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In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([CnC1im]+[NTf2]- and [C4C1im]+[I]-). A combination of measurements and quantum chemical calculations of C K and N K NEXAFS resonances is presented. The simulations, based on the transition potential density functional theory method (TP-DFT), reproduce all characteristic features observed by the experiment. Furthermore, a detailed assignment of resonance features to excitation centers (carbon or nitrogen atoms) leads to a consistent interpretation of the spectra.
Herein we present an efficient synthesis of a biomimetic probe with modular construction that can be specifically bound by the mannose binding FimH protein – a surface adhesion protein of E. coli bacteria. The synthesis combines the new and interesting DBD dye with the carbohydrate ligand mannose via a Click reaction. We demonstrate the binding to E. coli bacteria over a large concentration range and also present some special characteristics of those molecules that are of particular interest for the application as a biosensor. In particular, the mix-and-measure ability and the very good photo-stability should be highlighted here.
Die vorgelegte Dissertation präsentiert wissenschaftliche Ergebnisse, die in der Zeit vom Dezember 2012 bis August 2016, erarbeitet wurden. Der zentrale Inhalt der Arbeit ist die Simulation von Röntgenabsorptionsprozessen von verschiedenen Systemen in kondensierter Phase. Genauer gesagt, werden Nahkantenabsorptions- (NEXAFS) sowie Röntgenphotoelektronenspektren (XPS) berechnet. In beiden Fällen wird ein Röntgenphoton von einem molekularen System absorbiert. Aufgrund der hohen Photonenenergie wird ein stark gebundenes kernnahes Elektron angeregt. Bei der XPS gelangt dieses mit einer zu messenden kinetischen Energie in Kontinuumszustände. In Abhängigkeit der eingestrahlten Photonenenergie und der kinetischen Energie des austreten Elektrons, kann die Bindungsenergie berechnet werden, welche die zentrale Größe der XPS ist. Im Falle der NEXAFS-Spektroskopie wird das kernnahe Elektron in unbesetzte gebundene Zustände angeregt. Die zentrale Größe ist die Absorption als Funktion der eingestrahlten Photonenenergie. Das erste Kapitel meiner Arbeit erörtert detailliert die experimentellen Methoden sowie die daraus gewonnenen charakteristischen Größen.
Die experimentellen Spektren zeigen oft viele Resonanzen, deren Interpretation aufgrund fehlender Referenzmaterialien schwierig ist. In solchen Fällen bietet es sich an, die Spektren mittels quantenchemischer Methoden zu simulieren. Der dafür erforderliche mathematisch-physikalische Methodenkatalog wird im zweiten Kapitel der Arbeit erörtert.
Das erste von mir untersuchte System ist Graphen. In experimentellen Arbeiten wurde die Oberfläche mittels Bromplasma modifiziert. Die im Anschluss gemessenen NEXAFS-Spektren unterscheiden sich maßgeblich von den Spektren der unbehandelten Oberfläche. Mithilfe periodischer DFT-Rechnungen wurden verschiedene Gitterdefekte sowie bromierte Systeme untersucht und die NEXAFS-Spektren simuliert. Mittels der Simulationen können die Beiträge verschiedener Anregungszentren analysiert werden. Die Berechnungen erlauben den Schluss, dass Gitterdefekte maßgeblich für die entstandenen Veränderungen verantwortlich sind.
Polyvinylalkohol (PVA) wurde als zweites System behandelt. Hierbei sollte untersucht werden, wie groß der Einfluss der Molekularbewegung auf die Verbreiterung der Peaks im XP-Spektrum ist. Des Weiteren wurde untersucht, wie groß der Einfluss von intermolekularen Wechselwirkungen auf die Peakpositionen und Peakverbreiterung ist. Für die Berechnung dieses Systems wurde eine Kombination aus molekulardynamischen und quantenchemischen Methoden verwendet. Als Strukturen dienten Oligomermodelle, die unter dem Einfluss eines (ab initio) Potentials propagiert wurden. Entlang der erstellten Trajektorie wurden Schnappschüsse der Geometrien extrahiert und für die Berechnung der XP-Spektren verwendet. Die Spektren werden bereits mithilfe klassischer Molekulardynamik sehr gut reproduziert. Die erhaltenen Peakbreiten sind verglichen mit dem Experiment allerdings zu klein. Die Hauptursache der Peakverbreiterung ist die Molekularbewegung. Intermolekulare Wechselwirkungen verschieben die Peakpositionen um 0.6 eV zu kleineren Anregungsenergien.
Im dritten Teil der Arbeit stehen die NEXAFS-Spektren von ionischen Flüssigkeiten (ILs) im Fokus. Die experimentell gefundenen Spektren zeigen eine komplexe Struktur mit vielen Resonanzen. In der Arbeit wurden zwei ILs untersucht. Als Geometrien verwenden wir Clustermodelle, die aus experimentellen Kristallstrukturen extrahiert wurden. Die berechneten Spektren erlauben es, die Resonanzen den Anregungszentren zuzuordnen. Außerdem kann eine erstmals gemessene Doppelresonanz simuliert und erklärt werden. Insgesamt kann die Interpretation der Spektren mithilfe der Simulation signifikant erweitert werden.
In allen Systemen wurde zur Berechnung des NEXAFS-Spektrums eine auf Dichtefunktionaltheorie basierende Methode verwendet (die sogenannte Transition-Potential Methode). Gängige wellenfunktionsbasierte Methoden, wie die Konfigurationswechselwirkung mit Einfachanregungen (CIS), zeigen eine starke Blauverschiebung, wenn als Referenz eine Hartree-Fock Slaterdeterminante verwendet wird. Wir zeigen, dass die Verwendung von kernnah-angeregten Determinanten sowohl das resultierende Spektrum als auch die Anregungsenergien deutlich verbessert. Des Weiteren werden auch Referenzen aus Dichtefunktionalrechnungen getestet. Zusätzlich werden auch Referenzen mit gebrochenen Besetzungszahlen für kernnahe Elektronen verwendet. In der Arbeit werden die Resultate der verschiedenen Referenzen miteinander verglichen. Es zeigt sich, dass Referenzen mit gebrochenen Besetzungszahlen das Spektrum nicht weiter verbessern. Der Einfluss der verwendeten Elektronenstrukturmethode ist eher gering.
Surface-enhanced Raman scattering (SERS) is a promising tool to obtain rich chemical information about analytes at trace levels. However, in order to perform selective experiments on individual molecules, two fundamental requirements have to be fulfilled. On the one hand, areas with high local field enhancement, so-called “hot spots”, have to be created by positioning the supporting metal surfaces in close proximity to each other. In most cases hot spots are formed in the gap between adjacent metal nanoparticles (NPs). On the other hand, the analyte has to be positioned directly in the hot spot in order to profit from the highest signal amplification. The use of DNA origami substrates provides both, the arrangement of AuNPs with nm precision as well as the ability to bind analyte molecules at predefined positions. Consequently, the present cumulative doctoral thesis aims at the development of a novel SERS substrate based on a DNA origami template. To this end, two DNA-functionalized gold nanoparticles (AuNPs) are attached to one DNA origami substrate resulting in the formation of a AuNP dimer and thus in a hot spot within the corresponding gap. The obtained structures are characterized by correlated atomic force microscopy (AFM) and SERS imaging which allows for the combination of structural and chemical information.
Initially, the proof-of principle is presented which demonstrates the potential of the novel approach. It is shown that the Raman signal of 15 nm AuNPs coated with dye-modified DNA
(dye: carboxytetramethylrhodamine (TAMRA)) is significantly higher for AuNP dimers arranged on a DNA origami platform in comparison to single AuNPs. Furthermore, by attaching single TAMRA molecules in the hot spot between two 5 nm AuNPs and optimizing the size of the AuNPs by electroless gold deposition, SERS experiments at the few-molecule level are presented. The initially used DNA origami-AuNPs design is further optimized in many respects. On the one hand, larger AuNPs up to a diameter of 60 nm are used which are additionally treated with a silver enhancement solution to obtain Au-Ag-core-shell NPs. On the other hand, the arrangement of both AuNPs is altered to improve the position of the dye molecule within the hot spot as well as to decrease the gap size between the two particles. With the optimized design the detection of single dye molecules (TAMRA and cyanine 3 (Cy3)) by means of SERS is demonstrated. Quantitatively, enhancement factors up to 10^10 are estimated which is sufficiently high to detect single dye molecules.
In the second part, the influence of graphene as an additional component of the SERS substrate is investigated. Graphene is a two-dimensional material with an outstanding combination of electronical, mechanical and optical properties. Here, it is demonstrated that
single layer graphene (SLG) replicates the shape of underlying non-modified DNA origami
substrates very well, which enables the monitoring of structural alterations by AFM imaging.
In this way, it is shown that graphene encapsulation significantly increases the structural
stability of bare DNA origami substrates towards mechanical force and prolonged exposure
to deionized water.
Furthermore, SLG is used to cover DNA origami substrates which are functionalized with a
40 nm AuNP dimer. In this way, a novel kind of hybrid material is created which exhibits
several advantages compared to the analogue non-covered SERS substrates. First, the fluorescence background of dye molecules that are located in between the AuNP surface and SLG is efficiently reduced. Second, the photobleaching rate of the incorporated dye molecules is decreased up to one order of magnitude. Third, due to the increased photostability of the investigated dye molecules, the performance of polarization-dependent series measurements on individual structures is enabled. This in turn reveals extensive information about the dye molecules in the hot spot as well as about the strain induced within the graphene lattice.
Although SLG can significantly influence the SERS substrate in the aforementioned ways, all
those effects are strongly related to the extent of contact with the underlying AuNP dimer.
Physikalische Hydrogele gewinnen derzeit als Zellsubstrate zunehmend an Interesse, da Viskoelastizität oder Stressrelaxation ein bedeutender Parameter in der Mechanotransduktion ist, der bisher vernachlässigt wurde. In dieser Arbeit wurden multi-funktionelle Polyurethane entworfen, die über einen neuartigen Gelierungsmechanismus physikalische Hydrogele bilden. In Wasser bilden die anionischen Polyurethane spontan Aggregate, welche durch elektrostatische Abstoßung in Lösung gehalten werden. Eine schnelle Gelierung kann von hier aus durch Ladungsabschirmung erreicht werden, wodurch die Aggregation voranschreitet und ein Netzwerk ausgebildet wird. Dies kann durch die Zugabe von verschiedenen Säuren oder Salzen geschehen, sodass sowohl saure (pH 4 - 5) als auch pH-neutrale Hydrogele erhalten werden können. Während konventionelle Hydrogele auf Polyurethan-Basis in der Regel durch toxische isocyanat-haltige Präpolymere hergestellt werden, eignet sich der hier beschriebene physikalische Gelierungsmechanismus für in situ Anwendungen in sensitiven Umgebungen. Sowohl Härte als auch Stressrelaxation der Hydrogele können unabhängig voneinander über einen breiten Bereich eingestellt werden. Darüberhinaus zeichnen sich die Hydrogele durch exzellente Stressregeneration aus.
Luhmann in da Contact Zone
(2016)
Our aim in this contribution is to productively engage with the abstractions and complexities of Luhmann’s conceptions of society from a postcolonial perspective, with a particular focus on the explanatory powers of his sociological systems theory when it leaves the realms of Europe and ventures to describe regions of the global South. In view of its more recent global reception beyond Europe, our aim is to thus – following the lead of Dipesh Chakrabarty – provincialize Luhmann’s system theory especially with regard to its underlying assumptions about a global “world society”. For these purposes, we intend to revisit Luhmann in the post/colonial contact zone: We wish to reread Luhmann in the context of spaces of transcultural encounter where “global designs and local histories” (Mignolo), where inclusion into and exclusion from “world society” (Luhmann) clash and interact in intricate ways. The title of our contribution, ‘Luhmann in da Contact Zone’ is deliberately ambiguous: On the one hand, we of course use ‘Luhmann’ metonymically, as representative of a highly complex theoretical design. We shall cursorily outline this design with a special focus on the notion of a singular, modern “world society”, only to confront it with the epistemic challenges of the contact zone. On the other hand, this critique will also involve the close observation of Niklas Luhman as a human observer (a category which within the logic of systems theory actually does not exist) who increasingly transpires in his late writings on exclusion in the global South. By following this dual strategy, we wish to trace an increasing fracture between one Luhmann and the other, between abstract theoretical design and personalized testimony. It is by exploring and measuring this fracture that we hope to eventually be able to map out the potential of a possibly more productive encounter between systems theory and specific strands of postcolonial theory for a pluritopic reading of global modernity.
Recollecting Bones
(2016)
In the same “guarded, roundabout and reticent way” which Lindsay Barrett invokes for Australian conversations about imperial injustice, Germans, too, must begin to more systematically explore, in Paul Gilroy’s words, “the connections and the differences between anti-semitism and anti-black and other racisms and asses[s] the issues that arise when it can no longer be denied that they interacted over a long time in what might be seen as Fascism’s intellectual, ethical and scientific pre-history” (Gilroy 1996: 26). In the meantime, we need to care for the dead. We need to return them, first, from the status of scientific objects to the status of ancestral human beings, and then progressively, and proactively, as close as possible to the care of those communities from whom they were stolen.
Kleine Kosmopolitismen
(2016)
Postcolonial Justice
(2016)
Postcolonial Piracy
(2016)
Media piracy is a contested term in the academic as much as the public debate. It is used by the corporate industries as a synonym for the theft of protected media content with disastrous economic consequences. It is celebrated by technophile elites as an expression of freedom that ensures creativity as much as free market competition. Marxist critics and activists promote flapiracy as a subversive practice that undermines the capitalist world system and its structural injustices. Artists and entrepreneurs across the globe curse it as a threat to their existence, while many use pirate infrastructures and networks fundamentally for the production and dissemination of their art. For large sections of the population across the global South, piracy is simply the only means of accessing the medial flows of a progressively globalising planet.
Reflections of Lusáni Cissé
(2016)
Sexual Aggression Victimization and Perpetration among Male and Female College Students in Chile
(2016)
Evidence on the prevalence of sexual aggression among college students is primarily based on studies from Western countries. In Chile, a South American country strongly influenced by the Catholic Church, little research on sexual aggression among college students is available. Therefore, the purpose of the present study was to examine the prevalence of sexual aggression victimization and perpetration since the age of 14 (the legal age of consent) in a sample of male and female students aged between 18 and 29 years from five Chilean universities (N = 1135), to consider possible gender differences, and to study the extent to which alcohol was involved in the reported incidents of perpetration and victimization. Sexual aggression victimization and perpetration was measured with a Chilean Spanish version of the Sexual Aggression and Victimization Scale (SAV-S), which includes three coercive strategies (use or threat of physical force, exploitation of an incapacitated state, and verbal pressure), three victim-perpetrator constellations (current or former partners, friends/acquaintances, and strangers), and four sexual acts (sexual touch, attempted sexual intercourse, completed sexual intercourse, and other sexual acts, such as oral sex). Overall, 51.9% of women and 48.0% of men reported at least one incident of sexual victimization, and 26.8% of men and 16.5% of women reported at least one incident of sexual aggression perpetration since the age of 14. For victimization, only few gender differences were found, but significantly more men than women reported sexual aggression perpetration. A large proportion of perpetrators also reported victimization experiences. Regarding victim-perpetrator relationship, sexual aggression victimization and perpetration were more common between persons who knew each other than between strangers. Alcohol use by the perpetrator, victim, or both was involved in many incidents of sexual aggression victimization and perpetration, particularly among strangers. The present data are the first to provide a systematic and detailed picture of sexual aggression among college students in Chile, including victimization and perpetration reports by both men and women and confirming the critical role of alcohol established in past research from Western countries.
Rapidly uplifting coastlines are frequently associated with convergent tectonic boundaries, like subduction zones, which are repeatedly breached by giant megathrust earthquakes. The coastal relief along tectonically active realms is shaped by the effect of sea-level variations and heterogeneous patterns of permanent tectonic deformation, which are accumulated through several cycles of megathrust earthquakes. However, the correlation between earthquake deformation patterns and the sustained long-term segmentation of forearcs, particularly in Chile, remains poorly understood. Furthermore, the methods used to estimate permanent deformation from geomorphic markers, like marine terraces, have remained qualitative and are based on unrepeatable methods. This contrasts with the increasing resolution of digital elevation models, such as Light Detection and Ranging (LiDAR) and high-resolution bathymetric surveys.
Throughout this thesis I study permanent deformation in a holistic manner: from the methods to assess deformation rates, to the processes involved in its accumulation. My research focuses particularly on two aspects: Developing methodologies to assess permanent deformation using marine terraces, and comparing permanent deformation with seismic cycle deformation patterns under different spatial scales along the M8.8 Maule earthquake (2010) rupture zone. Two methods are developed to determine deformation rates from wave-built and wave-cut terraces respectively. I selected an archetypal example of a wave-built terrace at Santa Maria Island studying its stratigraphy and recognizing sequences of reoccupation events tied with eleven radiocarbon sample ages (14C ages). I developed a method to link patterns of reoccupation with sea-level proxies by iterating relative sea level curves for a range of uplift rates. I find the best fit between relative sea-level and the stratigraphic patterns for an uplift rate of 1.5 +- 0.3 m/ka.
A Graphical User Interface named TerraceM® was developed in Matlab®. This novel software tool determines shoreline angles in wave-cut terraces under different geomorphic scenarios. To validate the methods, I select test sites in areas of available high-resolution LiDAR topography along the Maule earthquake rupture zone and in California, USA. The software allows determining the 3D location of the shoreline angle, which is a proxy for the estimation of permanent deformation rates. The method is based on linear interpolations to define the paleo platform and cliff on swath profiles. The shoreline angle is then located by intersecting these interpolations. The
accuracy and precision of TerraceM® was tested by comparing its results with previous assessments, and through an experiment with students in a computer lab setting at the University
of Potsdam.
I combined the methods developed to analyze wave-built and wave-cut terraces to assess regional patterns of permanent deformation along the (2010) Maule earthquake rupture. Wave-built terraces are tied using 12 Infra Red Stimulated luminescence ages (IRSL ages) and shoreline angles in wave-cut terraces are estimated from 170 aligned swath profiles. The comparison of coseismic slip, interseismic coupling, and permanent deformation, leads to three areas of high permanent uplift, terrace warping, and sharp fault offsets. These three areas correlate with regions of high slip and low coupling, as well as with the spatial limit of at least eight historical megathrust ruptures (M8-9.5). I propose that the zones of upwarping at Arauco and Topocalma reflect changes in frictional properties of the megathrust, which result in discrete boundaries for the propagation of mega earthquakes.
To explore the application of geomorphic markers and quantitative morphology in offshore areas I performed a local study of patterns of permanent deformation inferred from hitherto unrecognized drowned shorelines at the Arauco Bay, at the southern part of the (2010) Maule earthquake rupture zone. A multidisciplinary approach, including morphometry, sedimentology, paleontology, 3D morphoscopy, and a landscape Evolution Model is used to recognize, map, and assess local rates and patterns of permanent deformation in submarine environments. Permanent deformation patterns are then reproduced using elastic models to assess deformation rates of an active submarine splay fault defined as Santa Maria Fault System. The best fit suggests a reverse structure with a slip rate of 3.7 m/ka for the last 30 ka. The register of land level changes during the earthquake cycle at Santa Maria Island suggest that most of the deformation may be accrued through splay fault reactivation during mega earthquakes, like the (2010) Maule event. Considering a recurrence time of 150 to 200 years, as determined from historical and geological observations, slip between 0.3 and 0.7 m per event would be required to account for the 3.7 m/ka millennial slip rate. However, if the SMFS slips only every ~1000 years, representing a few megathrust earthquakes, then a slip of ~3.5 m per event would be required to account for the long- term rate. Such event would be equivalent to a magnitude ~6.7 earthquake capable to generate a local tsunami.
The results of this thesis provide novel and fundamental information regarding the amount of permanent deformation accrued in the crust, and the mechanisms responsible for this accumulation at millennial time-scales along the M8.8 Maule earthquake (2010) rupture zone. Furthermore, the results of this thesis highlight the application of quantitative geomorphology and the use of repeatable methods to determine permanent deformation, improve the accuracy of marine terrace assessments, and estimates of vertical deformation rates in tectonically active coastal areas. This is vital information for adequate coastal-hazard assessments and to anticipate realistic earthquake and tsunami scenarios.
Seit der Einführung von Antibiotika in die medizinische Behandlung von bakteriellen Infektionskrankheiten existiert ein Wettlauf zwischen der Evolution von Bakterienresistenzen und der Entwicklung wirksamer Antibiotika. Während bis in die 80er Jahre verstärkt an neuen Antibiotika geforscht wurde, gewinnen multiresistente Keime heute zunehmend die Oberhand. Um einzelne Pathogene erfolgreich nachzuweisen und zu bekämpfen, ist ein grundlegendes Wissen über den Erreger unumgänglich. Bakterielle Proteine, die bei einer Infektion vorrangig vom Immunsystem prozessiert und präsentiert werden, könnten für die Entwicklung von Impfstoffen oder gezielten Therapeutika nützlich sein. Auch für die Diagnostik wären diese immundominanten Proteine interessant. Allerdings herrscht ein Mangel an Wissen über spezifische Antigene vieler pathogener Bakterien, die eine eindeutige Diagnostik eines einzelnen Erregers erlauben würden.
