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Innerhalb dieser Arbeit erfolgte die erstmalige systematische Untersuchung von Vinylsulfonsäureethylester (1a), Phenylvinylsulfon (1b), N-Benzyl-N-methylethensulfonamid (1c) in der FUJIWARA-MORITANI Reaktion (alternativ als DHR bezeichnet). Bei dieser übergangsmetallkatalysierten Reaktion erfolgt der Aufbau einer neuen C-C-Bindung unter der doppelten Aktivierung einer C-H-Bindung. Somit kann ein atomökonomischer Aufbau von Molekülen realisiert werden, da keine Beiprodukte in Form von Salzen entstehen. Als aromatischer Reaktant wurden Acetanilide (2) verwendet, damit eine regiospezifische Kupplung durch die katalysatordirigierende Acetamid-Gruppe (CDG) erfolgt. Für die Pd-katalysierte DHR wurde eine umfangreiche Optimierung durchgeführt und anschließend konnten neun verschieden, substituierte 2 mit 1a und sieben verschieden, substituierte 2 mit 1b funktionalisiert werden. Da eine Reaktion mit 1c ausblieb, erfolgte ein Wechsel auf eine Ru-katalysierte Methode für die DHR. Mit dieser Methode konnte 1c mit Acetaniliden funktionalisiert werden und das Spektrum der verwendeten 2, in Form von deaktivierenden Substituenten erweitert werden.
Im Anschluss wurden die sulfalkenylierten Acetanilide in weiterführenden Reaktionen untersucht. Hierfür wurde eine Reaktionssequenz bestehend aus einer DeacetylierungDiazotierung-Kupplungsreaktion verwendet, um die Acetamid-Gruppe in eine Abgangsgruppe zu überführen und danach in einer MATSUDA-HECK Reaktion zu kuppeln. Mit dieser Methode konnten mehrere 1,2-Dialkenylbenzole erhalten werden und die CDG ein weiteres Mal genutzt werden. Neben der Überführung der CDG in eine Abgangsgruppe konnte diese auch in die Synthese verschiedener Heterozyklen integriert werden. Dafür erfolgte zunächst eine 1,3-Zykloaddition durch deprotonierten Tosylmethylisocanid an der elektronenarmen Sulfalkenylgruppe zur Synthese von Pyrrolen. Anschließend erfolgte eine Kupplung der PyrrolFunktion und der CDG durch Zyklokondensation, wodurch Quinoline dargestellt wurden. Durch diese Synthesen konnten Schwefelanaloga des Naturstoffes Marinoquionolin A erhalten werden.
Ein weitere übergangsmetallkatalysierte C-H-Aktivierungsreaktion, die MATSUDA-HECK Reaktion, wurde genutzt, um 1b zu mit verschieden, subtituierten Diazoniumsalzen zu arylieren. Hier konnten zahlreichen Styrenylsulfone erhalten werden. Der erfolgreiche Einsatz der Vinylsulfonylverbindungen in der Kreuzmetathese konnte innerhalb dieser Arbeit nicht erreicht werden. Daher erfolgte die Synthese verschiedener dialkenylierter Sulfonamide. Hierfür wurde die Kettenlänge der Alkenyl-Gruppe am Schwefel zwischen 2-3 und am Stickstoff zwischen 3-4 variiert. Der Einsatz der dialkenylierten Sulfonamide erfolgte in den zuvor untersuchten C-H-Aktivierungsmethoden.
N-Allyl-N-phenylethensulfonamid (3) konnte erfolgreich in der DHR und HECK Reaktion funktionalisiert werden. Hierbei erfolgte eine methodenspezifische Kupplung in Abhängigkeit von der Elektronendichte der entsprechenden Alkenyl-Gruppe. Die DHR führte zur selektiven Arylierung der Vinyl-Gruppe und die HECK Reaktion zur Arylierung an der Allyl-Gruppe. Gemischte Produkte wurden nicht erhalten. Für die weiteren Diolefine wurde komplexe Produktgemische erhalten. Des Weiteren wurden die Diolefine in der Ringschlussmetathese untersucht und die entsprechenden Sultame in sehr guten Ausbeuten erhalten. Die Verwendung der Sultame in der C-H-Aktivierung war erfolglos. Es wird vermutet, dass für diese zweifachsubstituierten Sulfonamide die vorhandenen Reaktionsbedingungen optimiert werden müssen.
