergänzt gleichwertig diesen ersten Teil. Die Kontextualisierung der Ergebnisse hilft dabei, ein Bild von der Kunst und Architektur des in Süditalien an Monumenten eher armen 10. Jahrhunderts zu generieren und erlaubt Rückschlüsse auf den geistigen Hintergrund, vor dem die drei Hofkirchen entstanden sind.
Monoclonal antibodies (mAbs) are an innovative group of drugs with increasing clinical importance in oncology, combining high specificity with generally low toxicity. There are, however, numerous challenges associated with the development of mAbs as therapeutics. Mechanistic understanding of factors that govern the pharmacokinetics (PK) of mAbs is critical for drug development and the optimisation of effective therapies; in particular, adequate dosing strategies can improve patient quality life and lower drug cost. Physiologically-based PK (PBPK) models offer a physiological and mechanistic framework, which is of advantage in the context of animal to human extrapolation. Unlike for small molecule drugs, however, there is no consensus on how to model mAb disposition in a PBPK context. Current PBPK models for mAb PK hugely vary in their representation of physiology and parameterisation. Their complexity poses a challenge for their applications, e.g., translating knowledge from animal species to humans.
In this thesis, we developed and validated a consensus PBPK model for mAb disposition taking into account recent insights into mAb distribution (antibody biodistribution coefficients and interstitial immunoglobulin G (IgG) pharmacokinetics) to predict tissue PK across several pre-clinical species and humans based on plasma data only. The model allows to a priori predict target-independent (unspecific) mAb disposition processes as well as mAb disposition in concentration ranges, for which the unspecific clearance (CL) dominates target-mediated CL processes. This is often the case for mAb therapies at steady state dosing.
The consensus PBPK model was then used and refined to address two important problems:
1) Immunodeficient mice are crucial models to evaluate mAb efficacy in cancer therapy. Protection from elimination by binding to the neonatal Fc receptor is known to be a major pathway influencing the unspecific CL of both, endogenous and therapeutic IgG. The concentration of endogenous IgG, however, is reduced in immunodeficient mouse models, and this effect on unspecific mAb CL is unknown, yet of great importance for the extrapolation to human in the context of mAb cancer therapy.
2) The distribution of mAbs into solid tumours is of great interest. To comprehensively investigate mAb distribution within tumour tissue and its implications for therapeutic efficacy, we extended the consensus PBPK model by a detailed tumour distribution model incorporating a cell-level model for mAb-target interaction. We studied the impact of variations in tumour microenvironment on therapeutic efficacy and explored the plausibility of different mechanisms of action in mAb cancer therapy.
The mathematical findings and observed phenomena shed new light on therapeutic utility and dosing regimens in mAb cancer treatment.
Suchmaschinen spielen eine überragend wichtige Rolle für den Informationszugang im Internet und damit für die individuelle und kollektive Meinungsbildung. Gleichzeitig wird der Suchmaschinenmarkt nahezu vollständig von einem einzigen Anbieter beherrscht – Google. Angesichts dessen wird vermehrt eine Regulierung von Suchmaschinen zur Sicherung der für die Demokratie unabdingbaren Meinungsvielfalt gefordert. Die Untersuchung geht der Gebotenheit und den Grenzen einer solchen Regulierung nach und stellt die Frage nach einem kommunikationsverfassungsrechtlichen Schutz von und vor Suchmaschinen.
Anne-Katrin Wolf beschäftigt sich mit der Aktivlegitimation im Individualbeschwerdeverfahren der UN-Menschenrechtskonventionen. Sie gibt einerseits eine leitfadenartige Übersicht zum Zulässigkeitskriterium der Aktivlegitimation. Andererseits zeigt sie, dass die Auslegungspraxis der UN-Ausschüsse zu dessen Voraussetzungen derzeit an einigen Stellen zu eng gefasst ist, um einen effektiven Menschenrechtsschutz zu gewährleisten. Im Zentrum steht dabei die Kategorisierung der UN-Menschenrechtskonventionen anhand der jeweiligen Regelungsmaterie und die daran anknüpfende, unterschiedlich weit reichenden Beschwerdemöglichkeiten von Individuen und Kollektiven wie Verbänden oder Nichtregierungsorganisationen. Sofern eine Ausgestaltung durch die Ausschüsse selbst noch nicht erfolgt ist oder die Autorin bisher angewendeten Kriterien als defizitär bewertet, entwickelt sie Vorschläge zu einer möglichen Ausformung des Kriteriums der Aktivlegitimation in der Zusammenschau mit dem jeweiligen Schutzgehalt der Konvention.
On a small scale
(2018)
This study argues that micro relations matter in peacekeeping. Asking what makes the implementation of peacekeeping interventions complex and how complexity is resolved, I find that formal, contractual mechanisms only rarely effectively reduce complexity – and that micro relations fill this gap. Micro relations are personal relationships resulting from frequent face-to-face interaction in professional and – equally importantly – social contexts.
This study offers an explanation as to why micro relations are important for coping with complexity, in the form of a causal mechanism. For this purpose, I bring together theoretical and empirical knowledge: I draw upon the current debate on ‘institutional complexity’ (Greenwood et al. 2011) in organizational institutionalism as well as original empirical evidence from a within-case study of the peacekeeping intervention in Haiti, gained in ten weeks of field research. In this study, scholarship on institutional complexity serves to identify theoretical causal channels which guide empirical analysis. An additional, secondary aim is pursued with this mechanism-centered approach: testing the utility of Beach and Pedersen’s (2013) theory-testing process tracing.
Regarding the first research question – what makes the implementation of peacekeeping interventions complex –, the central finding is that complexity manifests itself in the dual role of organizations as cooperation partners and competitors for (scarce) resources, turf and influence. UN organizations, donor agencies and international NGOs implementing peacekeeping activities in post-conflict environments have chronic difficulty mastering both roles because they entail contradictory demands: effective cooperation requires information exchange, resource and responsibility-sharing as well as external scrutiny, whereas prevailing over competitors demands that organizations conceal information, guard resources, increase relative turf and influence, as well as shield themselves from scrutiny. Competition fuels organizational distrust and friction – and impedes cooperation.
How is this complexity resolved? The answer to this second research question is that deep-seated organizational competition is routinely mediated – and cooperation motivated – in micro relations and micro interaction. Regular, frequent face-to-face interaction between individual organizational members generates social resources that help to transcend organizational distrust and conflict, most importantly familiarity with each other, personal trust and belief in reciprocity. Furthermore, informal conflict mediation and control mechanisms – namely, open discussion, mutual monitoring in direct interaction and social exclusion – enhance solidarity and mutual support.
Bürgerwindparks
(2018)
In Deutschland stößt der Ausbau der Windenergie mit dem zunehmenden Heranrücken an Wohnbebauungen immer häufiger auf Widerstand bei der lokalen Bevölkerung. Die Stärkung von Bürgerwindparks gegenüber dem alleinigen Betrieb durch große Energiekonzerne bildet die Chance wieder mehr Akzeptanz für die Windenergie zu schaffen. Das Werk widmet sich in diesem Zusammenhang einer Reihe von Fragestellungen, die verschiedene Rechtsgebiete berühren. Angesichts nur noch begrenzt zur Verfügung stehender Windenergieflächen wird untersucht, ob und mit welchen Mitteln, beispielsweise des Raumordnungs- und Bauplanungsrechts sowie vertraglicher Instrumente, Flächen speziell für Bürgerwindparks gesichert werden können.
Daneben erfährt der Leser in welchem Rahmen die Regelungen des Kommunalwirtschaftsrechts Gemeinden eine Beteiligung an Bürgerwindparks erlauben. Schließlich werden verschiedenste Gesellschaftsformen daraufhin analysiert, ob sie sich als Organisationsform eines Bürgerwindparks eignen.
Nanoparticles (NPs) are particles between 1 and 100 nanometers in size. They have attracted enormous research interests owing to their remarkable physicochemical properties and potential applications in the optics, catalysis, sensing, electronics, or optical devices. The thesis investigates systems of NPs attached to planar substrates.
In the first part of the results section of the thesis a new method is presented to immobilize NPs. In many NP applications a strong, persistent adhesion to substrates is a key requirement. Up to now this has been achieved with various methods, which are not always the optimum regarding adhesion strength or applicability. We propose a new method which uses capillarity to enhance the binding agents in the contact area between NP and substrate. The adhesion strength resulting from the new approach is investigated in detail and it is shown that the new approach is superior to older methods in several ways.
The following section presents the optical visualization of nano-sized objects through a combination of thin film surface distortion and interference enhanced optical reflection microscopy. It is a new, fast and non-destructive technique. It not only reveals the location of NPs as small as 20nm attached to planar surfaces and embedded in a molecularly thin liquid film. It also allows the measurement of the geometry of the surface distortion of the liquid film. Even for small NPs the meniscus reaches out for micrometers, which is the reason why the NPs produce such a pronounced optical footprint.
The nucleation and growth of individual bubbles is presented in chapter 5. Nucleation is a ubiquitous natural phenomenon and of great importance in numerous industrial processes. Typically it occurs on very small scales (nanometers) and it is of a random nature (thermodynamics of small systems). Up to now most experimental nucleation studies deal with a large number of individual nucleation processes to cope with its inherently statistical, spatio-temporal character. In contrast, in this thesis the individual O2-bubble formation from single localized platinum NP active site is studied experimentally. The bubble formation is initiated by the catalytic reaction of H2O2 on the Pt surface. It is studied how the bubble nucleation and growth depends on the NP size, the H2O2 concentration and the substrate surface properties. It is observed that in some cases the bubbles move laterally over the substrate surface, driven by the O2-production and the film ablation.
Mit dieser Arbeit zeigt der Autor die vielfältigen Wege der politischen Willensbildung im Bundestag einschließlich außerparlamentarischer Einflussnahmen auf und misst sie speziell am Grundgesetz.
Aufgrund der Fülle der im Parlament behandelten Thematiken kann nicht jeder Abgeordnete auf jedem Gebiet über ausreichende Sachkenntnisse verfügen. Dies zieht eine Zusammenarbeit der Abgeordneten in Fraktionen und Ausschüssen sowie Kontakte zu außerparlamentarischen Dritten nach sich. Beides dient auch dazu, fremde Wissensressourcen zu erschließen. Wenngleich dies nicht die einzige Ursache für außerparlamentarische Zusammenarbeit ist, zeigt sich hieran, dass Praktiken der Kooperation nicht grundsätzlich unlauter sein können. Der Autor zeigt die Grenzen/Bedingungen der Zulässigkeit auf.
Neuroinflammatory and neurodegenerative diseases such as Parkinson's (PD) and multiple sclerosis (MS) often result in a severe impairment of the patient´s quality of life. Effective therapies for the treatment are currently not available, which results in a high socio-economic burden. Due to the heterogeneity of the disease subtypes, stratification is particularly difficult in the early phase of the disease and is mainly based on clinical parameters such as neurophysiological tests and central nervous imaging. Due to good accessibility and stability, blood and cerebrospinal fluid metabolite markers could serve as surrogates for neurodegenerative processes. This can lead to an improved mechanistic understanding of these diseases and further be used as "treatment response" biomarkers in preclinical and clinical development programs. Therefore, plasma and CSF metabolite profiles will be identified that allow differentiation of PD from healthy controls, association of PD with dementia (PDD) and differentiation of PD subtypes such as akinetic rigid and tremor dominant PD patients. In addition, plasma metabolites for the diagnosis of primary progressive MS (PPMS) should be investigated and tested for their specificity to relapsing-remitting MS (RRMS) and their development during PPMS progression.
By applying untargeted high-resolution metabolomics of PD patient samples and in using random forest and partial least square machine learning algorithms, this study identified 20 plasma metabolites and 14 CSF metabolite biomarkers. These differentiate against healthy individuals with an AUC of 0.8 and 0.9 in PD, respectively. We also identify ten PDD specific serum metabolites, which differentiate against healthy individuals and PD patients without dementia with an AUC of 1.0, respectively. Furthermore, 23 akinetic-rigid specific plasma markers were identified, which differentiate against tremor-dominant PD patients with an AUC of 0.94 and against healthy individuals with an AUC of 0.98. These findings also suggest more severe disease pathology in the akinetic-rigid PD than in tremor dominant PD. In the analysis of MS patient samples a partial least square analysis yielded predictive models for the classification of PPMS and resulted in 20 PPMS specific metabolites. In another MS study unknown changes in human metabolism were identified after administration of the multiple sclerosis drug dimethylfumarate, which is used for the treatment of RRMS. These results allow to describe and understand the hitherto completely unknown mechanism of action of this new drug and to use these findings for the further development of new drugs and targets against RRMS.
In conclusion, these results have the potential for improved diagnosis of these diseases and improvement of mechanistic understandings, as multiple deregulated pathways were identified. Moreover, novel Dimethylfumarate targets can be used to aid drug development and treatment efficiency. Overall, metabolite profiling in combination with machine learning identified as a promising approach for biomarker discovery and mode of action elucidation.
Der 20. Juli 1944 zählt zu den Schlüsselereignissen der deutschen Geschichte des 20. Jahrhunderts. Das missglückte Attentat von Claus Schenk Graf von Stauffenberg auf Adolf Hitler und der anschließende Umsturzversuch sind zum Symbol des Widerstandes gegen den Nationalsozialismus geworden. Von den Ereignissen völlig überrascht, hatte das NS-Regime in Bezug auf die Gruppe der Verschwörer sofort festgelegt, dass in der Öffentlichkeit nur von einer »ganz kleinen Clique« die Rede sein dürfe – eine Formulierung, die mitunter noch heute das Bild des Widerstandskreises prägt.
Die vorliegende Analyse zeigt erstmals anhand von zahlreichen Netzwerkvisualisierungen, was die NS-Ermittler tatsächlich über das große und komplexe zivile und militärische Netzwerk vom 20. Juli 1944 wussten, das so unterschiedliche gesellschaftliche Gruppen umfasste wie Offiziere, Verwaltungsbeamte, Diplomaten, Juristen, Industrielle, Theologen, Gutsbesitzer, Gewerkschafter und Sozialdemokraten. Zeitgenössische Briefe und Tagebücher verdeutlichen schließlich das geschickte Agieren der Verschwörer vor und nach dem Umsturzversuch und offenbaren zudem die Fehlerhaftigkeit der NS-Quellen.
Die Frage nach dem Zusammenhalt einer ganzen Gesellschaft ist eine der zentralen Fragen der Sozialwissenschaften und Soziologie. Seit dem Übergang in die Moderne bildet das Problem des Zusammenhalts von sich differenzierenden Gesellschaften den Gegenstand des wissenschaftlichen und gesellschaftlichen Diskurses. In der vorliegenden Studie stellt soziale Integration eine Form der gelungenen Vergesellschaftung dar, die sich in der Reproduktion von symbolischen und nicht-symbolischen Ressourcen artikuliert. Das Resultat dieser Reproduktion sind pluralistische Vergesellschaftungen, die, bezogen auf politische Präferenzen, konfligierende Interessen verursachen. Diese Präferenzen kommen in unterschiedlichen Formen, in ihrer Intensität und Wahrnehmung der politischen Partizipation zum Ausdruck. Da moderne politische Herrschaft aufgrund der rechtlichen und institutionellen Ausstattung einen bedeutsamen Einfluss auf soziale Reproduktion ausüben kann (z.B. durch Sozialpolitik), stellt direkte Beeinflussung politischer Entscheidungen, als Artikulation von sich aus den Konfliktlinien etablierenden, unterschiedlichen Präferenzen, das einzige legitime Mittel zwecks Umverteilung von Ressourcen auf der Ebene des Politischen dar. Somit wird die Konnotation zwischen Integration und politischer Partizipation sichtbar. In die Gesellschaft gut integrierte Mitglieder sind aufgrund einer breiten Teilnahme an Reproduktionsprozessen in der Lage, eigene Interessen zu erkennen und durch politische Aktivitäten zum Ausdruck zu bringen. Die empirischen Befunde scheinen den Eindruck zu vermitteln, dass der demokratische Konflikt in der modernen Gesellschaft nicht mehr direkt von Klassenzugehörigkeit und Klasseninteressen geprägt wird, sondern durch den Zugang zu und die Verfügbarkeit von symbolischen und nicht-symbolischen Ressourcen geformt wird. In der Konsequenz lautet die Fragestellung der vorliegenden Arbeit, ob integrierte Gesellschaften politisch aktiver sind.
Die Fragestellung der Arbeit wird mithilfe von Aggregatdaten demokratisch-verfasster politischer Systemen untersucht, die als etablierte Demokratien gelten und unterschiedlich Breite wohlfahrtstaatlichen Maßnahmen aufweisen. Die empirische Überprüfung der Hypothesen erfolgte mithilfe von bivariaten und multivariaten Regressionsanalysen. Die überprüften Hypothesen lassen sich folgend in einer Hypothese zusammenfassen: Je stärker die soziale Integration einer Gesellschaft, desto größer ist die konventionelle bzw. unkonventionelle politische Partizipation. Verallgemeinert ist die Aussage zulässig, dass soziale Integration einer Gesellschaft positive Effekte auf die Häufigkeit politischer Partizipation innerhalb dieser Gesellschaft hat. Stärker integrierte Gesellschaften sind politisch aktiver und dies unabhängig von der Form (konventionelle oder unkonventionelle) politischer Beteiligung. Dabei ist der direkte Effekt der gesamtgesellschaftlichen Integration auf die konventionellen Formen stärker als auf unkonventionellen. Diese Aussage ist nur zulässig, wenn die Elemente des Wahlsystems, wie z.B. Verhältniswahlrecht, und das BIP nicht berücksichtigt werden. Auf der Grundlage der Ergebnisse mit Kontrollvariablen erlauben die Daten die auf die Makroebene bezogene Aussage, dass neben einem hohen Niveau sozialer Integration auch ein durch (Mit-)Beteiligung bestimmtes Wahlsystem und ein hoher wirtschaftlicher Entwicklungsgrad begünstigend für ein hohes Niveau politischer Partizipation sind.
Das Nonaffektationsprinzip
(2018)
Reversible-deactivation radical polymerization (RDRP) is without any doubt one of the most prevalent and powerful strategies for polymer synthesis, by which well-defined living polymers with targeted molecular weight (MW), low molar dispersity (Ɖ) and diverse morphologies can be prepared in a controlled fashion. Atom transfer radical polymerization (ATRP) as one of the most extensive studied types of RDRP has been particularly emphasized due to the high accessibility to hybrid materials, multifunctional copolymers and diverse end group functionalities via commercially available precursors. However, due to catalyst-induced side reactions and chain-chain coupling termination in bulk environment, synthesis of high MW polymers with uniform chain length (low Ɖ) and highly-preserved chain-end fidelity is usually challenging. Besides, owing to the inherited radical nature, the control of microstructure, namely tacticity control, is another laborious task. Considering the applied catalysts, the utilization of large amounts of non-reusable transition metal ions which lead to cumbersome purification process, product contamination and complicated reaction procedures all delimit the scope ATRP techniques.
Metal-organic frameworks (MOFs) are an emerging type of porous materials combing the properties of both organic polymers and inorganic crystals, characterized with well-defined crystalline framework, high specific surface area, tunable porous structure and versatile nanochannel functionalities. These promising properties of MOFs have thoroughly revolutionized academic research and applications in tremendous aspects, including gas processing, sensing, photoluminescence, catalysis and compartmentalized polymerization. Through functionalization, the microenvironment of MOF nanochannel can be precisely devised and tailored with specified functional groups for individual host-guest interactions. Furthermore, properties of high transition metal density, accessible catalytic sites and crystalline particles all indicate MOFs as prominent heterogeneous catalysts which open a new avenue towards unprecedented catalytic performance. Although beneficial properties in catalysis, high agglomeration and poor dispersibility restrain the potential catalytic capacity to certain degree.
Due to thriving development of MOF sciences, fundamental polymer science is undergoing a significant transformation, and the advanced polymerization strategy can eventually refine the intrinsic drawbacks of MOF solids reversely. Therefore, in the present thesis, a combination of low-dimensional polymers with crystalline MOFs is demonstrated as a robust and comprehensive approach to gain the bilateral advantages from polymers (flexibility, dispersibility) and MOFs (stability, crystallinity). The utilization of MOFs for in-situ polymerizations and catalytic purposes can be realized to synthesize intriguing polymers in a facile and universal process to expand the applicability of conventional ATRP methodology. On the other hand, through the formation of MOF/polymer composites by surface functionalization, the MOF particles with environment-adjustable dispersibility and high catalytic property can be as-prepared.
In the present thesis, an approach via combination of confined porous textures from MOFs and controlled radical polymerization is proposed to advance synthetic polymer chemistry. Zn2(bdc)2(dabco) (Znbdc) and the initiator-functionalized Zn MOFs, ZnBrbdc, are utilized as a reaction environment for in-situ polymerization of various size-dependent methacrylate monomers (i.e. methyl, ethyl, benzyl and isobornyl methacrylate) through (surface-initiated) activators regenerated by electron transfer (ARGET/SI-ARGET) ATRP, resulting in polymers with control over dispersity, end functionalities and tacticity with respect to distinct molecular size. While the functionalized MOFs are applied, due to the strengthened compartmentalization effect, the accommodated polymers with molecular weight up to 392,000 can be achieved. Moreover, a significant improvement in end-group fidelity and stereocontrol can be observed. The results highlight a combination of MOFs and ATRP is a promising and universal methodology to synthesize versatile well-defined polymers with high molecular weight, increment in isotactic trial and the preserved chain-end functionality.
More than being a host only, MOFs can act as heterogeneous catalysts for metal-catalyzed polymerizations. A Cu(II)-based MOF, Cu2(bdc)2(dabco), is demonstrated as a heterogeneous, universal catalyst for both thermal or visible light-triggered ARGET ATRP with expanded monomer range. The accessible catalytic metal sites enable the Cu(II) MOF to polymerize various monomers, including benzyl methacrylate (BzMA), styrene, methyl methacrylate (MMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA) in the fashion of ARGET ATRP. Furthermore, due to the robust frameworks, surpassing the conventional homogeneous catalyst, the Cu(II) MOF can tolerate strongly coordinating monomers and polymerize challenging monomers (i.e. 4-vinyl pyridine, 2-vinyl pyridine and isoprene), in a well-controlled fashion. Therefore, a synthetic procedure can be significantly simplified, and catalyst-resulted chelation can be avoided as well. Like other heterogeneous catalysts, the Cu(II) MOF catalytic complexes can be easily collected by centrifugation and recycled for an arbitrary amount of times.
The Cu(II) MOF, composed of photostimulable metal sites, is further used to catalyze controlled photopolymerization under visible light and requires no external photoinitiator, dye sensitizer or ligand. A simple light trigger allows the photoreduction of Cu(II) to the active Cu(I) state, enabling controlled polymerization in the form of ARGET ATRP. More than polymerization application, the synergic effect between MOF frameworks and incorporated nucleophilic monomers/molecules is also observed, where the formation of associating complexes is able to adjust the photochemical and electrochemical properties of the Cu(II) MOF, altering the band gap and light harvesting behavior. Owing to the tunable photoabsorption property resulting from the coordinating guests, photoinduced Reversible-deactivation radical polymerization (PRDRP) can be achieved to further simplify and fasten the polymerization.
More than the adjustable photoabsorption ability, the synergistic strategy via a combination of controlled/living polymerization technique and crystalline MOFs can be again evidenced as demonstrated in the MOF-based heterogeneous catalysts with enhanced dispersibility in solution. Through introducing hollow pollen pivots with surface immobilized environment-responsive polymer, PDMAEMA, highly dispersed MOF nanocrystals can be prepared after associating on polymer brushes via the intrinsic amine functionality in each DMAEMA monomer. Intriguingly, the pollen-PDMAEMA composite can serve as a “smart” anchor to trap nanoMOF particles with improved dispersibility, and thus to significantly enhance liquid-phase photocatalytic performance. Furthermore, the catalytic activity can be switched on and off via stimulable coil-to-globule transition of the PDMAEMA chains exposing or burying MOF catalytic sites, respectively.