Daher wurden in dieser Arbeit vier verschiedene Humanpathogene mittels Phage Display untersucht: Neisseria gonorrhoeae, Neisseria meningitidis, Borrelia burgdorferi und Clostridium difficile. Hierfür wurden aus der genomischen DNA der vier Erreger Bibliotheken konstruiert und durch wiederholte Selektion und Amplifikation, dem sogenannten Panning, immunogene Proteine isoliert. Für alle Erreger bis auf C. difficile wurden immunogene Proteine aus den jeweiligen Bibliotheken isoliert. Die identifizierten Proteine von N. meningitidis und B. burgdorferi waren größtenteils bekannt, konnten aber in dieser Arbeit durch Phage Display verifiziert werden. Für N. gonorrhoeae wurden 21 potentiell immunogene Oligopeptide isoliert, von denen sechs Proteine als neue zuvor unbeschriebene Proteine mit immunogenem Charakter identifiziert wurden. Von den Phagen-präsentierten Oligopeptide der 21 immunogenen Proteine wurden Epitopmappings mit verschiedenen polyklonalen Antikörpern durchgeführt, um immunogene Bereiche näher zu identifizieren und zu charakterisieren. Bei zehn Proteinen wurden lineare Epitope eindeutig mit drei polyklonalen Antikörpern identifiziert, von fünf weiteren Proteinen waren Epitope mit mindestens einem Antikörper detektierbar. Für eine weitere Charakterisierung der ermittelten Epitope wurden Alaninscans durchgeführt, die eine detaillierte Auskunft über kritische Aminosäuren für die Bindung des Antikörpers an das Epitop geben.
Ausgehend von dem neu identifizierten Protein mit immunogenem Charakter NGO1634 wurden 26 weitere Proteine aufgrund ihrer funktionellen Ähnlichkeit ausgewählt und mithilfe bioinformatischer Analysen auf ihre Eignung zur Entwicklung einer diagnostischen Anwendung analysiert. Durch Ausschluss der meisten Proteine aufgrund ihrer Lokalisation, Membrantopologie oder unspezifischen Proteinsequenz wurden scFv-Antikörper gegen acht Proteine mittels Phage Display generiert und anschließend als scFv-Fc-Fusionsantikörper produziert und charakterisiert.
Die hier identifizierten Proteine und linearen Epitope könnten einen Ansatzpunkt für die Entwicklung einer diagnostischen oder therapeutischen Anwendung bieten. Lineare Epitopsequenzen werden häufig für die Impfstoffentwicklung eingesetzt, sodass vor allem die in dieser Arbeit bestimmten Epitope von Membranproteinen interessante Kandidaten für weitere Untersuchungen in diese Richtung sind. Durch weitere Untersuchungen könnten möglicherweise unbekannte Virulenzfaktoren entdeckt werden, deren Inhibierung einen entscheidenden Einfluss auf Infektionen haben könnten.
Diese Arbeit zu Grunde liegenden Forschung zielte darauf ab, neue schmelzbare Acrylnitril-Copolymere zu entwickeln. Diese sollten im Anschluss über ein Schmelzspinnverfahren zur Chemiefaser geformt und im letzten Schritt zur Carbonfaser konvertiert werden. Zu diesem Zweck wurden zunächst orientierende Untersuchungen an unterschiedlichen Copolymeren des Acrylnitril aus Lösungspolymerisation durchgeführt. Die Untersuchungen zeigten, dass elektrostatische Wechselwirkungen besser als sterische Abschirmung dazu geeignet sind, Schmelzbarkeit unterhalb der Zersetzungstemperatur von Polyacrylnitril zu bewirken. Aus der Vielzahl untersuchter Copolymere stellten sich jene mit Methoxyethylacrylat (MEA) als am effektivsten heraus. Für diese Copolymere wurden sowohl die Copolymerisationsparameter bestimmt als auch die grundlegende Kinetik der Lösungspolymerisation untersucht. Die Copolymere mit MEA wurden über Schmelzspinnen zur Faser umgeformt und diese dann untersucht. Hierbei wurden auch Einflüsse verschiedener Parameter, wie z.B. die der Molmasse, auf die Fasereigenschaften und -herstellung untersucht. Zuletzt wurde ein Heterophasenpolymerisationsverfahren zur Herstellung von Copolymeren aus AN/MEA entwickelt; dadurch konnten die Materialeigenschaften weiter verbessert werden. Zur Unterdrückung der thermoplastischen Eigenschaften der Fasern wurde ein geeignetes Verfahren entwickelt und anschließend die Konversion zu Carbonfasern durchgeführt.
Intermontane valley fills
(2016)
Sedimentary valley fills are a widespread characteristic of mountain belts around the world. They transiently store material over time spans ranging from thousands to millions of years and therefore play an important role in modulating the sediment flux from the orogen to the foreland and to oceanic depocenters. In most cases, their formation can be attributed to specific fluvial conditions, which are closely related to climatic and tectonic processes. Hence, valley-fill deposits constitute valuable archives that offer fundamental insight into landscape evolution, and their study may help to assess the impact of future climate change on sediment dynamics.
In this thesis I analyzed intermontane valley-fill deposits to constrain different aspects of the climatic and tectonic history of mountain belts over multiple timescales. First, I developed a method to estimate the thickness distribution of valley fills using artificial neural networks (ANNs). Based on the assumption of geometrical similarity between exposed and buried parts of the landscape, this novel and highly automated technique allows reconstructing fill thickness and bedrock topography on the scale of catchments to entire mountain belts.
Second, I used the new method for estimating the spatial distribution of post-glacial sediments that are stored in the entire European Alps. A comparison with data from exploratory drillings and from geophysical surveys revealed that the model reproduces the measurements with a root mean squared error (RMSE) of 70m and a coefficient of determination (R2) of 0.81. I used the derived sediment thickness estimates in combination with a model of the Last Glacial Maximum (LGM) icecap to infer the lithospheric response to deglaciation, erosion and deposition, and deduce their relative contribution to the present-day rock-uplift rate. For a range of different lithospheric and upper mantle-material properties, the results suggest that the long-wavelength uplift signal can be explained by glacial isostatic adjustment with a small erosional contribution and a substantial but localized tectonic component exceeding 50% in parts of the Eastern Alps and in the Swiss Rhône Valley. Furthermore, this study reveals the particular importance of deconvolving the potential components of rock uplift when interpreting recent movements along active orogens and how this can be used to constrain physical properties of the Earth’s interior.
In a third study, I used the ANN approach to estimate the sediment thickness of alluviated reaches of the Yarlung Tsangpo River, upstream of the rapidly uplifting Namche Barwa massif. This allowed my colleagues and me to reconstruct the ancient river profile of the Yarlung Tsangpo, and to show that in the past, the river had already been deeply incised into the eastern margin of the Tibetan Plateau. Dating of basal sediments from drill cores that reached the paleo-river bed to 2–2.5 Ma are consistent with mineral cooling ages from the Namche Barwa massif, which indicate initiation of rapid uplift at ~4 Ma. Hence, formation of the Tsangpo gorge and aggradation of the voluminous valley fill was most probably a consequence of rapid uplift of the Namche Barwa massif and thus tectonic activity.
The fourth and last study focuses on the interaction of fluvial and glacial processes at the southeastern edge of the Karakoram. Paleo-ice-extent indicators and remnants of a more than 400-m-thick fluvio-lacustrine valley fill point to blockage of the Shyok River, a main tributary of the upper Indus, by the Siachen Glacier, which is the largest glacier in the Karakoram Range. Field observations and 10Be exposure dating attest to a period of recurring lake formation and outburst flooding during the penultimate glaciation prior to ~110 ka. The interaction of Rivers and Glaciers all along the Karakorum is considered a key factor in landscape evolution and presumably promoted headward erosion of the Indus-Shyok drainage system into the western margin of the Tibetan Plateau.
The results of this thesis highlight the strong influence of glaciation and tectonics on valley-fill formation and how this has affected the evolution of different mountain belts. In the Alps valley-fill deposition influenced the magnitude and pattern of rock uplift since ice retreat approximately 17,000 years ago. Conversely, the analyzed valley fills in the Himalaya are much older and reflect environmental conditions that prevailed at ~110 ka and ~2.5 Ma, respectively. Thus, the newly developed method has proven useful for inferring the role of sedimentary valley-fill deposits in landscape evolution on timescales ranging from 1,000 to 10,000,000 years.
Introduction: Adequate cognitive function in patients is a prerequisite for successful implementation of patient education and lifestyle coping in comprehensive cardiac rehabilitation (CR) programs. Although the association between cardiovascular diseases and cognitive impairments (CIs) is well known, the prevalence particularly of mild CI in CR and the characteristics of affected patients have been insufficiently investigated so far.
Methods: In this prospective observational study, 496 patients (54.5 ± 6.2 years, 79.8% men) with coronary artery disease following an acute coronary event (ACE) were analyzed. Patients were enrolled within 14 days of discharge from the hospital in a 3-week inpatient CR program. Patients were tested for CI using the Montreal Cognitive Assessment (MoCA) upon admission to and discharge from CR. Additionally, sociodemographic, clinical, and physiological variables were documented. The data were analyzed descriptively and in a multivariate stepwise backward elimination regression model with respect to CI.
Results: At admission to CR, the CI (MoCA score < 26) was determined in 182 patients (36.7%). Significant differences between CI and no CI groups were identified, and CI group was associated with high prevalence of smoking (65.9 vs 56.7%, P = 0.046), heavy (physically demanding) workloads (26.4 vs 17.8%, P < 0.001), sick leave longer than 1 month prior to CR (28.6 vs 18.5%, P = 0.026), reduced exercise capacity (102.5 vs 118.8 W, P = 0.006), and a shorter 6-min walking distance (401.7 vs 421.3 m, P = 0.021) compared to no CI group. The age- and education-adjusted model showed positive associations with CI only for sick leave more than 1 month prior to ACE (odds ratio [OR] 1.673, 95% confidence interval 1.07–2.79; P = 0.03) and heavy workloads (OR 2.18, 95% confidence interval 1.42–3.36; P < 0.01).
Conclusion: The prevalence of CI in CR was considerably high, affecting more than one-third of cardiac patients. Besides age and education level, CI was associated with heavy workloads and a longer sick leave before ACE.
Die Empirie des beginnenden 21. Jahrhunderts weist mehr autoritäre Regime aus als am Ende des 20. Jahrhunderts angenommen. Die gegenwärtige Autoritarismusforschung versucht die Fortdauer dieses Regimetyps in Hinblick auf die politischen Institutionen zu erklären – dabei bleiben politische Akteure, die nicht zum Herrschaftszentrum gehören, außen vor.
Das vorliegende Projekt untersucht die Rolle und Funktion politischer Opposition in autoritären Regimen. Es wird davon ausgegangen, dass sich an der Opposition eine signifikante Charakteristik autoritärer Regime manifestiert. Das akteurszentrierte Projekt ist der qualitativ orientierten Politikwissenschaft zuzurechnen und verknüpft das Autoritarismuskonzept von Juan Linz mit klassischen Ansätzen der Oppositionsforschung und macht diese Theorien für die gegenwärtige Autoritarismusforschung nutzbar.
Die eigens entwickelte elitenorientierte Oppositionstypologie wird am Beispiel Kenias im Zeitraum 1990-2005 angewendet. Die Oppositionsgruppen werden im Institutionengefüge autoritärer Regime verortet und ihr politisches Agieren in den Dimensionen Handlungsstatus, Handlungsüberzeugung und Handlungsstrategie analysiert. Unter Beachtung der historisch gewachsenen regionalen und kulturellen Spezifika wird angenommen, dass generelle, Regionen übergreifende Aussagen zur Opposition in autoritären Regimen getroffen werden können: Kein Oppositionstyp kann allein einen Herrschaftswechsel bewirken. Der Wechsel bzw. die Fortdauer der Herrschaft hängt von der Dominanz bestimmter Oppositionstypen im Oppositionsgeflecht sowie der gleichzeitigen Schwäche anderer Oppositionstypen ab.
Durch die konzeptionelle Beschäftigung mit Opposition sowie deren empirische Erschließung soll ein substantieller Beitrag für die notwendige Debatte um autoritäre Regime im 21. Jahrhundert geleistet werden.
The Earth’s shallow subsurface with sedimentary cover acts as a waveguide to any incoming wavefield. Within the framework of my thesis, I focused on the characterization of this shallow subsurface within tens to few hundreds of meters of sediment cover. I imaged the seismic 1D shear wave velocity (and possibly the 1D compressional wave velocity). This information is not only required for any seismic risk assessment, geotechnical engineering or microzonation activities, but also for exploration and global seismology where site effects are often neglected in seismic waveform modeling.
First, the conventional frequency-wavenumber (f - k) technique is used to derive the dispersion characteristic of the propagating surface waves recorded using distinct arrays of seismometers in 1D and 2D configurations. Further, the cross-correlation technique is applied to seismic array data to estimate the Green’s function between receivers pairs combination assuming one is the source and the other the receiver. With the consideration of a 1D media, the estimated cross-correlation Green’s functions are sorted with interstation distance in a virtual 1D active seismic experiment. The f - k technique is then used to estimate the dispersion curves. This integrated analysis is important for the interpretation of a large bandwidth of the phase velocity dispersion curves and therefore improving the resolution of the estimated 1D Vs profile.
Second, the new theoretical approach based on the Diffuse Field Assumption (DFA) is used for the interpretation of the observed microtremors H/V spectral ratio. The theory is further extended in this research work to include not only the interpretation of the H/V measured at the surface, but also the H/V measured at depths and in marine environments. A modeling and inversion of synthetic H/V spectral ratio curves on simple predefined geological structures shows an almost perfect recovery of the model parameters (mainly Vs and to a lesser extent Vp). These results are obtained after information from a receiver at depth has been considered in the inversion.
Finally, the Rayleigh wave phase velocity information, estimated from array data, and the H/V(z, f) spectral ratio, estimated from a single station data, are combined and inverted for the velocity profile information. Obtained results indicate an improved depth resolution in comparison to estimations using the phase velocity dispersion curves only. The overall estimated sediment thickness is comparable to estimations obtained by inverting the full micortremor H/V spectral ratio.
We study the interplay between analysis on manifolds with singularities and complex analysis and develop new structures of operators based on the Mellin transform and tools for iterating the calculus for higher singularities. We refer to the idea of interpreting boundary value problems (BVPs) in terms of pseudo-differential operators with a principal symbolic hierarchy, taking into account that BVPs are a source of cone and edge operator algebras. The respective cone and edge pseudo-differential algebras in turn are the starting point of higher corner theories. In addition there are deep relationships between corner operators and complex analysis. This will be illustrated by the Mellin symbolic calculus.
Transmorphic
(2016)
Defining Graphical User Interfaces (GUIs) through functional abstractions can reduce the complexity that arises from mutable abstractions. Recent examples, such as Facebook's React GUI framework have shown, how modelling the view as a functional projection from the application state to a visual representation can reduce the number of interacting objects and thus help to improve the reliabiliy of the system. This however comes at the price of a more rigid, functional framework where programmers are forced to express visual entities with functional abstractions, detached from the way one intuitively thinks about the physical world.
In contrast to that, the GUI Framework Morphic allows interactions in the graphical domain, such as grabbing, dragging or resizing of elements to evolve an application at runtime, providing liveness and directness in the development workflow. Modelling each visual entity through mutable abstractions however makes it difficult to ensure correctness when GUIs start to grow more complex. Furthermore, by evolving morphs at runtime through direct manipulation we diverge more and more from the symbolic description that corresponds to the morph. Given that both of these approaches have their merits and problems, is there a way to combine them in a meaningful way that preserves their respective benefits?
As a solution for this problem, we propose to lift Morphic's concept of direct manipulation from the mutation of state to the transformation of source code. In particular, we will explore the design, implementation and integration of a bidirectional mapping between the graphical representation and a functional and declarative symbolic description of a graphical user interface within a self hosted development environment. We will present Transmorphic, a functional take on the Morphic GUI Framework, where the visual and structural properties of morphs are defined in a purely functional, declarative fashion. In Transmorphic, the developer is able to assemble different morphs at runtime through direct manipulation which is automatically translated into changes in the code of the application. In this way, the comprehensiveness and predictability of direct manipulation can be used in the context of a purely functional GUI, while the effects of the manipulation are reflected in a medium that is always in reach for the programmer and can even be used to incorporate the source transformations into the source files of the application.
The visceral protein transthyretin (TTR) is frequently affected by oxidative post-translational protein modifications (PTPMs) in various diseases. Thus, better insight into structure-function relationships due to oxidative PTPMs of TTR should contribute to the understanding of pathophysiologic mechanisms. While the in vivo analysis of TTR in mammalian models is complex, time- and resource-consuming, transgenic Caenorhabditis elegans expressing hTTR provide an optimal model for the in vivo identification and characterization of drug-mediated oxidative PTPMs of hTTR by means of matrix assisted laser desorption/ionization – time of flight – mass spectrometry (MALDI-TOF-MS). Herein, we demonstrated that hTTR is expressed in all developmental stages of Caenorhabditis elegans, enabling the analysis of hTTR metabolism during the whole life-cycle. The suitability of the applied model was verified by exposing worms to D-penicillamine and menadione. Both drugs induced substantial changes in the oxidative PTPM pattern of hTTR. Additionally, for the first time a covalent binding of both drugs with hTTR was identified and verified by molecular modelling.
Variations in the distribution of mass within an orogen may lead to transient sediment storage, which in turn might affect the state of stress and the level of fault activity. Distinguishing between different forcing mechanisms causing variations of sediment flux and tectonic activity, is therefore one of the most challenging tasks in understanding the spatiotemporal evolution of active mountain belts.
The Himalayan mountain belt is one of the most significant Cenozoic collisional mountain belt, formed due to collision between northward-bound Indian Plate and the Eurasian Plate during the last 55-50 Ma. Ongoing convergence of these two tectonic plates is accommodated by faulting and folding within the Himalayan arc-shaped orogen and the continued lateral and vertical growth of the Tibetan Plateau and mountain belts adjacent to the plateau as well as regions farther north. Growth of the Himalayan orogen is manifested by the development of successive south-vergent thrust systems. These thrust systems divide the orogen into different morphotectonic domains. From north to south these thrusts are the Main Central Thrust (MCT), the Main Boundary Thrust (MBT) and the Main Frontal Thrust (MFT). The growing topography interacts with moisture-bearing monsoonal winds, which results in pronounced gradients in rainfall, weathering, erosion and sediment transport toward the foreland and beyond. However, a fraction of this sediment is trapped and transiently stored within the intermontane valleys or ‘dun’s within the lower-elevation foothills of the range. Improved understanding of the spatiotemporal evolution of these sediment archives could provide a unique opportunity to decipher the triggers of variations in sediment production, delivery and storage in an actively deforming mountain belt and support efforts to test linkages between sediment volumes in intermontane basins and changes in the shallow crustal stress field. As sediment redistribution in mountain belts on timescales of 102-104 years can effect cultural characteristics and infrastructure in the intermontane valleys and may even impact the seismotectonics of a mountain belt, there is a heightened interest in understanding sediment-routing processes and causal relationships between tectonism, climate and topography. It is here at the intersection between tectonic processes and superposed climatic and sedimentary processes in the Himalayan orogenic wedge, where my investigation is focused on. The study area is the intermontane Kangra Basin in the northwestern Sub-Himalaya, because the characteristics of the different Himalayan morphotectonic provinces are well developed, the area is part of a region strongly influenced by monsoonal forcing, and the existence of numerous fluvial terraces provides excellent strain markers to assess deformation processes within the Himalayan orogenic wedge. In addition, being located in front of the Dhauladhar Range the region is characterized by pronounced gradients in past and present-day erosion and sediment processes associated with repeatedly changing climatic conditions. In light of these conditions I analysed climate-driven late Pleistocene-Holocene sediment cycles in this tectonically active region, which may be responsible for triggering the tectonic re-organization within the Himalayan orogenic wedge, leading to out-of-sequence thrusting, at least since early Holocene.
The Kangra Basin is bounded by the MBT and the Sub-Himalayan Jwalamukhi Thrust (JMT) in the north and south, respectively and transiently stores sediments derived from the Dhauladhar Range. The Basin contains ~200-m-thick conglomerates reflecting two distinct aggradation phases; following aggradation, several fluvial terraces were sculpted into these fan deposits. 10Be CRN surface exposure dating of these terrace levels provides an age of 53.4±3.2 ka for the highest-preserved terrace (AF1); subsequently, this surface was incised until ~15 ka, when the second fan (AF2) began to form. AF2 fan aggradation was superseded by episodic Holocene incision, creating at least four terrace levels. We find a correlation between variations in sediment transport and ∂18O records from regions affected by the Indian Summer Monsoon (ISM). During strengthened ISMs sand post-LGM glacial retreat, aggradation occurred in the Kangra Basin, likely due to high sediment flux, whereas periods of a weakened ISM coupled with lower sediment supply coincided with renewed re-incision.