Abschließend wurden verschiedene, enantiomerenreine Olefine ausgehend von Levoglucosenon dargestellt. Hierfür wurde Levoglucosenon zunächst mit einem Allyl- und 3-Butenylgrignard Reagenz umgesetzt. Die entsprechenden Produkte wurden in moderaten Ausbeuten erhalten. Eine weitere Methode begann mit der Reduktion von Levoglucosenon zum Levoglucosenol. Dieser Alkohol wurde mit Allylbromid erfolgreich verethert. Neben der Untersuchungen zur Ethersynthese, erfolgte die Veresterung von Levoglucosenol mit verschiedenen Sulfonylchloriden zu den entsprechenden Sulfonsäureestern. Diese Olefine wurden in einer Dominometathesereaktion untersucht. Ausgehend vom Allyllevoglucosenylether erfolgte die Darstellung eines Dihydrofurans.
Trotz der hohen innovationspolitischen Bedeutung der außeruniversitären Forschungseinrichtungen (AUF) sind sie bisher selten Gegenstand empirischer Untersuchungen. Keine der bisher vorliegenden Arbeiten legt ihren Fokus auf die Zusammenarbeit von Wissenschaftler:innen in Forschungsteams, obwohl wissenschaftliche Zusammenarbeit ein weitgehend unerforschtes Gebiet ist. Dies verwundert insofern, da gerade innovative und komplexe Aufgaben, wie sie im Bereich der Forschung bestehen, das kreative Potenzial Einzelner sowie eine gut funktionierende Kooperation der einzelnen Individuen benötigen. Die Zusammenarbeit von Wissenschaftler:innen in den AUF findet in einem kompetitiven Umfeld statt. Einerseits stehen die AUF auf Organisationsebene im Wettbewerb zueinander und konkurrieren um Forschungsgelder und wissenschaftliches Personal. Andererseits ist die kompetitive Einwerbung von Drittmitteln für Wissenschaftler:innen essentiell, um Leistungen, gemessen an hochrangigen Publikationen und Drittmittelquoten, für die eigene Karriere zu erbringen. Ein zunehmender Anteil an Drittmittelfinanzierung in den Einrichtungen hat zudem Auswirkungen auf die Personalpolitik und die Anzahl befristeter Arbeitsverhältnisse. Gleichzeitig wird Forschungsförderung häufig an Kollaborationen von Wissenschaftler:innen geknüpft und bei Publikationen und Forschungsergebnissen zeigen Studien, dass diese überwiegend das Resultat von mehreren Personen sind. Dieses Spannungsfeld zwischen Zusammenarbeit und Wettbewerb wird verstärkt durch die fehlenden Möglichkeiten für den wissenschaftlichen Nachwuchs in der Wissenschaft zu bleiben. Auch wenn die Bundesregierung auf diese Herausforderungen reagiert, muss der Einzelne seinen Weg zwischen Zusammenarbeit und Konkurrenz finden.
Zielsetzung dieser Arbeit ist es, nachfolgende Forschungsfragen zu beantworten:
1. Wie können naturwissenschaftliche Forschungsteams in AUF charakterisiert werden?
2. Wie agiert die einzelne Forscherin/ der einzelne Forscher im Spannungsfeld zwischen Kooperation und Wettbewerb?
3. Welche Potentiale und Hemmnisse lassen sich auf Individual-, Team- und Umweltebene für eine erfolgreiche Arbeit von Forschungsteams in AUF ausmachen?
Um die Forschungsfragen beantworten zu können, wurde eine empirische Untersuchung im Mixed Method Design, bestehend aus einer deutschlandweiten Onlinebefragung von 574 Naturwissenschaftler:innen in AUF und qualitativen Interviews mit 122 Teammitgliedern aus 20 naturwissenschaftlichen Forschungsteams in AUF, durchgeführt.