Due to a challenging population growth and environmental changes, a need for new routes to provide required chemicals for human necessities arises. An effective solution discussed in this thesis is industrial heterogeneous catalysis. The development of an advanced industrial heterogeneous catalyst is investigated herein by considering porous carbon nano-material as supports and modifying their surface chemistry structure with heteroatoms. Such modifications showed a significant influence on the performance of the catalyst and provided a deeper insight regarding the interaction between the surface structure of the catalyst and the surrounding phase. This thesis contributes to the few present studies about heteroatoms effect on the catalyst performance and emphasizes on the importance of understanding surface structure functionalization in a catalyst in different phases (liquid and gaseous) and for different reactions (hydrogenolysis, oxidation, and hydrogenation/ polymerization). Herein, the heteroatoms utilized for the modifications are hydrogen (H), oxygen (O), and nitrogen (N). The heteroatoms effect on the metal particle size, on the polarity of the support/ the catalyst, on the catalytic performance (activity, selectivity, and stability), and on the interaction with the surrounding phase has been explored. First hierarchical porous carbon nanomaterials functionalized with heteroatoms (N) is synthesized and applied as supports for nickel nanoparticles for hydrogenolysis process of kraft lignin in liquid phase. This reaction has been performed in batch and flow reactors for three different catalysts, two of comparable hierarchical porosity, yet one is modified with N and the other is not, and a third is a prepared catalyst from a commercial carbon support. The reaction production and analyses show that the catalysts with hierarchical porosity perform catalytically much better than in presence of a commercial carbon support with lower surface area. Moreover, the modification with N-heteroatoms enhanced the catalytic performance because the heteroatom modified porous carbon material with nickel nanoparticles catalyst (Ni-NDC) performed highest among the other catalysts. In the flow reactor, Ni-NDC selectively degraded the ether bonds (β-O-4) in kraft lignin with an activity of 2.2 x10^-4 mg lignin mg Ni-1 s-1 for 50 h at 350°C and 3.5 mL min-1 flow, providing ~99 % conversion to shorter chained chemicals (mainly guaiacol derivatives). Then, the functionalization of carbon surface was further studied in selective oxidation of glucose to gluconic acid using < 1 wt. % of gold (Au) deposited on the previously-mentioned synthesized carbon (C) supports with different functionalities (Au-CGlucose, Au-CGlucose-H, Au-CGlucose-O, Au-CGlucoseamine). Except for Au-CGlucose-O, the other catalysts achieved full glucose conversion within 40-120 min and 100% selectivity towards gluconic acid with a maximum activity of 1.5 molGlucose molAu-1 s-1 in an aqueous phase at 45 °C and pH 9. Each heteroatom influenced the polarity of the carbon differently, affecting by that the deposition of Au on the support and thus the activity of the catalyst and its selectivity. The heteroatom effect was further investigated in a gas phase. The Fischer-Tropsch reaction was applied to convert synthetic gas (CO and H2) to short olefins and paraffins using surface-functionalized carbon nanotubes (CNTs) with heteroatoms as supports for ion (Fe) deposition in presence and absence of promoters (Na and S). The results showed the promoted Fe-CNT doped with nitrogen catalyst to be stable up to 180 h and selective to the formation of olefins (~ 47 %) and paraffins (~6 %) with a conversion of CO ~ 92 % at a maximum activity of 94 *10^-5 mol CO g Fe-1 s-1. The more information given regarding this topic can open wide range of applications not only in catalysis, but in other approaches as well. In conclusion, incorporation of heteroatoms can be the next approach for an advanced industrial heterogeneous catalyst, but also for other applications (e.g. electrocatalysis, gas adsorption, or supercapacitors).
The utilization of lignin as renewable electrode material for electrochemical energy storage is a sustainable approach for future batteries and supercapacitors. The composite electrode was fabricated from Kraft lignin and conductive carbon and the charge storage contribution was determined in terms of electrical double layer (EDL) and redox reactions. The important factors at play for achieving high faradaic charge storage capacity contribute to high surface area, accessibility of redox sites in lignin and their interaction with conductive additives. A thinner layer of lignin covering the high surface area of carbon facilitates the electron transfer process with a shorter pathway from the active sites of nonconductive lignin to the current collector leading to the improvement of faradaic charge storage capacity.
Composite electrodes from lignin and carbon would be even more sustainable if the fluorinated binder can be omitted. A new route to fabricate a binder-free composite electrode from Kraft lignin and high surface area carbon has been proposed by crosslinking lignin with glyoxal. A high molecular weight of lignin is obtained to enhance both electroactivity and binder capability in composite electrodes. The order of the processing step of crosslinking lignin on the composite electrode plays a crucial role in achieving a stable electrode and high charge storage capacity. The crosslinked lignin based electrodes are promising since they allow for more stable, sustainable, halogen-free and environmentally benign devices for energy storage applications. Furthermore, improvement of the amount of redox active groups (quinone groups) in lignin is useful to enhance the capacity in lithium battery applications. Direct oxidative demethylation by cerium ammonium nitrate has been carried out under mild conditions. This proves that an increase of quinone groups is able to enhance the performance of lithium battery. Thus, lignin is a promising material and could be a good candidate for application in sustainable energy storage devices.
Photocatalysis is considered significant in this new energy era, because the inexhaustibly abundant, clean, and safe energy of the sun can be harnessed for sustainable, nonhazardous, and economically development of our society. In the research of photocatalysis, the current focus was held by the design and modification of photocatalyst.
As one of the most promising photocatalysts, g-C3N4 has gained considerable attention for its eye-catching properties. It has been extensively explored in photocatalysis applications, such as water splitting, organic pollutant degradation, and CO2 reduction. Even so, it also has its own drawbacks which inhibit its further application. Inspired by that, this thesis will mainly present and discuss the process and achievement on the preparation of some novel photocatalysts and their photocatalysis performance. These materials were all synthesized via the alteration of classic g-C3N4 preparation method, like using different pre-compositions for initial supramolecular complex and functional group post-modification. By taking place of cyanuric acid, 2,5-Dihydroxy-1,4-benzoquinone and chloranilic acid can form completely new supramolecular complex with melamine. After heating, the resulting products of the two complex shown 2D sheet-like and 1D fiber-like morphologies, respectively, which maintain at even up to high temperature of 800 °C. These materials cover crystals, polymers and N-doped carbons with the increase of synthesis temperature. Based on their different pre-compositions, they show different dye degradation performances. For CLA-M-250, it shows the highest photocatalytic activity and strong oxidation capacity. It shows not only great photo-performance in RhB degradation, but also oxygen production in water splitting. In the post-modification method, a novel photocatalysis solution was proposed to modify carbon nitride scaffold with cyano group, whose content can be well controlled by the input of sodium thiocyanate. The cyanation modification leads to narrowed band gap as well as improved photo-induced charges separation. Cyano group grafted carbon nitride thus shows dramatically enhanced performance in the photocatalytic coupling reaction between styrene and sodium benzenesulfinate under green light irradiation, which is in stark contrast with the inactivity of pristine g-C3N4.
Vom Neandertal nach Afrika
(2018)
Spektakuläre Debatten um bedeutende Fossilienfunde begleiteten die Suche nach unseren Ursprüngen.
Wer waren die ersten Menschen? Nachdem die Antwort darauf lange mit der Schöpfungsgeschichte verbunden war, entflammten ab Mitte des 19. Jahrhunderts neuartige Debatten. Funde menschlicher Fossilien führten zu Auseinandersetzungen über den Ursprung der Menschheit. Umkämpft war nicht nur die Frage, ob die ersten Menschen Deutsche, Engländer, Europäer oder Asiaten waren, ob schwarz oder weiß. Es ging um das Wesen des Menschen. Knochen aus dem Neandertal, von Java oder Südafrika bilden bis heute eine Projektionsfläche für das Verständnis des menschlichen Selbst. Entsprechend intensiv waren die internationalen wissenschaftlichen und öffentlichen Debatten, bis sich in den 1950er Jahren die Idee eines gemeinsamen afrikanischen Ursprungs durchsetzte.
Ellinor Schweighöfer geht am Beispiel spektakulärer Funde der Suche nach dem Ursprung nach. Sie untersucht, welche Zuschreibungen die Funde auslösten und mit welchen Techniken sich wissenschaftliche Fakten etablierten. Es ist eine Wissensgeschichte, bei der viele Stimmen einbezogen werden - Wissenschaftler ebenso wie Massenmedien. So macht die Autorin auch die Wechselwirkungen zwischen Weltanschauung, Politik und Wissenschaft deutlich.
Funde und Fiktionen
(2018)
Urgeschichte im Fernsehen als Spiegel gesellschaftlicher Themen der Gegenwart. Unser gesichertes Wissen über die Urgeschichte der Menschheit ist angesichts der dünnen Quellenlage sehr begrenzt. Dennoch werden seit längerer Zeit sehr erfolgreiche Fernsehdokumentationen ausgestrahlt, die minutiös den Alltag in der fernsten menschlichen Vergangenheit präsentieren. Georg Koch untersucht, wie diese Darstellungen aus dem Zusammenspiel von Filmemachern und Wissenschaftlern entstanden und welchen Wandel sie seit den 1950er Jahren in der Bundesrepublik und in Großbritannien durchliefen. Er zeigt, wie Archäologen zu Medienstars des frühen britischen Fernsehens wurden, wie Hightech, Exotik und Abenteuer Einzug in die Darstellung der Archäologie hielten und wie inszenierte Erzählungen ein Millionenpublikum erreichten. Dabei wird deutlich, dass sich in den Betrachtungen der Urgeschichte stets Projektionen der Gegenwart finden, die zeitgemäße Antworten auf gesellschaftliche Fragen bieten.
Welle der Konsumgesellschaft
(2018)
Wie beeinflussten sich Massenmedien und Massenkonsum im Frankreich der Nachkriegszeit gegenseitig?
Radio Luxembourg war in der europäischen Rundfunklandschaft der Nachkriegszeit eine Ausnahme: Die privatkommerzielle Radiostation sendete werbefinanzierte Unterhaltungsprogramme in die benachbarten Staaten und erreichte damit ein Millionenpublikum. Die Autorin Anna Jehle zeigt anhand verschiedener Untersuchungsfelder - der Unternehmens- und Programmgeschichte, der Zielgruppen, der Marketingaktivitäten und des Werbezeitenverkaufs -, wie eng die Entwicklung der Konsumgesellschaft im Frankreich der sogenannten trente glorieuses mit der Verbreitung und Nutzung des Radios verbunden war. Mit seinem ganz auf Massenkonsum ausgerichteten Rundfunkkonzept war Radio Luxembourg nicht nur integraler Bestandteil, sondern auch Katalysator und Agent der Konsummoderne. Dies hatte weitreichende Auswirkungen für das französische Rundfunksystem, das sich unter dem Einfluss Radio Luxembourgs kommerzialisierte, und zwar bereits lange vor der Deregulierung des Rundfunks in den 1980er Jahren.
Geben oder Nehmen
(2018)
Geben oder nehmen? Diese Frage war nach der Wiedervereinigung nicht einfach zu beantworten. Die Euphorie über das Ende der deutschen Teilung 1989/90 wurde besonders frühzeitig und lang anhaltend von Konflikten überschattet, die sich an ungeklärten Eigentumsfragen an Grundstücken in Ostdeutschland entzündeten. Wohl kaum ein anderes Thema hat das Zusammenwachsen zwischen Ost und West so belastet wie die Kontroversen um die Rückübertragung von Eigentum.
Der Band bietet eine – bislang fehlende – ausgewogene Gesamtdarstellung der Eigentumsfragen im Kontext der Wiedervereinigung. Dazu gehört die Darstellungen der Vorbedingung der Eigentumsproblematik vor 1990, die Betrachtung der Entscheidungsfindung, die zum umstrittenen Grundsatz geführt hat, eine intensive Auseinandersetzung mit den Umsetzungsproblemen der gesetzlichen Regelungen in der Praxis sowie der Versuch, die Auswirkungen für die Region Berlin/Brandenburg zu bilanzieren.
Scalable data profiling
(2018)
Data profiling is the act of extracting structural metadata from datasets. Structural metadata, such as data dependencies and statistics, can support data management operations, such as data integration and data cleaning. Data management often is the most time-consuming activity in any data-related project. Its support is extremely valuable in our data-driven world, so that more time can be spent on the actual utilization of the data, e. g., building analytical models. In most scenarios, however, structural metadata is not given and must be extracted first. Therefore, efficient data profiling methods are highly desirable.
Data profiling is a computationally expensive problem; in fact, most dependency discovery problems entail search spaces that grow exponentially in the number of attributes. To this end, this thesis introduces novel discovery algorithms for various types of data dependencies – namely inclusion dependencies, conditional inclusion dependencies, partial functional dependencies, and partial unique column combinations – that considerably improve over state-of-the-art algorithms in terms of efficiency and that scale to datasets that cannot be processed by existing algorithms. The key to those improvements are not only algorithmic innovations, such as novel pruning rules or traversal strategies, but also algorithm designs tailored for distributed execution. While distributed data profiling has been mostly neglected by previous works, it is a logical consequence on the face of recent hardware trends and the computational hardness of dependency discovery.
To demonstrate the utility of data profiling for data management, this thesis furthermore presents Metacrate, a database for structural metadata. Its salient features are its flexible data model, the capability to integrate various kinds of structural metadata, and its rich metadata analytics library. We show how to perform a data anamnesis of unknown, complex datasets based on this technology. In particular, we describe in detail how to reconstruct the schemata and assess their quality as part of the data anamnesis.
The data profiling algorithms and Metacrate have been carefully implemented, integrated with the Metanome data profiling tool, and are available as free software. In that way, we intend to allow for easy repeatability of our research results and also provide them for actual usage in real-world data-related projects.
Die Folgen einer lebensmittelbedingten Erkrankung sind zum Teil gravierend, insbesondere für Kinder und immunsupprimierte Menschen. Hierbei gehören Salmonella und Campylobacter zu den häufigsten Erregern, die verantwortlich für gastrointestinale Erkrankungen in Deutschland sind. Trotz umfassender Maßnahmen der EU zur Prävention und Bekämpfung von Salmonellen in Geflügelbeständen und der Lebensmittel-Industrie, wird von einem stagnierenden Trend von Infektionszahlen berichtet. Zoonose-Erreger wie Salmonellen können über Nutztiere in die Nahrungskette des Menschen gelangen, wodurch sich Infektionsherde schnell ausbreiten können. Dabei sind bestehende Präventionsstrategien für Geflügel vorhanden, die aber nicht auf den Menschen übertragbar sind. Folglich sind Diagnostik und Prävention in der Lebensmittelindustrie essentiell. Deshalb besteht ein hoher Bedarf für spezifische, sensitive und zuverlässige Nachweismethoden, die eine Point-of-care Diagnostik gewährleisten. Durch ein wachsendes Verständnis der wirtsspezifischen Faktoren von S. enterica Serovaren kann die Entwicklung sowohl neuartiger diagnostischer Methoden, als auch neuartiger Therapien und Impfstoffe maßgeblich vorangetrieben werden.
Infolgedessen wurde in dieser Arbeit ein infektionsähnliches in vitro Modell für S. Enteritidis etabliert und darauf basierend eine umfassende Untersuchung zur Identifizierung neuer Zielstrukturen für den Erreger durchgeführt. Während einer Salmonellen-Infektion ist die erste zelluläre Barriere im Wirt die Epithelschicht. Dementsprechend wurde eine humane Zelllinie (CaCo 2, Darmepithel) für die Pathogen-Wirt-Studie ausgewählt. Das Salmonellen-Transkriptom und morphologische Eigenschaften der Epithelzellen wurden in verschiedenen Phasen der Salmonellen-Infektion untersucht und mit bereits gut beschriebenen Virulenzfaktoren und Beobachtungen in Bezug gesetzt. Durch dieses Infektionsmodell konnte ein spezifischer Phänotyp für die intrazellulären Salmonellen in den Epithelzellen nachgewiesen werden. Zudem wurde aufgezeigt, dass bereits die Kultivierung in Flüssigmedium einen invasionsaktiven Zustand der Salmonellen erzeugt. Allerdings wurde durch die Kokultivierung mit Epithelzellen eine zusätzliche Expression relevanter Gene induziert, um eine effiziente Adhäsion und Transmembran-Transport zu gewährleisten. Letzterer ist charakteristisch für die intrazelluläre Limitierung von Nährstoffen und prägt den infektionsrelevanten Status. Unter Berücksichtigung dieser Faktoren ergab sich ein Phänotyp, der eindeutig Mechanismen zur Wirtsadaptation und möglicherweise auch Pathogenese aufzeigt. Die intrazellulären Bakterien müssen vom Wirt separiert werden, was ein wesentlicher Schritt für Pathogen-bestimmende Analysen ist. Hierbei wurde mithilfe einer Detergenz-basierten Lyse der eukaryotischen Zellmembran und differentieller Zentrifugation, der eukaryotische Eintrag minimal gehalten. Unter Verwendung der Virulenz-adaptierten Salmonellen wurden Untersuchungen in Hinblick auf die Identifizierung neuer Zielstrukturen für S. Enteritidis durchgeführt. Mithilfe eines immunologischen Screenings wurden neue potentielle Antigene entdeckt. Zu diesem Zweck wurden bakterielle cDNA-basierte Expressionsbibliotheken hergestellt, die durch eine vereinfachte Microarray-Anwendung ein Hochdurchsatzscreening von Proteinen als potentielle Binder ermöglichen. Folglich konnten neue unbeschriebene Proteine identifiziert werden, die sich durch eine Salmonella-Spezifität oder Membranständigkeit auszeichnen. Ebenso wurde ein Vergleich der im Screening identifizierten Proteine mit der Regulation der kodierenden Gene im infektionsähnlichen Modell durchgeführt. Dabei wurde deutlich, dass die Häufigkeit von Transkripten einen Einfluss auf die Verfügbarkeit in der cDNA-Bibliothek und folglich auch auf die Expressionsbibliothek nimmt. Angesichts eines Ungleichgewichts zwischen der Gesamtzahl protein-kodierender Gene in S. Enteritidis zu möglichen Klonen, die während des Microarray-Screenings untersucht werden können, besteht der Bedarf einer Anreicherung von Proteinen in der Expressionsbibliothek. Das infektionsähnliche Modell zeigte, dass nicht nur Virulenz-assoziierte, sondern auch Stress- und Metabolismus-relevante Gene hochreguliert werden. Durch die Konstruktion dieser spezifischen cDNA-Bibliotheken ist die Erkennung von charakteristischen molekularen Markern gegeben.
Weiterhin wurden anhand der Transkriptomanalyse spezifisch hochregulierte Gene identifiziert, die relevant für das intrazelluläre Überleben von S. Enteritidis in humanen Epithelzellen sind. Hiervon wurden drei Gene näher untersucht, indem ihr Einfluss im infektionsähnlichen Modell mittels entsprechender Gen-Knockout-Stämme analysiert wurde. Dabei wurde für eine dieser Mutanten ein reduziertes Wachstum in der späten intrazellulären Phase nachgewiesen. Weiterführende in vitro Analysen sind für die Charakterisierung des Knockout-Stamms notwendig, um den Einsatz als potenzielles Therapeutikum zu verifizieren.
Zusammenfassend wurde ein in vitro Infektionsmodell für S. Enteritidis etabliert, wodurch neue Zielstrukturen des Erregers identifiziert wurden. Diese sind für diagnostische oder therapeutische Anwendungen interessant. Das Modell lässt sich ebenso für andere intrazelluläre Pathogene übertragen und gewährleistet eine zuverlässige Identifizierung von potentiellen Antigenen.
Inzidenz und Therapie der Depression bei Patienten mit Osteoporose und Rheumatoider Arthritis
(2018)
Nanophotonics is the field of science and engineering aimed at studying the light-matter interactions on the nanoscale. One of the key aspects in studying such optics at the nanoscale is the ability to assemble the material components in a spatially controlled manner. In this work, DNA origami nanostructures were used to self-assemble dye molecules and DNA coated plasmonic nanoparticles. Optical properties of dye nanoarrays, where the dyes were arranged at distances where they can interact by Förster resonance energy transfer (FRET), were systematically studied according to the size and arrangement of the dyes using fluorescein (FAM) as the donor and cyanine 3 (Cy 3) as the acceptor. The optimized design, based on steady-state and time-resolved fluorometry, was utilized in developing a ratiometric pH sensor with pH-inert coumarin 343 (C343) as the donor and pH-sensitive FAM as the acceptor. This design was further applied in developing a ratiometric toxin sensor, where the donor C343 is unresponsive and FAM is responsive to thioacetamide (TAA) which is a well-known hepatotoxin. The results indicate that the sensitivity of the ratiometric sensor can be improved by simply arranging the dyes into a well-defined array. The ability to assemble multiple fluorophores without dye-dye aggregation also provides a strategy to amplify the signal measured from a fluorescent reporter, and was utilized here to develop a reporter for sensing oligonucleotides. By incorporating target capturing sequences and multiple fluorophores (ATTO 647N dye molecules), a reporter for microbead-based assay for non-amplified target oligonucleotide sensing was developed. Analysis of the assay using VideoScan, a fluorescence microscope-based technology capable of conducting multiplex analysis, showed the DNA origami nanostructure based reporter to have a lower limit of detection than a single stranded DNA reporter. Lastly, plasmonic nanostructures were assembled on DNA origami nanostructures as substrates to study interesting optical behaviors of molecules in the near-field. Specifically, DNA coated gold nanoparticles, silver nanoparticles, and gold nanorods, were placed on the DNA origami nanostructure aiming to study surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS) of molecules placed in the hotspot of coupled plasmonic structures.
Deoxyribonucleic acid (DNA) is the carrier of human genetic information and is exposed to environmental influences such as the ultraviolet (UV) fraction of sunlight every day. The photostability of the DNA against UV light is astonishing. Even if the DNA bases have a strong absorption maximum at around 260 nm/4.77 eV, their quantum yield of photoproducts remains very low 1. If the photon energies exceed the ionization energy (IE) of the nucleobases ( ̴ 8-9 eV) 2, the DNA can be severely damaged. Photoexcitation and -ionization reactions occur, which can induce strand breaks in the DNA. The efficiency of the excitation and ionization induced strand breaks in the target DNA sequences are represented by cross sections. If Si as a substrate material is used in the VUV irradiation experiments, secondary electrons with an energy below 3.6 eV are generated from the substrate. This low energy electrons (LEE) are known to induce dissociative electron attachment (DEA) in DNA and with it DNA strand breakage very efficiently. LEEs play an important role in cancer radiation therapy, since they are generated secondarily along the radiation track of ionizing radiation.
In the framework of this thesis, different single stranded DNA sequences were irradiated with 8.44 eV vacuum UV (VUV) light and cross sections for single strand breaks (SSB) were determined. Several sequences were also exposed to secondary LEEs, which additionally contributed to the SSBs. First, the cross sections for SSBs depending on the type of nucleobases were determined. Both types of DNA sequences, mono-nucleobase and mixed sequences showed very similar results upon VUV radiation. The additional influence of secondarily generated LEEs resulted in contrast in a clear trend for the SSB cross sections. In this, the polythymine sequence had the highest cross section for SSBs, which can be explained by strong anionic resonances in this energy range. Furthermore, SSB cross sections were determined as a function of sequence length. This resulted in an increase in the strand breaks to the same extent as the increase in the geometrical cross section. The longest DNA sequence (20 nucleotides) investigated in this series, however, showed smaller cross section values for SSBs, which can be explained by conformational changes in the DNA. Moreover, several DNA sequences that included the radiosensitizers 5-Bromouracil (5BrU) and 8-Bromoadenine (8BrA) were investigated and the corresponding SSB cross sections were determined. It was shown that 5BrU reacts very strongly to VUV radiation leading to high strand break yields, which showed in turn a strong sequence-dependency. 8BrA, on the other hand, showed no sensitization to the applied VUV radiation, since almost no increase in strand breakage yield was observed in comparison to non-modified DNA sequences.
In order to be able to identify the mechanisms of radiation damage by photons, the IEs of certain DNA sequences were further explored using photoionization tandem mass spectrometry. By varying the DNA sequence, both the IEs depending on the type of nucleobase as well as on the DNA strand length could be identified and correlated to the SSB cross sections. The influence of the IE on the photoinduced reaction in the brominated DNA sequences could be excluded.
New bio-based polymers
(2018)
Redox-responsive polymers, such as poly(disulfide)s, are a versatile class of polymers with potential applications including gene- and drug-carrier systems. Their degradability under reductive conditions allows for a controlled response to the different redox states that are present throughout the body. Poly(disulfide)s are typically synthesized by step growth polymerizations. Step growth polymerizations, however, may suffer from low conversions and therefore low molar masses, limiting potential applications. The purpose of this thesis was therefore to find and investigate new synthetic routes towards the synthesis of amino acid-based poly(disulfide)s.
The different routes in this thesis include entropy-driven ring opening polymerizations of novel macrocyclic monomers, derived from cystine derivatives. These monomers were obtained with overall yields of up to 77% and were analyzed by mass spectrometry as well as by 1D and 2D NMR spectroscopy. The kinetics of the entropy-driven ring-opening metathesis polymerization (ED-ROMP) were thoroughly investigated in dependence of temperature, monomer concentration, and catalyst concentration. The polymerization was optimized to yield poly(disulfide)s with weight average molar masses of up to 80 kDa and conversions of ~80%, at the thermodynamic equilibrium. Additionally, an alternative metal free polymerization, namely the entropy-driven ring-opening disulfide metathesis polymerization (ED-RODiMP) was established for the polymerization of the macrocyclic monomers. The effect of different solvents, concentrations and catalyst loadings on the polymerization process and its kinetics were studied. Polymers with very high weight average molar masses of up to 177 kDa were obtained. Moreover, various post-polymerization reactions were successfully performed.
This work provides the first example of the homopolymerization of endo-cyclic disulfides by ED-ROMP and the first substantial study into the kinetics of the ED-RODiMP process.