However, the evolution of fluvial terraces along Sub-Himalayan streams in the Kangra sector is also forced by tectonic processes. Back-tilted, folded terraces clearly document tectonic activity of the JMT. Offset of one of the terrace levels indicates a shortening rate of 5.6±0.8 to 7.5±1.0 mm.a-1 over the last ~10 ka. Importantly, my study reveals that late Pleistocene/Holocene out-of-sequence thrusting accommodates 40-60% of the total 14±2 mm.a-1 shortening partitioned throughout the Sub-Himalaya. Importantly, the JMT records shortening at a lower rate over longer timescales hints towards out-of-sequence activity within the Sub-Himalaya. Re-activation of the JMT could be related to changes in the tectonic stress field caused by large-scale sediment removal from the basin. I speculate that the deformation processes of the Sub-Himalaya behave according to the predictions of critical wedge model and assume the following: While >200m of sediment aggradation would trigger foreland-ward propagation of the deformation front, re-incision and removal of most of the stored sediments (nearly 80-85% of the optimum basin-fill) would again create a sub-critical condition of the wedge taper and trigger the retreat of the deformation front.
While tectonism is responsible for the longer-term processes of erosion associated with steepening hillslopes, sediment cycles in this environment are mainly the result of climatic forcing. My new 10Be cosmogenic nuclide exposure dates and a synopsis of previous studies show the late Pleistocene to Holocene alluvial fills and fluvial terraces studied here record periodic fluctuations of sediment supply and transport capacity on timescales of 1000-100000 years. To further evaluate the potential influence of climate change on these fluctuations, I compared the timing of aggradation and incision phases recorded within remnant alluvial fans and terraces with continental climate archives such as speleothems in neighboring regions affected by monsoonal precipitation. Together with previously published OSL ages yielding the timing of aggradation, I find a correlation between variations in sediment transport with oxygen-isotope records from regions affected by the Indian Summer Monsoon (ISM). Accordingly, during periods of increased monsoon intensity (transitions from dry and cold to wet and warm periods – MIS4 to MIS3 and MIS2 to MIS1) (MIS=marine isotope stage) and post-Last Glacial Maximum glacial retreat, aggradation occurred in the Kangra Basin, likely due to high sediment flux. Conversely, periods of weakened monsoon intensity or lower sediment supply coincide with re-incision of the existing basin-fill.
Finally, my study entails part of a low-temperature thermochronology study to assess the youngest exhumation history of the Dhauladhar Range. Zircon helium (ZHe) ages and existing low-temperature data sets (ZHe, apatite fission track (AFT)) across this range, together with 3D thermokinematic modeling (PECUBE) reveals constraints on exhumation and activity of the range-bounding Main Boundary Thrust (MBT) since at least mid-Miocene time. The modeling results indicate mean slip rates on the MBT-fault ramp of ~2 – 3 mm.a-1 since its activation. This has lead to the growth of the >5-km-high frontal Dhauladhar Range and continuous deep-seated exhumation and erosion. The obtained results also provide interesting constraints of deformation patterns and their variation along strike. The results point towards the absence of the time-transient ‘mid-crustal ramp’ in the basal decollement and
duplexing of the Lesser Himalayan sequence, unlike the nearby regions or even the central Nepal domain. A fraction of convergence (~10-15%) is accommodated along the deep-seated MBT-ramp, most likely merging into the MHT. This finding is crucial for a rigorous assessment of the overall level of tectonic activity in the Himalayan morphotectonic provinces as it contradicts recently-published geodetic shortening estimates. In these studies, it has been proposed that the total Himalayan shortening in the NW Himalaya is accommodated within the Sub-Himalaya whereas no tectonic activity is assigned to the MBT.
Interplay of coupling and common noise at the transition to synchrony in oscillator populations
(2016)
There are two ways to synchronize oscillators: by coupling and by common forcing, which can be pure noise. By virtue of the Ott-Antonsen ansatz for sine-coupled phase oscillators, we obtain analytically tractable equations for the case where both coupling and common noise are present. While noise always tends to synchronize the phase oscillators, the repulsive coupling can act against synchrony, and we focus on this nontrivial situation. For identical oscillators, the fully synchronous state remains stable for small repulsive coupling; moreover it is an absorbing state which always wins over the asynchronous regime. For oscillators with a distribution of natural frequencies, we report on a counter-intuitive effect of dispersion (instead of usual convergence) of the oscillators frequencies at synchrony; the latter effect disappears if noise vanishes.
Editorial (Dr. Roswitha Lohwaßer) ; Schon im Studium von gelingenden Schulen lernen (Jannis Andresen, Jakob Erichsen) ; Wie ein Funke überspringt (Laura Zrenner) ; Lerneffekte unter der Lupe (Ariane Faulian) ; Die Lernreise als Ultima Ratio? (Leroy Großmann) ; Die Lernreise als Schulperspektive (Laura Zrenner) ; Teamgeist gefragt (Cornelia Brückner) ; Wunschberuf Lehrerin (Robin Miska) ; Gelebte Integration (Cornelia Brückner) ; Souverän Führen im Unterricht (Dr. Helga Breuninger, Marina Rottig, Prof. Dr. Wilfried Schley) ; Was lernen Lehramtsstudierende durch ein videogestütztes Klassenmanagement-Training? (Dr. Janine Neuhaus, Mirko Wendland)
This thesis is focused on the study and the exact simulation of two classes of real-valued Brownian diffusions: multi-skew Brownian motions with constant drift and Brownian diffusions whose drift admits a finite number of jumps.
The skew Brownian motion was introduced in the sixties by Itô and McKean, who constructed it from the reflected Brownian motion, flipping its excursions from the origin with a given probability. Such a process behaves as the original one except at the point 0, which plays the role of a semipermeable barrier. More generally, a skew diffusion with several semipermeable barriers, called multi-skew diffusion, is a diffusion everywhere except when it reaches one of the barriers, where it is partially reflected with a probability depending on that particular barrier. Clearly, a multi-skew diffusion can be characterized either as solution of a stochastic differential equation involving weighted local times (these terms providing the semi-permeability) or by its infinitesimal generator as Markov process.
In this thesis we first obtain a contour integral representation for the transition semigroup of the multiskew Brownian motion with constant drift, based on a fine analysis of its complex properties. Thanks to this representation we write explicitly the transition densities of the two-skew Brownian motion with constant drift as an infinite series involving, in particular, Gaussian functions and their tails.
Then we propose a new useful application of a generalization of the known rejection sampling method. Recall that this basic algorithm allows to sample from a density as soon as one finds an - easy to sample - instrumental density verifying that the ratio between the goal and the instrumental densities is a bounded function. The generalized rejection sampling method allows to sample exactly from densities for which indeed only an approximation is known. The originality of the algorithm lies in the fact that one finally samples directly from the law without any approximation, except the machine's.
As an application, we sample from the transition density of the two-skew Brownian motion with or without constant drift. The instrumental density is the transition density of the Brownian motion with constant drift, and we provide an useful uniform bound for the ratio of the densities. We also present numerical simulations to study the efficiency of the algorithm.
The second aim of this thesis is to develop an exact simulation algorithm for a Brownian diffusion whose drift admits several jumps. In the literature, so far only the case of a continuous drift (resp. of a drift with one finite jump) was treated. The theoretical method we give allows to deal with any finite number of discontinuities. Then we focus on the case of two jumps, using the transition densities of the two-skew Brownian motion obtained before. Various examples are presented and the efficiency of our approach is discussed.
Understanding the role of natural climate variability under the pressure of human induced changes of climate and landscapes, is crucial to improve future projections and adaption strategies. This doctoral thesis aims to reconstruct Holocene climate and environmental changes in NE Germany based on annually laminated lake sediments. The work contributes to the ICLEA project (Integrated CLimate and Landscape Evolution Analyses). ICLEA intends to compare multiple high-resolution proxy records with independent chronologies from the N central European lowlands, in order to disentangle the impact of climate change and human land use on landscape development during the Lateglacial and Holocene. In this respect, two study sites in NE Germany are investigated in this doctoral project, Lake Tiefer See and palaeolake Wukenfurche. While both sediment records are studied with a combination of high-resolution sediment microfacies and geochemical analyses (e.g. µ-XRF, carbon geochemistry and stable isotopes), detailed proxy understanding mainly focused on the continuous 7.7 m long sediment core from Lake Tiefer See covering the last ~6000 years. Three main objectives are pursued at Lake Tiefer See: (1) to perform a reliable and independent chronology, (2) to establish microfacies and geochemical proxies as indicators for climate and environmental changes, and (3) to trace the effects of climate variability and human activity on sediment deposition.
Addressing the first aim, a reliable chronology of Lake Tiefer See is compiled by using a multiple-dating concept. Varve counting and tephra findings form the chronological framework for the last ~6000 years. The good agreement with independent radiocarbon dates of terrestrial plant remains verifies the robustness of the age model. The resulting reliable and independent chronology of Lake Tiefer See and, additionally, the identification of nine tephras provide a valuable base for detailed comparison and synchronization of the Lake Tiefer See data set with other climate records. The sediment profile of Lake Tiefer See exhibits striking alternations between well-varved and non-varved sediment intervals. The combination of microfacies, geochemical and microfossil (i.e. Cladocera and diatom) analyses indicates that these changes of varve preservation are caused by variations of lake circulation in Lake Tiefer See. An exception is the well-varved sediment deposited since AD 1924, which is mainly influenced by human-induced lake eutrophication. Well-varved intervals before the 20th century are considered to reflect phases of reduced lake circulation and, consequently, stronger anoxic conditions. Instead, non-varved intervals indicate increased lake circulation in Lake Tiefer See, leading to more oxygenated conditions at the lake ground. Furthermore, lake circulation is not only influencing sediment deposition, but also geochemical processes in the lake. As, for example, the proxy meaning of δ13COM varies in time in response to changes of the oxygen regime in the lake hypolinion. During reduced lake circulation and stronger anoxic conditions δ13COM is influenced by microbial carbon cycling. In contrast, organic matter degradation controls δ13COM during phases of intensified lake circulation and more oxygenated conditions. The varve preservation indicates an increasing trend of lake circulation at Lake Tiefer See after ~4000 cal a BP. This trend is superimposed by decadal to centennial scale variability of lake circulation intensity. Comparison to other records in Central Europe suggests that the long-term trend is probably related to gradual changes in Northern Hemisphere orbital forcing, which induced colder and windier conditions in Central Europe and, therefore, reinforced lake circulation. Decadal to centennial scale periods of increased lake circulation coincide with settlement phases at Lake Tiefer See, as inferred from pollen data of the same sediment record. Deforestation reduced the wind shelter of the lake, which probably increased the sensitivity of lake circulation to wind stress. However, results of this thesis also suggest that several of these phases of increased lake circulation are additionally reinforced by climate changes. A first indication is provided by the comparison to the Baltic Sea record, which shows striking correspondence between major non-varved intervals at Lake Tiefer See and bioturbated sediments in the Baltic Sea. Furthermore, a preliminary comparison to the ICLEA study site Lake Czechowskie (N central Poland) shows a coincidence of at least three phases of increased lake circulation in both lakes, which concur with periods of known climate changes (2.8 ka event, ’Migration Period’ and ’Little Ice Age’). These results suggest an additional over-regional climate forcing also on short term increased of lake circulation in Lake Tiefer See.
In summary, the results of this thesis suggest that lake circulation at Lake Tiefer See is driven by a combination of long-term and short-term climate changes as well as of anthropogenic deforestation phases. Furthermore, the lake circulation drives geochemical cycles in the lake affecting the meaning of proxy data. Therefore, the work presented here expands the knowledge of climate and environmental variability in NE Germany. Furthermore, the integration of the Lake Tiefer See multi-proxy record in a regional comparison with another ICLEA side, Lake Czechowskie, enabled to better decipher climate changes and human impact on the lake system. These first results suggest a huge potential for further detailed regional comparisons to better understand palaeoclimate dynamics in N central Europe.
Services that operate over the Internet are under constant threat of being exposed to fraudulent use. Maintaining good user experience for legitimate users often requires the classification of entities as malicious or legitimate in order to initiate countermeasures. As an example, inbound email spam filters decide for spam or non-spam. They can base their decision on both the content of each email as well as on features that summarize prior emails received from the sending server. In general, discriminative classification methods learn to distinguish positive from negative entities. Each decision for a label may be based on features of the entity and related entities. When labels of related entities have strong interdependencies---as can be assumed e.g. for emails being delivered by the same user---classification decisions should not be made independently and dependencies should be modeled in the decision function. This thesis addresses the formulation of discriminative classification problems that are tailored for the specific demands of the following three Internet security applications. Theoretical and algorithmic solutions are devised to protect an email service against flooding of user inboxes, to mitigate abusive usage of outbound email servers, and to protect web servers against distributed denial of service attacks.
In the application of filtering an inbound email stream for unsolicited emails, utilizing features that go beyond each individual email's content can be valuable. Information about each sending mail server can be aggregated over time and may help in identifying unwanted emails. However, while this information will be available to the deployed email filter, some parts of the training data that are compiled by third party providers may not contain this information. The missing features have to be estimated at training time in order to learn a classification model. In this thesis an algorithm is derived that learns a decision function that integrates over a distribution of values for each missing entry. The distribution of missing values is a free parameter that is optimized to learn an optimal decision function.
The outbound stream of emails of an email service provider can be separated by the customer IDs that ask for delivery. All emails that are sent by the same ID in the same period of time are related, both in content and in label. Hijacked customer accounts may send batches of unsolicited emails to other email providers, which in turn might blacklist the sender's email servers after detection of incoming spam emails. The risk of being blocked from further delivery depends on the rate of outgoing unwanted emails and the duration of high spam sending rates. An optimization problem is developed that minimizes the expected cost for the email provider by learning a decision function that assigns a limit on the sending rate to customers based on the each customer's email stream.
Identifying attacking IPs during HTTP-level DDoS attacks allows to block those IPs from further accessing the web servers. DDoS attacks are usually carried out by infected clients that are members of the same botnet and show similar traffic patterns. HTTP-level attacks aim at exhausting one or more resources of the web server infrastructure, such as CPU time. If the joint set of attackers cannot increase resource usage close to the maximum capacity, no effect will be experienced by legitimate users of hosted web sites. However, if the additional load raises the computational burden towards the critical range, user experience will degrade until service may be unavailable altogether. As the loss of missing one attacker depends on block decisions for other attackers---if most other attackers are detected, not blocking one client will likely not be harmful---a structured output model has to be learned. In this thesis an algorithm is developed that learns a structured prediction decoder that searches the space of label assignments, guided by a policy.
Each model is evaluated on real-world data and is compared to reference methods. The results show that modeling each classification problem according to the specific demands of the task improves performance over solutions that do not consider the constraints inherent to an application.
Der Klimawandel
(2016)
Was ist Gerechtigkeit? Wie könnten gerechte Regelungen aussehen für die Katastrophen und Leiden, die der Klimawandel auslöst bzw. auslösen wird? Diese sind häufig ungerecht, weil sie oft deutlich stärker diejenigen treffen, die am wenigsten zur Klimaveränderung beigetragen haben.
Doch was genau verstehen wir unter dem Schlagwort: ‚Klimawandel‘? Und kann dieser wirklich den Menschen direkt treffen? Ein kurzer naturwissenschaftlicher Abriss klärt hier die wichtigsten Fragen.
Da es sich hierbei um eine philosophische Arbeit handelt, muss zunächst geklärt werden, ob der Mensch überhaupt die Ursache von so etwas sein kann wie z.B. der Klimaerwärmung. Robert Spaemanns These dazu ist, dass der Mensch durch seinen freien Willen mit seinen Einzelhandlungen das Weltgeschehen verändern kann. Hans Jonas fügt dem hinzu, dass wir durch diese Fähigkeit, verantwortlich sind für die gewollten und ungewollten Folgen unserer Handlungen.
Damit wäre aus naturwissenschaftlicher Sicht (1. Teil der Arbeit) und aus philosophischer Sicht (Anfang 2. Teil) geklärt, dass der Mensch mit größter Wahrscheinlichkeit die Ursache des Klimawandels ist und diese Verursachung moralische Konsequenzen für ihn hat.
Ein philosophischer Gerechtigkeitsbegriff wird aus der Kantischen Rechts- und Moralphilosophie entwickelt, weil diese die einzige ist, die dem Menschen überhaupt ein Recht auf Rechte zusprechen kann. Diese entspringt der transzendentalen Freiheitsfähigkeit des Menschen, weshalb jedem das Recht auf Rechte absolut und immer zukommt. Gleichzeitig mündet Kants Philosophie wiederum in dem Freiheitsgedanken, indem Gerechtigkeit nur existiert, wenn alle Menschen gleichermaßen frei sein können.
Was heißt das konkret? Wie könnte Gerechtigkeit in der Realität wirklich umgesetzt werden? Die Realisierung schlägt zwei Grundrichtungen ein. John Rawls und Stefan Gosepath beschäftigen sich u.a. eingehend mit der prozeduralen Gerechtigkeit, was bedeutet, dass gerechte Verfahren gefunden werden, die das gesellschaftliche Zusammenleben regeln. Das leitende Prinzip hierfür ist vor allem: ein Mitbestimmungsrecht aller, so dass sich im Prinzip alle Bürger ihre Gesetze selbst geben und damit frei handeln.
In Bezug auf den Klimawandel steht die zweite Ausrichtung im Vordergrund – die distributive oder auch Verteilungs-Gerechtigkeit. Materielle Güter müssen so aufgeteilt werden, dass auch trotz empirischer Unterschiede alle Menschen als moralische Subjekte anerkannt werden und frei sein können.
Doch sind diese philosophischen Schlussfolgerungen nicht viel zu abstrakt, um auf ein ebenso schwer fassbares und globales Problem wie den Klimawandel angewendet zu werden? Was könnte daher eine Klimagerechtigkeit sein?
Es gibt viele Gerechtigkeitsprinzipien, die vorgeben, eine gerechte Grundlage für die Klimaprobleme zu bieten wie z.B. das Verursacherprinzip, das Fähigkeitsprinzip oder das Grandfathering-Prinzip, bei dem die Hauptverursacher nach wie vor am meisten emittieren dürfen (dieses Prinzip leitete die bisherigen internationalen Verhandlungen).
Das Ziel dieser Arbeit ist, herauszufinden, wie die Klimaprobleme gelöst werden können, so dass für alle Menschen unter allen Umständen die universellen Menschenrechte her- und sichergestellt werden und diese frei und moralisch handeln können.
Die Schlussfolgerung dieser Arbeit ist, dass Kants Gerechtigkeitsbegriff durch eine Kombination des Subsistenzemissions-Rechts, des Greenhouse-Development-Rights-Principles (GDR-Prinzip) und einer internationalen Staatlichkeit durchgesetzt werden könnte.
Durch das Subsistenzemissions-Recht hat jeder Mensch das Recht, so viel Energie zu verbrauchen und damit zusammenhängende Emissionen zu produzieren, dass er ein menschenwürdiges Leben führen kann. Das GDR-Prinzip errechnet den Anteil an der weltweiten Gesamtverantwortung zum Klimaschutz eines jeden Landes oder sogar eines jeden Weltbürgers, indem es die historischen Emissionen (Klimaschuld) zu der jetzigen finanziellen Kapazität des Landes/ des Individuums (Verantwortungsfähigkeit) hinzuaddiert. Die Implementierung von internationalen Gremien wird verteidigt, weil es ein globales, grenzüberschreitendes Problem ist, dessen Effekte und dessen Verantwortung globale Ausmaße haben.
Ein schlagendes Argument für fast alle Klimaschutzmaßnahmen ist, dass sie Synergien aufweisen zu anderen gesellschaftlichen Bereichen aufweisen wie z.B. Gesundheit und Armutsbekämpfung, in denen auch noch um die Durchsetzung unserer Menschenrechte gerungen wird.
Ist dieser Lösungsansatz nicht völlig utopisch?
Dieser Vorschlag stellt für die internationale Gemeinschaft eine große Herausforderung dar, wäre jedoch die einzig gerechte Lösung unserer Klimaprobleme. Des Weiteren wird an dem Kantischen Handlungsgrundsatz festgehalten, dass das ewige Streben auf ideale Ziele hin, die beste Verwirklichung dieser durch menschliche, fehlbare Wesen ist.
Protektiver Effekt von 6-Shogaol, Ellagsäure und Myrrhe auf die intestinale epitheliale Barriere
(2016)
Viele bioaktive Pflanzeninhaltsstoffe bzw. Pflanzenmetabolite besitzen antiinflammatorische Eigenschaften. Diese versprechen ein hohes Potential für den Einsatz in der Phytotherapie bzw. Prävention von chronisch-entzündlichen Darmerkrankungen (CED). Eine intestinale Barrieredysfunktion ist ein typisches Charakteristikum von CED Patienten, die dadurch an akuter Diarrhoe leiden.
In dieser Arbeit werden die Pflanzenkomponenten 6-Shogaol, Ellagsäure und Myrrhe an den intestinalen Kolonepithelzellmodellen HT-29/B6 und Caco-2 auf ihr Potential hin, die intestinale Barriere zu stärken bzw. eine Barrieredysfunktion zu verhindern, untersucht. Hauptschwerpunkt der Analysen ist die parazelluläre Barrierefunktion und die Regulation der dafür entscheidenden Proteinfamilie der Tight Junctions (TJs), der Claudine.