Die Ergebnisse zeigen, dass die Teams eher als Arbeitsgruppen bezeichnet werden können, da v.a. in der Grundlagenforschung kein gemeinsames Ziel als vielmehr ein gemeinsamer inhaltlicher Rahmen vorliegt, in dem die Forschenden ihre individuellen Ziele verfolgen. Die Arbeit im Team wird überwiegend als positiv und kooperativ beschrieben und ist v.a. durch gegenseitige Unterstützung bei Problemen und weniger durch einen thematisch wissenschaftlichen Erkenntnisprozess geprägt. Dieser findet vielmehr in Form kleiner Untergruppen innerhalb der Arbeitsgruppe und vor allem in enger Abstimmung mit der Teamleitung (TL) statt. Als wettbewerbsverschärfend werden vor allem organisationale Rahmenbedingungen, wie Befristungen und der Flaschenhals, thematisiert.
Die TL nimmt die zentrale Rolle im Team ein, trägt die wissenschaftliche, finanzielle und personelle Verantwortung und muss den Forderungen der Organisation gerecht werden. Promovierende konzentrieren sich fast ausschließlich auf ihre Qualifizierungsarbeit. Bei Postdocs ist ein Spannungsfeld zu erkennen, da sie eigene Projekte und Ziele verfolgen, die neben den Anforderungen der TL bestehen. Die Gatekeeperfunktion der TL wird gestärkt durch ihre Rolle bei der Weitergabe von karriererelevanten Informationen im Team, z.B. bei anstehenden Konferenzen. Sie hat die wichtigen Kontakte, sorgt für die Vernetzung des Teams und ist für die Netzwerkpflege zuständig. Der wissenschaftliche Nachwuchs verlässt sich bei seinen Aufgaben und den karriererelevanten Faktoren sehr auf ihre Unterstützung. Nicht-wissenschaftliche Mitarbeitende gilt es stärker zu berücksichtigen, dies sowohl in ihrer Funktion in den Teams als auch in der Gesamtorganisation. Sie sind die zentralen Ansprechpersonen des wissenschaftlichen Personals und sorgen für eine Kontinuität bei der Wissensspeicherung und -weitergabe. Für die Organisationen gilt es, unterstützende Rahmen-, Arbeits- und Aufgabenbedingungen für die TL zu schaffen und den wissenschaftlichen Nachwuchs bei einer frühzeitigen Verantwortung für wissenschaftliche und karriererelevante Aufgaben zu unterstützen. Dafür bedarf es verbesserter Personalentwicklungskonzepte und -angebote. Darüber hinaus gilt es, Kooperationsmöglichkeiten innerhalb der Einrichtung und zwischen den Gruppen zu schaffen, z.B. durch offene Räume und Netzwerkmöglichkeiten, und innovative Arbeitsumgebungen zu fördern, um neue Formen einer innovationsfreundlichen Wissenschaftskultur zu etablieren.
Die vorliegende Studie beschäftigt sich mit der Planung und Durchführung des Lernprozesses von Schauspielern, wobei das Hauptaugenmerk auf dem Einsatz von Lernstrategien liegt. Es geht darum, welcher Strategien sich professionell Lernende bedienen, um die für die Berufsausübung erforderliche Textsicherheit zu erlangen, nicht um die Optimierung des Lernerfolges.
Die Literaturrecherche machte deutlich, dass aktuelle Studien zum Lernen von Erwachsenen vor allem im berufsspezifischen Kontext angesiedelt sind und sich auf den Erwerb von Kompetenzen, Problemlösestrategien und gesellschaftliche Teilhabe beziehen. Dem Lernen von Schauspielern liegt aber keine Absicht einer Verhaltensänderung oder eines konkreten Wissenszuwachses zugrunde.
Für Schauspieler ist der Auftritt Bestandteil ihrer Berufskultur. Angesichts der Tatsache, dass präzisem Faktenwissen als Grundlage für kompetentes, überzeugendes Präsentieren entscheidende Bedeutung zukommt, sind die Ergebnisse der Studie auch für Berufsgruppen relevant, die öffentlich auftreten müssen, wie z. B. für Priester, Juristen und Lehrende. Das gilt ebenso für Schüler und Studenten, die Referate halten und/oder Arbeiten präsentieren müssen.