Utilization of sunlight for energy harvesting has been foreseen as sustainable replacement for fossil fuels, which would also eliminate side effects arising from fossil fuel consumption such as drastic increase of CO2 in Earth atmosphere. Semiconductor materials can be implemented for energy harvesting, and design of ideal energy harvesting devices relies on effective semiconductor with low recombination rate, ease of processing, stability over long period, non-toxicity and synthesis from abundant sources. Aforementioned criteria have attracted broad interest for graphitic carbon nitride (g-CN) materials, metal-free semiconductor which can be synthesized from low cost and abundant precursors. Furthermore, physical properties such as band gap, surface area and absorption can be tuned. g-CN was investigated as heterogeneous catalyst, with diversified applications from water splitting to CO2 reduction and organic coupling reactions. However, low dispersibility of g-CN in water and organic solvents was an obstacle for future improvements.
Tissue engineering aims to mimic natural tissues mechanically and biologically, so that synthetic materials can replace natural ones in future. Hydrogels are crosslinked networks with high water content, therefore are prime candidates for tissue engineering. However, the first requirement is synthesis of hydrogels with mechanical properties that are matching to natural tissues. Among different approaches for reinforcement, nanocomposite reinforcement is highly promising.
This thesis aims to investigate aqueous and organic dispersions of g-CN materials. Aqueous g-CN dispersions were utilized for visible light induced hydrogel synthesis, where g-CN acts as reinforcer and photoinitiator. Varieties of methodologies were presented for enhancing g-CN dispersibility, from co-solvent method to prepolymer formation, and it was shown that hydrogels with diversified mechanical properties (from skin-like to cartilage-like) are accessible via g-CN utilization. One pot photografting method was introduced for functionalization of g-CN surface which provides functional groups towards enhanced dispersibility in aqueous and organic media. Grafting vinyl thiazole groups yields stable additive-free organodispersions of g-CN which are electrostatically stabilized with increased photophysical properties. Colloidal stability of organic systems provides transparent g-CN coatings and printing g-CN from commercial inkjet printers.
Overall, application of g-CN in dispersed media is highly promising, and variety of materials can be accessible via utilization of g-CN and visible light with simple chemicals and synthetic conditions. g-CN in dispersed media will bridge emerging research areas from tissue engineering to energy harvesting in near future.
Understanding how humans move their eyes is an important part for understanding the functioning of the visual system. Analyzing eye movements from observations of natural scenes on a computer screen is a step to understand human visual behavior in the real world. When analyzing eye-movement data from scene-viewing experiments, the impor- tant questions are where (fixation locations), how long (fixation durations) and when (ordering of fixations) participants fixate on an image. By answering these questions, computational models can be developed which predict human scanpaths. Models serve as a tool to understand the underlying cognitive processes while observing an image, especially the allocation of visual attention.
The goal of this thesis is to provide new contributions to characterize and model human scanpaths on natural scenes. The results from this thesis will help to understand and describe certain systematic eye-movement tendencies, which are mostly independent of the image. One eye-movement tendency I focus on throughout this thesis is the tendency to fixate more in the center of an image than on the outer parts, called the central fixation bias. Another tendency, which I will investigate thoroughly, is the characteristic distribution of angles between successive eye movements.
The results serve to evaluate and improve a previously published model of scanpath generation from our laboratory, the SceneWalk model. Overall, six experiments were conducted for this thesis which led to the following five core results:
i) A spatial inhibition of return can be found in scene-viewing data. This means that locations which have already been fixated are afterwards avoided for a certain time interval (Chapter 2).
ii) The initial fixation position when observing an image has a long-lasting influence of up to five seconds on further scanpath progression (Chapter 2 & 3).
iii) The often described central fixation bias on images depends strongly on the duration of the initial fixation. Long-lasting initial fixations lead to a weaker central fixation bias than short fixations (Chapter 2 & 3).
iv) Human observers adjust their basic eye-movement parameters, like fixation dura- tions and saccade amplitudes, to the visual properties of a target they look for in visual search (Chapter 4).
v) The angle between two adjacent saccades is an indicator for the selectivity of the upcoming saccade target (Chapter 4).
All results emphasize the importance of systematic behavioral eye-movement tenden- cies and dynamic aspects of human scanpaths in scene viewing.
Arctic warming has implications for the functioning of terrestrial Arctic ecosystems, global climate and socioeconomic systems of northern communities. A research gap exists in high spatial resolution monitoring and understanding of the seasonality of permafrost degradation, spring snowmelt and vegetation phenology. This thesis explores the diversity and utility of dense TerraSAR-X (TSX) X-Band time series for monitoring ice-rich riverbank erosion, snowmelt, and phenology of Arctic vegetation at long-term study sites in the central Lena Delta, Russia and on Qikiqtaruk (Herschel Island), Canada. In the thesis the following three research questions are addressed:
• Is TSX time series capable of monitoring the dynamics of rapid permafrost degradation in ice-rich permafrost on an intra-seasonal scale and can these datasets in combination with climate data identify the climatic drivers of permafrost degradation?
• Can multi-pass and multi-polarized TSX time series adequately monitor seasonal snow cover and snowmelt in small Arctic catchments and how does it perform compared to optical satellite data and field-based measurements?
• Do TSX time series reflect the phenology of Arctic vegetation and how does the recorded signal compare to in-situ greenness data from RGB time-lapse camera data and vegetation height from field surveys?
To answer the research questions three years of TSX backscatter data from 2013 to 2015 for the Lena Delta study site and from 2015 to 2017 for the Qikiqtaruk study site were used in quantitative and qualitative analysis complimentary with optical satellite data and in-situ time-lapse imagery.
The dynamics of intra-seasonal ice-rich riverbank erosion in the central Lena Delta, Russia were quantified using TSX backscatter data at 2.4 m spatial resolution in HH polarization and validated with 0.5 m spatial resolution optical satellite data and field-based time-lapse camera data. Cliff top lines were automatically extracted from TSX intensity images using threshold-based segmentation and vectorization and combined in a geoinformation system with manually digitized cliff top lines from the optical satellite data and rates of erosion extracted from time-lapse cameras. The results suggest that the cliff top eroded at a constant rate throughout the entire erosional season. Linear mixed models confirmed that erosion was coupled with air temperature and precipitation at an annual scale, seasonal fluctuations did not influence 22-day erosion rates. The results highlight the potential of HH polarized X-Band backscatter data for high temporal resolution monitoring of rapid permafrost degradation.
The distinct signature of wet snow in backscatter intensity images of TSX data was exploited to generate wet snow cover extent (SCE) maps on Qikiqtaruk at high temporal resolution. TSX SCE showed high similarity to Landsat 8-derived SCE when using cross-polarized VH data. Fractional snow cover (FSC) time series were extracted from TSX and optical SCE and compared to FSC estimations from in-situ time-lapse imagery. The TSX products showed strong agreement with the in-situ data and significantly improved the temporal resolution compared to the Landsat 8 time series. The final combined FSC time series revealed two topography-dependent snowmelt patterns that corresponded to in-situ measurements. Additionally TSX was able to detect snow patches longer in the season than Landsat 8, underlining the advantage of TSX for detection of old snow. The TSX-derived snow information provided valuable insights into snowmelt dynamics on Qikiqtaruk previously not available.
The sensitivity of TSX to vegetation structure associated with phenological changes was explored on Qikiqtaruk. Backscatter and coherence time series were compared to greenness data extracted from in-situ digital time-lapse cameras and detailed vegetation parameters on 30 areas of interest. Supporting previous results, vegetation height corresponded to backscatter intensity in co-polarized HH/VV at an incidence angle of 31°. The dry, tall shrub dominated ecological class showed increasing backscatter with increasing greenness when using the cross polarized VH/HH channel at 32° incidence angle. This is likely driven by volume scattering of emerging and expanding leaves. Ecological classes with more prostrate vegetation and higher bare ground contributions showed decreasing backscatter trends over the growing season in the co-polarized VV/HH channels likely a result of surface drying instead of a vegetation structure signal. The results from shrub dominated areas are promising and provide a complementary data source for high temporal monitoring of vegetation phenology.
Overall this thesis demonstrates that dense time series of TSX with optical remote sensing and in-situ time-lapse data are complementary and can be used to monitor rapid and seasonal processes in Arctic landscapes at high spatial and temporal resolution.
Fluvial terraces, floodplains, and alluvial fans are the main landforms to store sediments and to decouple hillslopes from eroding mountain rivers. Such low-relief landforms are also preferred locations for humans to settle in otherwise steep and poorly accessible terrain. Abundant water and sediment as essential sources for buildings and infrastructure make these areas amenable places to live at. Yet valley floors are also prone to rare and catastrophic sedimentation that can overload river systems by abruptly increasing the volume of sediment supply, thus causing massive floodplain aggradation, lateral channel instability, and increased flooding. Some valley-fill sediments should thus record these catastrophic sediment pulses, allowing insights into their timing, magnitude, and consequences.
This thesis pursues this theme and focuses on a prominent ~150 km2 valley fill in the Pokhara Valley just south of the Annapurna Massif in central Nepal. The Pokhara Valley is conspicuously broad and gentle compared to the surrounding dissected mountain terrain,
and is filled with locally more than 70 m of clastic debris. The area’s main river, Seti Khola, descends from the Annapurna Sabche Cirque at 3500-4500 m asl down to 900 m asl where it incises into this valley fill. Humans began to settle on this extensive
fan surface in the 1750’s when the Trans-Himalayan trade route connected the Higher Himalayas, passing Pokhara city, with the subtropical lowlands of the Terai. High and unstable river terraces and steep gorges undermined by fast flowing rivers with highly seasonal (monsoon-driven) discharge, a high earthquake risk, and a growing population make the Pokhara Valley an ideal place to study the recent geological and geomorphic history of its sediments and the implication for natural hazard appraisals.
The objective of this thesis is to quantify the timing, the sedimentologic and geomorphic processes as well as the fluvial response to a series of strong sediment pulses. I report
diagnostic sedimentary archives, lithofacies of the fan terraces, their geochemical provenance, radiocarbon-age dating and the stratigraphic relationship between them. All these various and independent lines of evidence show consistently that multiple sediment pulses filled the Pokhara Valley in medieval times, most likely in connection with, if not triggered by, strong seismic ground shaking. The geomorphic and sedimentary evidence is
consistent with catastrophic fluvial aggradation tied to the timing of three medieval Himalayan earthquakes in ~1100, 1255, and 1344 AD. Sediment provenance and calibrated radiocarbon-age data are the key to distinguish three individual sediment pulses, as these are not evident from their sedimentology alone. I explore various measures of adjustment and fluvial response of the river system following these massive aggradation pulses. By using proxies such as net volumetric erosion, incision and erosion rates, clast provenance on active river banks, geomorphic markers such as re-exhumed tree trunks in growth position, and knickpoint locations in tributary valleys, I estimate the response of the river network in the Pokhara Valley to earthquake disturbance over several centuries. Estimates of the removed volumes since catastrophic valley filling began, require average net sediment
yields of up to 4200 t km−2 yr−1 since, rates that are consistent with those reported for Himalayan rivers. The lithological composition of active channel-bed load differs from that of local bedrock material, confirming that rivers have adjusted 30-50% depending on data of different tributary catchments, locally incising with rates of 160-220 mm yr−1. In many tributaries to the Seti Khola, most of the contemporary river loads come from a Higher Himalayan source, thus excluding local hillslopes as sources. This imbalance in sediment provenance emphasizes how the medieval sediment pulses must have rapidly traversed up to 70 km downstream to invade the downstream reaches of the tributaries
up to 8 km upstream, thereby blocking the local drainage and thus reinforcing, or locally creating new, floodplain lakes still visible in the landscape today.
Understanding the formation, origin, mechanism and geomorphic processes of this valley fill is crucial to understand the landscape evolution and response to catastrophic sediment pulses. Several earthquake-triggered long-runout rock-ice avalanches or catastrophic dam burst in the Higher Himalayas are the only plausible mechanisms to explain both the geomorphic and sedimentary legacy that I document here. In any case, the Pokhara Valley was most likely hit by a cascade of extremely rare processes over some two centuries starting in the early 11th century. Nowhere in the Himalayas do we find valley fills of
comparable size and equally well documented depositional history, making the Pokhara Valley one of the most extensively dated valley fill in the Himalayas to date. Judging from the growing record of historic Himalayan earthquakes in Nepal that were traced and
dated in fault trenches, this thesis shows that sedimentary archives can be used to directly aid reconstructions and predictions of both earthquake triggers and impacts from a sedimentary-response perspective. The knowledge about the timing, evolution, and response of the Pokhara Valley and its river system to earthquake triggered sediment pulses is important to address the seismic and geomorphic risk for the city of Pokhara. This
thesis demonstrates how geomorphic evidence on catastrophic valley infill can help to independently verify paleoseismological fault-trench records and may initiate re-thinking on post-seismic hazard assessments in active mountain regions.
The formation and breaching of natural dammed lakes have formed the landscapes, especially in seismically active high-mountain regions. Dammed lakes pose both, potential water resources, and hazard in case of dam breaching. Central Asia has mostly arid and semi-arid climates. Rock glaciers already store more water than ice-glaciers in some semi-arid regions of the world, but their distribution and advance mechanisms are still under debate in recent research. Their impact on the water availability in Central Asia will likely increase as temperatures rise and glaciers diminish.
This thesis provides insight to the relative age distribution of selected Kyrgyz and Kazakh rock glaciers and their single lobes derived from lichenometric dating. The size of roughly 8000 different lichen specimens was used to approximate an exposure age of the underlying debris surface. We showed that rock-glacier movement differs signifcantly on small scales. This has several implications for climatic inferences from rock glaciers. First, reactivation of their lobes does not necessarily point to climatic changes, or at least at out-of-equilibrium conditions. Second, the elevations of rock-glacier toes can no longer be considered as general indicators of the limit of sporadic mountain permafrost as they have been used traditionally.
In the mountainous and seismically active region of Central Asia, natural dams, besides rock glaciers, also play a key role in controlling water and sediment infux into river valleys. However, rock glaciers advancing into valleys seem to be capable of infuencing the stream network, to dam rivers, or to impound lakes. This influence has not previously been addressed. We quantitatively explored these controls using a new inventory of 1300 Central Asian rock glaciers. Elevation, potential incoming solar radiation, and the size of rock glaciers and their feeder basins played key roles in predicting dam appearance. Bayesian techniques were used to credibly distinguish between lichen sizes on rock glaciers and their lobes, and to find those parameters of a rock-glacier system that are most credibly expressing the potential to build natural dams.
To place these studies in the region's history of natural dams, a combination of dating of former lake levels and outburst flood modelling addresses the history and possible outburst flood hypotheses of the second largest mountain lake of the world, Issyk Kul in Kyrgyzstan. Megafoods from breached earthen or glacial dams were found to be a likely explanation for some of the lake's highly fluctuating water levels. However, our detailed analysis of candidate lake sediments and outburst-flood deposits also showed that more localised dam breaks to the west of Issyk Kul could have left similar geomorphic and sedimentary evidence in this Central Asian mountain landscape. We thus caution against readily invoking megafloods as the main cause of lake-level drops of Issyk Kul. In summary, this thesis addresses some new pathways for studying rock glaciers and natural dams with several practical implications for studies on mountain permafrost and natural hazards.
Mitöffentlichkeit
(2018)
Im Mittelpunkt dieser beziehungsgeschichtlichen Darstellung steht die Geschichte der deutsch-deutschen Arbeit der Evangelischen Akademie Berlin-Brandenburg seit ihrer Gründung 1951 bis Ende der 1970er- bzw. Anfang der 1980er-Jahre. Nach einem Überblick zur Geschichte der Ev. Akademien und der Evangelischen Akademie Berlin-Brandenburg wird sie als ein exemplarischer deutsch-deutscher Ort literarischer Kommunikation, der „Vergangenheitsbewältigung“ und des christlich-jüdischen Dialogs als Teil der NS-Auseinandersetzung beschrieben. Im Rahmen der literarischen Arbeit wurden häufig in der DDR – noch – nicht veröffentlichte westdeutsche und westeuropäische Texte in den literarischen Kreislauf eingespeist; hiermit konstitutiv verbunden ist das ebenfalls hochpolitische und gesamtdeutsch dimensionierte Thema der Vergangenheitsbewältigung. Über den Kontext der Akademie hinaus versteht sich die Arbeit auch als ein Beitrag zur deutsch-deutschen Geschichte der Vergangenheitsbewältigung. Mit den seit 1961 durchgeführten Israel-Tagungen institutionalisierte sich der christlich-jüdische Dialog etwa 15 Jahre früher als in der evangelischen Kirche in der DDR. Damit bietet diese Arbeit auch neue Aspekte der Geschichte des Protestantismus in Ostdeutschland und der christlich-jüdischen Beziehungen in der DDR. Hinsichtlich der kirchlichen Vergangenheitsbewältigung leistete die Akademie Pionierarbeit. Im Horizont deutschland-, kultur- und kirchenpolitischer Entwicklungen schwächte sich ab Ende der 1960er-Jahre der gesamtdeutsche Bezug ab. Die Akademie war durch Nähe und Distanz zu staatlichen und kirchlichen Kontexten geprägt. Massive Überwachungen durch die Staatssicherheit und Konflikte mit staatlichen Organen sind Ausdruck dieses „Eigen-Sinns“. Als christlicher Akteur beharrte die Akademie auf Mitgestaltung und Mitwirkung und erzeugte durch ihre Arbeit Mitöffentlichkeit. Dieser neu eingeführte Begriff entzieht sich dem Dualismus von offizieller Öffentlichkeit und Gegenöffentlichkeit und leistet eine wesentliche Differenzierung des Formenkreises von Öffentlichkeit in der DDR.
Landslides are frequent natural hazards in rugged terrain, when the resisting frictional force of the surface of rupture yields to the gravitational force. These forces are functions of geological and morphological factors, such as angle of internal friction, local slope gradient or curvature, which remain static over hundreds of years; whereas more dynamic triggering events, such as rainfall and earthquakes, compromise the force balance by temporarily reducing resisting forces or adding transient loads. This thesis investigates landslide distribution and orientation due to landslide triggers (e.g. rainfall) at different scales (6-4∙10^5 km^2) and aims to link rainfall movement with the landslide distribution. It additionally explores the local impacts of the extreme rainstorms on landsliding and the role of precursory stability conditions that could be induced by an earlier trigger, such as an earthquake.
Extreme rainfall is a common landslide trigger. Although several studies assessed rainfall intensity and duration to study the distribution of thus triggered landslides, only a few case studies quantified spatial rainfall patterns (i.e. orographic effect). Quantifying the regional trajectories of extreme rainfall could aid predicting landslide prone regions in Japan. To this end, I combined a non-linear correlation metric, namely event synchronization, and radial statistics to assess the general pattern of extreme rainfall tracks over distances of hundreds of kilometers using satellite based rainfall estimates. Results showed that, although the increase in rainfall intensity and duration positively correlates with landslide occurrence, the trajectories of typhoons and frontal storms were insufficient to explain landslide distribution in Japan. Extreme rainfall trajectories inclined northwestwards and were concentrated along some certain locations, such as coastlines of southern Japan, which was unnoticed in the landslide distribution of about 5000 rainfall-triggered landslides. These landslides seemed to respond to the mean annual rainfall rates.
Above mentioned findings suggest further investigation on a more local scale to better understand the mechanistic response of landscape to extreme rainfall in terms of landslides. On May 2016 intense rainfall struck southern Germany triggering high waters and landslides. The highest damage was reported at the Braunsbach, which is located on the tributary-mouth fan formed by the Orlacher Bach. Orlacher Bach is a ~3 km long creek that drains a catchment of about ~6 km^2. I visited this catchment in June 2016 and mapped 48 landslides along the creek. Such high landslide activity was not reported in the nearby catchments within ~3300 km^2, despite similar rainfall intensity and duration based on weather radar estimates. My hypothesis was that several landslides were triggered by rainfall-triggered flash floods that undercut hillslope toes along the Orlacher Bach. I found that morphometric features such as slope and curvature play an important role in landslide distribution on this micro scale study site (<10 km^2). In addition, the high number of landslides along the Orlacher Bach could also be boosted by accumulated damages on hillslopes due karst weathering over longer time scales.
Precursory damages on hillslopes could also be induced by past triggering events that effect landscape evolution, but this interaction is hard to assess independently from the latest trigger. For example, an earthquake might influence the evolution of a landscape decades long, besides its direct impacts, such as landslides that follow the earthquake. Here I studied the consequences of the 2016 Kumamoto Earthquake (MW 7.1) that triggered some 1500 landslides in an area of ~4000 km^2 in central Kyushu, Japan. Topography, i.e. local slope and curvature, both amplified and attenuated seismic waves, thus controlling the failure mechanism of those landslides (e.g. progressive). I found that topography fails in explaining the distribution and the preferred orientation of the landslides after the earthquake; instead the landslides were concentrated around the northeast of the rupture area and faced mostly normal to the rupture plane. This preferred location of the landslides was dominated mainly by the directivity effect of the strike-slip earthquake, which is the propagation of wave energy along the fault in the rupture direction; whereas amplitude variations of the seismic radiation altered the preferred orientation. I suspect that the earthquake directivity and the asymmetry of seismic radiation damaged hillslopes at those preferred locations increasing landslide susceptibility. Hence a future weak triggering event, e.g. scattered rainfall, could further trigger landslides at those damaged hillslopes.
The Sun is the nearest star to the Earth. It consists of an interior and an atmosphere. The convection zone is the outermost layer of the solar interior. A flux rope may emerge as a coherent structure from the convection zone into the solar atmosphere or be formed by magnetic reconnection in the atmosphere. A flux rope is a bundle of magnetic field lines twisting around an axis field line, creating a helical shape by which dense filament material can be supported against gravity. The flux rope is also considered as the key structure of the most energetic phenomena in the solar system, such as coronal mass ejections (CMEs) and flares. These magnetic flux ropes can produce severe geomagnetic storms. In particular, to improve the ability to forecast space weather, it is important to enrich our knowledge about the dynamic formation of flux ropes and the underlying physical mechanisms that initiate their eruption, such as a CME.
A confined eruption consists of a filament eruption and usually an associated are, but does not evolve into a CME; rather, the moving plasma is halted in the solar corona and usually seen to fall back. The first detailed observations of a confined filament eruption were obtained on 2002 May 27by the TRACE satellite in the 195 A band. So, in the Chapter 3, we focus on a flux rope instability model. A twisted flux rope can become unstable by entering the kink instability regime. We show that the kink instability, which occurs if the twist of a flux rope exceeds a critical value, is capable of initiating of an eruption. This model is tested against the well observed confined eruption on 2002 May 27 in a parametric magnetohydrodynamic (MHD) simulation study that comprises all phases of the event. Very good agreement with the essential observed properties is obtained, only except for a relatively poor matching of the initial filament height.
Therefore, in Chapter 4, we submerge the center point of the flux rope deeper below the photosphere to obtain a flatter coronal rope section and a better matching with the initial height profile of the erupting filament. This implies a more realistic inclusion of the photospheric line tying. All basic assumptions and the other parameter settings are kept the same as in Chapter 3. This complement of the parametric study shows that the flux rope instability model can yield an even better match with the observational data. We also focus in Chapters 3 and 4 on the magnetic reconnection during the confined eruption, demonstrating that it occurs in two distinct locations and phases that correspond to the observed brightenings and changes of topology, and consider the fate of the erupting flux, which can reform a (less twisted) flux rope.
The Sun also produces series of homologous eruptions, i.e. eruptions which occur repetitively in the same active region and are of similar morphology. Therefore, in Chapter 5, we employ the reformed flux rope as a new initial condition, to investigate the possibility of subsequent homologous eruptions. Free magnetic energy is built up by imposing motions in the bottom boundary, such as converging motions, leading to flux cancellation. We apply converging motions in the sunspot area, such that a small part of the flux from the sunspots with different polarities is transported toward the polarity inversion line (PIL) and cancels with each other. The reconnection associated with the cancellation process forms more helical magnetic flux around the reformed flux rope, which leads to a second and a third eruption. In this study, we obtain the first MHD simulation results of a homologous sequence of eruptions that show a transition from a confined to two ejective eruptions, based on the reformation of a flux rope after each eruption.
This research addressed the question, if it is possible to simplify current microcontact printing systems for the production of anisotropic building blocks or patchy particles, by using common chemicals while still maintaining reproducibility, high precision and tunability of the Janus-balance
Chapter 2 introduced the microcontact printing materials as well as their defined electrostatic interactions. In particular polydimethylsiloxane stamps, silica particles and high molecular weight polyethylenimine ink were mainly used in this research. All of these components are commercially available in large quantities and affordable, which gives this approach a huge potential for further up-scaling developments. The benefits of polymeric over molecular inks was described including its flexible influence on the printing pressure. With this alteration of the µCP concept, a new method of solvent assisted particle release mechanism enabled the switch from two-dimensional surface modification to three-dimensional structure printing on colloidal silica particles, without changing printing parameters or starting materials. This effect opened the way to use the internal volume of the achieved patches for incorporation of nano additives, introducing additional physical properties into the patches without alteration of the surface chemistry.