Die Barrierefunktion wird durch Messung des transepithelialen Widerstands (TER) und der Fluxmessung in der Ussing-Kammer bestimmt. Dazu werden die HT-29/B6- und Caco-2-Monolayer mit den Pflanzenkomponenten (6-Shogaol, Ellagsäure, Myrrhe), dem proinflammatorischen Zytokin TNF-α oder der Kombination von beiden Subsztanzen für 24 oder 48 h behandelt. Außerdem wurden zur weiteren Charakterisierung die Expression sowie die Lokalisation der für die parazelluläre Barriere relevanten Claudine, die TJ-Ultrastruktur und verschiedene Signalwege analysiert.
In Caco-2-Monolayern führten Ellagsäure und Myrrhe, nicht aber 6-Shogaol, allein zu einem TER-Anstieg bedingt durch eine verringerte Permeabilität für Natriumionen. Myrrhe verminderte die Expression des Kationenkanal-bildenden TJ-Proteins Claudin-2 über die Inhibierung des PI3K/Akt-Signalweges, während Ellagsäure die Expression der TJ-Proteine Claudin-4 und -7 reduzierte. Alle Pflanzenkomponenten schützten in den Caco-2-Zellen vor einer TNF-α-induzierten Barrieredysfunktion.
An den HT-29/B6-Monolayern änderte keine der Pflanzenkomponenten allein die Barrierefunktion. Die HT-29/B6-Zellen reagierten auf TNF-α mit einer deutlichen Verminderung des TER und einer erhöhten Fluoreszein-Permeabilität. Die TER-Abnahme war durch eine PI3K/Akt-vermittelte gesteigerte Claudin-2-Expression sowie eine NFκB-vermittelte Umverteilung des abdichtenden TJ-Proteins Claudin-1 gekennzeichnet. 6-Shogaol konnte den TER-Abfall partiell hemmen sowie die PI3K/Akt-induzierte Claudin-2-Expression und die NFκB-bedingte Claudin-1-Umverteilung verhindern. Ebenso inhibierte Myrrhe, nicht aber Ellagsäure, den TNF-α-induzierten TER-Abfall. Dabei konnte Myrrhe zwar den Claudin-2-Expressionsanstieg und die Claudin-1-Umverteilung unterbinden, jedoch weder die NFκB- noch die PI3K/Akt-Aktivierung hemmen. Diese Arbeit zeigt, dass auch STAT6 an dem Claudin-2-Expressionsanstieg durch
TNF-α in HT-29/B6-Zellen beteiligt ist. So wurde durch Myrrhe die TNF-α-induzierte Phosphorylierung von STAT6 und die erhöhte Claudin-2-Expression inhibiert.
Die Ergebnisse deuten darauf hin, dass die Pflanzenkomponenten 6-Shogaol, Ellagsäure und Myrrhe mit unterschiedlichen Mechanismen stärkend auf die Barriere einwirken. Zur Behandlung von intestinalen Erkrankungen mit Barrieredysfunktion könnten daher Kombinationspräparate aus verschiedenen Pflanzen effektiver sein als Monopräparate.
Gene expression describes the process of making functional gene products (e.g. proteins or special RNAs) from instructions encoded in the genetic information (e.g. DNA). This process is heavily regulated, allowing cells to produce the appropriate gene products necessary for cell survival, adapting production as necessary for different cell environments. Gene expression is subject to regulation at several levels, including transcription, mRNA degradation, translation and protein degradation. When intact, this system maintains cell homeostasis, keeping the cell alive and adaptable to different environments. Malfunction in the system can result in disease states and cell death. In this dissertation, we explore several aspects of gene expression control by analyzing data from biological experiments. Most of the work following uses a common mathematical model framework based on Markov chain models to test hypotheses, predict system dynamics or elucidate network topology. Our work lies in the intersection between mathematics and biology and showcases the power of statistical data analysis and math modeling for validation and discovery of biological phenomena.
Das Ziel der Doktorarbeit war die Entwicklung und Evaluation eines skillsbasierten primären Präventionsprogramms (Mainzer Schultraining zur Essstörungsprävention (MaiStep)) für partielle und manifeste Essstörungen. Dabei wurde die Wirksamkeit durch einen primären (Reduktion vorhandener Essstörungssymptome) und sekundären (assoziierte Psychopathologie) Zielparameter 3 und 12 Monate nach Durchführung des Trainings überprüft. Innerhalb der randomisiert kontrollierten Studie gab es zwei Interventionsgruppe und eine aktive Kontrollgruppe. 1.654 Jugendliche (weiblich/männlich: 781/873; mittleres Alter: 13.1±0.7; BMI: 20.0±3.5) konnten für die Studie, an zufällig ausgewählten Schulen in Rheinland-Pfalz, rekrutiert werden. Die Entwicklung des Präventionsprogramms basiert auf einem systematischen Literaturreview von 63 wissenschaftlichen Studien über die Prävention von Essstörungen im Kindes- und Jugendalter. Eine Interventionsgruppe wurde durch Psychologinnen/Psychologen und eine zweite durch Lehrkräfte angeleitet. Das in der aktiven Kontrollgruppe durchgeführte Sucht- bzw. Stresspräventionsprogramm wurde durch Lehrkräfte geleitet. MaiStep zeigte zur 3-Monatskatamnese keine signifikanten Effekte im Vergleich zur aktiven Kontrollgruppe. Allerdings zeigten sich nach 12 Monaten multiple signifikante Effekte zwischen den Interventions- und der aktiven Kontrollgruppe. Im Rahmen der Analyse des primären Parameters wurden in den Interventionsgruppen signifikant weniger Jugendliche mit einer partiellen Anorexia nervosa (CHI²(2) = 8.74, p = .01**) und/oder partiellen Bulimia nervosa (CHI²(2) = 7.25, p = .02*) gefunden. Im Rahmen der sekundären Zielparameter zeigten sich signifikante Veränderungen in Subskalen des Eating Disorder Inventory (EDI-2) Schlankheitsstreben (F (2, 355) = 3.94, p = .02*) und Perfektionismus (F (2, 355) = 4.19, p = .01**) sowie dem Body Image Avoidance Questionnaire (BIAQ) (F (2, 525) = 18.79, p = .01**) zwischen den Interventions- und der aktiven Kontrollgruppe. MaiStep kann somit als erfolgreiches Programm zur Reduktion von partiellen Essstörungen für die Altersgruppe der 13- 15-jährigen bezeichnet werden. Trotz unterschiedlicher Wirkmechanismen zeigten sich die Lehrkräfte im Vergleich zu den Psychologinnen/Psychologen ebenso erfolgreich in der Durchführung.
Trial registration MaiStep is registered at the German Clinical Trials Register (DRKS00005050).
Das Wissen um die lokale Struktur von Seltenen Erden Elementen (SEE) in silikatischen und aluminosilikatischen Schmelzen ist von fundamentalem Interesse für die Geochemie der magmatischen Prozesse, speziell wenn es um ein umfassendes Verständnis der Verteilungsprozesse von SEE in magmatischen Systemen geht. Es ist allgemein akzeptiert, dass die SEE-Verteilungsprozesse von Temperatur, Druck, Sauerstofffugazität (im Fall von polyvalenten Kationen) und der Kristallchemie kontrolliert werden. Allerdings ist wenig über den Einfluss der Schmelzzusammensetzung selbst bekannt. Ziel dieser Arbeit ist, eine Beziehung zwischen der Variation der SEE-Verteilung mit der Schmelzzusammensetzung und der Koordinationschemie dieser SEE in der Schmelze zu schaffen.
Dazu wurden Schmelzzusammensetzungen von Prowatke und Klemme (2005), welche eine deutliche Änderung der Verteilungskoeffizienten zwischen Titanit und Schmelze ausschließlich als Funktion der Schmelzzusammensetzung zeigen, sowie haplogranitische bzw. haplobasaltische Schmelzzusammensetzungen als Vertreter magmatischer Systeme mit La, Gd, Yb und Y dotiert und als Glas synthetisiert. Die Schmelzen variierten systematisch im Aluminiumsättigungsindex (ASI), welcher bei den Prowatke und Klemme (2005) Zusammensetzungen einen Bereich von 0.115 bis 0.768, bei den haplogranitischen Zusammensetzungen einen Bereich von 0.935 bis 1.785 und bei den haplobasaltischen Zusammensetzungen einen Bereich von 0.368 bis 1.010 abdeckt. Zusätzlich wurden die haplogranitischen Zusammensetzungen mit 4 % H2O synthetisiert, um den Einfluss von Wasser auf die lokale Umgebung von SEE zu studieren. Um Informationen über die lokalen Struktur von Gd, Yb und Y zu erhalten wurde die Röntgenabsorptionsspektroskopie angewendet. Dabei liefert die Untersuchung der Feinstruktur mittels der EXAFS-Spektroskopie (engl. Extended X-Ray Absorption Fine Structure) quantitative Informationen über die lokale Umgebung, während RIXS (engl. resonant inelastic X-ray scattering), sowie die daraus extrahierte hoch aufgelöste Nahkantenstruktur, XANES (engl. X-ray absorption near edge structure) qualitative Informationen über mögliche Koordinationsänderungen von La, Gd und Yb in den Gläsern liefert. Um mögliche Unterschiede der lokalen Struktur oberhalb der Glastransformationstemperatur (TG) zur Raumtemperatur zu untersuchen, wurden exemplarisch Hochtemperatur Y-EXAFS Untersuchungen durchgeführt.
Für die Auswertung der EXAFS-Messungen wurde ein neu eingeführter Histogramm-Fit verwendet, der auch nicht-symmetrische bzw. nichtgaußförmige Paarverteilungsfunktionen beschreiben kann, wie sie bei einem hohen Grad der Polymerisierung bzw. bei hohen Temperaturen auftreten können. Die Y-EXAFS-Spektren für die Prowatke und Klemme (2005) Zusammensetzungen zeigen mit Zunahme des ASI, eine Zunahme der Asymmetrie und Breite der Y-O Paarverteilungsfunktion, welche sich in sich in der Änderung der Koordinationszahl von 6 nach 8 und einer Zunahme des Y-O Abstand um 0.13Å manifestiert. Ein ähnlicher Trend lässt sich auch für die Gd- und Yb-EXAFS-Spektren beobachten. Die hoch aufgelösten XANESSpektren für La, Gd und Yb zeigen, dass sich die strukturellen Unterschiede zumindest halb-quantitativ bestimmen lassen. Dies gilt insbesondere für Änderungen im mittleren Abstand zu den Sauerstoffatomen. Im Vergleich zur EXAFS-Spektroskopie liefert XANES jedoch keine Informationen über die Form und Breite von Paarverteilungsfunktionen. Die Hochtemperatur EXAFS-Untersuchungen von Y zeigen Änderungen der lokalen Struktur oberhalb der Glasübergangstemperatur an, welche sich vordergründig auf eine thermisch induzierte Erhöhung des mittleren Y-O Abstandes zurückführen lassen. Allerdings zeigt ein Vergleich der Y-O Abstände für Zusammensetzungen mit einem ASI von 0.115 bzw. 0.755, ermittelt bei Raumtemperatur und TG, dass der im Glas beobachtete strukturelle Unterschied entlang der Zusammensetzungsserie in der Schmelze noch stärker ausfallen kann, als bisher für die Gläser angenommen wurde.
Die direkte Korrelation der Verteilungsdaten von Prowatke und Klemme (2005) mit den strukturellen Änderungen der Schmelzen offenbart für Y eine lineare Korrelation, wohingegen Yb und Gd eine nicht lineare Beziehung zeigen. Aufgrund seines Ionenradius und seiner Ladung wird das 6-fach koordinierte SEE in den niedriger polymerisierten Schmelzen bevorzugt durch nicht-brückenbildende Sauerstoffatome koordiniert, um stabile Konfigurationen zu bilden. In den höher polymerisierten Schmelzen mit ASI-Werten in der Nähe von 1 ist 6-fache Koordination nicht möglich, da fast nur noch brückenbildende Sauerstoffatome zur Verfügung stehen. Die Überbindung von brückenbildenden Sauerstoffatomen um das SEE wird durch Erhöhung der Koordinationszahl und des mittleren SEE-O Abstandes ausgeglichen. Dies bedeutet eine energetisch günstigere Konfiguration in den stärker depolymerisierten Zusammensetzungen, aus welcher die beobachtete Variation des Verteilungskoeffizienten resultiert, welcher sich jedoch für jedes Element stark unterscheidet. Für die haplogranitischen und haplobasaltischen Zusammensetzungen wurde mit Zunahme der Polymerisierung auch eine Zunahme der Koordinationszahl und des durchschnittlichen Bindungsabstands, einhergehend mit der Zunahme der Schiefe und der Asymmetrie der Paarverteilungsfunktion, beobachtet. Dies impliziert, dass das jeweilige SEE mit Zunahme der Polymerisierung auch inkompatibler in diesen Zusammensetzungen wird. Weiterhin zeigt die Zugabe von Wasser, dass die Schmelzen depolymerisieren, was in einer symmetrischeren Paarverteilungsfunktion resultiert, wodurch die Kompatibilität wieder zunimmt.
Zusammenfassend zeigt sich, dass die Veränderungen der Schmelzzusammensetzungen in einer Änderung der Polymerisierung der Schmelzen resultieren, die dann einen signifikanten Einfluss auf die lokale Umgebung der SEE hat. Die strukturellen Änderungen lassen sich direkt mit Verteilungsdaten korrelieren, die Trends unterscheiden sich aber stark zwischen leichten, mittleren und schweren SEE. Allerdings konnte diese Studie zeigen, in welcher Größenordnung die Änderungen liegen müssen, um einen signifikanten Einfluss auf den Verteilungskoeffizenten zu haben. Weiterhin zeigt sich, dass der Einfluss der Schmelzzusammensetzung auf die Verteilung der Spurenelemente mit Zunahme der Polymerisierung steigt und daher nicht vernachlässigt werden darf.
In complement to the well-established zwitterionic monomers 3-((2-(methacryloyloxy)ethyl)dimethylammonio)propane-1-sulfonate (“SPE”) and 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (“SPP”), the closely related sulfobetaine monomers were synthesized and polymerized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar mass were characterized with respect to their solubility in water, deuterated water, and aqueous salt solutions. These poly(sulfobetaine)s show thermoresponsive behavior in water, exhibiting upper critical solution temperatures (UCST). Phase transition temperatures depend notably on the molar mass and polymer concentration, and are much higher in D2O than in H2O. Also, the phase transition temperatures are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed structure of the zwitterionic side chain, on the other hand. For the polymers with the same zwitterionic side chain, it is found that methacrylamide-based poly(sulfobetaine)s exhibit higher UCST-type transition temperatures than their methacrylate analogs. The extension of the distance between polymerizable unit and zwitterionic groups from 2 to 3 methylene units decreases the UCST-type transition temperatures. Poly(sulfobetaine)s derived from aliphatic esters show higher UCST-type transition temperatures than their analogs featuring cyclic ammonium cations. The UCST-type transition temperatures increase markedly with spacer length separating the cationic and anionic moieties from 3 to 4 methylene units. Thus, apparently small variations of their chemical structure strongly affect the phase behavior of the polyzwitterions in specific aqueous environments.
Water-soluble block copolymers were prepared from the zwitterionic monomers and the non-ionic monomer N-isopropylmethacrylamide (“NIPMAM”) by the RAFT polymerization. Such block copolymers with two hydrophilic blocks exhibit twofold thermoresponsive behavior in water. The poly(sulfobetaine) block shows an UCST, whereas the poly(NIPMAM) block exhibits a lower critical solution temperature (LCST). This constellation induces a structure inversion of the solvophobic aggregate, called “schizophrenic micelle”. Depending on the relative positions of the two different phase transitions, the block copolymer passes through a molecularly dissolved or an insoluble intermediate regime, which can be modulated by the polymer concentration or by the addition of salt. Whereas, at low temperature, the poly(sulfobetaine) block forms polar aggregates that are kept in solution by the poly(NIPMAM) block, at high temperature, the poly(NIPMAM) block forms hydrophobic aggregates that are kept in solution by the poly(sulfobetaine) block. Thus, aggregates can be prepared in water, which switch reversibly their “inside” to the “outside”, and vice versa.
In this thesis we use integral-field spectroscopy to detect and understand of Lyman α (Lyα) emission from high-redshift galaxies.
Intrinsically the Lyα emission at λ = 1216 Å is the strongest recombination line from galaxies. It arises from the 2p → 1s transition in hydrogen. In star-forming galaxies the line is powered by ionisation of the interstellar gas by hot O- and B- stars. Galaxies with star-formation rates of 1 - 10 Msol/year are expected to have Lyα luminosities of 42 dex - 43 dex (erg/s), corresponding to fluxes ~ -17 dex - -18 dex (erg/s/cm²) at redshifts z~3, where Lyα is easily accessible with ground-based telescopes. However, star-forming galaxies do not show these expected Lyα fluxes. Primarily this is a consequence of the high-absorption cross-section of neutral hydrogen for Lyα photons σ ~ -14 dex (cm²). Therefore, in typical interstellar environments Lyα photons have to undergo a complex radiative transfer. The exact conditions under which Lyα photons can escape a galaxy are poorly understood.
Here we present results from three observational projects. In Chapter 2, we show integral field spectroscopic observations of 14 nearby star-forming galaxies in Balmer α radiation (Hα, λ = 6562.8 Å). These observations were obtained with the Potsdam Multi Aperture Spectrophotometer at the Calar-Alto 3.5m Telescope}. Hα directly traces the intrinsic Lyα radiation field. We present Hα velocity fields and velocity dispersion maps spatially registered onto Hubble Space Telescope Lyα and Hα images. From our observations, we conjecture a causal connection between spatially resolved Hα kinematics and Lyα photometry for individual galaxies. Statistically, we find that dispersion-dominated galaxies are more likely to emit Lyα photons than galaxies where ordered gas-motions dominate. This result indicates that turbulence in actively star-forming systems favours an escape of Lyα radiation.
Not only massive stars can power Lyα radiation, but also non-thermal emission from an accreting super-massive black hole in the galaxy centre. If a galaxy harbours such an active galactic nucleus, the rate of hydrogen-ionising photons can be more than 1000 times higher than that of a typical star-forming galaxy. This radiation can potentially ionise large regions well outside the main stellar body of galaxies. Therefore, it is expected that the neutral hydrogen from these circum-galactic regions shines fluorescently in Lyα. Circum-galactic gas plays a crucial role in galaxy formation. It may act as a reservoir for fuelling star formation, and it is also subject to feedback processes that expel galactic material. If Lyα emission from this circum-galactic medium (CGM) was detected, these important processes could be studied in-situ around high-z galaxies. In Chapter 3, we show observations of five radio-quiet quasars with PMAS to search for possible extended CGM emission in the Lyα line. However, in four of the five objects, we find no significant traces of this emission. In the fifth object, there is evidence for a weak and spatially quite compact Lyα excess at several kpc outside the nucleus. The faintness of these structures is consistent with the idea that radio-quiet quasars typically reside in dark matter haloes of modest masses. While we were not able to detect Lyα CGM emission, our upper limits provide constraints for the new generation of IFS instruments at 8--10m class telescopes.
The Multi Unit Spectroscopic Explorer (MUSE) at ESOs Very Large Telescopeis such an unique instrument. One of the main motivating drivers in its construction was the use as a survey instrument for Lyα emitting galaxies at high-z. Currently, we are conducting such a survey that will cover a total area of ~100 square arcminutes with 1 hour exposures for each 1 square arcminute MUSE pointing. As a first result from this survey we present in Chapter 5 a catalogue of 831 emission-line selected galaxies from a 22.2 square arcminute region in the Chandra Deep Field South. In order to construct the catalogue, we developed and implemented a novel source detection algorithm -- LSDCat -- based on matched filtering for line emission in 3D spectroscopic datasets (Chapter 4). Our catalogue contains 237 Lyα emitting galaxies in the redshift range 3 ≲ z ≲ 6. Only four of those previously had spectroscopic redshifts in the literature. We conclude this thesis with an outlook on the construction of a Lyα luminosity function based on this unique sample (Chapter 6).
In order to evade detection by network-traffic analysis, a growing proportion of malware uses the encrypted HTTPS protocol. We explore the problem of detecting malware on client computers based on HTTPS traffic analysis. In this setting, malware has to be detected based on the host IP address, ports, timestamp, and data volume information of TCP/IP packets that are sent and received by all the applications on the client. We develop a scalable protocol that allows us to collect network flows of known malicious and benign applications as training data and derive a malware-detection method based on a neural networks and sequence classification. We study the method's ability to detect known and new, unknown malware in a large-scale empirical study.
Meter and syntax have overlapping elements in music and speech domains, and individual differences have been documented in both meter perception and syntactic comprehension paradigms. Previous evidence insinuated but never fully explored the relationship that metrical structure has to syntactic comprehension, the comparability of these processes across music and language domains, and the respective role of individual differences. This dissertation aimed to investigate neurocognitive entrainment to meter in music and language, the impact that neurocognitive entrainment had on syntactic comprehension, and whether individual differences in musical expertise, temporal perception and working memory played a role during these processes.