Für die empirische Untersuchung werden zwölf renommierte Schauspieler mittels problemzentriertem Interview befragt, anschließend wird eine qualitative Inhaltsanalyse durchgeführt.
In der Auswertung der Daten kann ein deutlicher Zusammenhang zwischen Körper und Sprechpraxis nachgewiesen werden. Ebenso ergibt die Analyse, wie wichtig Bewegung für den Lernprozess ist. Es können Ergebnisse in Bezug auf kognitive, metakognitive und ressourcenorientierte Strategien generiert werden, wobei der Lernumgebung und dem Lernen mit Kollegen entscheidende Bedeutung zukommt.
Zum Einfluss von Adaptivität auf die Wahrnehmung von Komplexität in der Mensch-Technik-Interaktion
(2021)
Wir leben in einer Gesellschaft, die von einem stetigen Wunsch nach Innovation und Fortschritt geprägt ist. Folgen dieses Wunsches sind die immer weiter fortschreitende Digitalisierung und informatische Vernetzung aller Lebensbereiche, die so zu immer komplexeren sozio-technischen Systemen führen. Ziele dieser Systeme sind u. a. die Unterstützung von Menschen, die Verbesserung ihrer Lebenssituation oder Lebensqualität oder die Erweiterung menschlicher Möglichkeiten. Doch haben neue komplexe technische Systeme nicht nur positive soziale und gesellschaftliche Effekte. Oft gibt es unerwünschte Nebeneffekte, die erst im Gebrauch sichtbar werden, und sowohl Konstrukteur*innen als auch Nutzer*innen komplexer vernetzter Technologien fühlen sich oft orientierungslos. Die Folgen können von sinkender Akzeptanz bis hin zum kompletten Verlust des Vertrauens in vernetze Softwaresysteme reichen. Da komplexe Anwendungen, und damit auch immer komplexere Mensch-Technik-Interaktionen, immer mehr an Relevanz gewinnen, ist es umso wichtiger, wieder Orientierung zu finden. Dazu müssen wir zuerst diejenigen Elemente identifizieren, die in der Interaktion mit vernetzten sozio-technischen Systemen zu Komplexität beitragen und somit Orientierungsbedarf hervorrufen.
Mit dieser Arbeit soll ein Beitrag geleistet werden, um ein strukturiertes Reflektieren über die Komplexität vernetzter sozio-technischer Systeme im gesamten Konstruktionsprozess zu ermöglichen. Dazu wird zuerst eine Definition von Komplexität und komplexen Systemen erarbeitet, die über das informatische Verständnis von Komplexität (also der Kompliziertheit von Problemen, Algorithmen oder Daten) hinausgeht. Im Vordergrund soll vielmehr die sozio-technische Interaktion mit und in komplexen vernetzten Systemen stehen. Basierend auf dieser Definition wird dann ein Analysewerkzeug entwickelt, welches es ermöglicht, die Komplexität in der Interaktion mit sozio-technischen Systemen sichtbar und beschreibbar zu machen.
Ein Bereich, in dem vernetzte sozio-technische Systeme zunehmenden Einzug finden, ist jener digitaler Bildungstechnologien. Besonders adaptiven Bildungstechnologien wurde in den letzten Jahrzehnten ein großes Potential zugeschrieben. Zwei adaptive Lehr- bzw. Trainingssysteme sollen deshalb exemplarisch mit dem in dieser Arbeit entwickelten Analysewerkzeug untersucht werden. Hierbei wird ein besonderes Augenmerkt auf den Einfluss von Adaptivität auf die Komplexität von Mensch-Technik-Interaktionssituationen gelegt. In empirischen Untersuchungen werden die Erfahrungen von Konstrukteur*innen und Nutzer*innen jener adaptiver Systeme untersucht, um so die entscheidenden Kriterien für Komplexität ermitteln zu können. Auf diese Weise können zum einen wiederkehrende Orientierungsfragen bei der Entwicklung adaptiver Bildungstechnologien aufgedeckt werden. Zum anderen werden als komplex wahrgenommene Interaktionssituationen identifiziert. An diesen Situationen kann gezeigt werden, wo aufgrund der Komplexität des Systems die etablierten Alltagsroutinen von Nutzenden nicht mehr ausreichen, um die Folgen der Interaktion mit dem System vollständig erfassen zu können. Dieses Wissen kann sowohl Konstrukteur*innen als auch Nutzer*innen helfen, in Zukunft besser mit der inhärenten Komplexität moderner Bildungstechnologien umzugehen.