The success of this system and its achievable range was further investigated in chapter 3 by giving detailed information about patch geometry parameters including diameter, thickness and yield. For this purpose, silica particles in a size range between 1µm and 5µm were printed with different ink concentrations to change the Janus-balance of these single patched particles. A necessary intermediate step, consisting of air-plasma treatment, for the production of trivalent particles using "sandwich" printing was discovered and comparative studies concerning the patch geometry of single and double patched particles were conducted. Additionally, the usage of structured PDMS stamps during printing was described. These results demonstrate the excellent precision of this approach and opens the pathway for even greater accuracy as further parameters can be finely tuned and investigated, e.g. humidity and temperature during stamp loading.
The performance of these synthesized anisotropic colloids was further investigated in chapter 4, starting with behaviour studies in alcoholic and aqueous dispersions. Here, the stability of the applied patches was studied in a broad pH range, discovering a release mechanism by disabling the electrostatic bonding between particle surface and polyelectrolyte ink. Furthermore, the absence of strong attractive forces between divalent particles in water was investigated using XPS measurements. These results lead to the conclusion that the transfer of small PDMS oligomers onto the patch surface is shielding charges, preventing colloidal agglomeration. However, based on this knowledge, further patch modifications for particle self-assembly were introduced including physical approaches using magnetic nano additives, chemical patch functionalization with avidin-biotin or the light responsive cyclodextrin-arylazopyrazoles coupling as well as particle surface modification for the synthesis of highly amphiphilic colloids. The successful coupling, its efficiency, stability and behaviour in different solvents were evaluated to find a suitable coupling system for future assembly experiments. Based on these results the possibility of more sophisticated structures by colloidal self-assembly is given.
Certain findings needed further analysis to understand their underlying mechanics, including the relatively broad patch diameter distribution and the decreasing patch thickness for smaller silica particles. Mathematical assumptions for both effects are introduced in chapter 5. First, they demonstrate the connection between the naturally occurring particle size distribution and the broadening of the patch diameter, indicating an even higher precision for this µCP approach. Second, explaining the increase of contact area between particle and ink surface due to higher particle packaging, leading to a decrease in printing pressure for smaller particles.
These calculations ultimately lead to the development of a new mechanical microcontact printing approach, using centrifugal forces for high pressure control and excellent parallel alignment of printing substrates. First results with this device and the comparison with previously conducted by-hand experiments conclude this research. It furthermore displays the advantages of such a device for future applications using a mechanical printing approach, especially for accessing even smaller nano particles with great precision and excellent yield.
In conclusion, this work demonstrates the successful adjustment of the µCP approach using commercially available and affordable silica particles and polyelectrolytes for high flexibility, reduced costs and higher scale-up value. Furthermore, its was possible to increase the modification potential by introducing three-dimensional patches for additional functionalization volume. While keeping a high colloidal stability, different coupling systems showed the self-assembly capabilities of this toolbox for anisotropic particles.
This text is a contribution to the research on the worldwide success of evangelical Christianity and offers a new perspective on the relationship between late modern capitalism and evangelicalism. For this purpose, the utilization of affect and emotion in evangelicalism towards the mobilization of its members will be examined in order to find out what similarities to their employment in late modern capitalism can be found. Different examples from within the evangelical spectrum will be analyzed as affective economies in order to elaborate how affective mobilization is crucial for evangelicalism’s worldwide success. Pivotal point of this text is the exploration of how evangelicalism is able to activate the voluntary commitment of its members, financiers, and missionaries. Gathered here are examples where both spheres—evangelicalism and late modern capitalism—overlap and reciprocate, followed by a theoretical exploration of how the findings presented support a view of evangelicalism as an inner-worldly narcissism that contributes to an assumed re-enchantment of the world.
Valide generierte Daten aus Verhandlungen bilden die Grundlage zum Ergründen von Art und Umfang verschiedener Einflussfaktoren auf den Verhandlungsprozess und das Verhandlungsergebnis. Die Wahl einer bestimmten Datenerhebungsmethode wird weitestgehend von der jeweiligen Problemstellung einer Untersuchung bedingt. Aus diesem Zusammenhang erschließt sich die Notwendigkeit, fundierte Erkenntnisse und Empfehlungen für die Anwendung von bestimmten Datenerhebungsmethoden in der Verhandlungsforschung zu entwickeln. Damit einhergehend können sowohl Verbesserungspotenziale für die methodische Vorgehensweise zukünftiger Forschungsvorhaben aufgefunden als auch – basierend auf den generierten Daten – gehaltvolle Handlungsempfehlungen für die Verhandlungspraxis ausgesprochen werden. Zunächst nimmt der Verfasser eine umfangreiche Literaturanalyse über die methodischen Praktiken der Datengewinnung in verhandlungsrelevanten Studien im Zeitraum 2005 bis 2014 vor. Basierend auf einer ergänzend durchgeführten Befragung unter Verhandlungswissenschaftlern liefert er eine Prognose der zukünftigen Anwendungshäufigkeiten der Erhebungsmethoden und leitet methodische Erkenntnisse im Zeitverlauf ab. Insbesondere durch die Analyse der Passung zwischen Untersuchungsfragestellung und Datenerhebungsmethode sowie weiterer Aspekte (z. B. Art der Verhandlung, Forschungsdisziplin, Journal der Publikation, Korrespondenzautor und dessen Affiliation), welche die jeweilige Untersuchung beeinflussen könnten, schafft der Autor eine kontemporäre Entscheidungshilfe für kommende verhandlungsbezogene Forschungsaktivitäten.
This doctoral dissertation aims at elucidating the development of hot and cool executive functions in middle childhood and at gaining insight about their role in childhood overweight. The dissertation is based on three empirical studies which have been published in peer-reviewed journals. Data from a large 3-year longitudinal study (the “PIER-study”) was used.
The findings presented in the dissertation demonstrated that both hot and cool EF abilities increase during middle childhood. They also supported the notion that hot and cool EF facets are distinguishable from each other in middle childhood, that they have distinct developmental trajectories, and different predictors.
Evidence was found for associations of hot and cool EF with body weight in middle childhood, which is in line with the notion that they might play a role in the self-regulation of eating and the multifactorial etiology of childhood overweight.
Veränderungen im thermalen Regime des Permafrosts verursachen Störungen der Erdoberfläche. Diese Veränderungen werden durch die in der Arktis seit Jahrzehnten ansteigenden Temperaturen verstärkt. Thermokarst ist ein Prozess, welcher die Erdoberfläche durch Schmelzen von Grundeis, oder Auftauen von Permafrost absacken lässt, wodurch charakteristische Landformen entstehen. Thermokarst ist vor allem entlang von Hängen weit verbreitet und die Anzahl der damit verbundenen Landformen in der Arktis steigt stetig an. Dieser Prozess mobilisiert große Mengen an Material, welche in Richtung Meer transportiert oder entlang von Hängen akkumuliert werden. Während entlang von Hängen auftretender Thermokarst terrestrische sowie aquatische Ökosysteme stark verändert, ist dessen Einfluss auf regionaler Skala zurzeit noch Gegenstand der Forschung.
In dieser Arbeit quantifizieren wir die Auswirkungen von Thermokarstprozessen entlang von Hängen auf die umliegenden Ökosysteme der küstennahen Täler und Nahküstenbereiche entlang der Yukon Küste in Kanada. Mittels überwachtem maschinellen Lernen haben wir geomorphische Faktoren identifiziert, welche die Entwicklung von retrogressiven Auftaurutschungen (RTS) begünstigen. RTS sind eine Erscheinungsform von Thermokarst entlang von Hängen. Die Küstengeomorphologie, sowie der Grundeistyp und -inhalt sind die wesentlichen bestimmenden Faktoren für das Auftreten von RTS. Wir haben Luftbildaufnahmen und Satellitenbilder genutzt, um die Evolution von RTS im Zeitraum von 1952 bis 2011 zu verfolgen. Während dieser Zeit ist die Anzahl und Ausdehnung von RTS linear angestiegen. Wir zeigen, dass 56% der RTS welche entlang der Küste in 2011 identifiziert wurden, 16.6 × 106 m3 an Material erodiert haben. Hiervon wurden 45% durch Küstenprozesse entlang der Küste transportiert. RTS tragen wesentlich zu dem Kohlenstoff-Budget des Nahküstenbereiches bei: 17% der in 2011 identifizierten RTS, haben 0.6% des organischen Kohlenstoffes transportiert, welcher durch Küstenerosion entlang der Yukon Küste jährlich freigesetzt wird. Um den Einfluss von Thermokarst entlang von Hängen auf das terrestrische Ökosystem zu beurteilen, haben wir die räumliche Verteilung von organischem Bodenkohlenstoff und Stickstoff (SOC, TN) entlang von Hangprofilen in drei arktischen Tälern analysiert.Wir weisen auf eine hohe räumliche Variabilität in der Verteilung von SOC und TN hin, welche auf komplexe Bodenprozesse zurückzuführen ist, welche entlang von Hängen auftreten. Thermokarst entlang von Hängen hat einen großen Einfluss auf die Degradierung von organischem Material und die Speicherung von SOC und TN.
Studien zum Bildungserfolg in Deutschland weisen auf verschiedene Ungleichheitsdimensionen hin. So wurde wiederholt ein enger Zusammenhang zwischen der sozialen Herkunft und dem schulischen Bildungserfolg dokumentiert. Des Weiteren stellen auch Geschlechterunterschiede im Bildungserfolg einen vielfach berichteten und sowohl wissenschaftlich als auch gesellschaftlich diskutierten Befund dar. Der großen Anzahl an Studien, die sich jeweils einer dieser Ungleichheitsdimensionen widmen, steht jedoch ein Forschungsbedarf bezüglich des systematischen Wissens über die Wechselwirkung von Geschlecht und sozialer Herkunft im Bildungserfolg gegenüber. Vor diesem Hintergrund hat die vorliegende Arbeit zum Ziel, das Zusammenspiel von Geschlecht und sozialer Herkunft zu untersuchen, wobei sie von zwei übergeordneten Fragestellungen geleitet wird, die im Rahmen von vier Teilstudien untersucht werden.Erstens wurde das Zusammenspiel von Geschlecht und sozioökonomischem Status (SES) in unterschiedlichen Facetten des Bildungserfolges sowie in den Berufsaspirationen analysiert (Teilstudien 1-3). Zweitens wurde untersucht, inwiefern die elterlichen Geschlechterrollenvorstellungen mit den Schulleistungen ihres Kindes assoziiert sind. Vor diesem Hintergrund wurde ebenso der Zusammenhang zwischen den elterlichen Geschlechterrollenvorstellungen und Merkmalen des familiären Hintergrundes analysiert (Teilstudie 4). Zusammenfassend betrachtet weisen die Ergebnisse der Teilstudien auf eine Wechselwirkung von Geschlechtszugehörigkeit und sozialer Herkunft im Bildungserfolg sowie in den beruflichen Aspirationen hin, auch wenn die entsprechenden Effekte eher klein ausfallen. Entgegen der gesellschaftlichen Konnotation von Mathematik als „Jungenfach“ stellen die Befunde damit beispielsweise einen Hinweis darauf dar, dass die vielfach zitierten Geschlechterunterschiede in den mathematischen Kompetenzen nicht als „naturgegeben“ sondern beeinflussbar verstanden werden können. Damit untermauern die Ergebnisse die unter anderem im Rahmen verschiedener Theorien herausgestellte Bedeutsamkeit des Sozialisationskontextes für die Entwicklung der Fähigkeiten und Ziele von Jungen und Mädchen sowie die im internationalen Vergleich gezeigte Variabilität von Geschlechterunterschieden in Schulleistungen.
In this thesis we provide a construction of the operator framework starting from the functional formulation of group field theory (GFT). We define operator algebras on Hilbert spaces whose expectation values in specific states provide correlation functions of the functional formulation. Our construction allows us to give a direct relation between the ingredients of the functional GFT and its operator formulation in a perturbative regime. Using this construction we provide an example of GFT states that can not be formulated as states in a Fock space and lead to math- ematically inequivalent representations of the operator algebra. We show that such inequivalent representations can be grouped together by their symmetry properties and sometimes break the left translation symmetry of the GFT action. We interpret these groups of inequivalent representations as phases of GFT, similar to the classification of phases that we use in QFT’s on space-time.
Die stetig wachsenden internationalen und wirtschaftlichen Verflechtungen sowohl von Unternehmen als auch von Einzelsteuerpflichtigen stellen die deutsche Finanzverwaltung vor eine große Herausforderung. Hintergrund dafür ist, dass sich das deutsche Steuerrecht nicht nur auf rein nationale Sachverhalte beschränkt, sondern vielmehr auch an Vorgänge und Zustände anknüpft, die sich im Ausland befinden.
Das Auftreten solcher grenzüberschreitender Sachverhalte und deren juristische Begleiterscheinungen sind jedoch nicht ganz unproblematisch, da für die korrekte Besteuerung jener Sachverhalte sowohl das rein nationale Recht als auch die ausländischen Rechtsgrundlagen beachtet werden müssen. Diese werden in meiner Arbeit detailliert vorgestellt, wobei stets eine Unterscheidung zwischen gemeinschaftsrechtlichen Rechtsgrundlagen, multilateralen, bilateralen und unilateralen Rechtsquellen erfolgt.
Zuvor werden die vielfältigen Probleme bei der Besteuerung grenzüberschreitender Sachverhalte, wie z.B. die Gefahr der Doppelbesteuerung oder der Steuerflucht dargestellt, um danach die nationalen Lösungsansätze, wie die erweiterten Anzeige- und Mitwirkungspflichten auf Seiten der Steuerpflichtigen und den Untersuchungsgrundsatz auf Seiten der Finanzverwaltung aufzuzeigen. Dabei werden die europäischen Grundfreiheiten als Diskriminierungs- und Beschränkungsverbote abgebildet, wobei auch die anerkannten geschriebenen und ungeschriebenen Rechtfertigungsgründe dargestellt werden. Die vielfältigen Auswirkungen des europäischen Primärrechts auf das deutsche Besteuerungsverfahren werden anhand von verschiedenen EuGH-Urteilen veranschaulicht, wobei auch die praktische Umsetzung der europarechtlichen Vorgaben beispielhaft durch das Aktionsprogramm FISCALIS 2020, die Informationszentrale für steuerliche Auslandsbeziehungen in Bonn und das internationale Steuerzentrum in München vorgestellt werden.
Three Essays on EFRAG
(2018)
This cumulative doctoral thesis consists of three papers that deal with the role of one specific European accounting player in the international accounting standard-setting, namely the European Financial Reporting Advisory Group (EFRAG). The first paper examines whether and how EFRAG generally fulfills its role in articulating Europe’s interests toward the International Accounting Standards Board (IASB). The qualitative data from the conducted interviews reveal that EFRAG influences the IASB’s decision making at a very early stage, long before other constituents are officially asked to comment on the IASB’s proposals. The second paper uses quantitative data and investigates the formal participation behavior of European constituents that seek to determine EFRAG’s voice. More precisely, this paper analyzes the nature of the constituents’ participation in EFRAG’s due process in terms of representation (constituent groups and geographical distribution) and the drivers of their participation behavior. EFRAG’s official decision making process is dominated by some specific constituent groups (such as preparers and the accounting profession) and by constituents from some specific countries (e.g. those with effective enforcement regimes). The third paper investigates in a first step who of the European constituents choose which lobbying channel (participation only at IASB, only at EFRAG, or at both institutions) and unveils in a second step possible reasons for their lobbying choices. The paper comprises quantitative and qualitative data. It reveals that English skills, time issues, the size of the constituent, and the country of origin are factors that can explain why the majority participates only in the IASB’s due process.
Das Werk unternimmt eine erstmalige zusammenfassende Darstellung der Umsatzbesteuerung von Energieleistungen sowie deren mehrwertsteuerrechtlichen Beurteilung unter besonderer Berücksichtigung aktueller Probleme und Zweifelsfragen. Hierfür werden Problembereiche grundlegend und rechtsdogmatisch beleuchtet. Ziel der Arbeit ist es, die wesentlichen Geschäftspraktiken im Energiesektor einer mehrwertsteuerrechtlichen Analyse zu unterwerfen, die stets das unionsrechtliche Mehrwertsteuerrecht und das nationale Umsatzsteuerrecht betrachtet. Es wird untersucht, ob und inwieweit die gegenwärtigen Vorschriften zur umsatzsteuerrechtlichen Behandlung von Energieleistungen mit dem europäischen Unionsrecht vereinbar, praxistauglich und angemessen sind. Im Lichte der unaufhaltsam voranschreitenden Energiewende will die vorliegende Untersuchung einen systemimmanenten Überblick der energierechtlichen Implikationen auf das Mehrwertsteuerrecht in einem einheitlichen mehrwertsteuerrechtlichen Gesamtkontext geben.
Die Norminterdependenzen des Grunderwerbsteuergesetzes bei Umstrukturierungen inländischer Konzerne
(2018)
Neben der vorherrschenden Unternehmenskultur existieren innerhalb der Organisationen unterschiedliche Subkulturen. Eine solche Subkultur - die berufliche - ist im Kontext dieser Arbeit von Bedeutung. Ihr Einfluss auf das Individuum in Form einer sekundären Sozialisation fängt in der Regel noch vor dem Eintritt im Unternehmen an und kann je nach Dauer der Einflussnahme und Stärke der Unternehmens- und der Subkulturen unterschiedlich sein. Im Mittelpunkt des Buches steht die Untersuchung der Abhängigkeiten zwischen der beruflichen kulturellen Prägung der Mitarbeiter und dem Umgang mit Wissen im Unternehmenskontext. Das Buch bietet einen theoretischen Überblick über die relevanten Themenfelder, stellt die Entwicklung eines Modells der Interdependenzen zwischen Wissensmanagement, Unternehmenskultur und beruflicher Subkultur vor und diskutiert erste Ergebnisse zur empirischen Untersuchung der Interdependenzen sowie das hierzu entwickelte Instrument.
Amorphous calcium carbonate(ACC) is a wide spread biological material found in many organisms, such as sea Urchins and mollusks, where it serves as either a precursor phase for the crystalline biominerals or is stabilized and used in the amorphous state. As ACC readily crystallizes, stabilizers such as anions, cations or macromolecules are often present to avoid or delay unwanted crystallization. Furthermore, additives often control the properties of the materials to suit the specific function needed for the organism. E.g. cystoliths in leaves that scatter light to optimize energy uptake from the sun or calcite/aragonite crystals used in protective shells in mussels and gastropods. Lifetime of the amorphous phase is controlled by the kinetic stability against crystallization. This has often been linked to water which plays a role in the mobility of ions and hence the probability of forming crystalline nuclei to initiate crystallization. However, it is unclear how the water molecules are incorporated within the amorphous phase, either as liquid confined in pores, as structural water binding to the ions or as a mixture of both. It is also unclear how this is perturbed when additives are added, especially Mg2+, one the most common additives found in biogenic samples. Mg2+ are expected to have a strong influence on the water incorporated into ACC, given the high energy barrier to dehydration of magnesium ions compared to calcium ions in solution.
During the last 10-15 years, there has been a large effort to understand the local environment of the ions/molecules and how this affects the properties of the amorphous phase. But only a few aspects of the structure have so far been well-described in literature. The reason for this is partly caused by the low stability of ACC if exposed to air, where it tends to crystallize within minutes and by the limited quantities of ACC produced in traditional synthesis routes. A further obstacle has been the difficulty in modeling the local structure based on experimental data. To solve the problem of stability and sample size, a few studies have used stabilizers such as Mg2+ or OH- and severely dehydrated samples so as to stabilize the amorphous state, allowing for combined neutron and x-ray analysis to be performed. However, so far, a clear description of the local environments of water present in the structure has not been reported.
In this study we show that ACC can be synthesized without any stabilizing additives in quantities necessary for neutron measurements and that accurate models can be derived with the help of empirical-potential structural refinement. These analyses have shown that there is a wide range of local environments for all of the components in the system suggesting that the amorphous phase is highly inhomogeneous, without any phase separation between ions and water. We also showed that the water in ACC is mainly structural and that there is no confined or liquid-like water present in the system. Analysis of amorphous magnesium carbonate also showed that there is a large difference in the local structure of the two cations and that Mg2+ surprisingly interacts with significantly less water molecules then Ca2+ despite the higher dehydration energy. All in all, this shows that the role of water molecules as a structural component of ACC, with a strong binding to cat- and anions probably retard or prevents the crystallization of the amorphous phase.
This dissertation consists of four self-contained papers that deal with the implications of financial market imperfections and heterogeneity. The analysis mainly relates to the class of incomplete-markets models but covers different research topics.
The first paper deals with the distributional effects of financial integration for developing countries. Based on a simple heterogeneous-agent approach, it is shown that capital owners experience large welfare losses while only workers moderately gain due to higher wages. The large welfare losses for capital owners contrast with the small average welfare gains from representative-agent economies and indicate that a strong opposition against capital market opening has to be expected.
The second paper considers the puzzling observation of capital flows from poor to rich countries and the accompanying changes in domestic economic development. Motivated by the mixed results from the literature, we employ an incomplete-markets model with different types of idiosyncratic risk and borrowing constraints. Based on different scenarios, we analyze under what conditions the presence of financial market imperfections contributes to explain the empirical findings and how the conditions may change with different model assumptions.
The third paper deals with the interplay of incomplete information and financial market imperfections in an incomplete-markets economy. In particular, it analyzes the impact of incomplete information about idiosyncratic income shocks on aggregate saving. The results show that the effect of incomplete information is not only quantitatively substantial but also qualitatively ambiguous and varies with the influence of the income risk and the borrowing constraint.
Finally, the fourth paper analyzes the influence of different types of fiscal rules on the response of key macroeconomic variables to a government spending shock. We find that a strong temporary increase in public debt contributes to stabilizing consumption and leisure in the first periods following the change in government spending, whereas a non-debt-intensive fiscal rule leads to a faster recovery of consumption, leisure, capital and output in later periods. Regarding optimal debt policy, we find that a debt-intensive fiscal rule leads to the largest aggregate welfare benefit and that the individual welfare gain is particularly high for wealth-poor agents.
There are numerous situations in which people ask for something or make a request, e.g. asking a favor, asking for help or requesting compliance with specific norms. For this reason, how to ask for something in order to increase people’s willingness to fulfill such requests is one of the most important question for many people working in various different fields of responsibility such as charitable giving, marketing, management or policy making.
This dissertation consists of four chapters that deal with the effects of small changes in the decision-making environment on altruistic decision-making and compliance behavior. Most notably, written communication as an influencing factor is the focus of the first three chapters. The starting point was the question how to devise a request in order to maximize its chance of success (Chapter 1). The results of the first chapter originate the ideas for the second and third chapter. Chapter 2 analyzes how communication by a neutral third-party, i.e. a text from the experimenters that either reminds potential benefactors of their responsibility or highlights their freedom of choice, affects altruistic decision-making. Chapter 3 elaborates on the effect of thanking people in advance when asking them for help. While being not as closely related to the other chapters as the three first ones are, the fourth chapter deals as well with the question how compliance (here: compliance with norms and rules) is affected by subtle manipulations of the environment in which decisions are made. This chapter analyzes the effect of default settings in a tax return on tax compliance.
In order to study the research questions outlined above, controlled experiments were conducted. Chapter 1, which analyzes the effect of text messages on the decision to give something to another person, employs a mini-dictator game. The recipient sends a free-form text message to the dictator before the latter makes a binary decision whether or not to give part of her or his endowment to the recipient. We find that putting effort into the message by writing a long note without spelling mistakes increases dictators’ willingness to give. Moreover, writing in a humorous way and mentioning reasons why the money is needed pays off. Furthermore, men and women seem to react differently to some message categories. Only men react positively to efficiency arguments, while only women react to messages that emphasize the dictator’s power and responsibility.
Building on this last result, Chapter 2 attempts to disentangle the effect of reminding potential benefactors of their responsibility for the potential beneficiary and the effect of highlighting their decision power and freedom of choice on altruistic decision-making by studying the effects of two different texts on giving in a dictator game. We find that only men react positively to a text that stresses their responsibility for the recipient by giving more to her or him, whereas only women seem to react positively to a text that emphasizes their decision power and freedom of choice.
Chapter 3 focuses on the compliance with a request. In the experiment, participants are asked to provide a detailed answer to an open question. Compliance is measured by the effort participants spend on answering the question. The treatment variable is whether or not they see the text “thanks in advance.” We find that participants react negatively by putting less effort into complying with the request in response to the phrase “thanks in advance.”
Chapter 4 studies the effect of prefilled tax returns with mostly inaccurate default values on tax compliance. In a laboratory experiment, participants earn income by performing a real-effort task and must subsequently file a tax return for three consecutive rounds. In the main treatment, the tax return is prefilled with a default value, resulting from participants’ own performance in previous rounds, which varies in its relative size. The results suggest that there is no lasting effect of a default value on tax honesty, neither for relatively low nor relatively high defaults. However, participants who face a default that is lower than their true income in the first round evade significantly and substantially more taxes in this round than participants in the control treatment without a default.