A theoretical framework was developed, which linked neural entrainment, cognitive entrainment, and syntactic comprehension while detailing previously documented effects of individual differences on meter perception and syntactic comprehension. The framework was developed in both music and language domains and was tested using behavioral and EEG methods across three studies (seven experiments). In order to satisfy empirical evaluation of neurocognitive entrainment and syntactic aspects of the framework, original melodies and sentences were composed. Each item had four permutations: regular and irregular metricality, based on the hierarchical organization of strong and weak notes and syllables, and preferred and non-preferred syntax, based on structurally alternate endings. The framework predicted — for both music and language domains — greater neurocognitive entrainment in regular compared to irregular metricality conditions, and accordingly, better syntactic integration in regular compared to irregular metricality conditions. Individual differences among participants were expected for both entrainment and syntactic processes.
Altogether, the dissertation was able to support a holistic account of neurocognitive entrainment to musical meter and its subsequent influence on syntactic integration of melodies, with musician participants. The theoretical predictions were not upheld in the language domain with musician participants, but initial behavioral evidence in combination with previous EEG evidence suggest that perhaps non-musician language EEG data would support the framework’s predictions. Musicians’ deviation from hypothesized results in the language domain were suspected to reflect heightened perception of acoustic features stemming from musical training, which caused current ‘overly’ regular stimuli to distract the cognitive system. The individual-differences approach was vindicated by the surfacing of two factors scores, Verbal Working Memory and Time and Pitch Discrimination, which in turn correlated with multiple experimental data across the three studies.
Over the last decades, the world’s population has been growing at a faster rate, resulting in increased urbanisation, especially in developing countries. More than half of the global population currently lives in urbanised areas with an increasing tendency. The growth of cities results in a significant loss of vegetation cover, soil compaction and sealing of the soil surface which in turn results in high surface runoff during high-intensity storms and causes the problem of accelerated soil water erosion on streets and building grounds. Accelerated soil water erosion is a serious environmental problem in cities as it gives rise to the contamination of aquatic bodies, reduction of ground water recharge and increase in land degradation, and also results in damages to urban infrastructures, including drainage systems, houses and roads. Understanding the problem of water erosion in urban settings is essential for the sustainable planning and management of cities prone to water erosion. However, in spite of the vast existence of scientific literature on water erosion in rural regions, a concrete understanding of the underlying dynamics of urban erosion still remains inadequate for the urban dryland environments.
This study aimed at assessing water erosion and the associated socio-environmental determinants in a typical dryland urban area and used the city of Windhoek, Namibia, as a case study. The study used a multidisciplinary approach to assess the problem of water erosion. This included an in depth literature review on current research approaches and challenges of urban erosion, a field survey method for the quantification of the spatial extent of urban erosion in the dryland city of Windhoek, and face to face interviews by using semi-structured questionnaires to analyse the perceptions of stakeholders on urban erosion.
The review revealed that around 64% of the literatures reviewed were conducted in the developed world, and very few researches were carried out in regions with extreme climate, including dryland regions. Furthermore, the applied methods for erosion quantification and monitoring are not inclusive of urban typical features and they are not specific for urban areas. The reviewed literature also lacked aspects aimed at addressing the issues of climate change and policies regarding erosion in cities. In a field study, the spatial extent and severity of an urban dryland city, Windhoek, was quantified and the results show that nearly 56% of the city is affected by water erosion showing signs of accelerated erosion in the form of rills and gullies, which occurred mainly in the underdeveloped, informal and semi-formal areas of the city. Factors influencing the extent of erosion in Windhoek included vegetation cover and type, socio-urban factors and to a lesser extent slope estimates. A comparison of an interpolated field survey erosion map with a conventional erosion assessment tool (the Universal Soil Loss Equation) depicted a large deviation in spatial patterns, which underlines the inappropriateness of traditional non-urban erosion tools to urban settings and emphasises the need to develop new erosion assessment and management methods for urban environments. It was concluded that measures for controlling water erosion in the city need to be site-specific as the extent of erosion varied largely across the city.
The study also analysed the perceptions and understanding of stakeholders of urban water erosion in Windhoek, by interviewing 41 stakeholders using semi-structured questionnaires. The analysis addressed their understanding of water erosion dynamics, their perceptions with regards to the causes and the seriousness of erosion damages, and their attitudes towards the responsibilities for urban erosion. The results indicated that there is less awareness of the process as a phenomenon, instead there is more awareness of erosion damages and the factors contributing to the damages. About 69% of the stakeholders considered erosion damages to be ranging from moderate to very serious. However, there were notable disparities between the private householders and public authority groups. The study further found that the stakeholders have no clear understanding of their responsibilities towards the management of the control measures and payment for the damages. The private householders and local authority sectors pointed fingers at each other for the responsibilities for erosion damage payments and for putting up prevention measures. The reluctance to take responsibility could create a predicament for areas affected, specifically in the informal settlements where land management is not carried out by the local authority and land is not owned by the occupants.
The study concluded that in order to combat urban erosion, it is crucial to understand diverse dynamics aggravating the process of urbanisation from different scales. Accordingly, the study suggests that there is an urgent need for the development of urban-specific approaches that aim at: (a) incorporating the diverse socio-economic-environmental aspects influencing erosion, (b) scientifically improving natural cycles that influence water storages and nutrients for plants in urbanised dryland areas in order to increase the amount of vegetation cover, (c) making use of high resolution satellite images to improve the adopted methods for assessing urban erosion, (d) developing water erosion policies, and (e) continuously monitoring the impact of erosion and the influencing processes from local, national and international levels.
In the interest of producing functional catalysts from sustainable building-blocks, 1, 3-dicarboxylate imidazolium salts derived from amino acids were successfully modified to be suitable as N-Heterocyclic carbene (NHC) ligands within metal complexes. Complexes of Ag(I), Pd(II), and Ir(I) were successfully produced using known procedures using ligands derived from glycine, alanine, β-alanine and phenylalanine. The complexes were characterized in solid state using X-Ray crystallography, which allowed for the steric and electronic comparison of these ligands to well-known NHC ligands within analogous metal complexes.
The palladium complexes were tested as catalysts for aqueous-phase Suzuki-Miyaura cross-coupling. Water-solubility could be induced via ester hydrolysis of the N-bound groups in the presence of base. The mono-NHC–Pd complexes were seen to be highly active in the coupling of aryl bromides with phenylboronic acid; the active catalyst of which was determined to be mostly Pd(0) nanoparticles. Kinetic studies determined that reaction proceeds quickly in the coupling of bromoacetophenone, for both pre-hydrolyzed and in-situ hydrolysis catalyst dissolution. The catalyst could also be recycled for an extra run by simply re-using the aqueous layer.
The imidazolium salts were also used to produce organosilica hybrid materials. This was attempted via two methods: by post-grafting onto a commercial organosilica, and co-condensation of the corresponding organosilane. The co-condensation technique harbours potential for the production of solid-support catalysts.
Since 1998, elite athletes’ sport injuries have been monitored in single sport event, which leads to the development of first comprehensive injury surveillance system in multi-sport Olympic Games in 2008. However, injury and illness occurred in training phases have not been systematically studied due to its multi-facets, potentially interactive risk related factors. The present thesis aim to address issues of feasibility of establishing a validated measure for injury/illness, training environment and psychosocial risk factors by creating the evaluation tool namely risk of injury questionnaire (Risk-IQ) for elite athletes, which based on IOC consensus statement 2009 recommended content of preparticipation evaluation(PPE) and periodic health exam (PHE).
A total of 335 top level athletes and a total of 88 medical care providers from Germany and Taiwan participated in tow “cross-sectional plus longitudinal” Risk-IQ and MCPQ surveys respectively. Four categories of injury/illness related risk factors questions were asked in Risk-IQ for athletes while injury risk and psychological related questions were asked in MCPQ for MCP cohorts. Answers were quantified scales wise/subscales wise before analyzed with other factors/scales. In addition, adapted variables such as sport format were introduced for difference task of analysis.
Validated with 2-wyas translation and test-retest reliabilities, the Risk-IQ was proved to be in good standard which were further confirmed by analyzed results from official surveys in both Germany and Taiwan. The result of Risk-IQ revealed that elite athletes’ accumulated total injuries, in general, were multi-factor dependent; influencing factors including but not limited to background experiences, medical history, PHE and PPE medical resources as well as stress from life events. Injuries of different body parts were sport format and location specific. Additionally, medical support of PPE and PHE indicated significant difference between German and Taiwan.
The result of the present thesis confirmed that it is feasible to construct a comprehensive evalua-tion instrument for heterogeneous elite athletes cohorts’ risk factor analysis for injury/illness oc-curred during their non-competition periods. In average and with many moderators involved, Ger-man elite athletes have superior medical care support yet suffered more severe injuries than Tai-wanese counterparts. Opinions of injury related psychological issues reflected differently on vari-ous MCP groups irrespective of different nationalities. In general, influencing factors and interac-tions existed among relevant factors in both studies which implied further investigation with multiple regression analysis is needed for better understanding.
Ionothermal carbon materials
(2016)
Alternative concepts for energy storage and conversion have to be developed, optimized and employed to fulfill the dream of a fossil-independent energy economy. Porous carbon materials play a major role in many energy-related devices. Among different characteristics, distinct porosity features, e.g., specific surface area (SSA), total pore volume (TPV), and the pore size distribution (PSD), are important to maximize the performance in the final device. In order to approach the aim to synthesize carbon materials with tailor-made porosity in a sustainable fashion, the present thesis focused on biomass-derived precursors employing and developing the ionothermal carbonization.
During the ionothermal carbonization, a salt melt simultaneously serves as solvent and porogen. Typically, eutectic mixtures containing zinc chloride are employed as salt phase. The first topic of the present thesis addressed the possibility to precisely tailor the porosity of ionothermal carbon materials by an experimentally simple variation of the molar composition of the binary salt mixture. The developed pore tuning tool allowed the synthesis of glucose derived carbon materials with predictable SSAs in the range of ~ 900 to ~ 2100 m2 g-1. Moreover, the nucleobase adenine was employed as precursor introducing nitrogen functionalities in the final material. Thereby, the chemical properties of the carbon materials are varied leading to new application fields. Nitrogen doped carbons (NDCs) are able to catalyze the oxygen reduction reaction (ORR) which takes place on the cathodic site of a fuel cell. The herein developed porosity tailoring allowed the synthesis of adenine derived NDCs with outstanding SSAs of up to 2900 m2 g-1 and very large TPV of 5.19 cm3 g-1. Furthermore, the influence of the porosity on the ORR could be directly investigated enabling the precise optimization of the porosity characteristics of NDCs for this application. The second topic addressed the development of a new method to investigate the not-yet unraveled mechanism of the oxygen reduction reaction using a rotating disc electrode setup. The focus was put on noble-metal free catalysts. The results showed that the reaction pathway of the investigated catalysts is pH-dependent indicating different active species at different pH-values. The third topic addressed the expansion of the used salts for the ionothermal approach towards hydrated calcium and magnesium chloride. It was shown that hydrated salt phases allowed the introduction of a secondary templating effect which was connected to the coexistence of liquid and solid salt phases. The method enabled the synthesis of fibrous NDCs with SSAs of up to 2780 m2 g-1 and very large TPV of 3.86 cm3 g-1. Moreover, the concept of active site implementation by a facile low-temperature metalation employing the obtained NDCs as solid ligands could be shown for the first time in the context of ORR.
Overall, the thesis may pave the way towards highly porous carbon with tailor-made porosity materials prepared by an inexpensive and sustainable pathway, which can be applied in energy related field thereby supporting the needed expansion of the renewable energy sector.
Can the statistical properties of single-electron transfer events be correctly predicted within a common equilibrium ensemble description? This fundamental in nanoworld question of ergodic behavior is scrutinized within a very basic semi-classical curve-crossing problem. It is shown that in the limit of non-adiabatic electron transfer (weak tunneling) well-described by the Marcus–Levich–Dogonadze(MLD) rate the answer is yes. However, in the limit of the so-called solvent-controlled adiabatic electron transfer, a profound breaking of ergodicity occurs. Namely, a common description based on the ensemble reduced density matrix with an initial equilibrium distribution of the reaction coordinate is not able to reproduce the statistics of single-trajectory events in this seemingly classical regime. For sufficiently large activation barriers, the ensemble survival probability in a state remains nearly exponential with the inverse rate given by the sum of the adiabatic curve crossing (Kramers) time and the inverse MLD rate. In contrast, near to the adiabatic regime, the single-electron survival probability is clearly non-exponential, even though it possesses an exponential tail which agrees well with the ensemble description. Initially, it is well described by a Mittag-Leffler distribution with a fractional rate. Paradoxically, the mean transfer time in this classical on the ensemble level regime is well described by the inverse of the nonadiabatic quantum tunneling rate on a single particle level. An analytical theory is developed which perfectly agrees with stochastic simulations and explains our findings.
A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers’ precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.
Die Dissertation befasst sich mit der Organisation von humanitären Lufttransporten bei internationalen Katastrophen. Diese Flüge finden immer dann statt, wenn die eigene Hilfeleistungsfähigkeit der von Katastrophen betroffenen Regionen überfordert ist und Hilfe aus dem Ausland angefordert wird. Bei jedem der darauffolgenden Hilfseinsätze stehen Hilfsorganisationen und weitere mit der Katastrophenhilfe beteiligte Akteure erneut vor der Herausforderung, in kürzester Zeit eine logistische Kette aufzubauen, damit die Güter zum richtigen Zeitpunkt in der richtigen Menge am richtigen Ort eintreffen.
Humanitäre Lufttransporte werden in der Regel als Charterflüge organisiert und finden auf langen Strecken zu Zielen statt, die nicht selten abseits der hochfrequentierten Warenströme liegen. Am Markt ist das Angebot für derartige Transportdienstleistungen nicht gesichert verfügbar und unter Umständen müssen Hilfsorganisationen warten bis Kapazitäten mit geeigneten Flugzeugen zur Verfügung stehen. Auch qualitativ sind die Anforderungen von Hilfsorganisationen an die Hilfsgütertransporte höher als im regulären Linientransport.
Im Rahmen der Dissertation wird ein alternatives Organisationsmodell für die Beschaffung und den Betrieb sowie die Finanzierung von humanitären Lufttransporten aufgebaut. Dabei wird die gesicherte Verfügbarkeit von besonders flexibel einsetzbaren Flugzeugen in Betracht gezogen, mit deren Hilfe die Qualität und insbesondere die Planbarkeit der Hilfeleistung verbessert werden könnte.
Ein idealtypisches Modell wird hier durch die Kopplung der Kollektivgütertheorie, die der Finanzwissenschaft zuzuordnen ist, mit der Vertragstheorie als Bestandteil der Neuen Institutionenökonomik erarbeitet.
Empirische Beiträge zur Vertragstheorie bemängeln, dass es bei der Beschaffung von transaktionsspezifischen Investitionsgütern, wie etwa Flugzeugen mit besonderen Eigenschaften, aufgrund von Risiken und Umweltunsicherheiten zu ineffizienten Lösungen zwischen Vertragspartnern kommt. Die vorliegende Dissertation zeigt eine Möglichkeit auf, wie durch Aufbau einer gemeinsamen Informationsbasis ex-ante, also vor Vertragsschluss, Risiken und Umweltunsicherheiten reduziert werden können. Dies geschieht durch eine temporale Erweiterung eines empirischen Modells zur Bestimmung der Organisationsform bei transaktionsspezifischen Investitionsgütern aus der Regulierungsökonomik.
Die Arbeitet leistet darüber hinaus einen Beitrag zur Steigerung der Effizienz in der humanitären Logistik durch die fallspezifische Betrachtung von horizontalen Kooperationen und Professionalisierung der Hilfeleistung im Bereich der humanitären Luftfahrt.
It is commonly recognized that soil moisture exhibits spatial heterogeneities occurring in a wide range of scales. These heterogeneities are caused by different factors ranging from soil structure at the plot scale to land use at the landscape scale. There is an urgent need for effi-cient approaches to deal with soil moisture heterogeneity at large scales, where manage-ment decisions are usually made. The aim of this dissertation was to test innovative ap-proaches for making efficient use of standard soil hydrological data in order to assess seep-age rates and main controls on observed hydrological behavior, including the role of soil het-erogeneities.
As a first step, the applicability of a simplified Buckingham-Darcy method to estimate deep seepage fluxes from point information of soil moisture dynamics was assessed. This was done in a numerical experiment considering a broad range of soil textures and textural het-erogeneities. The method performed well for most soil texture classes. However, in pure sand where seepage fluxes were dominated by heterogeneous flow fields it turned out to be not applicable, because it simply neglects the effect of water flow heterogeneity. In this study a need for new efficient approaches to handle heterogeneities in one-dimensional water flux models was identified.
As a further step, an approach to turn the problem of soil moisture heterogeneity into a solu-tion was presented: Principal component analysis was applied to make use of the variability among soil moisture time series for analyzing apparently complex soil hydrological systems. It can be used for identifying the main controls on the hydrological behavior, quantifying their relevance, and describing their particular effects by functional averaged time series. The ap-proach was firstly tested with soil moisture time series simulated for different texture classes in homogeneous and heterogeneous model domains. Afterwards, it was applied to 57 mois-ture time series measured in a multifactorial long term field experiment in Northeast Germa-ny.
The dimensionality of both data sets was rather low, because more than 85 % of the total moisture variance could already be explained by the hydrological input signal and by signal transformation with soil depth. The perspective of signal transformation, i.e. analyzing how hydrological input signals (e.g., rainfall, snow melt) propagate through the vadose zone, turned out to be a valuable supplement to the common mass flux considerations. Neither different textures nor spatial heterogeneities affected the general kind of signal transfor-mation showing that complex spatial structures do not necessarily evoke a complex hydro-logical behavior. In case of the field measured data another 3.6% of the total variance was unambiguously explained by different cropping systems. Additionally, it was shown that dif-ferent soil tillage practices did not affect the soil moisture dynamics at all.
The presented approach does not require a priori assumptions about the nature of physical processes, and it is not restricted to specific scales. Thus, it opens various possibilities to in-corporate the key information from monitoring data sets into the modeling exercise and thereby reduce model uncertainties.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε ∼ 5 × 10−4 is calibrated by ultrafast X-ray diffraction.
Well-developed phonological awareness skills are a core prerequisite for early literacy development. Although effective phonological awareness training programs exist, children at risk often do not reach similar levels of phonological awareness after the intervention as children with normally developed skills. Based on theoretical considerations and first promising results the present study explores effects of an early musical training in combination with a conventional phonological training in children with weak phonological awareness skills. Using a quasi-experimental pretest-posttest control group design and measurements across a period of 2 years, we tested the effects of two interventions: a consecutive combination of a musical and a phonological training and a phonological training alone. The design made it possible to disentangle effects of the musical training alone as well the effects of its combination with the phonological training. The outcome measures of these groups were compared with the control group with multivariate analyses, controlling for a number of background variables. The sample included N = 424 German-speaking children aged 4–5 years at the beginning of the study. We found a positive relationship between musical abilities and phonological awareness. Yet, whereas the well-established phonological training produced the expected effects, adding a musical training did not contribute significantly to phonological awareness development. Training effects were partly dependent on the initial level of phonological awareness. Possible reasons for the lack of training effects in the musical part of the combination condition as well as practical implications for early literacy education are discussed.
www.BrAnD2. Wille.
(2016)
2014 fand der Potsdamer Lateintag zum 10. Mal statt. Das Jubiläum war ein angemessener Anlass, unser neues Projekt vorzustellen. Die Robert Bosch-Stiftung fördert wieder für drei Jahre die Zusammenarbeit der Klassischen Philologie der Universität Potsdam mit Schulen aus Brandenburg. Der Titel lautet: www.BrAnD2. Wille. Würde. Wissen. Zweites Brandenburger Antike-Denkwerk. Zur Auftaktveranstaltung zum Thema „Wille“ erschienen wieder über 500 Teilnehmerinnen und Teilnehmer. Der Band versammelt einen Projektbericht, die Vorträge von Frau Prof. Dr. Christiane Kunst und Herrn Prof. Dr. Christoph Horn sowie eine Auswahl an Materialen der betreuenden Studierenden.
Software-Fehlerinjektion
(2016)
Fehlerinjektion ist ein essentielles Werkzeug, um die Fehlertoleranz komplexer Softwaresysteme experimentell zu evaluieren.
Wir berichten über das Seminar zum Thema Software-Fehlerinjektion, das am Fachgebiet für Betriebssysteme und Middleware am Hasso-Plattner-Institut der Universität Potsdam im Sommersemester 2015 stattfand.
In dem Seminar ging es darum, verschiedene Fehlerinjektionsansätze und -werkzeuge anzuwenden und hinsichtlich ihrer Anwendbarkeit in verschiedenen Szenarien zu bewerten.
In diesem Bericht werden die studierten Ansätze vorgestellt und verglichen.
Widespread landscape changes are presently observed in the Arctic and are most likely to
accelerate in the future, in particular in permafrost regions which are sensitive to climate warming. To assess current and future developments, it is crucial to understand past
environmental dynamics in these landscapes. Causes and interactions of environmental variability can hardly be resolved by instrumental records covering modern time scales. However, long-term
environmental variability is recorded in paleoenvironmental archives. Lake sediments are important archives that allow reconstruction of local limnogeological processes as well as past environmental changes driven directly or indirectly by climate dynamics. This study aims at
reconstructing Late Quaternary permafrost and thermokarst dynamics in central-eastern Beringia,
the terrestrial land mass connecting Eurasia and North America during glacial sea-level low stands. In order to investigate development, processes and influence of thermokarst dynamics, several sediment cores from extant lakes and drained lake basins were analyzed to answer the
following research questions:
1. When did permafrost degradation and thermokarst lake development take place and what were enhancing and inhibiting environmental factors?