The present work deals with the variation in the linearisation of German infinitival complements from a diachronic perspective. Based on the observation that in present-day German the position of infinitival complements is restricted by properties of the matrix verb (Haider, 2010, Wurmbrand, 2001), whereas this appears much more liberal in older stages of German (Demske, 2008, Maché and Abraham, 2011, Demske, 2015), this dissertation investigates the emergence of those restrictions and the factors that have led to a reduced, yet still existing variability. The study contrasts infinitival complements of two types of matrix verbs, namely raising and control verbs. In present-day German, these show different syntactic behaviour and opposite preferences as far as the position of the infinitive is concerned: while infinitival complements of raising verbs build a single clausal domain with the with the matrix verb and occur obligatorily intraposed, infinitive complements of control verbs can form clausal constituents and occur predominantly extraposed. This correlation is not attested in older stages of German, at least not until Early New High German.
Drawing on diachronic corpus data, the present work provides a description of the changes in the linearisation of infinitival complements from Early New High German to present-day German which aims at finding out when the correlation between infinitive type and word order emerged and further examines their possible causes. The study shows that word order change in German infinitival complements is not a case of syntactic change in the narrow sense, but that the diachronic variation results from the interaction of different language-internal and language-external factors and that it reflects, on the one hand, the influence of language modality on the emerging standard language and, on the other hand, a process of specialisation.
Das Schulfach Geographie war in der DDR eines der Fächer, das sehr stark mit politischen Themen im Sinne des Marxismus-Leninismus bestückt war. Ein anderer Aspekt sind die sozialistischen Erziehungsziele, die in der Schulbildung der DDR hoch im Kurs standen. Im Fokus stand diesbezüglich die Erziehung der Kinder zu sozialistischen Persönlichkeiten. Die Arbeit versucht einen klaren Blick auf diesen Umstand zu werfen, um zu erfahren, was da von den Lehrkräften gefordert wurde und wie es in der Schule umzusetzen war.
Durch den Fall der Mauer war natürlich auch eine Umstrukturierung des Bildungssystems im Osten unausweichlich. Hier will die Arbeit Einblicke geben, wie die Geographielehrkräfte diese Transformation mitgetragen und umgesetzt haben. Welche Wesenszüge aus der Sozialisierung in der DDR haben sich bei der Gestaltung des Unterrichtes und dessen Ausrichtung auf die neuen Erziehungsziele erhalten?
Hierzu wurden Geographielehrkräfte befragt, die sowohl in der DDR als auch im geeinten Deutschland unterrichtet haben. Die Fragen bezogen sich in erster Linie auf die Art und Weise des Unterrichtens vor, während und nach der Wende und der daraus entstandenen Systemtransformation.
Die Befragungen kommen zu dem Ergebnis, dass sich der Geographieunterricht in der DDR thematisch von dem in der BRD nicht sonderlich unterschied. Von daher bedurfte es keiner umfangreichen inhaltlichen Veränderung des Geographieunterrichts. Schon zu DDR-Zeiten wurden durch die Lehrkräfte offenbar eigenmächtig ideologiefreie physisch-geographische Themen oft ausgedehnt, um die Ideologie des Faches zu reduzieren. So fiel den meisten eine Anpassung ihres Unterrichts an das westdeutsche System relativ leicht. Die humanistisch geprägte Werteerziehung des DDR-Bildungssystems wurde unter Ausklammerung des sozialistischen Aspektes ebenso fortgeführt, da es auch hier viele Parallelen zum westdeutschen System gegeben hat. Deutlich wird eine Charakterisierung des Faches als Naturwissenschaft von Seiten der ostdeutschen Lehrkräfte, obwohl das Fach an den Schulen den Gesellschaftswissenschaften zugeordnet wird und auch in der DDR eine starke wirtschaftsgeographische Ausrichtung hatte.