Im Januar 1916 eroberte die Armee des Habsburgerreichs das Königreich Montenegro, den kleinsten und bevölkerungsärmsten Staat Südosteuropas, der an der Seite Serbiens in den Ersten Weltkrieg eingetreten war. Bereits im Sommer 1916 formierte sich bewaffneter Widerstand gegen die Besatzer, 1918 eskalierte dieser zu einer Aufstandsbewegung. Diese Studie zum k. u. k. Militärgeneralgouvernement in Montenegro macht deutlich, welche Relevanz (Fehl-)Einschätzungen und (Fehl-)Entscheidungen in Besatzungssituationen zukommt. Außerdem arbeitet sie die Bedeutung der Geografie des Besatzungsgebiets, des strategischen Kontexts der Besatzung sowie des soziokulturellen Referenzrahmens der Besatzer wie der Besetzten heraus.
Spatio-temporal data denotes a category of data that contains spatial as well as temporal components. For example, time-series of geo-data, thematic maps that change over time, or tracking data of moving entities can be interpreted as spatio-temporal data.
In today's automated world, an increasing number of data sources exist, which constantly generate spatio-temporal data. This includes for example traffic surveillance systems, which gather movement data about human or vehicle movements, remote-sensing systems, which frequently scan our surroundings and produce digital representations of cities and landscapes, as well as sensor networks in different domains, such as logistics, animal behavior study, or climate research.
For the analysis of spatio-temporal data, in addition to automatic statistical and data mining methods, exploratory analysis methods are employed, which are based on interactive visualization. These analysis methods let users explore a data set by interactively manipulating a visualization, thereby employing the human cognitive system and knowledge of the users to find patterns and gain insight into the data.
This thesis describes a software framework for the visualization of spatio-temporal data, which consists of GPU-based techniques to enable the interactive visualization and exploration of large spatio-temporal data sets. The developed techniques include data management, processing, and rendering, facilitating real-time processing and visualization of large geo-temporal data sets. It includes three main contributions:
- Concept and Implementation of a GPU-Based Visualization Pipeline.
The developed visualization methods are based on the concept of a GPU-based visualization pipeline, in which all steps -- processing, mapping, and rendering -- are implemented on the GPU. With this concept, spatio-temporal data is represented directly in GPU memory, using shader programs to process and filter the data, apply mappings to visual properties, and finally generate the geometric representations for a visualization during the rendering process. Data processing, filtering, and mapping are thereby executed in real-time, enabling dynamic control over the mapping and a visualization process which can be controlled interactively by a user.
- Attributed 3D Trajectory Visualization.
A visualization method has been developed for the interactive exploration of large numbers of 3D movement trajectories. The trajectories are visualized in a virtual geographic environment, supporting basic geometries such as lines, ribbons, spheres, or tubes. Interactive mapping can be applied to visualize the values of per-node or per-trajectory attributes, supporting shape, height, size, color, texturing, and animation as visual properties. Using the dynamic mapping system, several kind of visualization methods have been implemented, such as focus+context visualization of trajectories using interactive density maps, and space-time cube visualization to focus on the temporal aspects of individual movements.
- Geographic Network Visualization.
A method for the interactive exploration of geo-referenced networks has been developed, which enables the visualization of large numbers of nodes and edges in a geographic context. Several geographic environments are supported, such as a 3D globe, as well as 2D maps using different map projections, to enable the analysis of networks in different contexts and scales. Interactive filtering, mapping, and selection can be applied to analyze these geographic networks, and visualization methods for specific types of networks, such as coupled 3D networks or temporal networks have been implemented.
As a demonstration of the developed visualization concepts, interactive visualization tools for two distinct use cases have been developed. The first contains the visualization of attributed 3D movement trajectories of airplanes around an airport. It allows users to explore and analyze the trajectories of approaching and departing aircrafts, which have been recorded over the period of a month. By applying the interactive visualization methods for trajectory visualization and interactive density maps, analysts can derive insight from the data, such as common flight paths, regular and irregular patterns, or uncommon incidents such as missed approaches on the airport.
The second use case involves the visualization of climate networks, which are geographic networks in the climate research domain. They represent the dynamics of the climate system using a network structure that expresses statistical interrelationships between different regions. The interactive tool allows climate analysts to explore these large networks, analyzing the network's structure and relating it to the geographic background. Interactive filtering and selection enables them to find patterns in the climate data and identify e.g. clusters in the networks or flow patterns.
Der am 15. Juni 1875 in Frankfurt (Oder) geborene und langjährig in seiner Wahlheimat Potsdam praktizierende Allgemeinmediziner Georg Otto Schneider war einer der bedeutendsten ärztlichen Standesvertreter der ersten Hälfte des 20. Jahrhunderts. Eng verknüpft mit seinem Namen sind eine geradlinige, liberale Berufspolitik sowie die Entfaltung und der Erhalt beruflicher Selbstverwaltung in der brandenburgischen und gesamtdeutschen Ärzteschaft. Als führendes Mitglied in mehreren provinzialen und reichsweiten Verbänden engagierte sich Schneider über vier historische Epochen stets im Sinne einer freien Ausübung und autonomen Verwaltung des Arztberufes.
Im Deutschen Kaiserreich war Schneiders standespolitisches Handeln zunächst noch regional begrenzt. 1912 initiierte er die Errichtung eines Schutzverbandes für die Ärzte des Bezirks Potsdam, dem er über zehn Jahre vorsaß. In der Weimarer Republik stieg Schneider sodann zu einer Schlüsselfigur der Gesundheits- und ärztlichen Berufspolitik auf. 1920 belebte er den Ärzteverband für die Provinz Brandenburg, ab 1928 leitete er dazu in Personalunion die brandenburgische Ärztekammer. Bereits zwei Jahre zuvor hatte er die Geschäftsführung des Deutschen Ärztevereinsbundes übernommen. Infolge der Machtübernahme der Nationalsozialisten schied Schneider bis Mitte 1934 aus allen Ämtern aus, seine Bemühungen für den Erhalt der Berufsautonomie waren vergebens. Anders sah es zunächst nach Ende des Zweiten Weltkriegs aus. In der Sowjetischen Besatzungszone saß Schneider der Fachgruppe Ärzte im Freien Deutschen Gewerkschaftsbund Brandenburg vor und verteidigte die Möglichkeiten der selbstständigen Berufsverwaltung. Zudem war er von 1946 an bis zu seinem Tod am 26. Oktober 1949 Fraktionsvorsitzender der Liberal-Demokratischen Partei im brandenburgischen Landtag.
Vor dem Hintergrund des Lebens und Wirkens Georg Schneiders untersucht die Dissertation Kontinuitäten und Brüche im ärztlichen Organisationswesen, ausgehend vom Deutschen Kaiserreich über die Weimarer Epoche und den Nationalsozialismus bis hin zur Zeit der sowjetischen Besatzung. Die Arbeit stellt die Auswirkungen der jeweiligen politischen, sozioökonomischen und gesellschaftlichen Entwicklungen auf den Ärztestand und die entsprechenden Reaktionen der ärztlichen Berufsvertreter, allen voran Georg Schneiders, gegenüber. Dabei hinterfragt sie, inwiefern sich die ärztlichen Organisationsstrukturen dem jeweiligen System anpassten und welchen Einfluss Schneider als einzelne Person in den größeren Institutionen entfalten konnte.
Von einer Säkularisierung in einem Land wie Israel zu sprechen, wo die Religion offensichtlich einen wichtigen Teil des öffentlichen Lebens darstellt, scheint widersprüchlich zu sein. Doch Israel befindet sich bedingt durch Globalisierung, Pluralisierung und Modernisierung an einem Scheideweg. Teile der israelischen Gesellschaft säkularisieren sich bereits. Die religiöse orthodoxe Vorherrschaft scheint zu bröckeln. Kann jedoch deswegen von einem Mentalitätswandel oder einer Säkularisierung des Staates gesprochen werden? Kann ein Säkularisierungsprozess in Israel erfolgreich sein? Wie muss ein säkularer Staat beschaffen sein, um den unterschiedlichen religiösen Denominationen die gleichen Möglichkeiten zu bieten? Welche Rolle spielen dabei die jüdische Diaspora, Einwanderungen und gesellschaftliche Minderheiten? Ziel der vorliegenden Arbeit ist es diese Fragen zu erörtern. Auch wenn die enge Verknüpfung von Nation und Religion im Judentum eine Säkularisierung scheinbar unmöglich macht, so erlaubt unter Bezugnahme der Konzepte von Säkularismus und Nationalismus im Kontext der historischen Entwicklungen des Judentums eine differenziertere Betrachtung dieser Verknüpfung. Durch die Nutzung von unterschiedlichen qualitativen Methoden, wie der hermeneutischen Methode zur Betrachtung der verschiedenen theoretischen Begriffe und der Analyse des Verhältnisses von Nation und Religion im Judentum; der Nutzung von Zeitungsartikel zur Aufarbeitung der aktuellen Debatten in der israelischen Gesellschaft; der Auswertung von Statistiken; sowie der Durchführung von Experteninterviews erlauben einen vielseitigen Zugang zum Forschungsgegenstand. Letztendlich soll aufgezeigt werden, dass sich Israel zwar zunehmend säkularisiert, aber vor verschiedenen Herausforderungen, wie dem gesellschaftlichen Pluralismus, der instabilen Sicherheitslage, sowie einem zunehmenden religiösen Nationalismus steht.
This publication based thesis, which consists of seven published articles, summarizes my contributions to the research field of laser excited ultrafast structural dynamics. The coherent and incoherent lattice dynamics on microscopic length scales are detected by ultrashort optical and X-ray pulses. The understanding of the complex physical processes is essential for future improvements of technological applications. For this purpose, tabletop soruces and large scale facilities, e.g. synchrotrons, are employed to study structural dynamics of longitudinal acoustic strain waves and heat transport. The investigated effects cover timescales from hundreds of femtoseconds up to several microseconds.
The main part of this thesis is dedicated to the investigation of tailored phonon wave packets propagating in perovskite nanostructures. Tailoring is achieved either by laser excitation of nanostructured bilayer samples or by a temporal series of laser pulses. Due to the propagation of longitudinal acoustic phonons, the out-of-plane lattice spacing of a thin film insulator-metal bilayer sample is modulated on an ultrafast timescale. This leads to an ultrafast modulation of the X-ray diffraction efficiency which is employed as a phonon Bragg switch to shorten hard X-ray pulses emitted from a 3rd generation synchrotron.
In addition, we have observed nonlinear mixing of high amplitude phonon wave packets which originates from an anharmonic interatomic potential. A chirped optical pulse sequence excites a narrow band phonon wave packet with specific momentum and energy. The second harmonic generation of these phonon wave packets is followed by ultrafast X-ray diffraction. Phonon upconversion takes place because the high amplitude phonon wave packet modulates the acoustic properties of the crystal which leads to self steepening and to the successive generation of higher harmonics of the phonon wave packet.
Furthermore, we have demonstrated ultrafast strain in direction parallel to the sample surface. Two consecutive so-called transient grating excitations displaced in space and time are used to coherently control thermal gradients and surface acoustic modes. The amplitude of the coherent and incoherent surface excursion is disentangled by time resolved X-ray reflectivity measurements. We calibrate the absolute amplitude of thermal and acoustic surface excursion with measurements of longitudinal phonon propagation. In addition, we develop a diffraction model which allows for measuring the surface excursion on an absolute length scale with sub-Äangström precision. Finally, I demonstrate full coherent control of an excited surface deformation by amplifying and suppressing thermal and coherent excitations at the surface of a laser-excited Yttrium-manganite sample.
Numbers are omnipresent in daily life. They vary in display format and in their meaning so that it does not seem self-evident that our brains process them more or less easily and flexibly. The present thesis addresses mental number representations in general, and specifically the impact of finger counting on mental number representations. Finger postures that result from finger counting experience are one of many ways to convey numerical information. They are, however, probably the one where the numerical content becomes most tangible. By investigating the role of fingers in adults’ mental number representations the four presented studies also tested the Embodied Cognition hypothesis which predicts that bodily experience (e.g., finger counting) during concept acquisition (e.g., number concepts) stays an immanent part of these concepts. The studies focussed on different aspects of finger counting experience. First, consistency and further details of spontaneously used finger configurations were investigated when participants repeatedly produced finger postures according to specific numbers (Study 1). Furthermore, finger counting postures (Study 2), different finger configurations (Study 2 and 4), finger movements (Study 3), and tactile finger perception (Study 4) were investigated regarding their capability to affect number processing. Results indicated that active production of finger counting postures and single finger movements as well as passive perception of tactile stimulation of specific fingers co-activated associated number knowledge and facilitated responses towards corresponding magnitudes and number symbols. Overall, finger counting experience was reflected in specific effects in mental number processing of adult participants. This indicates that finger counting experience is an immanent part of mental number representations.
Findings are discussed in the light of a novel model. The MASC (Model of Analogue and Symbolic Codes) combines and extends two established models of number and magnitude processing. Especially a symbolic motor code is introduced as an essential part of the model. It comprises canonical finger postures (i.e., postures that are habitually used to represent numbers) and finger-number associations. The present findings indicate that finger counting functions both as a sensorimotor magnitude and as a symbolic representational format and that it thereby directly mediates between physical and symbolic size. The implications are relevant both for basic research regarding mental number representations and for pedagogic practices regarding the effectiveness of finger counting as a means to acquire a fundamental grasp of numbers.
Virtual 3D city models represent and integrate a variety of spatial data and georeferenced data related to urban areas. With the help of improved remote-sensing technology, official 3D cadastral data, open data or geodata crowdsourcing, the quantity and availability of such data are constantly expanding and its quality is ever improving for many major cities and metropolitan regions. There are numerous fields of applications for such data, including city planning and development, environmental analysis and simulation, disaster and risk management, navigation systems, and interactive city maps.
The dissemination and the interactive use of virtual 3D city models represent key technical functionality required by nearly all corresponding systems, services, and applications. The size and complexity of virtual 3D city models, their management, their handling, and especially their visualization represent challenging tasks. For example, mobile applications can hardly handle these models due to their massive data volume and data heterogeneity. Therefore, the efficient usage of all computational resources (e.g., storage, processing power, main memory, and graphics hardware, etc.) is a key requirement for software engineering in this field. Common approaches are based on complex clients that require the 3D model data (e.g., 3D meshes and 2D textures) to be transferred to them and that then render those received 3D models. However, these applications have to implement most stages of the visualization pipeline on client side. Thus, as high-quality 3D rendering processes strongly depend on locally available computer graphics resources, software engineering faces the challenge of building robust cross-platform client implementations.
Web-based provisioning aims at providing a service-oriented software architecture that consists of tailored functional components for building web-based and mobile applications that manage and visualize virtual 3D city models. This thesis presents corresponding concepts and techniques for web-based provisioning of virtual 3D city models. In particular, it introduces services that allow us to efficiently build applications for virtual 3D city models based on a fine-grained service concept. The thesis covers five main areas:
1. A Service-Based Concept for Image-Based Provisioning of
Virtual 3D City Models It creates a frame for a broad range of services related to the rendering and image-based dissemination of virtual 3D city models.
2. 3D Rendering Service for Virtual 3D City Models This service provides efficient, high-quality 3D rendering functionality for virtual 3D city models. In particular, it copes with requirements such as standardized data formats, massive model texturing, detailed 3D geometry, access to associated feature data, and non-assumed frame-to-frame coherence for parallel service requests. In addition, it supports thematic and artistic styling based on an expandable graphics effects library.
3. Layered Map Service for Virtual 3D City Models It generates a map-like representation of virtual 3D city models using an oblique view. It provides high visual quality, fast initial loading times, simple map-based interaction and feature data access. Based on a configurable client framework, mobile and web-based applications for virtual 3D city models can be created easily.
4. Video Service for Virtual 3D City Models It creates and synthesizes videos from virtual 3D city models. Without requiring client-side 3D rendering capabilities, users can create camera paths by a map-based user interface, configure scene contents, styling, image overlays, text overlays, and their transitions. The service significantly reduces the manual effort typically required to produce such videos. The videos can automatically be updated when the underlying data changes.
5. Service-Based Camera Interaction It supports task-based 3D camera interactions, which can be integrated seamlessly into service-based visualization applications. It is demonstrated how to build such web-based interactive applications for virtual 3D city models using this camera service.
These contributions provide a framework for design, implementation, and deployment of future web-based applications, systems, and services for virtual 3D city models. The approach shows how to decompose the complex, monolithic functionality of current 3D geovisualization systems into independently designed, implemented, and operated service- oriented units. In that sense, this thesis also contributes to microservice architectures for 3D geovisualization systems—a key challenge of today’s IT systems engineering to build scalable IT solutions.
In this work, different strategies for the construction of biohybrid photoelectrodes are investigated and have been evaluated according to their intrinsic catalytic activity for the oxidation of the cofactor NADH or for the connection with the enzymes PQQ glucose dehydrogenase (PQQ-GDH), FAD-dependent glucose dehydrogenase (FAD-GDH) and fructose dehydrogenase (FDH). The light-controlled oxidation of NADH has been analyzed with InGaN/GaN nanowire-modified electrodes. Upon illumination with visible light the InGaN/GaN nanowires generate an anodic photocurrent, which increases in a concentration-dependent manner in the presence of NADH, thus allowing determination of the cofactor. Furthermore, different approaches for the connection of enzymes to quantum dot (QD)-modified electrodes via small redox molecules or redox polymers have been analyzed and discussed. First, interaction studies with diffusible redox mediators such as hexacyanoferrate(II) and ferrocenecarboxylic acid have been performed with CdSe/ZnS QD-modified gold electrodes to build up photoelectrochemical signal chains between QDs and the enzymes FDH and PQQ-GDH. In the presence of substrate and under illumination of the electrode, electrons are transferred from the enzyme via the redox mediators to the QDs. The resulting photocurrent is dependent on the substrate concentration and allows a quantification of the fructose and glucose content in solution. A first attempt with immobilized redox mediator, i.e. ferrocenecarboxylic acid chemically coupled to PQQ-GDH and attached to QD-modified gold electrodes, reveal the potential to build up photoelectrochemical signal chains even without diffusible redox mediators in solution. However, this approach results in a significant deteriorated photocurrent response compared to the situation with diffusing mediators. In order to improve the photoelectrochemical performance of such redox mediator-based, light-switchable signal chains, an osmium complex-containing redox polymer has been evaluated as electron relay for the electronic linkage between QDs and enzymes. The redox polymer allows the stable immobilization of the enzyme and the efficient wiring with the QD-modified electrode. In addition, a 3D inverse opal TiO2 (IO-TiO2) electrode has been used for the integration of PbS QDs, redox polymer and FAD-GDH in order to increase the electrode surface. This results in a significantly improved photocurrent response, a quite low onset potential for the substrate oxidation and a broader glucose detection range as compared to the approach with ferrocenecarboxylic acid and PQQ-GDH immobilized on CdSe/ZnS QD-modified gold electrodes. Furthermore, IO-TiO2 electrodes are used to integrate sulfonated polyanilines (PMSA1) and PQQ-GDH, and to investigate the direct interaction between the polymer and the enzyme for the light-switchable detection of glucose. While PMSA1 provides visible light excitation and ensures the efficient connection between the IO-TiO2 electrode and the biocatalytic entity, PQQ-GDH enables the oxidation of glucose. Here, the IO-TiO2 electrodes with pores of approximately 650 nm provide a suitable interface and morphology, which is required for a stable and functional assembly of the polymer and enzyme. The successful integration of the polymer and the enzyme can be confirmed by the formation of a glucose-dependent anodic photocurrent. In conclusion, this work provides insights into the design of photoelectrodes and presents different strategies for the efficient coupling of redox enzymes to photoactive entities, which allows for light-directed sensing and provides the basis for the generation of power from sun light and energy-rich compounds.
Signals stored in sediment
(2018)
Tectonic and climatic boundary conditions determine the amount and the characteristics (size distribution and composition) of sediment that is generated and exported from mountain regions. On millennial timescales, rivers adjust their morphology such that the incoming sediment (Qs,in) can be transported downstream by the available water discharge (Qw). Changes in climatic and tectonic boundary conditions thus trigger an adjustment of the downstream river morphology. Understanding the sensitivity of river morphology to perturbations in boundary conditions is therefore of major importance, for example, for flood assessments, infrastructure and habitats. Although we have a general understanding of how rivers evolve over longer timescales, the prediction of channel response to changes in boundary conditions on a more local scale and over shorter timescales remains a major challenge. To better predict morphological channel evolution, we need to test (i) how channels respond to perturbations in boundary conditions and (ii) how signals reflecting the persisting conditions are preserved in sediment characteristics. This information can then be applied to reconstruct how local river systems have evolved over time.
In this thesis, I address those questions by combining targeted field data collection in the Quebrada del Toro (Southern Central Andes of NW Argentina) with cosmogenic nuclide analysis and remote sensing data. In particular, I (1) investigate how information on hillslope processes is preserved in the 10Be concentration (geochemical composition) of fluvial sediments and how those signals are altered during downstream transport. I complement the field-based approach with physical experiments in the laboratory, in which I (2) explore how changes in sediment supply (Qs,in) or water discharge (Qw) generate distinct signals in the amount of sediment discharge at the basin outlet (Qs,out). With the same set of experiments, I (3) study the adjustments of alluvial channel morphology to changes in Qw and Qs,in, with a particular focus in fill-terrace formation. I transfer the findings from the experiments to the field to (4) reconstruct the evolution of a several-hundred meter thick fluvial fill-terrace sequence in the Quebrada del Toro. I create a detailed terrace chronology and perform reconstructions of paleo-Qs and Qw from the terrace deposits. In the following paragraphs, I summarize my findings on each of these four topics.
First, I sampled detrital sediment at the outlet of tributaries and along the main stem in the Quebrada del Toro, analyzed their 10Be concentration ([10Be]) and compared the data to a detailed hillslope-process inventory. The often observed non-linear increase in catchment-mean denudation rate (inferred from [10Be] in fluvial sediment) with catchment-median slope, which has commonly been explained by an adjustment in landslide-frequency, coincided with a shift in the main type of hillslope processes. In addition, the [10Be] in fluvial sediments varied with grain-size. I defined the normalized sand-gravel-index (NSGI) as the 10Be-concentration difference between sand and gravel fractions divided by their summed concentrations. The NSGI increased with median catchment slope and coincided with a shift in the prevailing hillslope processes active in the catchments, thus making the NSGI a potential proxy for the evolution of hillslope processes over time from sedimentary deposits. However, the NSGI recorded hillslope-processes less well in regions of reduced hillslope-channel connectivity and, in addition, has the potential to be altered during downstream transport due to lateral sediment input, size-selective sediment transport and abrasion.
Second, my physical experiments revealed that sediment discharge at the basin outlet (Qs,out) varied in response to changes in Qs,in or Qw. While changes in Qw caused a distinct signal in Qs,out during the transient adjustment phase of the channel to new boundary conditions, signals related to changes in Qs,in were buffered during the transient phase and likely only become apparent once the channel is adjusted to the new conditions. The temporal buffering is related to the negative feedback between Qs,in and channel-slope adjustments. In addition, I inferred from this result that signals extracted from the geochemical composition of sediments (e.g., [10Be]) are more likely to represent modern-day conditions during times of aggradation, whereas the signal will be temporally buffered due to mixing with older, remobilized sediment during times of channel incision.
Third, the same set of experiments revealed that river incision, channel-width narrowing and terrace cutting were initiated by either an increase in Qw, a decrease in Qs,in or a drop in base level. The lag-time between the external perturbation and the terrace cutting determined (1) how well terrace surfaces preserved the channel profile prior to perturbation and (2) the degree of reworking of terrace-surface material. Short lag-times and well preserved profiles occurred in cases with a rapid onset of incision. Also, lag-times were synchronous along the entire channel after upstream perturbations (Qw, Qs,in), whereas base-level fall triggered an upstream migrating knickzone, such that lag-times increased with distance upstream. Terraces formed after upstream perturbations (Qw, Qs,in) were always steeper when compared to the active channel in new equilibrium conditions. In the base-level fall experiment, the slope of the terrace-surfaces and the modern channel were similar. Hence, slope comparisons between the terrace surface and the modern channel can give insights into the mechanism of terrace formation.
Fourth, my detailed terrace-formation chronology indicated that cut-and-fill episodes in the Quebrada del Toro followed a ~100-kyr cyclicity, with the oldest terraces ~ 500 kyr old. The terraces were formed due to variability in upstream Qw and Qs. Reconstructions of paleo-Qs over the last 500 kyr, which were restricted to times of sediment deposition, indicated only minor (up to four-fold) variations in paleo-denudation rates. Reconstructions of paleo-Qw were limited to the times around the onset of river incision and revealed enhanced discharge from 10 to 85% compared to today. Such increases in Qw are in agreement with other quantitative paleo-hydrological reconstructions from the Eastern Andes, but have the advantage of dating further back in time.