2. What are the dominant processes during thermokarst lake development and how are
they reflected in proxy records?
3. How did, and still do, thermokarst dynamics contribute to the inventory and properties of organic matter in sediments and the carbon cycle?
Methods applied in this study are based upon a multi-proxy approach combining
sedimentological, geochemical, geochronological, and micropaleontological analyses, as well as
analyses of stable isotopes and hydrochemistry of pore-water and ice. Modern field observations of water quality and basin morphometrics complete the environmental investigations.
The investigated sediment cores reveal permafrost degradation and thermokarst dynamics on different time scales. The analysis of a sediment core from GG basin on the northern Seward
Peninsula (Alaska) shows prevalent terrestrial accumulation of yedoma throughout the Early to
Mid Wisconsin with intermediate wet conditions at around 44.5 to 41.5 ka BP. This first wetland
development was terminated by the accumulation of a 1-meter-thick airfall tephra most likely originating from the South Killeak Maar eruption at 42 ka BP. A depositional hiatus between 22.5 and 0.23 ka BP may indicate thermokarst lake formation in the surrounding of the site which forms a yedoma upland till today. The thermokarst lake forming GG basin initiated 230 ± 30 cal a
BP and drained in Spring 2005 AD. Four years after drainage the lake talik was still unfrozen below 268 cm depth.
A permafrost core from Mama Rhonda basin on the northern Seward Peninsula preserved a
full lacustrine record including several lake phases. The first lake generation developed at 11.8 cal ka BP during the Lateglacial-Early Holocene transition; its old basin (Grandma Rhonda) is still partially preserved at the southern margin of the study basin. Around 9.0 cal ka BP a shallow and more dynamic thermokarst lake developed with actively eroding shorelines and potentially intermediate shallow water or wetland phases (Mama Rhonda). Mama Rhonda lake drainage at 1.1 cal ka BP was followed by gradual accumulation of terrestrial peat and top-down refreezing of the lake talik. A significant lower organic carbon content was measured in Grandma Rhonda deposits (mean TOC of 2.5 wt%) than in Mama Rhonda deposits (mean TOC of 7.9 wt%) highlighting the impact of thermokarst dynamics on biogeochemical cycling in different lake generations by thawing and mobilization of organic carbon into the lake system.
Proximal and distal sediment cores from Peatball Lake on the Arctic Coastal Plain of Alaska revealed young thermokarst dynamics since about 1,400 years along a depositional gradient based on reconstructions from shoreline expansion rates and absolute dating results. After its initiation as a remnant pond of a previous drained lake basin, a rapidly deepening lake with increasing oxygenation of the water column is evident from laminated sediments, and higher Fe/Ti and Fe/S ratios in the sediment. The sediment record archived characterizing shifts in depositional regimes and sediment sources from upland deposits and re-deposited sediments from drained thaw lake basins depending on the gradually changing shoreline configuration. These changes are evident from alternating organic inputs into the lake system which highlights the potential for thermokarst lakes to recycle old carbon from degrading permafrost deposits of its catchment.
The lake sediment record from Herschel Island in the Yukon (Canada) covers the full Holocene period. After its initiation as a thermokarst lake at 11.7 cal ka BP and intense thermokarst activity until 10.0 cal ka BP, the steady sedimentation was interrupted by a depositional hiatus at 1.6 cal ka BP which likely resulted from lake drainage or allochthonous slumping due to collapsing shore lines. The specific setting of the lake on a push moraine composed of marine deposits is reflected in the sedimentary record. Freshening of the maturing lake is indicated by decreasing electrical conductivity in pore-water. Alternation of marine to freshwater ostracods and foraminifera confirms decreasing salinity as well but also reflects episodical re-deposition of allochthonous marine sediments.
Based on permafrost and lacustrine sediment records, this thesis shows examples of the Late Quaternary evolution of typical Arctic permafrost landscapes in central-eastern Beringia and the complex interaction of local disturbance processes, regional environmental dynamics and global climate patterns. This study confirms that thermokarst lakes are important agents of organic matter recycling in complex and continuously changing landscapes.
The ever-increasing fat content in Western diet, combined with decreased levels of physical activity, greatly enhance the incidence of metabolic-related diseases. Cancer cachexia (CC) and Metabolic syndrome (MetS) are both multifactorial highly complex metabolism related syndromes, whose etiology is not fully understood, as the mechanisms underlying their development are not completely unveiled. Nevertheless, despite being considered “opposite sides”, MetS and CC share several common issues such as insulin resistance and low-grade inflammation. In these scenarios, tissue macrophages act as key players, due to their capacity to produce and release inflammatory mediators. One of the main features of MetS is hyperinsulinemia, which is generally associated with an attempt of the β-cell to compensate for diminished insulin sensitivity (insulin resistance). There is growing evidence that hyperinsulinemia per se may contribute to the development of insulin resistance, through the establishment of low grade inflammation in insulin responsive tissues, especially in the liver (as insulin is secreted by the pancreas into the portal circulation). The hypothesis of the present study was that insulin may itself provoke an inflammatory response culminating in diminished hepatic insulin sensitivity. To address this premise, firstly, human cell line U937 differentiated macrophages were exposed to insulin, LPS and PGE2. In these cells, insulin significantly augmented the gene expression of the pro-inflammatory mediators IL-1β, IL-8, CCL2, Oncostatin M (OSM) and microsomal prostaglandin E2 synthase (mPGES1), and of the anti-inflammatory mediator IL-10. Moreover, the synergism between insulin and LPS enhanced the induction provoked by LPS in IL-1β, IL-8, IL-6, CCL2 and TNF-α gene. When combined with PGE2, insulin enhanced the induction provoked by PGE2 in IL-1β, mPGES1 and COX2, and attenuated the inhibition induced by PGE2 in CCL2 and TNF-α gene expression contributing to an enhanced inflammatory response by both mechanisms. Supernatants of insulin-treated U937 macrophages reduced the insulin-dependent induction of glucokinase in hepatocytes by 50%. Cytokines contained in the supernatant of insulin-treated U937 macrophages also activated hepatocytes ERK1/2, resulting in inhibitory serine phosphorylation of the insulin receptor substrate. Additionally, the transcription factor STAT3 was activated by phosphorylation resulting in the induction of SOCS3, which is capable of interrupting the insulin receptor signal chain. MicroRNAs, non-coding RNAs linked to protein expression regulation, nowadays recognized as active players in the generation of several inflammatory disorders such as cancer and type II diabetes are also of interest. Considering that in cancer cachexia, patients are highly affected by insulin resistance and inflammation, control, non-cachectic and cachectic cancer patients were selected and the respective circulating levels of pro-inflammatory mediators and microRNA-21-5p, a posttranscriptional regulator of STAT3 expression, assessed and correlated. Cachectic patients circulating cytokines IL-6 and IL-8 levels were significantly higher than those of non-cachectic and controls, and the expression of microRNA-21-5p was significantly lower. Additionally, microRNA-21-5p reduced expression correlated negatively with IL-6 plasma levels. These results indicate that hyperinsulinemia per se might contribute to the low grade inflammation prevailing in MetS patients and thereby promote the development
of insulin resistance particularly in the liver. Diminished MicroRNA-21-5p expression may enhance inflammation and STAT3 expression in cachectic patients, contributing to the development of insulin resistance.
BACKGROUND: The etiology of low back pain (LBP), one of the most prevalent and costly diseases of our time, is accepted to be multi-causal, placing functional factors in the focus of research. Thereby, pain models suggest a centrally controlled strategy of trunk stiffening in LBP. However, supporting biomechanical evidence is mostly limited to static measurements during maximum voluntary contractions (MVC), probably influenced by psychological factors in LBP. Alternatively, repeated findings indicate that the neuromuscular efficiency (NME), characterized by the strength-to-activation relationship (SAR), of lower back muscles is impaired in LBP. Therefore, a dynamic SAR protocol, consisting of normalized trunk muscle activation recordings during submaximal loads (SMVC) seems to be relevant. This thesis aimed to investigate the influence of LBP on the NME and activation pattern of trunk muscles during dynamic trunk extensions.
METHODS: The SAR protocol consisted of an initial MVC reference trial (MVC1), followed by SMVCs at 20, 40, 60 and 80% of MVC1 load. An isokinetic trunk dynamometer (Con-Trex TP, ROM: 45° flexion to 10° extension, velocity: 45°/s) and a trunk surface EMG setup (myon, up to 12 leads) was used. Extension torque output [Nm] and muscular activation [V] were assessed in all trials. Finally, another MVC trial was performed (MVC2) for reliability analysis. For SAR evaluation the SMVC trial values were normalized [%MVC1] and compared inter- and intra-individually.
The methodical validity of the approach was tested in an isometric SAR single-case pilot study (S1a: N = 2, female LBP patient vs. healthy male). In addition, the validity of the MVC reference method was verified by comparing different contraction modes (S1b: N = 17, healthy individuals). Next, the isokinetic protocol was validated in terms of content for its applicability to display known physiological differences between sexes in a cross-sectional study (S2: each n = 25 healthy males/females). Finally, the influence of acute pain on NME was investigated longitudinally by comparing N = 8 acute LBP patients with the retest after remission of pain (S3). The SAR analysis focused on normalized agonistic extensor activation and abdominal and synergistic extensor co-activation (t-tests, ANOVA, α = .05) as well as on reliability of MVC1/2 outcomes.
RESULTS: During the methodological validation of the protocol (S1a), the isometric SAR was found to be descriptively different between individuals. Whereas torque output was highest during eccentric MVC, no relevant difference in peak EMG activation was found between contraction modes (S1b). The isokinetic SAR sex comparison (S2), though showing no significant overall effects, revealed higher normalized extensor activation at moderate submaximal loads in females (13 ± 4%), primarily caused by pronounced thoracic activation. Similarly, co-activation analysis resulted in significantly higher antagonistic activation at moderate loads compared to males (33 ± 9%). During intra-individual analysis of SAR in LBP patients (S3), a significant effect of pain status on the SAR has been identified, manifesting as increased normalized EMG activation of extensors during acute LBP (11 ± 8%) particularly at high load. Abdominal co-activation tended to be elevated (27 ± 11%) just as the thoracic extensor parts seemed to take over proportions of lumbar activation. All together, the M. erector spinae behaviour during the SAR protocol was rather linear with the tendency to rise exponentially during high loads. For the level of normalized EMG activation during SMVCs, a clear increasing trend from healthy males to females over to non-acute and acute LBP patients was discovered. This was associated by elevated antagonistic activation and a shift of synergistic towards lumbar extensor activation. The MVC data revealed overall good reliability, with clearly higher variability during acute LBP.
DISCUSSION: The present thesis demonstrates that the NME of lower back muscles is impaired in LBP patients, especially during an acute pain episode. A new dynamic protocol has been developed that makes it possible to display the underlying SAR using normalized trunk muscle EMG during submaximal isokinetic loads. The protocol shows promise as a biomechanical tool for diagnostic analysis of NME in LBP patients and monitoring of rehabilitation progress. Furthermore, reliability not of maximum strength but rather of peak EMG of MVC measurements seems to be decreased in LBP patients. Meanwhile, the findings of this thesis largely substantiate the assumptions made by the recently presented ‘motor adaptation to pain’ model, suggesting a pain-related intra- and intermuscular activation redistribution affecting movement and stiffness of the trunk. Further research is needed to distinguish the grade of NME impairment between LBP subgroups.
Der deutsche Zeitungsmarkt ist von einem breiten Angebot überregionaler Tageszeitungen gekennzeichnet, denen innerhalb der Bevölkerung unterschiedliche politische Ausrichtungen zugeschrieben werden. Als konservatives Blatt gilt die „Frankfurter Allgemeine Zeitung“ (F.A.Z.), wohingegen sich die „taz.die tageszeitung“ (taz) durch eine linksalternative Orientierung auszeichnet. Ausgehend von diesem Unterschied untersucht die Arbeit die sprachliche Gestaltung der Überschriften, Unter- und Zwischenzeilen der F.A.Z. und der taz zu den Themen „Alternative für Deutschland“ (AfD), „Nationalsozialistischer Untergrund“ (NSU) und „Front National“ (FN). Die qualitativ-quantitative Korpusuntersuchung fokussiert neben lexikalischen und syntaktischen auch sprachstilistische Faktoren, die eine Stellungnahme zu der Forschungsthese, dass mit der sprachlichen Formulierung der Haupt-, Unter- und Zwischenzeilen die politische Ausrichtung und ideologische Grundhaltung der Zeitungen deutlich wird, erlauben. Die Grundlage für die Analysen bildet ein konstruktivistischer Ansatz, der auf systemtheoretischen Annahmen beruht. Dadurch kann zum einen gezeigt werden, wie sich die Ergebnisse der sprachlichen Analysen mit den unterschiedlichen zugrunde liegenden Wirklichkeitskonstruktionen der Zeitungen verbinden lassen, zum anderen wird deutlich, dass sich die Formulierung der Überschriften auch auf die individuelle Realitätskonstruktion der Rezipienten auswirkt. Die vergleichenden Auswertungen geben unterschiedlich gewichtete Hinweise auf die Einstellung der Kommunikatoren und bestätigen, dass die jeweiligen Perspektivierungen der Wirklichkeit sowie ideologischen Grundhaltungen der F.A.Z. und der taz bereits in der sprachlichen Gestaltung ihrer Titelkomplexe deutlich werden.
In experiments investigating sentence processing, eye movement measures such as fixation durations and regression proportions while reading are commonly used to draw conclusions about processing difficulties. However, these measures are the result of an interaction of multiple cognitive levels and processing strategies and thus are only indirect indicators of processing difficulty. In order to properly interpret an eye movement response, one has to understand the underlying principles of adaptive processing such as trade-off mechanisms between reading speed and depth of comprehension that interact with task demands and individual differences. Therefore, it is necessary to establish explicit models of the respective mechanisms as well as their causal relationship with observable behavior. There are models of lexical processing and eye movement control on the one side and models on sentence parsing and memory processes on the other. However, no model so far combines both sides with explicitly defined linking assumptions.
In this thesis, a model is developed that integrates oculomotor control with a parsing mechanism and a theory of cue-based memory retrieval. On the basis of previous empirical findings and independently motivated principles, adaptive, resource-preserving mechanisms of underspecification are proposed both on the level of memory access and on the level of syntactic parsing. The thesis first investigates the model of cue-based retrieval in sentence comprehension of Lewis & Vasishth (2005) with a comprehensive literature review and computational modeling of retrieval interference in dependency processing. The results reveal a great variability in the data that is not explained by the theory. Therefore, two principles, 'distractor prominence' and 'cue confusion', are proposed as an extension to the theory, thus providing a more adequate description of systematic variance in empirical results as a consequence of experimental design, linguistic environment, and individual differences. In the remainder of the thesis, four interfaces between parsing and eye movement control are defined: Time Out, Reanalysis, Underspecification, and Subvocalization. By comparing computationally derived predictions with experimental results from the literature, it is investigated to what extent these four interfaces constitute an appropriate elementary set of assumptions for explaining specific eye movement patterns during sentence processing. Through simulations, it is shown how this system of in itself simple assumptions results in predictions of complex, adaptive behavior.
In conclusion, it is argued that, on all levels, the sentence comprehension mechanism seeks a balance between necessary processing effort and reading speed on the basis of experience, task demands, and resource limitations. Theories of linguistic processing therefore need to be explicitly defined and implemented, in particular with respect to linking assumptions between observable behavior and underlying cognitive processes. The comprehensive model developed here integrates multiple levels of sentence processing that hitherto have only been studied in isolation. The model is made publicly available as an expandable framework for future studies of the interactions between parsing, memory access, and eye movement control.
Seit Mitte der 2000er Jahre richtet sich angesichts der starken Schülerzahlenrückgänge die wissenschaftliche und bildungspolitische Aufmerksamkeit wieder stärker auf Fragen der Gestaltung beruflicher Bildung in ländlich-peripheren Räumen. Einerseits knüpft sich an die demografische Entwicklung die Erwartung einer Entspannung der lange Zeit sehr prekären Ausbildungsplatzsituation in diesen Räumen. Andererseits ist offen, inwiefern mit den Anpassungsprozessen die Ausbildung neuer räumlichen Disparitäten verbunden ist, etwa durch die Schließung von Berufsschulen. Die Arbeit setzt sich mit der aktuellen Situation und dem Umgang mit Berufsschulen unter den folgenden Fragestellungen auseinander: Wie kann in Regionen mit dünner Besiedlung auf der einen und einer schwierigen regionalökonomischen Situation auf der anderen Seite diese komplexe Infrastruktur betrieben werden? Welche Steuerungsinstrumente kommen in dem anstehenden Rückbauprozess zum Tragen und welche Rolle spielen demographische Entwicklungen, strukturelle Faktoren und Akteurshandeln? Ein besonderer Fokus liegt auf der theoretischen und empirischen Verknüpfung von raumspezifischen Fragestellungen mit der Komplexität von Berufsschulen als ausdifferenzierte Institutionen zwischen Schulsystem und Wirtschaft.
Untersucht wurde die Entwicklung des brandenburgischen Berufsschulnetzes ab den 1990er Jahren mit einer vertieften Fallstudie im Landkreis Uckermark. Entgegen der Annahme eines starken Einbruchs der Infrastrukturversorgung in Folge des Schülerzahlenrückganges wird gezeigt, dass sich die brandenburgische Berufsschullandschaft seit den 2000er Jahren durch eine relative Stabilität auszeichnet. Allerdings erfolgte eine berufsspezifische Ausdünnung des Angebotes. Im Jahr 2013 fanden nur 41% aller Auszubilden in ihrem jeweiligen Ausbildungsberuf ein relativ flächendeckendes Berufsschulnetz vor. Als Faktoren für gelingende Steuerungsprozesse (in ländlich-peripheren Räumen) zeigten sich das Subsidaritätsprinzip, ein gemeinsam geteiltes Professionsverständnis sowie die Orientierung auf einen gewissen räumlichen Ausgleich. Erfolgreiche Interventionen gegen Konzentration basierten maßgeblich auf einem ausgeprägten, fachlichen „Selbstbewusstsein“ und Anspruch von Bildungsorganisationen. Demgegenüber konnten unspezifische Bezugnahmen auf Peripherisierungen keine handlungswirksamen Strategien entfalten. Teilentwicklungen im Schulberufssystem sind durch die Expansion privater Berufsschulen in einen ausgeprägten institutionellen Wandel eingebettet. Die Infrastrukturentwicklung führte in diesem Segment zur Ausbildung eines spezifischen Marktes, der teilweise nur begrenzt einem klassischen Angebots-Nachfrage-Modell folgt und potentiell zu Überausbildung führt.
Die vorgefundenen Steuerungsformen sind angesichts von Ressourcenmangel, der sektoralen Zersplitterung sowie des Mangels an Institutionen für die Ausbildung von Regionen als Handlungsräume in der Berufsausbildung ambivalent. Der demografische Diskurs führte (bisher) nicht zur Ausbildung von Steuerungsformen, welche die in der Infrastrukturgestaltung dominierenden, sektoralen Zuständigkeiten „überwinden“. Daher fungiert der Diskurs teilweise nur begrenzt als eine neue Orientierung für die Ausbildung von „peripheriespezifischen“ Infrastrukturstrategien und alternativen Steuerungsmodellen. Er kann dann neue, über klassische Anpassungsprozesse hinausgehende, Optionen generieren, wenn er sich stärker auf die Bedarfe der Akteure und Adressaten von Berufsbildung im ländlichen Raum bezieht und enger mit den Fachdiskursen verbindet.
Personal fabrication tools, such as 3D printers, are on the way of enabling a future in which non-technical users will be able to create custom objects. However, while the hardware is there, the current interaction model behind existing design tools is not suitable for non-technical users. Today, 3D printers are operated by fabricating the object in one go, which tends to take overnight due to the slow 3D printing technology. Consequently, the current interaction model requires users to think carefully before printing as every mistake may imply another overnight print. Planning every step ahead, however, is not feasible for non-technical users as they lack the experience to reason about the consequences of their design decisions.
In this dissertation, we propose changing the interaction model around personal fabrication tools to better serve this user group. We draw inspiration from personal computing and argue that the evolution of personal fabrication may resemble the evolution of personal computing: Computing started with machines that executed a program in one go before returning the result to the user. By decreasing the interaction unit to single requests, turn-taking systems such as the command line evolved, which provided users with feedback after every input. Finally, with the introduction of direct-manipulation interfaces, users continuously interacted with a program receiving feedback about every action in real-time. In this dissertation, we explore whether these interaction concepts can be applied to personal fabrication as well.
We start with fabricating an object in one go and investigate how to tighten the feedback-cycle on an object-level: We contribute a method called low-fidelity fabrication, which saves up to 90% fabrication time by creating objects as fast low-fidelity previews, which are sufficient to evaluate key design aspects. Depending on what is currently being tested, we propose different conversions that enable users to focus on different parts: faBrickator allows for a modular design in the early stages of prototyping; when users move on WirePrint allows quickly testing an object's shape, while Platener allows testing an object's technical function. We present an interactive editor for each technique and explain the underlying conversion algorithms.