Remote sensing technology, such as airborne, mobile, or terrestrial laser scanning, and photogrammetric techniques, are fundamental approaches for efficient, automatic creation of digital representations of spatial environments. For example, they allow us to generate 3D point clouds of landscapes, cities, infrastructure networks, and sites. As essential and universal category of geodata, 3D point clouds are used and processed by a growing number of applications, services, and systems such as in the domains of urban planning, landscape architecture, environmental monitoring, disaster management, virtual geographic environments as well as for spatial analysis and simulation.
While the acquisition processes for 3D point clouds become more and more reliable and widely-used, applications and systems are faced with more and more 3D point cloud data. In addition, 3D point clouds, by their very nature, are raw data, i.e., they do not contain any structural or semantics information. Many processing strategies common to GIS such as deriving polygon-based 3D models generally do not scale for billions of points. GIS typically reduce data density and precision of 3D point clouds to cope with the sheer amount of data, but that results in a significant loss of valuable information at the same time.
This thesis proposes concepts and techniques designed to efficiently store and process massive 3D point clouds. To this end, object-class segmentation approaches are presented to attribute semantics to 3D point clouds, used, for example, to identify building, vegetation, and ground structures and, thus, to enable processing, analyzing, and visualizing 3D point clouds in a more effective and efficient way. Similarly, change detection and updating strategies for 3D point clouds are introduced that allow for reducing storage requirements and incrementally updating 3D point cloud databases. In addition, this thesis presents out-of-core, real-time rendering techniques used to interactively explore 3D point clouds and related analysis results. All techniques have been implemented based on specialized spatial data structures, out-of-core algorithms, and GPU-based processing schemas to cope with massive 3D point clouds having billions of points.
All proposed techniques have been evaluated and demonstrated their applicability to the field of geospatial applications and systems, in particular for tasks such as classification, processing, and visualization. Case studies for 3D point clouds of entire cities with up to 80 billion points show that the presented approaches open up new ways to manage and apply large-scale, dense, and time-variant 3D point clouds as required by a rapidly growing number of applications and systems.
Obwohl der sozioökonomische Status (SES) eine in der Sozialepidemiologie häufig gebrauchte Variable darstellt, ist seine Verwendung mit methodischen Problemen verknüpft: Seine latente Struktur führt dazu, dass sich verschiedene Möglichkeiten der Operationalisierung eröffnen. Diese reichen von klassischen Ungleichheitsindikatoren wie Bildung, Einkommen oder Berufsposition, über multidimensionale oder über Nachbarschaftsmerkmale konstruierte Indizes, bis hin zu subjektiven Statuseinschätzungen. Problematisch ist dies insofern, als verschiedene Indikatoren auf unterschiedlichen theoretischen Konstrukten beruhen und unterschiedliche Schlussfolgerungen erlauben.
In dieser Arbeit wird deshalb in einem ersten Schritt anhand eines systematischen Reviews zum Zusammenhang von SES und Rückenschmerzen überprüft, welche Indikatoren in wissenschaftlichen Publikationen eingesetzt werden und wie die Auswahl begründet wird. Das Ergebnis zeigt eine klare Präferenz für klassische Indikatoren (Bildung, Einkommen und Berufsposition). Erläutert wurde die jeweilige Auswahl allerdings nur in einem geringen Prozentsatz der untersuchten Artikel, obwohl die unterschiedlichen Studienergebnisse nahelegen, dass der gewählte Indikator einen Einfluss auf den gefundenen Zusammenhang ausüben könnte.
Deshalb wurde in einem weiteren Schritt überprüft, wie unterschiedliche SES-Indikatoren mit der Verbesserung von Rückenschmerzen nach einer Rehabilitation (Studie 1) und der Neuentstehung von Rückenschmerzen (Studie 2) zusammenhängen. Außerdem wurde untersucht, ob ein einfaches Modell den Zusammenhang von SES und Gesundheit so darstellen kann, dass a priori abzuschätzen ist, wie hoch der Einfluss unterschiedlicher Indikatoren auf einen bestimmten Gesundheitsoutput sein könnte.
Es zeigt sich, dass sich der errechnete Zusammenhang zwischen den verschiedenen Indikatoren und chronischen Rückenschmerzen erheblich unterscheidet: Für Menschen, die bereits wegen Rückenschmerzen in Rehabilitation waren, erwiesen sich Bildung und Berufsposition als ähnlich einflussreiche Einflussfaktoren, während für das Einkommen kein bedeutender Zusammenhang festgestellt werden konnte. Für die Neuentstehung chronischer Rückenschmerzen zeigte sich die Berufsposition als wichtigster Indikator, gefolgt von Bildung, während für Einkommen kein signifikanter Zusammenhang gefunden werden konnte.
Folglich bestimmt die Wahl des Indikators die Höhe des festgestellten Zusammenhangs stark mit. Unterschiedliche Indikatoren dürfen deshalb nicht als austauschbar betrachtet werden und es muss bei jeder Forschungsfrage genau überlegt werden, welcher Indikator für die jeweilige Fragestellung am besten verwendet werden kann. Das vorgeschlagene theoretische Modell kann dabei als Unterstützung dienen.
In der vorliegenden Arbeit werden Wege zur Gewinnung verschiedener phenolischer Substanzen wie Lignin, Diarylheptanoide und 4-(3-Oxobutyl)phenol (Himbeerketon) aus dem Stamm der Hängebirke (Betula pendula) aufgezeigt. Durch Methacrylierung des 4-(3-Oxobutyl)phenols wurde ein Monomer erzeugt, welches mittels freier radikalischer Masse- und Lösungspolymerisation, sowie enzymatischer Polymerisation polymerisiert werden kann.
Eine erste Isolierung von Bestandteilen wurde durch Extraktion von Innenholz bzw. Rinde mit Methanol erzielt. Die in Methanol unlöslichen Bestandteile des Innenholzes und der Rinde wurden anschließend mit ausgewählten ionischen Flüssigkeiten extrahiert. Es wurde ein Verfahren zum selektiven Trennen der mit diesen ionischen Flüssigkeiten extrahierten Bestandteile in Cellulose, Hemicellulose, Lignin und mit Ethylacetat extrahierbare Bestandteile entwickelt. Hierdurch war es möglich, sowohl die verwendeten ionischen Flüssigkeiten als auch das Innenholz und die Rinde hinsichtlich ihres Extraktionsverhaltens miteinander zu vergleichen.
Ferner wurden verschiedene Strategien aufgezeigt, um insgesamt drei Spezies an Diarylheptanoiden aus dem methanolischen Extrakt der Rinde zu isolieren. Eines der gefundenen Diarylheptanoide (5 Hydroxy-1,7-bis(4-hydroxyphenyl)-3-heptanon) wurde via Retroaldolreaktion in 4 (3 Oxobutyl)phenol (Himbeerketon) und 3 (4 Hydroxyphenyl)propanal gespalten.
Es wurde die Verwendung des 4-(3-Oxobutyl)phenol als Monomerbestandteil untersucht. Hierfür wurde 4-(3-Oxobutyl)phenylmethacrylat synthetisiert und Wege zur Reinigung mittels Säulenchromatographie und Umkristallisation aufgezeigt. Anschließend wurde Poly(4-(3-oxobutyl)phenylmethacrylat) (PObMA) und Polybenzylmethacrylats (PBzMA) aus Massen- und Lösungspolymerisation hergestellt. Die Ausbeuten an PObpMA im Vergleich zum PBzMA liegen bei gleichen Reaktionsbedingungen auf gleichem Niveau. Im Kontrast hierzu ist der Polymerisationsgrad aus freier radikalischer Polymerisation in Masse des PObpMA im Vergleich zum PBzMA um den Faktor 3,7 größer. Die Glasübergangstemperaturen des PObpMA liegen bei gleichen Reaktionsbedingungen sowohl bei freier radikalischer Polymerisation in Masse, als auch bei Lösungspolymerisation über denen des PBzMA. Darüber hinaus wurde die Polymerisation von 4-(3-Oxobutyl)phenylmethacrylat und Benzylmethacrylat mit einem Initiatorsystem bestehend aus Meerrettichperoxidase, Acetylaceton und Wasserstoffperoxid bei Raumtemperatur beschrieben. Die mit enzymatischem Initiatorsystem erzeugten Produkte zeigten starke Übereinstimmung mit Produkten aus Lösungspolymerisationen, welche mit Azobis(isobutyronitril) initiiert wurden.
Die Arbeit beschäftigt sich mit den aktuellen Regelungen des deutschen Aufenthaltsrechts in Bezug auf die Möglichkeiten des Familiennachzuges. Es werden Schwachstellen der aktuellen Regelungen aufgezeigt, Ursachen, Rechtfertigungsgründe und mögliche Lösungsansätze betrachtet.
Schwerpunkt der Betrachtung sind die Konflikte, welche sich unter dem Begriff der Inländerdiskriminierung zusammenfassen lassen. Hierzu wird das Phänomen der Inländerdiskriminierung untersucht und die im Kontext des Familiennachzuges hierzu ergangene Rechtsprechung des EuGH betrachtet. Dabei gilt das Hauptaugenmerk der Figur des grenzüberschreitenden Bezuges, welche der EuGH im Ergebnis mittlerweile aufgelöst hat. Als Ergebnis dieses Abschnittes der Arbeit wird festgestellt, dass eine Unterscheidung von Nachzug zu Deutschen oder zu Unionsbürgern gegen Gleichheitssätze verstößt und aufzuheben ist.
Weiterhin betrachtet die Arbeit verschiedene alternative Lebensmodelle neben der klassischen verschiedengeschlechtlichen Ehe. In Bezug auf gleichgeschlechtliche Lebensgemeinschaften werden auch nach Einführung der „Ehe für alle“ weitere Schwachstellen verortet, die vor allem darauf fußen, dass Nachzugsrechte vom Bestehen eines Instituts abhängen, welches in großen Teilen der Welt nicht gibt. In Hinblick auf nichtehelichen Lebensgemeinschaften wird hingegen die geltende Rechtslage als ausreichend betrachtet. Zuletzt betrachtet die Arbeit Ehemodelle, welche im deutschen Recht nicht vorgesehen und anerkannt sind. Dies sind die Zwangs-, Kinder- und Mehrehe. Es wird beleuchtet, wie das deutsche Recht und insbesondere das Aufenthaltsrecht mit diesen Ehen umgeht und welcher Zweck mit den bestehenden Regelungen verfolgt wird. Während der Gesetzgeber den Schutz der Opfer solcher Eheschließungen vor Augen hatte, kommt die Untersuchung zu dem Ergebnis, dass vielmehr eine weitere Gefährdung eintritt, welche nur zu vermeiden wäre, wenn auch diese Ehemodelle zunächst anerkannt würden und den Opfern im Inland sodann Hilfe angeboten würde.
Insgesamt stellt die Arbeit gravierende Mängel in menschenrechtlicher Hinsicht im bestehenden Recht des Familiennachzugs fest und schlägt eine generelle Neuordnung vor.
Die betrachteten Regelungen entsprechen dem Regelungsstand im Juli 2018.
Business process automation improves organizations’ efficiency to perform work. Therefore, a business process is first documented as a process model which then serves as blueprint for a number of process instances representing the execution of specific business cases. In existing business process management systems, process instances run independently from each other. However, in practice, instances are also collected in groups at certain process activities for a combined execution to improve the process performance. Currently, this so-called batch processing is executed manually or supported by external software. Only few research proposals exist to explicitly represent and execute batch processing needs in business process models. These works also lack a comprehensive understanding of requirements.
This thesis addresses the described issues by providing a basic concept, called batch activity. It allows an explicit representation of batch processing configurations in process models and provides a corresponding execution semantics, thereby easing automation. The batch activity groups different process instances based on their data context and can synchronize their execution over one or as well multiple process activities. The concept is conceived based on a requirements analysis considering existing literature on batch processing from different domains and industry examples. Further, this thesis provides two extensions: First, a flexible batch configuration concept, based on event processing techniques, is introduced to allow run time adaptations of batch configurations. Second, a concept for collecting and batching activity instances of multiple different process models is given. Thereby, the batch configuration is centrally defined, independently of the process models, which is especially beneficial for organizations with large process model collections. This thesis provides a technical evaluation as well as a validation of the presented concepts. A prototypical implementation in an existing open-source BPMS shows that with a few extensions, batch processing is enabled. Further, it demonstrates that the consolidated view of several work items in one user form can improve work efficiency. The validation, in which the batch activity concept is applied to different use cases in a simulated environment, implies cost-savings for business processes when a suitable batch configuration is used. For the validation, an extensible business process simulator was developed. It enables process designers to study the influence of a batch activity in a process with regards to its performance.
In this thesis, we treat the extreme Newman-Penrose components of both the Maxwell field (s=±1) and the linearized gravitational perturbations (or "linearized gravity" for short) (s=±2) in the exterior of a slowly rotating Kerr black hole. Upon different rescalings, we can obtain spin s components which satisfy the separable Teukolsky master equation (TME). For each of these spin s components defined in Kinnersley tetrad, the resulting equations by performing some first-order differential operator on it once and twice (twice only for s=±2), together with the TME, are in the form of an "inhomogeneous spin-weighted wave equation" (ISWWE) with different potentials and constitute a linear spin-weighted wave system. We then prove energy and integrated local energy decay (Morawetz) estimates for this type of ISWWE, and utilize them to achieve both a uniform bound of a positive definite energy and a Morawetz estimate for the regular extreme Newman-Penrose components defined in the regular Hawking-Hartle tetrad.
We also present some brief discussions on mode stability for TME for the case of real frequencies. This says that in a fixed subextremal Kerr spacetime, there is no nontrivial separated mode solutions to TME which are purely ingoing at horizon and purely outgoing at infinity. This yields a representation formula for solutions to inhomogeneous Teukolsky equations, and will play a crucial role in generalizing the above energy and Morawetz estimates results to the full subextremal Kerr case.
In einer verschränkten Lektüre von Curtius, Auerbach und Bachtin macht die Dissertation sichtbar, wie die Autoren mit ihren Arbeiten zur europäischen Literaturgeschichte nach einer ethischen Orientierung in der Krise der Moderne suchen. Ihr Konzept einer philologisch fundierten Geschichtsphilosophie in praktischer Absicht wird sowohl kultur- und theoriegeschichtlich aufbereitet, als auch anhand detaillierter Textanalysen nachvollzogen.
Der Blick auf den geschichtsphilosophischen Aspekt ihrer Forschungsarbeit erweist sich hierbei nicht nur insoweit als fruchtbar, als er sich als Schlüssel offenbart, philologische Mikrologie und breite Zusammenschau sowie ideengeschichtliche und gesellschaftliche Entwicklungen zu verknüpfen. Ihr Ansatz offenbart sich auch als wesentlich differenzierter, als es die gängigen Vorbehalte gegenüber der Geschichtsphilosophie vermuten lassen.
Die Untersuchung erweitert aus diesem Grund den methodischen Diskurshorizont, indem sie die Möglichkeiten einer kritischen Geschichtsphilosophie für gegenwärtige Fragen der Literaturgeschichte neu justiert. Dies geschieht über den Zugang so unterschiedlicher Rezeptionen wie der von Anselm Haverkamp, Edward Said, Terry Eagleton und Homi Bhabha, die einen Diskussionsraum eröffnen, welcher den eigenen historischen Standpunkt der Dissertation im Kontext von Postmoderne und Postkolonialismus reflektiert.
Es gibt in Berlin eine einzigartige Vereinslandschaft im Amateur – und semiprofessionellen Fußballsport, in der einst von türkischen Migranten gegründete Vereine einen festen Platz einnehmen. Fußballsport bietet einen sozialen Raum für Jugendliche verschiedener kultureller, ethnischer und religiöser Herkunft, in dem Gruppen gebildet werden, um gegen einander zu konkurrieren. Ebenso eröffnet Fußball dem Einzelnen die Möglichkeit, die Gültigkeit und Relevanz von Vorurteilen und von gängigen Stereotypisierungen anderer Gruppen im Spielalltag einer ständigen Prüfung zu unterziehen. Fußballspieler können sich sowohl zwischen multi-kulturellen als auch mono-ethnischen Gruppenkonstellationen, in einigen Fällen auch in transnationalen Konstellationen bewegen, womit sie dabei wesentlich an der Sinngebung ihrer eigenen sozialen Zugehörigkeit mitwirken, die sich aus dem Spannungsfeld von Selbst- und Fremdwahrnehmungsmustern ergibt. In Folge dessen werden in diesem Raum Anerkennungsmechanismen konstituiert.
Die vorliegende Dissertation befasst sich mit dem alltäglichen Leben von türkisch-stämmigen, jugendlichen Amateur- und semiprofessionellen Fußballspielern (delikanli), sowie von anderen sozialen Akteuren der türkischen Fußballwelt, wie zum Beispiel „ältere“ Fußballspieler (agbi) und Fußballtrainer (hoca). Hauptanliegen der Arbeit war die Rekonstruktion kollektiver Wahrnehmungs-, Deutungs - und Handlungsmuster von Mitgliedern türkischer Fußballvereine im allgemeinen und ihrer Selbstdarstellung aber auch ihrer Wahrnehmung der „Anderen“ im besonderen. Mittels dieser Studie sollte nachvollzogen werden, ob und inwiefern sich traditionelle soziale Verhaltensmuster der gewählten Gruppe im technisch regulierten und stark Konkurrenz-orientierten Handlungsraum widerspiegeln und die reziproken Beziehungen zwischen dem „Selbst“ und den „Anderen“ regulieren. Dabei wurde die Relevanz von herkunftsbezogenen Stereotypisierungen und Vorurteilen in der kollektiven Konstitution von Selbstwahrnehmungen und Fremdverstehen im partikularen sozialen Feld (Bourdieu, 2001) des Fußballs rekonstruiert.
In dieser Arbeit wurde darüber hinaus beleuchtet, welche Rolle türkische Fußballvereine auf der einen Seite bei der Entstehung sozialer Raumzugehörigkeit zu den Stadtquartieren in Berlin einnehmen und welche Art von Mechanismen der sozialen Integration sie in diesen Vereinen herstellen. Auf der anderen Seite wurde hinterfragt, inwiefern sie zur sozialen Kohäsion zwischen diversen Kulturen beitragen. Daher wurde geprüft, ob und inwiefern die negativ konnotierte ethnozentrische Wahrnehmung von „Differenz“ (Bielefeld, 1998), die als soziales Konstrukt zwischen autochthonen und allochthonen Gruppen hergestellt wird, durch das Engagement der Vereinsakteure einen konstruktiven Wandel erfährt.
Übergeordnetes Ziel all dieser Forschungsfragen war es, ein fundiertes Verständnis über die Rolle von türkischen Fußballvereinen als soziale Mechanismen zu erlangen und deren Funktionsweise bei der Konstitution von Anpassungsstrategien in diesem sozialen Feld untersuchen. Detailliert wurde diese Rolle unter der Konzeptualisierung von sozialen Positionierungsmuster betrachtet, die als Gefüge von Deutungen des Alltäglichen verstanden werden, das individuelle und kollektive Handlungsmuster und implizit Muster des Fremdverstehens sowie des othering im Migrationskontext reguliert. Eine Rekonstruktion der sozialen Positionierungsmuster bietet eine eingehende soziologische Untersuchung dieser Teilnehmergruppe, die zudem Aufschluss über die Bedeutung und das Verständnis von ethnischer Zugehörigkeit für letztere gibt.
Neben umfangreicher Feldbeobachtung wurden in dieser qualitativen Studie mit Spielern verschiedener Vereine insgesamt zehn Gruppendiskussionen (Bohnsack, 2004) innerhalb ihrer Mannschaften zu gemeinsamen alltäglichen Erlebnissen und Erfahrungen durchgeführt, aufgezeichnet und mittels sozialwissenschaftlichem hermeneutischem Verfahren (Soeffner, 2004) interpretiert. Auch mit anderen Vereinsmitgliedern, d. h. mit Trainern bzw. hoca, Vorsitzenden, Managern und Sponsoren wurden jeweils zehn narrative und sieben biographische Einzelinterviews sowie sieben Experteninterviews durchgeführt. Deren Analyse erlaubt es, die Rolle dieser Mitglieder sowie wirkende Autoritätsmechanismen und kollektiv konstituierte Verhaltensmuster innerhalb der gesamten Vereinsgruppe zu rekonstruieren. Dabei wurde bezweckt, die Gesamtheit des sozialen Netzwerkes bzw. die Beziehungsschemata innerhalb der türkischen Fußballvereine Berlins zu verdeutlichen.
In der Arbeit werden zwei Standpunkte der theoretischen Auseinandersetzung verwendet. Auf der einen Seite wird die Lebensweltanalyse (Schütz und Luckmann, 1979, 1990) angewendet, um das soziale Erbe der in der Vergangenheit gesellschaftlich konstituierten Titulierung „Menschen mit Migrationshintergrund“ zu rekonstruieren, bzw. den Einfluss dieser sozialen Reproduktion auf die Wahrnehmungs-, Deutungs- und Handlungsmuster der Akteure zu untersuchen. Auf der anderen Seite wird die soziale Wirkung der tatsächlichen, alltäglichen Erfahrungsschemata im sozialen Feld des Fußballs auf die Selbstpositionierungen der Akteure mittels Goffmanscher Rahmenanalyse (Goffman, 1980) herausgearbeitet.
Thermoresponsive block copolymers of presumably highly biocompatible character exhibiting upper critical solution temperature (UCST) type phase behavior were developed. In particular, these polymers were designed to exhibit UCST-type cloud points (Tcp) in physiological saline solution (9 g/L) within the physiologically interesting window of 30-50°C. Further, their use as carrier for controlled release purposes was explored. Polyzwitterion-based block copolymers were synthesized by atom transfer radical polymerization (ATRP) via a macroinitiator approach with varied molar masses and co-monomer contents. These block copolymers can self-assemble in the amphiphilic state to form micelles, when the thermoresponsive block experiences a coil-to-globule transition upon cooling. Poly(ethylene glycol) methyl ether (mPEG) was used as the permanently hydrophilic block to stabilize the colloids formed, and polyzwitterions as the thermoresponsive block to promote the temperature-triggered assembly-disassembly of the micellear aggregates at low temperature.
Three zwitterionic monomers were used for this studies, namely 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (SPE), 4-((2-(methacryloyl- oxy)ethyl)dimethylammonio)butane-1-sulfonate (SBE), and 3-((2-(methacryloyloxy)ethyl)- dimethylammonio)propane-1-sulfate) (ZPE). Their (co)polymers were characterized with respect to their molecular structure by proton nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). Their phase behaviors in pure water as well as in physiological saline were studied by turbidimetry and dynamic light scattering (DLS). These (co)polymers are thermoresponsive with UCST-type phase behavior in aqueous solution. Their phase transition temperatures depend strongly on the molar masses and the incorporation of co-monomers: phase transition temperatures increased with increasing molar masses and content of poorly water-soluble co-monomer. In addition, the presence of salt influenced the phase transition dramatically. The phase transition temperature decreased with increasing salt content in the solution. While the PSPE homopolymers show a phase transition only in pure water, the PZPE homopolymers are able to exhibit a phase transition only in high salinity, as in physiological saline. Although both polyzwitterions have similar chemical structures that differ only in the anionic group (sulfonate group in SPE and sulfate group in ZPE), the water solubility is very different. Therefore, the phase transition temperatures of targeted block copolymers were modulated by using statistical copolymer of SPE and ZPE as thermoresponsive block, and varying the ratio of SPE to ZPE. Indeed, the statistical copolymers of P(SPE-co-ZPE) show phase transitions both in pure water as well as in physiological saline. Surprisingly, it was found that mPEG-b-PSBE block copolymer can display “schizophrenic” behavior in pure water, with the UCST-type cloud point occurring at lower temperature than the LCST-type one.
The block copolymer, which satisfied best the boundary conditions, is block copolymer mPEG114-b-P(SPE43-co-ZPE39) with a cloud point of 45°C in physiological saline. Therefore, it was chosen for solubilization studies of several solvatochromic dyes as models of active agents, using the thermoresponsive block copolymer as “smart” carrier. The uptake and release of the dyes were explored by UV-Vis and fluorescence spectroscopy, following the shift of the wavelength of the absorbance or emission maxima at low and high temperature. These are representative for the loaded and released state, respectively. However, no UCST-transition triggered uptake and release of these dyes could be observed. Possibly, the poor affinity of the polybetaines to the dyes in aqueous environtments may be related to the widely reported antifouling properties of zwitterionic polymers.