By interacting on smaller units, such as a single element of an object, we explore what it means to transition from systems that fabricate objects in one go to turn-taking systems. We start with a 2D system called constructable: Users draw with a laser pointer onto the workpiece inside a laser cutter. The drawing is captured with an overhead camera. As soon as the the user finishes drawing an element, such as a line, the constructable system beautifies the path and cuts it--resulting in physical output after every editing step. We extend constructable towards 3D editing by developing a novel laser-cutting technique for 3D objects called LaserOrigami that works by heating up the workpiece with the defocused laser until the material becomes compliant and bends down under gravity. While constructable and LaserOrigami allow for fast physical feedback, the interaction is still best described as turn-taking since it consists of two discrete steps: users first create an input and afterwards the system provides physical output.
By decreasing the interaction unit even further to a single feature, we can achieve real-time physical feedback: Input by the user and output by the fabrication device are so tightly coupled that no visible lag exists. This allows us to explore what it means to transition from turn-taking interfaces, which only allow exploring one option at a time, to direct manipulation interfaces with real-time physical feedback, which allow users to explore the entire space of options continuously with a single interaction. We present a system called FormFab, which allows for such direct control. FormFab is based on the same principle as LaserOrigami: It uses a workpiece that when warmed up becomes compliant and can be reshaped. However, FormFab achieves the reshaping not based on gravity, but through a pneumatic system that users can control interactively. As users interact, they see the shape change in real-time.
We conclude this dissertation by extrapolating the current evolution into a future in which large numbers of people use the new technology to create objects. We see two additional challenges on the horizon: sustainability and intellectual property. We investigate sustainability by demonstrating how to print less and instead patch physical objects. We explore questions around intellectual property with a system called Scotty that transfers objects without creating duplicates, thereby preserving the designer's copyright.
The title compounds, [(1R,3R,4R,5R,6S)-4,5-bis(acetyloxy)-7-oxo-2-oxabicyclo[4.2.0]octan-3-yl]methyl acetate, C14H18O8, (I), [(1S,4R,5S,6R)-5-acetyloxy-7-hydroxyimino-2-oxobicyclo[4.2.0]octan-4-yl acetate, C11H15NO6, (II), and [(3aR,5R,6R,7R,7aS)-6,7-bis(acetyloxy)-2-oxooctahydropyrano[3,2-b]pyrrol-5-yl]methyl acetate, C14H19NO8, (III), are stable bicyclic carbohydrate derivatives. They can easily be synthesized in a few steps from commercially available glycals. As a result of the ring strain from the four-membered rings in (I) and (II), the conformations of the carbohydrates deviate strongly from the ideal chair form. Compound (II) occurs in the boat form. In the five-membered lactam (III), on the other hand, the carbohydrate adopts an almost ideal chair conformation. As a result of the distortion of the sugar rings, the configurations of the three bicyclic carbohydrate derivatives could not be determined from their NMR coupling constants. From our three crystal structure determinations, we were able to establish for the first time the absolute configurations of all new stereocenters of the carbohydrate rings.
The population structure of the highly mobile marine mammal, the harbor porpoise (Phocoena phocoena), in the Atlantic shelf waters follows a pattern of significant isolation-by-distance. The population structure of harbor porpoises from the Baltic Sea, which is connected with the North Sea through a series of basins separated by shallow underwater ridges, however, is more complex. Here, we investigated the population differentiation of harbor porpoises in European Seas with a special focus on the Baltic Sea and adjacent waters, using a population genomics approach. We used 2872 single nucleotide polymorphisms (SNPs), derived from double digest restriction-site associated DNA sequencing (ddRAD-seq), as well as 13 microsatellite loci and mitochondrial haplotypes for the same set of individuals. Spatial principal components analysis (sPCA), and Bayesian clustering on a subset of SNPs suggest three main groupings at the level of all studied regions: the Black Sea, the North Atlantic, and the Baltic Sea. Furthermore, we observed a distinct separation of the North Sea harbor porpoises from the Baltic Sea populations, and identified splits between porpoise populations within the Baltic Sea. We observed a notable distinction between the Belt Sea and the Inner Baltic Sea sub-regions. Improved delineation of harbor porpoise population assignments for the Baltic based on genomic evidence is important for conservation management of this endangered cetacean in threatened habitats, particularly in the Baltic Sea proper. In addition, we show that SNPs outperform microsatellite markers and demonstrate the utility of RAD-tags from a relatively small, opportunistically sampled cetacean sample set for population diversity and divergence analysis.
The human immunodeficiency virus (HIV) has resisted nearly three decades of efforts targeting a cure. Sustained suppression of the virus has remained a challenge, mainly due
to the remarkable evolutionary adaptation that the virus exhibits by the accumulation of drug-resistant mutations in its genome. Current therapeutic strategies aim at achieving and maintaining a low viral burden and typically involve multiple drugs. The choice of optimal combinations of these drugs is crucial, particularly in the background of treatment failure having occurred previously with certain other drugs. An understanding of the dynamics of viral mutant genotypes aids in the assessment of treatment failure with a certain drug
combination, and exploring potential salvage treatment regimens.
Mathematical models of viral dynamics have proved invaluable in understanding the viral life cycle and the impact of antiretroviral drugs. However, such models typically use simplified and coarse-grained mutation schemes, that curbs the extent of their application to drug-specific clinical mutation data, in order to assess potential next-line therapies. Statistical
models of mutation accumulation have served well in dissecting mechanisms of resistance evolution by reconstructing mutation pathways under different drug-environments. While these models perform well in predicting treatment outcomes by statistical learning, they do not incorporate drug effect mechanistically. Additionally, due to an inherent lack of
temporal features in such models, they are less informative on aspects such as predicting mutational abundance at treatment failure. This limits their application in analyzing the
pharmacology of antiretroviral drugs, in particular, time-dependent characteristics of HIV therapy such as pharmacokinetics and pharmacodynamics, and also in understanding the impact of drug efficacy on mutation dynamics.
In this thesis, we develop an integrated model of in vivo viral dynamics incorporating drug-specific mutation schemes learned from clinical data. Our combined modelling
approach enables us to study the dynamics of different mutant genotypes and assess mutational abundance at virological failure. As an application of our model, we estimate in vivo
fitness characteristics of viral mutants under different drug environments. Our approach also extends naturally to multiple-drug therapies. Further, we demonstrate the versatility of our model by showing how it can be modified to incorporate recently elucidated mechanisms of drug action including molecules that target host factors.
Additionally, we address another important aspect in the clinical management of HIV disease, namely drug pharmacokinetics. It is clear that time-dependent changes in in vivo
drug concentration could have an impact on the antiviral effect, and also influence decisions on dosing intervals. We present a framework that provides an integrated understanding
of key characteristics of multiple-dosing regimens including drug accumulation ratios and half-lifes, and then explore the impact of drug pharmacokinetics on viral suppression.
Finally, parameter identifiability in such nonlinear models of viral dynamics is always a concern, and we investigate techniques that alleviate this issue in our setting.
Effektivität frühzeitiger Interventionen zur Prävention von Lese- und Rechtschreibschwierigkeiten
(2016)
Die vorliegende Studie beschäftigt sich mit der Förderung der Lese- und Schreibkompetenz in der Anfangsphase des Schriftspracherwerbs. Ziel der Untersuchung ist die Erprobung und Evaluierung frühzeitiger, diagnosegeleiteter Interventionen zur Prävention von Lese- und Rechtschreibschwierigkeiten. Im Unterschied zu vielen Studien in diesem Bereich werden alle Maßnahmen unter realen schulischen Bedingungen im Rahmen des Erstlese- und Schreibunterrichts durch die Klassenlehrer selbst durchgeführt, wobei diese von der Autorin unterstützt und begleitet werden. Förder- und Prozessdiagnose sowie Elemente diagnosegeleiteter Förderung werden aus Theorien und Forschungslage abgeleitet und zu einem Interventionsset verbunden. Die Effektivität der evidenzbasierten Maßnahmen wird durch Parallelgruppenvergleiche überprüft.
An der empirischen Untersuchung nahmen insgesamt 25 Schulklassen mit 560 Erstklässlern teil, geteilt in Versuchs- und Kontrollgruppe. Mit der Eingangsdiagnose am Schulbeginn wurden Voraussetzungen für den Schriftspracherwerb erhoben und mit der Evaluierungsdiagnose am Ende der ersten Schulstufe entwicklungsadäquate schriftsprachliche Kompetenzen auf der Wortebene überprüft. Zusätzlich erfasst wurden internale und externale Einflussfaktoren, deren Wirkung in der statistischen Auswertung berücksichtigt wurde. Alle Datenerhebungen wurden in Versuchs- und Kontrollgruppe durchgeführt, während die evidenzbasierten Treatments nur in der Versuchsgruppe stattfanden.
Die Auswertung bestätigt mit signifikanten Ergebnissen den engen Zusammenhang zwischen der Phonologischen Bewusstheit zu Beginn des Schriftspracherwerbs und der Lese- und Rechtschreibfähigkeit am Ende der ersten Schulstufe sowie zwischen Familiärer Literalität und Lesefertigkeit. Schriftsprachliche Vorkenntnisse weisen eine Tendenz zur Signifikanz hinsichtlich ihrer positiven Wirkung auf die Basale Lesefertigkeit auf. Eine höchst signifikante positive Wirkung auf die Basale Lesefertigkeit zeigt die Druckschrift als Ausgangsschrift.
Die Ergebnisse deuten auf eine Überlegenheit vorschulischer präliteraler Fertigkeiten hinsichtlich ihrer Wirkung auf die Lese- und Rechtschreibfertigkeit am Ende der ersten Schulstufe gegenüber Fördermaßnahmen unter realen schulischen Bedingungen hin. Die positive Wirkung einer unverbundenen Ausgangsschrift auf den Leseerwerb betont die Wichtigkeit der Wahl der Ausgangsschrift. Im frühen Schriftspracherwerb sollte die Druckschrift für das Lesen und Schreiben verwendet werden.
Widespread flooding in June 2013 caused damage costs of €6 to 8 billion in Germany, and awoke many memories of the floods in August 2002, which resulted in total damage of €11.6 billion and hence was the most expensive natural hazard event in Germany up to now. The event of 2002 does, however, also mark a reorientation toward an integrated flood risk management system in Germany. Therefore, the flood of 2013 offered the opportunity to review how the measures that politics, administration, and civil society have implemented since 2002 helped to cope with the flood and what still needs to be done to achieve effective and more integrated flood risk management. The review highlights considerable improvements on many levels, in particular (1) an increased consideration of flood hazards in spatial planning and urban development, (2) comprehensive property-level mitigation and preparedness measures, (3) more effective flood warnings and improved coordination of disaster response, and (4) a more targeted maintenance of flood defense systems. In 2013, this led to more effective flood management and to a reduction of damage. Nevertheless, important aspects remain unclear and need to be clarified. This particularly holds for balanced and coordinated strategies for reducing and overcoming the impacts of flooding in large catchments, cross-border and interdisciplinary cooperation, the role of the general public in the different phases of flood risk management, as well as a transparent risk transfer system. Recurring flood events reveal that flood risk management is a continuous task. Hence, risk drivers, such as climate change, land-use changes, economic developments, or demographic change and the resultant risks must be investigated at regular intervals, and risk reduction strategies and processes must be reassessed as well as adapted and implemented in a dialogue with all stakeholders.
Tarkovsky’s legacy
(2016)
„Vajanie iz vremeni“
(2016)
Die Museumsbesucher
(2016)
Блуждающие цитаты
(2016)
Erneuertes Gestern?
(2016)
Tarkovskijs Scham
(2016)
Der Jüdische Friedhof in Potsdam ist der einzige authentische Gedächtnisort, der vom Lebenszyklus der jüdischen Bevölkerung in der ehemaligen preußischen Residenz- und Garnisonstadt zeugt. Er ist zudem Ausdruck des unterschiedlichen Umgangs der Nachgeborenen mit ihrem Kulturgut. Außerdem ist dieser Jüdische Friedhof zurzeit als einziger in Deutschland durch die UNESCO als Welterbe anerkannt.
Da die jüdische Geschichte Potsdams bislang nur wenig bekannt ist, entstand ein durch die Stiftung „Erinnerung, Verantwortung und Zukunft“ gefördertes Projekt, in dem sich Schüler*innen des Potsdamer Humboldt-Gymnasiums im Rahmen eines Seminarkurses mit dem jüdischen Erbe ihrer Stadt intensiv auseinandersetzten. Neben einer Annäherung an das Thema über verschiedene, den Friedhof betreffende Sachthemen beschäftigten sich die Jugendlichen mit einzelnen jüdischen Potsdamern, ihren Familienschicksalen und Lebenskonzepten. Ergänzend wurden Aspekte des religiösen Verständnisses von Tod und Trauer im Judentum vorgestellt.
Die Ergebnisse all dieser Ausarbeitungen sind im vorliegenden Lehrmaterial vereinigt und dienen als Anregung für Lehrende und Lernende, die jüdische Geschichte ihrer jeweiligen Heimatorte zu thematisieren.
Computer Security deals with the detection and mitigation of threats to computer networks, data, and computing hardware. This
thesis addresses the following two computer security problems: email spam campaign and malware detection.
Email spam campaigns can easily be generated using popular dissemination tools by specifying simple grammars that serve as message templates. A grammar is disseminated to nodes of a bot net, the nodes create messages by instantiating the grammar at random. Email spam campaigns can encompass huge data volumes and therefore pose a threat to the stability of the infrastructure of email service providers that have to store them. Malware -software that serves a malicious purpose- is affecting web servers, client computers via active content, and client computers through executable files. Without the help of malware detection systems it would be easy for malware creators to collect sensitive information or to infiltrate computers.
The detection of threats -such as email-spam messages, phishing messages, or malware- is an adversarial and therefore intrinsically
difficult problem. Threats vary greatly and evolve over time. The detection of threats based on manually-designed rules is therefore
difficult and requires a constant engineering effort. Machine-learning is a research area that revolves around the analysis of data and the discovery of patterns that describe aspects of the data. Discriminative learning methods extract prediction models from data that are optimized to predict a target attribute as accurately as possible. Machine-learning methods hold the promise of automatically identifying patterns that robustly and accurately detect threats. This thesis focuses on the design and analysis of discriminative learning methods for the two computer-security problems under investigation: email-campaign and malware detection.
The first part of this thesis addresses email-campaign detection. We focus on regular expressions as a syntactic framework, because regular expressions are intuitively comprehensible by security engineers and administrators, and they can be applied as a detection mechanism in an extremely efficient manner. In this setting, a prediction model is provided with exemplary messages from an email-spam campaign. The prediction model has to generate a regular expression that reveals the syntactic pattern that underlies the entire campaign, and that a security engineers finds comprehensible and feels confident enough to use the expression to blacklist further messages at the email server. We model this problem as two-stage learning problem with structured input and output spaces which can be solved using standard cutting plane methods. Therefore we develop an appropriate loss function, and derive a decoder for the resulting optimization problem.
The second part of this thesis deals with the problem of predicting whether a given JavaScript or PHP file is malicious or benign. Recent malware analysis techniques use static or dynamic features, or both. In fully dynamic analysis, the software or script is executed and observed for malicious behavior in a sandbox environment. By contrast, static analysis is based on features that can be extracted directly from the program file. In order to bypass static detection mechanisms, code obfuscation techniques are used to spread a malicious program file in many different syntactic variants. Deobfuscating the code before applying a static classifier can be subjected to mostly static code analysis and can overcome the problem of obfuscated malicious code, but on the other hand increases the computational costs of malware detection by an order of magnitude. In this thesis we present a cascaded architecture in which a classifier first performs a static analysis of the original code and -based on the outcome of this first classification step- the code may be deobfuscated and classified again. We explore several types of features including token $n$-grams, orthogonal sparse bigrams, subroutine-hashings, and syntax-tree features and study the robustness of detection methods and feature types against the evolution of malware over time. The developed tool scans very large file collections quickly and accurately.
Each model is evaluated on real-world data and compared to reference methods. Our approach of inferring regular expressions to filter emails belonging to an email spam campaigns leads to models with a high true-positive rate at a very low false-positive rate that is an order of magnitude lower than that of a commercial content-based filter. Our presented system -REx-SVMshort- is being used by a commercial email service provider and complements content-based and IP-address based filtering.
Our cascaded malware detection system is evaluated on a high-quality data set of almost 400,000 conspicuous PHP files and a collection of more than 1,00,000 JavaScript files. From our case study we can conclude that our system can quickly and accurately process large data collections at a low false-positive rate.
Die vorliegende Modularbeit vergleicht die Häufigkeit des Imperativs auf Plakaten der Berliner Abgeordnetenhauswahl 2016 mit der auf den Plakaten der Weimarer Republik. Sie geht dabei der These nach, dass diese Häufigkeit abgenommen hat und kann diese bestätigen: 2016 tritt der Imperativ achtmal seltener (5,7 % zu 45,7 %) auf. Zusätzlich leistet die Arbeit einen Überblick zum Imperativ und weiteren Möglichkeiten, mittels der deutschen Sprache eine Aufforderung zu artikulieren.
Für die Untersuchung wurden zwei Untersuchungskorpora herangezogen, wovon der Korpus mit den Slogans zur Abgeordnetenhauswahl extra für diese Arbeit erstellt wurde und ihr auch beiliegt. In diesem, wie im Korpus zur Weimarer Republik, sind alle die Slogans enthalten und die verwendeten Imperative ausgezählt. So bietet sich ein Einblick in die politische Werbesprache der beiden Zeiten.
The goal of the presented work is to explore the interaction between gold nanorods (GNRs) and hyper-sound waves. For the generation of the hyper-sound I have used Azobenzene-containing polymer transducers. Multilayer polymer structures with well-defined thicknesses and smooth interfaces were built via layer-by-layer deposition. Anionic polyelectrolytes with Azobenzene side groups (PAzo) were alternated with cationic polymer PAH, for the creation of transducer films. PSS/PAH multilayer were built for spacer layers, which do not absorb in the visible light range. The properties of the PAzo/PAH film as a transducer are carefully characterized by static and transient optical spectroscopy. The optical and mechanical properties of the transducer are studied on the picosecond time scale. In particular the relative change of the refractive index of the photo-excited and expanded PAH/PAzo is Δn/n = - 2.6*10‐4. Calibration of the generated strain is performed by ultrafast X-ray diffraction calibrated the strain in a Mica substrate, into which the hyper-sound is transduced. By simulating the X-ray data with a linear-chain-model the strain in the transducer under the excitation is derived to be Δd/d ~ 5*10‐4.
Additional to the investigation of the properties of the transducer itself, I have performed a series of experiments to study the penetration of the generated strain into various adjacent materials. By depositing the PAzo/PAH film onto a PAH/PSS structure with gold nanorods incorporated in it, I have shown that nanoscale impurities can be detected via the scattering of hyper-sound.
Prior to the investigation of complex structures containing GNRs and the transducer, I have performed several sets of experiments on GNRs deposited on a small buffer of PSS/PAH. The static and transient response of GNRs is investigated for different fluence of the pump beam and for different dielectric environments (GNRs covered by PSS/PAH).
A systematic analysis of sample architectures is performed in order to construct a sample with the desired effect of GNRs responding to the hyper-sound strain wave. The observed shift of a feature related to the longitudinal plasmon resonance in the transient reflection spectra is interpreted as the event of GNRs sensing the strain wave. We argue that the shift of the longitudinal plasmon resonance is caused by the viscoelastic deformation of the polymer around the nanoparticle. The deformation is induced by the out of plane difference in strain in the area directly under a particle and next to it. Simulations based on the linear chain model support this assumption. Experimentally this assumption is proven by investigating the same structure, with GNRs embedded in a PSS/PAH polymer layer.
The response of GNRs to the hyper-sound wave is also observed for the sample structure with GNRs embedded in PAzo/PAH films. The response of GNRs in this case is explained to be driven by the change of the refractive index of PAzo during the strain propagation.
The global carbon cycle is closely linked to Earth’s climate. In the context of continuously unchecked anthropogenic CO₂ emissions, the importance of natural CO₂ bond and carbon storage is increasing. An important biogenic mechanism of natural atmospheric CO₂ drawdown is the photosynthetic carbon fixation in plants and the subsequent longterm deposition of plant detritus in sediments.
The main objective of this thesis is to identify factors that control mobilization and transport of plant organic matter (pOM) through rivers towards sedimentation basins. I investigated this aspect in the eastern Nepalese Arun Valley. The trans-Himalayan Arun River is characterized by a strong elevation gradient (205 − 8848 m asl) that is accompanied by strong changes in ecology and climate ranging from wet tropical conditions in the Himalayan forelad to high alpine tundra on the Tibetan Plateau. Therefore, the Arun is an excellent natural laboratory, allowing the investigation of the effect of vegetation cover, climate, and topography on plant organic matter mobilization and export in tributaries along the gradient.
Based on hydrogen isotope measurements of plant waxes sampled along the Arun River and its tributaries, I first developed a model that allows for an indirect quantification of pOM contributed to the mainsetm by the Arun’s tributaries. In order to determine the role of climatic and topographic parameters of sampled tributary catchments, I looked for significant statistical relations between the amount of tributary pOM export and tributary characteristics (e.g. catchment size, plant cover, annual precipitation or runoff, topographic measures). On one hand, I demonstrated that pOMsourced from the Arun is not uniformly derived from its entire catchment area. On the other, I showed that dense vegetation is a necessary, but not sufficient, criterion for high tributary pOM export. Instead, I identified erosion and rainfall and runoff as key factors controlling pOM sourcing in the Arun Valley. This finding is supported by terrestrial cosmogenic nuclide concentrations measured on river sands along the Arun and its tributaries in order to quantify catchment wide denudation rates. Highest denudation rates corresponded well with maximum pOM mobilization and export also suggesting the link between erosion and pOM sourcing.