For more than two centuries, plant ecologists have aimed to understand how environmental gradients and biotic interactions shape the distribution and co-occurrence of plant species. In recent years, functional trait–based approaches have been increasingly used to predict patterns of species co-occurrence and species distributions along environmental gradients (trait–environment relationships). Functional traits are measurable properties at the individual level that correlate well with important processes. Thus, they allow us to identify general patterns by synthesizing studies across specific taxonomic compositions, thereby fostering our understanding of the underlying processes of species assembly. However, the importance of specific processes have been shown to be highly dependent on the spatial scale under consideration. In particular, it remains uncertain which mechanisms drive species assembly and allow for plant species coexistence at smaller, more local spatial scales. Furthermore, there is still no consensus on how particular environmental gradients affect the trait composition of plant communities. For example, increasing drought because of climate change is predicted to be a main threat to plant diversity, although it remains unclear which traits of species respond to increasing aridity. Similarly, there is conflicting evidence of how soil fertilization affects the traits related to establishment ability (e.g., seed mass). In this cumulative dissertation, I present three empirical trait-based studies that investigate specific research questions in order to improve our understanding of species distributions along environmental gradients.
In the first case study, I analyze how annual species assemble at the local scale and how environmental heterogeneity affects different facets of biodiversity—i.e. taxonomic, functional, and phylogenetic diversity—at different spatial scales. The study was conducted in a semi-arid environment at the transition zone between desert and Mediterranean ecosystems that features a sharp precipitation gradient (Israel). Different null model analyses revealed strong support for environmentally driven species assembly at the local scale, since species with similar traits tended to co-occur and shared high abundances within microsites (trait convergence). A phylogenetic approach, which assumes that closely related species are functionally more similar to each other than distantly related ones, partly supported these results. However, I observed that species abundances within microsites were, surprisingly, more evenly distributed across the phylogenetic tree than expected (phylogenetic overdispersion). Furthermore, I showed that environmental heterogeneity has a positive effect on diversity, which was higher on functional than on taxonomic diversity and increased with spatial scale. The results of this case study indicate that environmental heterogeneity may act as a stabilizing factor to maintain species diversity at local scales, since it influenced species distribution according to their traits and positively influenced diversity. All results were constant along the precipitation gradient.
In the second case study (same study system as case study one), I explore the trait responses of two Mediterranean annuals (Geropogon hybridus and Crupina crupinastrum) along a precipitation gradient that is comparable to the maximum changes in precipitation predicted to occur by the end of this century (i.e., −30%). The heterocarpic G. hybridus showed strong trends in seed traits, suggesting that dispersal ability increased with aridity. By contrast, the homocarpic C. crupinastrum showed only a decrease in plant height as aridity increased, while leaf traits of both species showed no consistent pattern along the precipitation gradient. Furthermore, variance decomposition of traits revealed that most of the trait variation observed in the study system was actually found within populations. I conclude that trait responses towards aridity are highly species-specific and that the amount of precipitation is not the most striking environmental factor at this particular scale.
In the third case study, I assess how soil fertilization mediates—directly by increased nutrient addition and indirectly by increased competition—the effect of seed mass on establishment ability. For this experiment, I used 22 species differing in seed mass from dry grasslands in northeastern Germany and analyzed the interacting effects of seed mass with nutrient availability and competition on four key components of seedling establishment: seedling emergence, time of seedling emergence, seedling survival, and seedling growth. (Time of) seedling emergence was not affected by seed mass. However, I observed that the positive effect of seed mass on seedling survival is lowered under conditions of high nutrient availability, whereas the positive effect of seed mass on seedling growth was only reduced by competition. Based on these findings, I developed a conceptual model of how seed mass should change along a soil fertility gradient in order to reconcile conflicting findings from the literature. In this model, seed mass shows a U-shaped pattern along the soil fertility gradient as a result of changing nutrient availability and competition.
Overall, the three case studies highlight the role of environmental factors on species distribution and co-occurrence. Moreover, the findings of this thesis indicate that spatial heterogeneity at local scales may act as a stabilizing factor that allows species with different traits to coexist. In the concluding discussion, I critically debate intraspecific trait variability in plant community ecology, the use of phylogenetic relationships and easily measured key functional traits as a proxy for species’ niches. Finally, I offer my outlook for the future of functional plant community research.
Through IOs' Eyes
(2018)
Is global governance characterized by overlap and fragmentation, or by coordination and harmonization? There are two rather different narratives about the worlds in which international organizations (IOs) live. One way or another, IOs are part of a broader environment and engage in relations with other actors in it. Rather than being detached from their environment, IOs are shaped by and respond to developments taking place within it (e.g., overlap). Thus, the general research interest of this dissertation lies in organizational responses to such environmental developments. Therein, the emphasis is placed on IO positionality, meaning the position of an IO within a “web” of interorganizational relations, or, more precisely, an IO’s position within an organizational field as a specification of the IO environment.
Against this background, the dissertation poses the following research question: How does an IO’s position within an organizational field shape its responses to developments of the field? In that, three subquestions are advanced: Which position does an IO occupy within the organizational field? How does an IO perceive the organizational field? How does an IO respond to developments and features of the field? Theoretically, the dissertation combines an open system perspective on IOs with two variants of field theory inspired by Bourdieu and by DiMaggio and Powell. Building on the central concept of the organizational field, the dissertation understands IOs as actors with agency. Empirically, the dissertation consists of a qualitative, comparative study and analyzes two IOs located within the organizational field of global food security governance. I select IOs that occupy different positions within the field of food security governance, namely an IO at the core of the field (the United Nations Food and Agriculture Organization, or FAO) and an IO at the periphery of the field (the United Nations Industrial Development Organization, or UNIDO). I compare and analyze their respective perceptions of the field of food security governance, including their own role and their understandings of food security, and their responses over time. To investigate these IOs’ perceptions and responses over time, the method of choice consists of a qualitative content analysis of a wide range of organizational documents (e.g., governing bodies’ reports).
The main argument this dissertation advances is as follows: The position that an IO occupies within an organizational field influences how the organization perceives its environment—in particular, features of and developments within this environment. Against this background, the main findings of this dissertation are as follows: Overall, FAO and UNIDO both perceive proliferation, overlap, and duplication as relevant developments of the organizational field of global food security governance over time. While both IOs see developments in the field of food security governance (e.g., overlap and duplication) as problematic given their detrimental effects for food security governance, FAO and UNIDO differ in decisive regards. Whereas FAO holds a narrative that other actors were responsible for this state of affairs, and thus responsible for reducing or even eliminating overlap and duplication, UNIDO perceives these developments differently. UNIDO acknowledges its own role in the development of overlap and duplication, and therefore also sees a role for itself in addressing these developments. The two IOs thus differ in what they understand to be the causes and historical priors of field-specific developments. Furthermore, while both FAO and UNIDO attempt to demonstrate that they are constructive players within the UN development system, the two IOs differ in their responses: While FAO engages in balancing by voicing its commitment to UN processes and to coordination, yet early on making different reservations, UNIDO, in contrast, engages in UN processes without similar reservations. Accordingly, the two IOs also differ on the responses they employ to field-level harmonization demands.
The dissertation makes several contributions. Theoretically, I contribute an innovative argument on the influence of perceptions for organizational responses to developments in the IOs’ environment. This argument may help us to better understand how IOs as actors embedded within an organizational field deal with changes evolving within these fields. Empirically, I scrutinize developments in food security governance, such as proliferation and overlap, through the eyes of IOs in the field. While proliferation, overlap, and duplication are often referred to in academic debates on food security governance, we do not yet actually understand these phenomena very well. To this, I contribute a study that analyzes IO perceptions of these developments in the field, thus resulting in a more in-depth and nuanced picture of how IOs perceive these developments as a central type of actor in food security governance. Next, to this emphasis on the IO perspective, I also inductively develop a spectrum of IO responses to field developments, ranging from expanding scope to defending turf. Finally, I also make a methodological-conceptual contribution: While concepts such as “position” are well-known, they are sometimes drawn on without developing a clear foundation of how to assess different positions. I thus add an approach for bringing this concept of position to life by developing a range of criteria that can be used to approximate an IO’s position within an organizational field, depending on different types of capital.
More than a billion people rely on water from rivers sourced in High Mountain Asia (HMA), a significant portion of which is derived from snow and glacier melt. Rural communities are heavily dependent on the consistency of runoff, and are highly vulnerable to shifts in their local environment brought on by climate change. Despite this dependence, the impacts of climate change in HMA remain poorly constrained due to poor process understanding, complex terrain, and insufficiently dense in-situ measurements.
HMA's glaciers contain more frozen water than any region outside of the poles. Their extensive retreat is a highly visible and much studied marker of regional and global climate change. However, in many catchments, snow and snowmelt represent a much larger fraction of the yearly water budget than glacial meltwaters. Despite their importance, climate-related changes in HMA's snow resources have not been well studied.
Changes in the volume and distribution of snowpack have complex and extensive impacts on both local and global climates. Eurasian snow cover has been shown to impact the strength and direction of the Indian Summer Monsoon -- which is responsible for much of the precipitation over the Indian Subcontinent -- by modulating earth-surface heating. Shifts in the timing of snowmelt have been shown to limit the productivity of major rangelands, reduce streamflow, modify sediment transport, and impact the spread of vector-borne diseases. However, a large-scale regional study of climate impacts on snow resources had yet to be undertaken.
Passive Microwave (PM) remote sensing is a well-established empirical method of studying snow resources over large areas. Since 1987, there have been consistent daily global PM measurements which can be used to derive an estimate of snow depth, and hence snow-water equivalent (SWE) -- the amount of water stored in snowpack. The SWE estimation algorithms were originally developed for flat and even terrain -- such as the Russian and Canadian Arctic -- and have rarely been used in complex terrain such as HMA.
This dissertation first examines factors present in HMA that could impact the reliability of SWE estimates. Forest cover, absolute snow depth, long-term average wind speeds, and hillslope angle were found to be the strongest controls on SWE measurement reliability. While forest density and snow depth are factors accounted for in modern SWE retrieval algorithms, wind speed and hillslope angle are not. Despite uncertainty in absolute SWE measurements and differences in the magnitude of SWE retrievals between sensors, single-instrument SWE time series were found to be internally consistent and suitable for trend analysis.
Building on this finding, this dissertation tracks changes in SWE across HMA using a statistical decomposition technique. An aggregate decrease in SWE was found (10.6 mm/yr), despite large spatial and seasonal heterogeneities. Winter SWE increased in almost half of HMA, despite general negative trends throughout the rest of the year. The elevation distribution of these negative trends indicates that while changes in SWE have likely impacted glaciers in the region, climate change impacts on these two pieces of the cryosphere are somewhat distinct.
Following the discussion of relative changes in SWE, this dissertation explores changes in the timing of the snowmelt season in HMA using a newly developed algorithm. The algorithm is shown to accurately track the onset and end of the snowmelt season (70% within 5 days of a control dataset, 89% within 10). Using a 29-year time series, changes in the onset, end, and duration of snowmelt are examined. While nearly the entirety of HMA has experienced an earlier end to the snowmelt season, large regions of HMA have seen a later start to the snowmelt season. Snowmelt periods have also decreased in almost all of HMA, indicating that the snowmelt season is generally shortening and ending earlier across HMA.
By examining shifts in both the spatio-temporal distribution of SWE and the timing of the snowmelt season across HMA, we provide a detailed accounting of changes in HMA's snow resources. The overall trend in HMA is towards less SWE storage and a shorter snowmelt season. However, long-term and regional trends conceal distinct seasonal, temporal, and spatial heterogeneity, indicating that changes in snow resources are strongly controlled by local climate and topography, and that inter-annual variability plays a significant role in HMA's snow regime.
Metamaterial devices
(2018)
Digital fabrication machines such as 3D printers excel at producing arbitrary shapes, such as for decorative objects. In recent years, researchers started to engineer not only the outer shape of objects, but also their internal microstructure. Such objects, typically based on 3D cell grids, are known as metamaterials. Metamaterials have been used to create materials that, e.g., change their volume, or have variable compliance.
While metamaterials were initially understood as materials, we propose to think of them as devices.
We argue that thinking of metamaterials as devices enables us to create internal structures that offer functionalities to implement an input-process-output model without electronics, but purely within the material’s internal structure. In this thesis, we investigate three aspects of such metamaterial devices that implement parts of the input-process-output model: (1) materials that process analog inputs by implementing mechanisms based on their microstructure, (2) that process digital signals by embedding mechanical computation into the object’s microstructure, and (3) interactive metamaterial objects that output to the user by changing their outside to interact with their environment. The input to our metamaterial devices is provided directly by the users interacting with the device by means of physically pushing the metamaterial, e.g., turning a handle, pushing a button, etc.
The design of such intricate microstructures, which enable the functionality of metamaterial devices, is not obvious. The complexity of the design arises from the fact that not only a suitable cell geometry is necessary, but that additionally cells need to play together in a well-defined way. To support users in creating such microstructures, we research and implement interactive design tools. These tools allow experts to freely edit their materials, while supporting novice users by auto-generating cells assemblies from high-level input. Our tools implement easy-to-use interactions like brushing, interactively simulate the cell structures’ deformation directly in the editor, and export the geometry as a 3D-printable file. Our goal is to foster more research and innovation on metamaterial devices by allowing the broader public to contribute.
How can interactive devices connect with users in the most immediate and intimate way? This question has driven interactive computing for decades. Throughout the last decades, we witnessed how mobile devices moved computing into users’ pockets, and recently, wearables put computing in constant physical contact with the user’s skin. In both cases moving the devices closer to users allowed devices to sense more of the user, and thus act more personal. The main question that drives our research is: what is the next logical step?
Some researchers argue that the next generation of interactive devices will move past the user’s skin and be directly implanted inside the user’s body. This has already happened in that we have pacemakers, insulin pumps, etc. However, we argue that what we see is not devices moving towards the inside of the user’s body, but rather towards the body’s biological “interface” they need to address in order to perform their function.
To implement our vision, we created a set of devices that intentionally borrow parts of the user’s body for input and output, rather than adding more technology to the body.
In this dissertation we present one specific flavor of such devices, i.e., devices that borrow the user’s muscles. We engineered I/O devices that interact with the user by reading and controlling muscle activity. To achieve the latter, our devices are based on medical-grade signal generators and electrodes attached to the user’s skin that send electrical impulses to the user’s muscles; these impulses then cause the user’s muscles to contract.
While electrical muscle stimulation (EMS) devices have been used to regenerate lost motor functions in rehabilitation medicine since the 1960s, in this dissertation, we propose a new perspective: EMS as a means for creating interactive systems.
We start by presenting seven prototypes of interactive devices that we have created to illustrate several benefits of EMS. These devices form two main categories: (1) Devices that allow users eyes-free access to information by means of their proprioceptive sense, such as the value of a variable in a computer system, a tool, or a plot; (2) Devices that increase immersion in virtual reality by simulating large forces, such as wind, physical impact, or walls and heavy objects.
Then, we analyze the potential of EMS to build interactive systems that miniaturize well and discuss how they leverage our proprioceptive sense as an I/O modality. We proceed by laying out the benefits and disadvantages of both EMS and mechanical haptic devices, such as exoskeletons.
We conclude by sketching an outline for future research on EMS by listing open technical, ethical and philosophical questions that we left unanswered.
The prediction of the ground shaking that can occur at a site of interest due to an earthquake is crucial in any seismic hazard analysis. Usually, empirically derived ground-motion prediction equations (GMPEs) are employed within a logic-tree framework to account for this step. This is, however, challenging if the area under consideration has only low seismicity and lacks enough recordings to develop a region-specific GMPE. It is then usual practice to adapt GMPEs from data-rich regions (host area) to the area with insufficient ground-motion recordings (target area). Host GMPEs must be adjusted in such a way that they will capture the specific ground-motion characteristics of the target area. In order to do so, seismological parameters of the target region have to be provided as, for example, the site-specific attenuation factor kappa0. This is again an intricate task if data amount is too sparse to derive these parameters.
In this thesis, I explore methods that can facilitate the selection of non-endemic GMPEs in a logic-tree analysis or their adjustment to a data-poor region. I follow two different strategies towards this goal.
The first approach addresses the setup of a ground-motion logic tree if no indigenous GMPE is available. In particular, I propose a method to derive an optimized backbone model that captures the median ground-motion characteristics in the region of interest. This is done by aggregating several foreign GMPEs as weighted components of a mixture model in which the weights are inferred from observed data. The approach is applied to Northern Chile, a region for which no indigenous GMPE existed at the time of the study. Mixture models are derived for interface and intraslab type events using eight subduction zone GMPEs originating from different parts of the world. The derived mixtures provide satisfying results in terms of average residuals and average sample log-likelihoods. They outperform all individual non-endemic GMPEs and are comparable to a regression model that was specifically derived for that area.
The second approach is concerned with the derivation of the site-specific attenuation factor kappa0. kappa0 is one of the key parameters in host-to-target adjustments of GMPEs but is hard to derive if data amount is sparse. I explore methods to estimate kappa0 from ambient seismic noise. Seismic noise is, in contrast to earthquake recordings, continuously available. The rapidly emerging field of seismic interferometry gives the possibility to infer velocity and attenuation information from the cross-correlation or deconvolution of long noise recordings. The extraction of attenuation parameters from diffuse wavefields is, however, not straightforward especially not for frequencies above 1 Hz and at shallow depth. In this thesis, I show the results of two studies. In the first one, data of a small-scale array experiment in Greece are used to derive Love wave quality factors in
the frequency range 1-4 Hz. In a second study, frequency dependent quality factors of S-waves (5-15 Hz) are estimated by deconvolving noise recorded in a borehole and at a co-located surface station in West Bohemia/Vogtland. These two studies can be seen as preliminary steps towards the estimation of kappa0 from seismic noise.
Human actuation
(2018)
Ever since the conception of the virtual reality headset in 1968, many researchers have argued that the next step in virtual reality is to allow users to not only see and hear, but also feel virtual worlds. One approach is to use mechanical equipment to provide haptic feedback, e.g., robotic arms, exoskeletons and motion platforms. However, the size and the weight of such mechanical equipment tends to be proportional to its target’s size and weight, i.e., providing human-scale haptic feedback requires human-scale equipment, often restricting them to arcades and lab environments.
The key idea behind this dissertation is to bypass mechanical equipment by instead leveraging human muscle power. We thus create software systems that orchestrate humans in doing such mechanical labor—this is what we call human actuation. A potential benefit of such systems is that humans are more generic, flexible, and versatile than machines. This brings a wide range of haptic feedback to modern virtual reality systems.
We start with a proof-of-concept system—Haptic Turk, focusing on delivering motion experiences just like a motion platform. All Haptic Turk setups consist of a user who is supported by one or more human actuators. The user enjoys an interactive motion simulation such as a hang glider experience, but the motion is generated by those human actuators who manually lift, tilt, and push the user’s limbs or torso. To get the timing and force right, timed motion instructions in a format familiar from rhythm games are generated by the system.
Next, we extend the concept of human actuation from 3-DoF to 6-DoF virtual reality where users have the freedom to walk around. TurkDeck tackles this problem by orchestrating a group of human actuators to reconfigure a set of passive props on the fly while the user is progressing in the virtual environment. TurkDeck schedules human actuators by their distances from the user, and instructs them to reconfigure the props to the right place on the right time using laser projection and voice output.
Our studies in Haptic Turk and TurkDeck showed that human actuators enjoyed the experience but not as much as users. To eliminate the need of dedicated human actuators, Mutual Turk makes everyone a user by exchanging mechanical actuation between two or more users. Mutual Turk’s main functionality is that it orchestrates the users so as to actuate props at just the right moment and with just the right force to produce the correct feedback in each other's experience.
Finally, we further eliminate the need of another user, making human actuation applicable to single-user experiences. iTurk makes the user constantly reconfigure and animate otherwise passive props. This allows iTurk to provide virtual worlds with constantly varying or even animated haptic effects, even though the only animate entity present in the system is the user. Our demo experience features one example each of iTurk’s two main types of props, i.e., reconfigurable props (the foldable board from TurkDeck) and animated props (the pendulum).
We conclude this dissertation by summarizing the findings of our explorations and pointing out future directions. We discuss the development of human actuation compare to traditional machine actuation, the possibility of combining human and machine actuators and interaction models that involve more human actuators.
Die Nutzung sozialer Netzwerke ist für viele Menschen nicht mehr aus ihrem Alltag wegzudenken. Dies zeigt sich insbesondere an den Nutzerzahlen. Facebook hat beispielsweise mittlerweile mehr als 2,2 Milliarden Nutzer. Zu den wesentlichen Funktionen der sozialen Netzwerke gehört das Teilen von nutzergenerierten Inhalten, die beispielsweise als Fotos oder Videos dem Schutz des Urheberrechtsgesetzes unterfallen können.
Um diese geschützten Inhalte darstellen und verbreiten zu können, benötigen die sozialen Netzwerke die entsprechenden Nutzungsrechte ihrer Nutzer. Daher finden sich in den Allgemeinen Geschäftsbedingungen verschiedene Regelungen über die Einräumung der Rechte, die von den Nutzern in den allermeisten Fällen jedoch im Zuge der Registrierung ungelesen akzeptiert werden.
Im Rahmen der Untersuchung wird geprüft, ob eine Nutzungsrechtseinräumung an den urheberrechtlich geschützten Inhalten der Nutzer durch die Allgemeinen Geschäftsbedingungen der sozialen Netzwerke wirksam ist. Hierfür ist insbesondere entscheidend, ob die Rechtsprechung des Bundesgerichtshofs zum fehlenden Leitbildcharakter des Übertragungszweckgrundsatzes einer Inhaltskontrolle der Allgemeinen Geschäftsbedingungen der sozialen Netzwerke entgegensteht, oder, ob dieser als Maßstab für die Inhaltskontrolle herangezogen werden kann.
Eine Vergabesperre ist der längerfristige Ausschluss eines Unternehmens von der öffentlichen Auftragsvergabe. Sie geht damit in ihrer Intensität deutlich über den Einzelfallausschluss hinaus und kann für die betroffenen Unternehmen gegebenenfalls sogar existenzbedrohend sein. Obwohl die Verhängung von Vergabesperren seit langem praktiziert wird, hat sie auch im Zuge der Vergaberechtsreform im Jahr 2016 keine eindeutige Regelung erfahren. Diese Arbeit untersucht daher die rechtliche Zulässigkeit solcher Vergabesperren.
Die öffentliche Auftragsvergabe, die originär lediglich Beschaffungszwecken dient, wird seit einigen Jahren verstärkt zur Verfolgung anderer, häufig politischer Ziele eingesetzt. Schwerpunkt der Arbeit ist daher die Frage, ob eine Vergabesperre zur Verfolgung solcher öffentlicher Zwecke verhängt werden darf, die keinen unmittelbaren Zusammenhang zur Auftragsvergabe aufweisen. Von besonderer Bedeutung ist dabei der Einsatz der Vergabesperre als Sanktionsmittel.
מחקר זה עוסק במשנתו החדשנית של ר' צדוק הכהן מלובלין. לפי רוב החוקרים, ר' צדוק ממשיך את משנת רבו, ר' מרדכי יוסף ליינער מאיזביצה, ומציג פטליזם אקזיסטנציאליסטי: לאדם יש חופש כנגד החוק המקובל, לפי רצון האל הנגלה בליבו, אפילו בתשוקותיו, החורג מההלכה; ואולם, האדם אינו קובע את הרצון המתגלה בשורש נשמתו, אלא חושפו בלבד. בכתבי ר' צדוק ניתן למצוא ביטויים רבים, בתוכן ובצורה, לפטליזם זה; עם זאת, הוא מציג גם התבטאויות רבות בדבר הבחירה האנושית החופשית וכוחה היצירתי לכונן ולקבוע את שורשו של האדם, ולחדש ולהשפיע על העולמות האלוקיים ועל העולם-הזה. מחקר זה מתמקד בקטעים אלו שמרכזיותם הוזנחה במחקר עד כה, ומכאן הבנתו המחודשת במשנתו.
את עמדת ר' צדוק ניתן להסביר באמצעות התפיסה הפרדוקסלית, הטוענת לכוחם המלא של שני הקטבים הסותרים ואף להשפעה הדדית ביניהם, היוצרת מתח קשה אך פורה: בניגוד לתהליך הפורמלי, האניטלקטואלי והאפריורי של הפטליזם, שבו 'הידיעה' האלוהית מבטלת את 'הבחירה' האנושית החופשית, ר' צדוק מציג פטאליות, המזהה המציאות עצמה את הידיעה והרצון האלוהיים המצויים בכל. בפטליות זו הידיעה אינה מבטלת את הבחירה; להיפך: ללא הידיעה האלוקית אין לאף דבר קיום, ולכן רק מציאות הידיעה בבחירה היא המאפשרת את קיומה הממשי.
תפיסתו האונטולוגית של ר' צדוק מתקיימת לא רק בתוכן הישיר של דבריו, אלא גם בעקיפין, באופן דרשנותו ובמובן שהוא מעניק למושגים שבהם הוא דן; לכן, הפטליות מתגלה גם בתחומים נוספים, שבהם מצוי פער בין הממד המוחלט וההכרחי ('ידיעה') לממד הקונטינגנטי, הארעי והיחסי ('בחירה'): השקר, הדמיון, הרוע, החטא, הייסורים ועוד, אמנם קונטינגנטיים ויחסיים לעומת מוחלטות האמת, הטוב וכו'; אך לפי ר' צדוק, האל רוצה בהם ככאלה – כלומר יש להם ממשות שאינה מוחלטת, אלא ממשות ככאלה, כקונטינגנטיים. אך ממשות זו אינה מאשרת אותם כפי שהם, אלא יוצרת בהם-עצמם טרנספורמציה. למשל, הרוע אינו הופך לטוב מוחלט או נותר כרוע, אלא הופך ל'טוב מאד' שלפי ר' צדוק גדול מהטוב הרגיל.
מכאן עולה גם ההשפעה ההפוכה, זו של הבחירה על הידיעה. לפי ר' צדוק, משקבלה הקונטינגנטיות והיחסיות של 'הבחירה' – שהיא למעשה מהות הבריאה ומהות האדם ומעשיו – את ממשותה, בכוחה אף להוסיף כביכול על המוחלטות האלוקית הקבועה של 'הידיעה': 'נגע' החטא או הייסורים הופך בעצמו, בחילוף אותם אותיות, ל'ענג' הגדול מההנאה הרגילה; בכוח האדם להשפיע על העולמות העליונים בגזירת גזירות ובביטול גזירות אלוקיות; בכוחו אף להשפיע על העולם-הזה, בחידושו היומיומי על-ידי חידושי התושב"ע, ובקידוש החודש המסוגל לשנות את תנועת המזלות השמימיים. מצד אחד, היצירתיות האנושית של חידושי התושב"ע כלולה באמת האלוקית הגנוזה בתושב"כ האלוקית והיא רק חושפת אותה; אך לפי ר"צ, מצד אחר מתברר שמקור חידושי התושב"ע דווקא גבוה ממקור התושב"כ והם אלו היוצרים וקובעים אותה.
ר' צדוק מציג שני מושגים מרכזיים לפרדוקס שלו: בממד האונטולוגי – 'הייחוד הגמור' של האל, שבו הדואליות הקונטינגנטית (בין האל לנבראיו, והבחירה שהיא מאפשרת) של 'הייחוד התחתון' מתקיימת פרדוקסלית עם האחדות המוחלטת ו'הידיעה' האלוהית של 'הייחוד העליון'.
בממד של מצבו האקזיסטנציאלי של האדם – 'השורש הנעלם': בניגוד לר' מרדכי יוסף רבו, ר' צדוק טוען שהאדם קובע את גורלו על-ידי מעשיו הבחיריים והקונטינגנטיים; ואולם, במקביל, בדומה לרבו, הוא טוען גם שהשורש הקבוע של האדם נקבע על-ידי 'הידיעה' האלוהית והיא זו הקובעת את מעשיו לטוב או למוטב. אך מעל אלו מציג ר' צדוק שורש נוסף, 'נעלם' הגבוה מהשורש הקבוע: הוא אכן שורש מוחלט ('ידיעה'), אך הוא נקבע ומכוּנן על-ידי מעשיו הבחיריים של האדם, בדומה לבריאה האלוהית 'יש מאין'.
Die Arbeit widmet sich den Haushaltssperren auf den verschiedenen Ebenen und untersucht, ob ein einheitliches Instrument der Haushaltssperre im deutschen Recht existiert, oder ob sich hinter dem Begriff der Haushaltssperre verschiedene haushaltsrechtliche Maßnahmen verbergen. Dazu werden auf verfassungsrechtlicher Ebene der Aspekt der Gewaltenteilung gemäß Art. 20 II 2 GG sowie die kommunale Selbstverwaltungsgarantie des Art. 28 II GG betrachtet. Auf Bundes-, Landes- und kommunaler Ebene werden u.a. Sperrvermerke, Globale Minderausgaben, haushaltswirtschaftliche Sperren sowie Bewirtschaftungssperren eingehend dargestellt und erörtert. Ergänzend werden Aspekte wie weitere Instrumente zur Kontrolle des Haushalts und Rechtsschutz gegen Haushaltssperren dargestellt und Regelungsvorschläge unterbreitet. Im Fazit wird festgestellt, dass »Haushaltssperren« zu komplex und unterschiedlich sind, um ein einheitliches Institut der Haushaltssperre darstellen zu können.
Plant-derived Transcription Factors for Orthologous Regulation of Gene Expression in the Yeast Saccharomyces cerevisiae
Control of gene expression by transcription factors (TFs) is central in many synthetic biology projects where tailored expression of one or multiple genes is often needed. As TFs from evolutionary distant organisms are unlikely to affect gene expression in a host of choice, they represent excellent candidates for establishing orthogonal control systems. To establish orthogonal regulators for use in yeast (Saccharomyces cerevisiae), we chose TFs from the plant Arabidopsis thaliana. We established a library of 106 different combinations of chromosomally integrated TFs, activation domains (yeast GAL4 AD, herpes simplex virus VP64, and plant EDLL) and synthetic promoters harbouring cognate cis-regulatory motifs driving a yEGFP reporter. Transcriptional output of the different driver / reporter combinations varied over a wide spectrum, with EDLL being a considerably stronger transcription activation domain in yeast, than the GAL4 activation domain, in particular when fused to Arabidopsis NAC TFs. Notably, the strength of several NAC - EDLL fusions exceeded that of the strong yeast TDH3 promoter by 6- to 10-fold. We furthermore show that plant TFs can be used to build regulatory systems encoded by centromeric or episomal plasmids. Our library of TF – DNA-binding site combinations offers an excellent tool for diverse synthetic biology applications in yeast.
COMPASS: Rapid combinatorial optimization of biochemical pathways based on artificial transcription factors
We established a high-throughput cloning method, called COMPASS for COMbinatorial Pathway ASSembly, for the balanced expression of multiple genes in Saccharomyces cerevisiae. COMPASS employs orthogonal, plant-derived artificial transcription factors (ATFs) for controlling the expression of pathway genes, and homologous recombination-based cloning for the generation of thousands of individual DNA constructs in parallel. The method relies on a positive selection of correctly assembled pathway variants from both, in vivo and in vitro cloning procedures. To decrease the turnaround time in genomic engineering, we equipped COMPASS with multi-locus CRISPR/Cas9-mediated modification capacity. In its current realization, COMPASS allows combinatorial optimization of up to ten pathway genes, each transcriptionally controlled by nine different ATFs spanning a 10-fold difference in expression strength. The application of COMPASS was demonstrated by generating cell libraries producing beta-carotene and co-producing beta-ionone and biosensor-responsive naringenin. COMPASS will have many applications in other synthetic biology projects that require gene expression balancing.
CaPRedit: Genome editing using CRISPR-Cas9 and plant-derived transcriptional regulators for the redirection of flux through the FPP branch-point in yeast. Technologies developed over the past decade have made Saccharomyces cerevisiae a promising platform for production of different natural products. We developed CRISPR/Ca9- and plant derived regulator-mediated genome editing approach (CaPRedit) to greatly accelerate strain modification and to facilitate very low to very high expression of key enzymes using inducible regulators. CaPRedit can be implemented to enhance the production of yeast endogenous or heterologous metabolites in the yeast S. cerevisiae. The CaPRedit system aims to faciltiate modification of multiple targets within a complex metabolic pathway through providing new tools for increased expression of genes encoding rate-limiting enzymes, decreased expression of essential genes, and removed expression of competing pathways. This approach is based on CRISPR/Cas9-mediated one-step double-strand breaks to integrate modules containing IPTG-inducible plant-derived artificial transcription factor and promoter pair(s) in a desired locus or loci. Here, we used CaPRedit to redirect the yeast endogenous metabolic flux toward production of farnesyl diphosphate (FPP), a central precursor of nearly all yeast isoprenoid products, by overexpression of the enzymes lead to produce FPP from glutamate. We found significantly higher beta-carotene accumulation in the CaPRedit-mediated modified strain than in the wild type (WT) strain. More specifically, CaPRedit_FPP 1.0 strain was generated, in which three genes involved in FPP synthesis, tHMG1, ERG20, and GDH2, were inducibly overexpressed under the control of strong plant-derived ATFPs. The beta–carotene accumulated in CaPRedit_FPP 1.0 strain to a level 1.3-fold higher than the previously reported optimized strain that carries the same overexpressed genes (as well as additional genetic modifications to redirect yeast endogenous metabolism toward FPP production). Furthermore, the genetic modifications implemented in CaPRedit_FPP 1.0 strain resulted in only a very small growth defect (growth rate relative to the WT is ~ -0.03).
Characterization of altered inflorescence architecture in Arabidopsis thaliana BG-5 x Kro-0 hybrid
(2018)
A reciprocal cross between two A. thaliana accessions, Kro-0 (Krotzenburg, Germany) and BG-5 (Seattle, USA), displays purple rosette leaves and dwarf bushy phenotype in F1 hybrids when grown at 17 °C and a parental-like phenotype when grown at 21 °C. This F1 temperature-dependent-dwarf-bushy phenotype is characterized by reduced growth of the primary stem together with an increased number of branches. The reduced stem growth was the strongest at the first internode. In addition, we found that a temperature switch from 21 °C to 17 °C induced the phenotype only before the formation of the first internode of the stem. Similarly, the F1 dwarf-bushy phenotype could not be reversed when plants were shifted from 17 °C to 21 °C after the first internode was formed. Metabolic analysis showed that the F1 phenotype was associated with a significant upregulation of anthocyanin(s), kaempferol(s), salicylic acid, jasmonic acid and abscisic acid. As it has been previously shown that the dwarf-bushy phenotype is linked to two loci, one on chromosome 2 from Kro-0 and one on chromosome 3 from BG-5, an artificial micro-RNA approach was used to investigate the necessary genes on these intervals. From the results obtained, it was found that two genes, AT2G14120 that encodes for a DYNAMIN RELATED PROTEIN3B and AT2G14100 that encodes a member of the Cytochrome P450 family protein CYP705A13, were necessary for the appearance of the F1 phenotype on chromosome 2. It was also discovered that AT3G61035 that encodes for another cytochrome P450 family protein CYP705A13 and AT3G60840 that encodes for a MICROTUBULE-ASSOCIATED PROTEIN65-4 on chromosome 3 were both necessary for the induction of the F1 phenotype. To prove the causality of these genes, genomic constructs of the Kro-0 candidate genes on chromosome 2 were transferred to BG-5 and genomic constructs of the chromosome 3 candidate genes from BG-5 were transferred to Kro-0. The T1 lines showed that these genes are not sufficient alone to induce the phenotype. In addition to the F1 phenotype, more severe phenotypes were observed in the F2 generations that were grouped into five different phenotypic classes. Whilst seed yield was comparable between F1 hybrids and parental lines, three phenotypic classes in the F2 generation exhibited hybrid breakdown in the form of reproductive failure. This F2 hybrid breakdown was less sensitive to temperature and showed a dose-dependent effect of the loci involved in F1 phenotype. The severest class of hybrid breakdown phenotypes was observed only in the population of backcross with the parent Kro-0, which indicates a stronger contribution of the BG-5 allele when compared to the Kro-0 allele on the hybrid breakdown phenotypes. Overall, the findings of my thesis provide a further understanding of the genetic and metabolic factors underlying altered shoot architecture in hybrid dysfunction.
Ärgerliche Wirtshäuser, ergötzliche Häfen, empfindsame Kerker: Räume und Emotionen bilden emotionale Topografien, mit deren Hilfe sich die Akteure die Welt als Lebenswelt ordnen und aneignen. Der Autor untersucht den Zusammenhang zwischen Bewegung in frühneuzeitlichen Räumen und der emotionalen Bewegtheit der Akteure. Er kommt zu dem Schluss, dass Emotionen und Räume dabei nicht nur passiv erlebt, sondern aktiv vollzogen werden. Denn es handelt sich bei beiden um wechselseitig verbundene Handlungsanweisungen, die in Regeln, Topoi und Vorstellungen münden. Die sich ergebenden Verflechtungen nehmen verschiedene Formen an, die in kulturell, sozial und individuell bedingten emotionalen Topografien kulminieren, also in Anordnungen von Räumen und zugehörigen Emotionen. In dieser Struktur liegen somit Erklärungen für das Verhalten der Akteure verborgen.
The movement of organisms has formed our planet like few other processes. Movements shape populations, communities, entire ecosystems, and guarantee fundamental ecosystem functions and services, like seed dispersal and pollination. Global, regional and local anthropogenic impacts influence animal movements across ecosystems all around the world. In particular, land-use modification, like habitat loss and fragmentation disrupt movements between habitats with profound consequences, from increased disease transmissions to reduced species richness and abundance. However, neither the influence of anthropogenic change on animal movement processes nor the resulting effects on ecosystems are well understood. Therefore, we need a coherent understanding of organismal movement processes and their underlying mechanisms to predict and prevent altered animal movements and their consequences for ecosystem functions.
In this thesis I aim at understanding the influence of anthropogenically caused land-use change on animal movement processes and their underlying mechanisms. In particular, I am interested in the synergistic influence of large-scale landscape structure and fine-scale habitat features on basic-level movement behaviours (e.g. the daily amount of time spend running, foraging, and resting) and their emerging higher-level movements (home range formation). Based on my findings, I identify the likely consequences of altered animal movements that lead to the loss of species richness and abundances.
The study system of my thesis are hares in agricultural landscapes. European brown hares (Lepus europaeus) are perfectly suited to study animal movements in agricultural landscapes, as hares are hermerophiles and prefer open habitats. They have historically thrived in agricultural landscapes, but their numbers are in decline. Agricultural areas are undergoing strong land-use changes due to increasing food demand and fast developing agricultural technologies. They are already the largest land-use class, covering 38% of the world’s terrestrial surface. To consider the relevance of a given landscape structure for animal movement behaviour I selected two differently structured agricultural landscapes – a simple landscape in Northern Germany with large fields and few landscape elements (e.g. hedges and tree stands), and a complex landscape in Southern Germany with small fields and many landscape elements.
I applied GPS devices (hourly fixes) with internal high-resolution accelerometers (4 min samples) to track hares, receiving an almost continuous observation of the animals’ behaviours via acceleration analyses. I used the spatial and behavioural information in combination with remote sensing data (normalized difference vegetation index, or NDVI, a proxy for resource availability), generating an almost complete idea of what the animal was doing when, why and where. Apart from landscape structure (represented by the two differently structured study areas), I specifically tested whether the following fine-scale habitat features influence animal movements: resource, agricultural management events, habitat diversity, and habitat structure.
My results show that, irrespective of the movement process or mechanism and the type of fine-scale habitat features, landscape structure was the overarching variable influencing hare movement behaviour. High resource variability forces hares to enlarge their home ranges, but only in the simple and not in the complex landscape. Agricultural management events result in home range shifts in both landscapes, but force hares to increase their home ranges only in the simple landscape. Also the preference of habitat patches with low vegetation and the avoidance of high vegetation, was stronger in the simple landscape. High and dense crop fields restricted hare movements temporarily to very local and small habitat patch remnants. Such insuperable barriers can separate habitat patches that were previously connected by mobile links. Hence, the transport of nutrients and genetic material is temporarily disrupted. This mechanism is also working on a global scale, as human induced changes from habitat loss and fragmentation to expanding monocultures cause a reduction in animal movements worldwide.
The mechanisms behind those findings show that higher-level movements, like increasing home ranges, emerge from underlying basic-level movements, like the behavioural modes. An increasing landscape simplicity first acts on the behavioural modes, i.e. hares run and forage more, but have less time to rest. Hence, the emergence of increased home range sizes in simple landscapes is based on an increased proportion of time running and foraging, largely due to longer travelling times between distant habitats and scarce resource items in the landscape. This relationship was especially strong during the reproductive phase, demonstrating the importance of high-quality habitat for reproduction and the need to keep up self-maintenance first, in low quality areas. These changes in movement behaviour may release a cascade of processes that start with more time being allocated to running and foraging, resulting into an increased energy expenditure and may lead to a decline in individual fitness. A decrease in individual fitness and reproductive output will ultimately affect population viability leading to local extinctions.
In conclusion, I show that landscape structure has one of the most important effects on hare movement behaviour. Synergistic effects of landscape structure, and fine-scale habitat features, first affect and modify basic-level movement behaviours, that can scales up to altered higher-level movements and may even lead to the decline of species richness and abundances, and the disruption of ecosystem functions. Understanding the connection between movement mechanisms and processes can help to predict and prevent anthropogenically induced changes in movement behaviour. With regard to the paramount importance of landscape structure, I strongly recommend to decrease the size of agricultural fields and increase crop diversity. On the small-scale, conservation policies should assure the year round provision of areas with low vegetation height and high quality forage. This could be done by generating wildflower strips and additional (semi-) natural habitat patches. This will not only help to increase the populations of European brown hares and other farmland species, but also ensure and protects the continuity of mobile links and their intrinsic value for sustaining important ecosystem functions and services.
Polymeric materials, which can perform reversible shape changes after programming, in response to a thermal or electrical stimulation, can serve as (soft) actuating components in devices like artificial muscles, photonics, robotics or sensors. Such polymeric actuators can be realized with hydrogels, liquid crystalline elastomers, electro-active polymers or shape-memory polymers by controlling with stumuli such as heat, light, electrostatic or magnetic field. If the application conditions do not allow the direct heating or electric stimulation of these smart devices, noncontact triggering will be required. Remotely controlled actuation have been reported for liquid crystalline elastomer composites or shape-memory polymer network composites, when a persistent external stress is applied during inductive heating in an alternating magnetic field. However such composites cannot meet the demands of applications requiring remotely controlled free-standing motions of the actuating components.
The current thesis investigates, whether a reprogrammable remotely controlled soft actuator can be realized by magneto-sensitive multiphase shape-memory copolymer network composites containing magnetite nanoparticles as magneto-sensitive multivalent netpoints. A central hypothesis was that a magnetically controlled two-way (reversible bidirectional) shape-memory effect in such nanocomposites can be achieved without application of external stress (freestanding), when the required orientation of the crystallizable actuation domains (ADs) can be ensured by an internal skeleton like structure formed by a second crystallizable phase determing the samples´s geometry, while magneto-sensitive iron oxide nanoparticles covalently integrated in the ADs allow remote temperature control. The polymer matrix of these composites should exhibit a phase-segregated morphology mainly composed of cyrstallizable ADs, whereby a second set of higher melting crystallites can take a skeleton like, geometry determining function (geometry determining domains, GDs) after programming of the composite and in this way the orientation of the ADs is established and maintained during actuation. The working principle for the reversible bidirectional movements in the multiphase shape-memory polymer network composite is related to a melting-induced contraction (MIC) during inductive heating and the crystallization induced elongation (CIE) of the oriented ADs during cooling. Finally, the amount of multivalent magnetosensitive netpoints in such a material should be as low as possible to ensure an adequate overall elasticity of the nanocomposite and at the same time a complete melting of both ADs and GDs via inductive heating, which is mandatory for enabling reprogrammability.
At first, surface decorated iron oxide nanoparticles were synthesized and investigated. The coprecipitation method was applied to synthesize magnetic nanoparticles (mNPs) based on magnetite with size of 12±3 nm and in a next step a ring-opening polymerization (ROP) was utilized for covalent surface modification of such mNPs with oligo(ϵ-caprolactone) (OCL) or oligo(ω-pentadecalactone) (OPDL) via the “grafting from” approach. A successful coating of mNPs with OCL and OPDL was confirmed by differential scanning calorimetry (DSC) experiments showing melting peaks at 52±1 °C for mNP-OCL and 89±1 °C for mNP-OPDL. It was further explored whether two-layered surface decorated mNPs, can be prepared via a second surface-initiated ROP of mNP-OCL or mNP-OPDL with ω-pentadecalactone or ϵ-caprolactone. The observation of two distinct melting transitions in DSC experiments as well as the increase in molecular weight of the detached coatings determined by GPC and 1H-NMR indicated a successful synthesis of the twolayered nanoparticles mNP-OCL-OPDL and mNP-OPDL-OCL. In contrast TEM micrographs revealed a reduction of the thickness of the polymeric coating on the nanoparticles after the second ROP, indicating that the applied synthesis and purification required further optimization.
For evaluating the impact of the dispersion of mNPs within a polymer matrix on the resulting inductive heating capability of composites, plain mNPs as well as OCL coated magnetite nanoparticles (mNP-OCLs) were physically incorporated into crosslinked poly(ε-caprolactone) (PCL) networks. Inductive heating experiments were performed with both networks cPCL/mNP and cPCL/mNP-OCL in an alternating magnetic field (AMF) with a magnetic field strength of H = 30 kA·m-1. Here a bulk temperature of Tbulk = 74±2 °C was achieved for cPCL/mNP-OCL, which was almost 20 °C higher than the melting transition of the PCL-based polymer matrix. In contrast, the composite with plain mNPs could only reach a Tbulk of 48±2 °C, which is not sufficient for a complete melting of all PCL crystallites as required for actuation.
The inductive heating capability of a multiphase copolymer nanocomposite network (designed as soft actuators) containing surface decorated mNPs as covalent netpoints was investigated. Such composite was synthesized from star-shaped OCL and OPDL precursors, as well as mNP-OCLs via reaction with HDI. The weight ratio of OPDL and OCL in the starting reaction mixture was 15/85 (wt%/wt%) and the amount of iron oxide in the nanocomposite was 4 wt%. DSC experiments revealed two well separated melting and crystallization peaks confirming the required phase-segregated morphology in the nanocomposite NC-mNP-OCL. TEM images could illustrate a phase-segregated morphology of the polymer matrix on the microlevel with droplet shaped regions attributed to the OPDL domains dispersed in an OCL matrix. The TEM images could further demonstrate that the nanoparticulate netpoints in NC-mNP-OCL were almost homogeneously dispersed within the OCL domains. The tests of the inductive heating capability of the nanocomposites at a magnetic field strength of Hhigh = 11.2 kA·m-1 revealed a achievable plateau surface temperature of Tsurf = 57±1 °C for NC-mNP-OCL recorded by an infrared video camera. An effective heat generation constant (̅P) can be derived from a multi-scale model for the heat generation, which is proportional to the rate of heat generation per unit volume of the sample. NC-mNP-OCL with homogeneously dispersed mNP-OCLs exhibited a ̅P value of 1.04±0.01 K·s- 1 at Hhigh, while at Hreset = 30.0 kA·m-1 a Tsurf of 88±1 °C (where all OPDL related crystallite are molten) and a ̅P value of 1.93±0.02 K·s-1 was obtained indicating a high magnetic heating capability of the composite.
The free-standing magnetically-controlled reversible shape-memory effect (mrSME) was explored with originally straight nanocomposite samples programmed by bending to an angle of 180°. By switching the magnetic field on and off the composite sample was allowed to repetitively heat to 60 °C and cool to the ambient temperature. A pronounced mrSME, characterized by changes in bending angle of Δϐrev = 20±3° could be obtained for a composite sample programmed by bending when a magnetic field strength of Hhigh = 11.2 kA·m-1 was applied in a multi-cyclic magnetic bending experiment with 600 heating-cooling cycles it could be shown that the actuation performance did not change with increasing number of test cycles, demonstrating the accuracy and reproducibility of this soft actuator. The degree of actuation as well as the kinetics of the shape changes during heating could be tuned by variation of the magnetic filed strength between Hlow and Hhigh or the magnetic field exposure time. When Hreset = 30.0 kA·m-1 was applied the programmed geometry was erased and the composite sample returned to it´s originally straight shape. The reprogrammability of the nanocomposite actuators was demonstrated by one and the same test specimen first exhibiting reversible angle changes when programmed by bending, secondly reprogrammed to a concertina, which expands upon inductive heating and contracts during cooling and finally reprogrammed to a clip like shape, which closes during cooling and opens when Hhigh was applied. In a next step the applicability of the presented remote controllable shape-memory polymer actuators was demonstrated by repetitive opening and closing of a multiring device prepared from NC-mNP-OCL, which repetitively opens and closes when a alternating magnetic field (Hhigh = 11.2 kA·m-1) was switched on and off.
For investigation of the micro- and nanostructural changes related to the actuation of the developed nanocomposite, AFM and WAXS experiments were conducted with programmed nanocomposite samples under cyclic heating and cooling between 25 °C and 60 °C. In AFM experiments the change in the distance (D) between representative droplet-like structures related to the OPDL geometry determining domains was used to calculate the reversible change in D. Here Drev = 3.5±1% was found for NC-mNP-OCL which was in good agreement with the results of the magneto-mechanical actuation experiments. Finally, the analysis of azimuthal (radial) WAXS scattering profiles could support the oriented crystallization of the OCL actuation domains at 25 °C.
In conclusion, the results of this work successfully demonstrated that shape-memory polymer nanocomposites, containing mNPs as magneto-sensitive multifunctional netpoints in a covalently crosslinked multiphase polymer matrix, exhibit magnetically (remotely) controlled actuations upon repetitive exposure to an alternating magnetic field. Furthermore, the (shape) memory of such a nanocomposite can be erased by exposing it to temperatures above the melting temperature of the geometry forming domains, which allows a reprogramming of the actuator. These findings would be relevant for designing novel reprogrammable remotely controllable soft polymeric actuators.