The second part of this thesis focusses on the applicability of stable isotope records such as plant wax n-alkanes in sediment archives as qualitative and quantitative proxy for the variability of past Indian Summer Monsoon (ISM) strength. First, I determined how ISM strength affects the hydrogen and oxygen stable isotopic composition (reported as δD and δ18O values vs. Vienna Standard Mean Ocean Water) of precipitation in the Arun Valley and if this amount effect (Dansgaard, 1964) is strong enough to be recorded in potential paleo-ISM isotope proxies. Second, I investigated if potential isotope records across the Arun catchment reflect ISM strength dependent precipitation δD values only, or if the ISM isotope signal is superimposed by winter precipitation or glacial melt. Furthermore, I tested if δD values of plant waxes in fluvial deposits reflect δD values of environmental waters in the respective catchments.
I showed that surface water δD values in the Arun Valley and precipitation δD from south of the Himalaya both changed similarly during two consecutive years (2011 & 2012) with distinct ISM rainfall amounts (~20% less in 2012). In order to evaluate the effect of other water sources (Winter-Westerly precipitation, glacial melt) and evapotranspiration in the Arun Valley, I analysed satellite remote sensing data of rainfall distribution (TRMM 3B42V7), snow cover (MODIS MOD10C1), glacial coverage (GLIMSdatabase, Global Land Ice Measurements from Space), and evapotranspiration (MODIS MOD16A2). In addition to the predominant ISM in the entire catchment I found through stable isotope analysis of surface waters indications for a considerable amount of glacial melt derived from high altitude tributaries and the Tibetan Plateau. Remotely sensed snow cover data revealed that the upper portion of the Arun also receives considerable winter precipitation, but the effect of snow melt on the Arun Valley hydrology could not be evaluated as it takes place in early summer, several months prior to our sampling campaigns. However, I infer that plant wax records and other potential stable isotope proxy archives below the snowline are well-suited for qualitative, and potentially quantitative, reconstructions of past changes of ISM strength.
Background
Doping presents a potential health risk for young athletes. Prevention programs are intended to prevent doping by educating athletes about banned substances. However, such programs have their limitations in practice. This led Germany to introduce the National Doping Prevention Plan (NDPP), in hopes of ameliorating the situation among young elite athletes. Two studies examined 1) the degree to which the NDPP led to improved prevention efforts in elite sport schools, and 2) the extent to which newly developed prevention activities of the national anti-doping agency (NADA) based on the NDPP have improved knowledge among young athletes within elite sports schools.
Methods
The first objective was investigated in a longitudinal study (Study I: t0 = baseline, t1 = follow-up 4 years after NDPP introduction) with N = 22 teachers engaged in doping prevention in elite sports schools. The second objective was evaluated in a cross-sectional comparison study (Study II) in N = 213 elite sports school students (54.5 % male, 45.5 % female, age M = 16.7 ± 1.3 years (all students had received the improved NDDP measure in school; one student group had received additionally NADA anti-doping activities and a control group did not). Descriptive statistics were calculated, followed by McNemar tests, Wilcoxon tests and Analysis of Covariance (ANCOVA).
Results
Results indicate that 4 years after the introduction of the NDPP there have been limited structural changes with regard to the frequency, type, and scope of doping prevention in elite sport schools. On the other hand, in study II, elite sport school students who received further NADA anti-doping activities performed better on an anti-doping knowledge test than students who did not take part (F(1, 207) = 33.99, p <0.001), although this difference was small.
Conclusion
The integration of doping-prevention in elite sport schools as part of the NDPP was only partially successful. The results of the evaluation indicate that the introduction of the NDPP has contributed more to a change in the content of doping prevention activities than to a structural transformation in anti-doping education in elite sport schools. Moreover, while students who did receive additional education in the form of the NDPP“booster sessions” had significantly more knowledge about doping than students who did not receive such education, this difference was only small and may not translate to actual behavior.
Due to their multifunctionality, tablets offer tremendous advantages for research on handwriting dynamics or for interactive use of learning apps in schools. Further, the widespread use of tablet computers has had a great impact on handwriting in the current generation. But, is it advisable to teach how to write and to assess handwriting in pre- and primary schoolchildren on tablets rather than on paper? Since handwriting is not automatized before the age of 10 years, children's handwriting movements require graphomotor and visual feedback as well as permanent control of movement execution during handwriting. Modifications in writing conditions, for instance the smoother writing surface of a tablet, might influence handwriting performance in general and in particular those of non-automatized beginning writers. In order to investigate how handwriting performance is affected by a difference in friction of the writing surface, we recruited three groups with varying levels of handwriting automaticity: 25 preschoolers, 27 second graders, and 25 adults. We administered three tasks measuring graphomotor abilities, visuomotor abilities, and handwriting performance (only second graders and adults). We evaluated two aspects of handwriting performance: the handwriting quality with a visual score and the handwriting dynamics using online handwriting measures [e.g., writing duration, writing velocity, strokes and number of inversions in velocity (NIV)]. In particular, NIVs which describe the number of velocity peaks during handwriting are directly related to the level of handwriting automaticity. In general, we found differences between writing on paper compared to the tablet. These differences were partly task-dependent. The comparison between tablet and paper revealed a faster writing velocity for all groups and all tasks on the tablet which indicates that all participants—even the experienced writers—were influenced by the lower friction of the tablet surface. Our results for the group-comparison show advancing levels in handwriting automaticity from preschoolers to second graders to adults, which confirms that our method depicts handwriting performance in groups with varying degrees of handwriting automaticity. We conclude that the smoother tablet surface requires additional control of handwriting movements and therefore might present an additional challenge for learners of handwriting.
Loss to follow-up in a randomized controlled trial study for pediatric weight management (EPOC)
(2016)
Background
Attrition is a serious problem in intervention studies. The current study analyzed the attrition rate during follow-up in a randomized controlled pediatric weight management program (EPOC study) within a tertiary care setting.
Methods
Five hundred twenty-three parents and their 7–13-year-old children with obesity participated in the randomized controlled intervention trial. Follow-up data were assessed 6 and 12 months after the end of treatment. Attrition was defined as providing no objective weight data. Demographic and psychological baseline characteristics were used to predict attrition at 6- and 12-month follow-up using multivariate logistic regression analyses.
Results
Objective weight data were available for 49.6 (67.0) % of the children 6 (12) months after the end of treatment. Completers and non-completers at the 6- and 12-month follow-up differed in the amount of weight loss during their inpatient stay, their initial BMI-SDS, educational level of the parents, and child’s quality of life and well-being. Additionally, completers supported their child more than non-completers, and at the 12-month follow-up, families with a more structured eating environment were less likely to drop out. On a multivariate level, only educational background and structure of the eating environment remained significant.
Conclusions
The minor differences between the completers and the non-completers suggest that our retention strategies were successful. Further research should focus on prevention of attrition in families with a lower educational background.
The strong adhesion of sub-micron sized particles to surfaces is a nuisance, both for removing contaminating colloids from surfaces and for conscious manipulation of particles to create and test novel micro/nano-scale assemblies. The obvious idea of using detergents to ease these processes suffers from a lack of control: the action of any conventional surface-modifying agent is immediate and global. With photosensitive azobenzene containing surfactants we overcome these limitations. Such photo-soaps contain optical switches (azobenzene molecules), which upon illumination with light of appropriate wavelength undergo reversible trans-cis photo-isomerization resulting in a subsequent change of the physico-chemical molecular properties. In this work we show that when a spatial gradient in the composition of trans- and cis- isomers is created near a solid-liquid interface, a substantial hydrodynamic flow can be initiated, the spatial extent of which can be set, e.g., by the shape of a laser spot. We propose the concept of light induced diffusioosmosis driving the flow, which can remove, gather or pattern a particle assembly at a solid-liquid interface. In other words, in addition to providing a soap we implement selectivity: particles are mobilized and moved at the time of illumination, and only across the illuminated area.
Referential Choice
(2016)
We report a study of referential choice in discourse production, understood as the choice between various types of referential devices, such as pronouns and full noun phrases. Our goal is to predict referential choice, and to explore to what extent such prediction is possible. Our approach to referential choice includes a cognitively informed theoretical component, corpus analysis, machine learning methods and experimentation with human participants. Machine learning algorithms make use of 25 factors, including referent’s properties (such as animacy and protagonism), the distance between a referential expression and its antecedent, the antecedent’s syntactic role, and so on. Having found the predictions of our algorithm to coincide with the original almost 90% of the time, we hypothesized that fully accurate prediction is not possible because, in many situations, more than one referential option is available. This hypothesis was supported by an experimental study, in which participants answered questions about either the original text in the corpus, or about a text modified in accordance with the algorithm’s prediction. Proportions of correct answers to these questions, as well as participants’ rating of the questions’ difficulty, suggested that divergences between the algorithm’s prediction and the original referential device in the corpus occur overwhelmingly in situations where the referential choice is not categorical.
We study the adsorption–desorption transition of polyelectrolyte chains onto planar, cylindrical and spherical surfaces with arbitrarily high surface charge densities by massive Monte Carlo computer simulations. We examine in detail how the well known scaling relations for the threshold transition—demarcating the adsorbed and desorbed domains of a polyelectrolyte near weakly charged surfaces—are altered for highly charged interfaces. In virtue of high surface potentials and large surface charge densities, the Debye–Hückel approximation is often not feasible and the nonlinear Poisson–Boltzmann approach should be implemented. At low salt conditions, for instance, the electrostatic potential from the nonlinear Poisson–Boltzmann equation is smaller than the Debye–Hückel result, such that the required critical surface charge density for polyelectrolyte adsorption σc increases. The nonlinear relation between the surface charge density and electrostatic potential leads to a sharply increasing critical surface charge density with growing ionic strength, imposing an additional limit to the critical salt concentration above which no polyelectrolyte adsorption occurs at all. We contrast our simulations findings with the known scaling results for weak critical polyelectrolyte adsorption onto oppositely charged surfaces for the three standard geometries. Finally, we discuss some applications of our results for some physical–chemical and biophysical systems.
Geospatial data has become a natural part of a growing number of information systems and services in the economy, society, and people's personal lives. In particular, virtual 3D city and landscape models constitute valuable information sources within a wide variety of applications such as urban planning, navigation, tourist information, and disaster management. Today, these models are often visualized in detail to provide realistic imagery. However, a photorealistic rendering does not automatically lead to high image quality, with respect to an effective information transfer, which requires important or prioritized information to be interactively highlighted in a context-dependent manner.
Approaches in non-photorealistic renderings particularly consider a user's task and camera perspective when attempting optimal expression, recognition, and communication of important or prioritized information. However, the design and implementation of non-photorealistic rendering techniques for 3D geospatial data pose a number of challenges, especially when inherently complex geometry, appearance, and thematic data must be processed interactively. Hence, a promising technical foundation is established by the programmable and parallel computing architecture of graphics processing units.
This thesis proposes non-photorealistic rendering techniques that enable both the computation and selection of the abstraction level of 3D geospatial model contents according to user interaction and dynamically changing thematic information. To achieve this goal, the techniques integrate with hardware-accelerated rendering pipelines using shader technologies of graphics processing units for real-time image synthesis. The techniques employ principles of artistic rendering, cartographic generalization, and 3D semiotics—unlike photorealistic rendering—to synthesize illustrative renditions of geospatial feature type entities such as water surfaces, buildings, and infrastructure networks. In addition, this thesis contributes a generic system that enables to integrate different graphic styles—photorealistic and non-photorealistic—and provide their seamless transition according to user tasks, camera view, and image resolution.
Evaluations of the proposed techniques have demonstrated their significance to the field of geospatial information visualization including topics such as spatial perception, cognition, and mapping. In addition, the applications in illustrative and focus+context visualization have reflected their potential impact on optimizing the information transfer regarding factors such as cognitive load, integration of non-realistic information, visualization of uncertainty, and visualization on small displays.
Change points in time series are perceived as heterogeneities in the statistical or dynamical characteristics of the observations. Unraveling such transitions yields essential information for the understanding of the observed system’s intrinsic evolution and potential external influences. A precise detection of multiple changes is therefore of great importance for various research disciplines, such as environmental sciences, bioinformatics and economics. The primary purpose of the detection approach introduced in this thesis is the investigation of transitions underlying direct or indirect climate observations. In order to develop a diagnostic approach capable to capture such a variety of natural processes, the generic statistical features in terms of central tendency and dispersion are employed in the light of Bayesian inversion. In contrast to established Bayesian approaches to multiple changes, the generic approach proposed in this thesis is not formulated in the framework of specialized partition models of high dimensionality requiring prior specification, but as a robust kernel-based approach of low dimensionality employing least informative prior distributions.
First of all, a local Bayesian inversion approach is developed to robustly infer on the location and the generic patterns of a single transition. The analysis of synthetic time series comprising changes of different observational evidence, data loss and outliers validates the performance, consistency and sensitivity of the inference algorithm. To systematically investigate time series for multiple changes, the Bayesian inversion is extended to a kernel-based inference approach. By introducing basic kernel measures, the weighted kernel inference results are composed into a proxy probability to a posterior distribution of multiple transitions. The detection approach is applied to environmental time series from the Nile river in Aswan and the weather station Tuscaloosa, Alabama comprising documented changes. The method’s performance confirms the approach as a powerful diagnostic tool to decipher multiple changes underlying direct climate observations.
Finally, the kernel-based Bayesian inference approach is used to investigate a set of complex terrigenous dust records interpreted as climate indicators of the African region of the Plio-Pleistocene period. A detailed inference unravels multiple transitions underlying the indirect climate observations, that are interpreted as conjoint changes. The identified conjoint changes coincide with established global climate events. In particular, the two-step transition associated to the establishment of the modern Walker-Circulation contributes to the current discussion about the influence of paleoclimate changes on the environmental conditions in tropical and subtropical Africa at around two million years ago.
Die Elbe und ihr Einzugsgebiet sind vom Klimawandel betroffen. Um die Wirkkette von projizierten Klimaveränderungen auf den Wasserhaushalt und die daraus resultierenden Nährstoffeinträge und -frachten für große Einzugsgebiete wie das der Elbe zu analysieren, können integrierte Umweltmodellsysteme eingesetzt werden. Fallstudien, die mit diesen Modellsystemen ad hoc durchgeführt werden, repräsentieren den Istzustand von Modellentwicklungen und -unsicherheiten und sind damit statisch.
Diese Arbeit beschreibt den Einstieg in die Dynamisierung von Klimafolgenanalysen im Elbegebiet. Dies umfasst zum einen eine Plausibilitätsprüfung von Auswirkungsrechnungen, die mit Szenarien des statistischen Szenariengenerators STARS durchgeführt wurden, durch den Vergleich mit den Auswirkungen neuerer Klimaszenarien aus dem ISI-MIP Projekt, die dem letzten Stand der Klimamodellierung entsprechen. Hierfür wird ein integriertes Modellsystem mit "eingefrorenem Entwicklungsstand" verwendet. Die Klimawirkungsmodelle bleiben dabei unverändert. Zum anderen wird ein Bestandteil des integrierten Modellsystems – das ökohydrologische Modell SWIM – zu einer "live"-Version weiterentwickelt. Diese wird durch punktuelle Testung an langjährigen Versuchsreihen eines Lysimeterstandorts sowie an aktuellen Abflussreihen validiert und verbessert.
Folgende Forschungsfragen werden bearbeitet: (i) Welche Effekte haben unterschiedliche Klimaszenarien auf den Wasserhaushalt im Elbegebiet und ist eine Neubewertung der Auswirkung des Klimawandels auf den Wasserhaushalt notwendig?, (ii) Was sind die Auswirkungen des Klimawandels auf die Nährstoffeinträge und -frachten im Elbegebiet sowie die Wirksamkeit von Maßnahmen zur Reduktion der Nährstoffeinträge?, (iii) Ist unter der Nutzung (selbst einer sehr geringen Anzahl) verfügbarer tagesaktueller Witterungsdaten in einem stark heterogenen Einzugsgebiet eine valide Ansprache der aktuellen ökohydrologischen Situation des Elbeeinzugsgebiets möglich?
Die aktuellen Szenarien bestätigen die Richtung, jedoch nicht das Ausmaß der Klimafolgen: Die Rückgänge des mittleren jährlichen Gesamtabflusses und der monatlichen Abflüsse an den Pegeln bis Mitte des Jahrhunderts betragen für das STARS-Szenario ca. 30 %. Die Rückgänge bei den auf dem ISI-MIP-Szenario basierenden Modellstudien liegen hingegen nur bei ca. 10 %. Hauptursachen für diese Divergenz sind die Unterschiede in den Niederschlagsprojektionen sowie die Unterschiede in der jahreszeitlichen Verteilung der Erwärmung. Im STARS-Szenario gehen methodisch bedingt die Niederschläge zurück und der Winter erwärmt sich stärker als der Sommer. In dem ISI-MIP-Szenario bleiben die Niederschläge nahezu stabil und die Erwärmung im Sommer und Winter unterscheidet sich nur geringfügig.
Generell nehmen die Nährstoffeinträge und -frachten mit den Abflüssen in beiden Szenarien unterproportional ab, wobei die Frachten jeweils stärker als die Einträge zurückgehen. Die konkreten Effekte der Abflussänderungen sind gering und liegen im einstelligen Prozentbereich. Gleiches gilt für die Unterschiede zwischen den Szenarien. Der Effekt von zwei ausgewählten Maßnahmen zur Reduktion der Nährstoffeinträge und -frachten unterscheidet sich bei verschiedenen Abflussverhältnissen, repräsentiert durch unterschiedliche Klimaszenarien in unterschiedlich feuchter Ausprägung, ebenfalls nur geringfügig.
Die Beantwortung der ersten beiden Forschungsfragen zeigt, dass die Aktualisierung von Klimaszenarien in einem ansonsten "eingefrorenen" Verbund von ökohydrologischen Daten und Modellen eine wichtige Prüfoption für die Plausibilisierung von Klimafolgenanalysen darstellt. Sie bildet die methodische Grundlage für die Schlussfolgerung, dass bei der Wassermenge eine Neubewertung der Klimafolgen notwendig ist, während dies bei den Nährstoffeinträgen und -frachten nicht der Fall ist.
Die zur Beantwortung der dritten Forschungsfrage mit SWIM-live durchgeführten Validierungsstudien ergeben Diskrepanzen am Lysimeterstandort und bei den Abflüssen aus den Teilgebieten Saale und Spree. Sie lassen sich zum Teil mit der notwendigen Interpolationsweite der Witterungsdaten und dem Einfluss von Wasserbewirtschaftungsmaßnahmen erklären. Insgesamt zeigen die Validierungsergebnisse, dass schon die Pilotversion von SWIM-live für eine ökohydrologische Ansprache des Gebietswasserhaushaltes im Elbeeinzugsgebiet genutzt werden kann. SWIM-live ermöglicht eine unmittelbare Betrachtung und Beurteilung simulierter Daten. Dadurch werden Unsicherheiten bei der Modellierung direkt offengelegt und können infolge dessen reduziert werden. Zum einen führte die Verdichtung der meteorologischen Eingangsdaten durch die Verwendung von nun ca. 700 anstatt 19 Klima- bzw. Niederschlagstationen zu einer Verbesserung der Ergebnisse. Zum anderen wurde SWIM-live beispielhaft für einen Zyklus aus punktueller Modellverbesserung und flächiger Überprüfung der Simulationsergebnisse genutzt.
Die einzelnen Teilarbeiten tragen jeweils zur Dynamisierung von Klimafolgenanalysen im Elbegebiet bei. Der Anlass hierfür war durch die fehlerhaften methodischen Grundlagen von STARS gegeben. Die Sinnfälligkeit der Dynamisierung ist jedoch nicht an diesen konkreten Anlass gebunden, sondern beruht auf der grundlegenden Einsicht, dass Ad-hoc-Szenarienanalysen immer auch pragmatische Vereinfachungen zugrunde liegen, die fortlaufend überprüft werden müssen.
Ein Blick zurück
(2016)
1 Einleitung, 2 Die Entstehung des organisierten Turnens in Deutschland, 3 Vom Turnen zum Sport, 4 Friedrich Ludwig Jahn und die Herausbildung der deutschen Turnersprache, 5 Sportsprache in der Zeit des Nationalsozialismus, 6 Didaktische Anregungen, 7 Materialien und Diskussionsanregungen, 8 Literatur
Mit Korbmachern zum Sieg
(2016)
1 Hinführung und Zielstellung, 2 Angestrebte Ergebnisse der Entwicklung lexikalischer Kompetenz - vernetzt mit der Entwicklung von Lese-/Textverstehenskompetenz, 3 Arbeit am Wortschatz und Textverstehen - Textanalyse als das Erschließen eines Feldes von Möglichkeiten, 4 Die Tätigkeit des Schülers optimal in Gang setzen - handlungs-regulierende Aufgaben stellen, 5 Literatur