Von der Verantwortung sozialistische Persönlichkeiten zu erziehen, wurden die Lehrkräfte mit dem Ende der DDR entbunden und die in dieser Arbeit aufgeführten Interviewauszüge lassen keinen Zweifel daran, dass es dem Großteil der Befragten darum nicht leidtat, sie sich aber bis heute an der Werteorientierung aus DDR-Zeiten orientieren.
Was ist HipHop?
(2021)
Es handelt sich bei der vorliegenden Dissertation um eine investigative Forschungsarbeit, die sich mit dem dynamisch wandelnden HipHop-Phänomen befasst. Der Autor erläutert hierbei die anhaltende Attraktivität des kulturellen Phänomens HipHop und versucht die Tatsache der stetigen Reproduzierbarkeit des HipHops genauer zu erklären. Daher beginnt er mit einer historischen Diskursanalyse der HipHop-Kultur. Er analysiert hierfür die Formen, die Protagonisten und die Diskurse des HipHops, um diesen besser verstehen zu können. Durch die Herausarbeitung der genuinen Eigenschaft der Mehrfachkodierbarkeit des HipHops werden gängige Erklärungsmuster aus Wissenschaft und Medien relativiert und kritisiert. Der Autor kombiniert in seiner Studie kultur- und erziehungswissenschaftliche Literatur mit diversen aktuellen und historischen Darstellungen und Bildern. Es werden vor allem bildbasierte Selbstinszenierungen von HipHoppern und Selbstzeugnisse aus narrativen Interviews, die er selbst mit verschiedenen HipHoppern in Deutschland geführt hat, ausgewertet. Neben den narrativen Interviews dient vor allem die Bildinterpretation nach Bohnsack als Quelle zur Bildung der These der Mehrfachkodierbarkeit. Hierbei werden zwei Bilder der HipHopper Lady Bitch Ray und Kollegah nach Bohnsack (2014) interpretiert und gezeigt wie HipHop neben der lyrischen und der klanglichen Komponente auch visuell inszeniert und produziert wird. Hieraus wird geschlussfolgert, dass es im HipHop möglich ist konträre Sichtweisen bei gleichzeitiger Anwendung von typischen Kulturpraktiken wie zum Beispiel dem Boasting darzustellen und zu vermitteln. Die stetige Offenheit des HipHops wird durch Praktiken wie dem Sampling oder dem Battle deutlich und der Autor erklärt, dass durch diese Techniken die generative Eigenschaft der Mehrfachkodierbarkeit hergestellt wird. Damit vertritt er eine Art Baukasten-Theorie, die besagt, dass sich prinzipiell jeder aus dem Baukasten HipHop, je nach Vorliebe, Interesse und Affinität, bedienen kann. Durch die Vielfalt an Meinungen zu HipHop, die der Autor durch die Kodierung der geführten narrativen Interviews erhält, wird diese These verdeutlicht und es wird klar, dass es sich bei HipHop um mehr als nur eine Mode handelt. HipHop besitzt die prinzipielle Möglichkeit durch die Offenheit, die er in sich trägt, sich stetig neu zu wandeln und damit an Beliebtheit und Popularität zuzunehmen. Die vorliegende Arbeit erweitert damit die immer größer werdende Forschung in den HipHop-Studies und setzt wichtige Akzente um weiter zu forschen und HipHop besser verständlich zu machen.
Virtualizing physical space
(2021)
The true cost for virtual reality is not the hardware, but the physical space it requires, as a one-to-one mapping of physical space to virtual space allows for the most immersive way of navigating in virtual reality. Such “real-walking” requires physical space to be of the same size and the same shape of the virtual world represented. This generally prevents real-walking applications from running on any space that they were not designed for.
To reduce virtual reality’s demand for physical space, creators of such applications let users navigate virtual space by means of a treadmill, altered mappings of physical to virtual space, hand-held controllers, or gesture-based techniques. While all of these solutions succeed at reducing virtual reality’s demand for physical space, none of them reach the same level of immersion that real-walking provides.
Our approach is to virtualize physical space: instead of accessing physical space directly, we allow applications to express their need for space in an abstract way, which our software systems then map to the physical space available. We allow real-walking applications to run in spaces of different size, different shape, and in spaces containing different physical objects. We also allow users immersed in different virtual environments to share the same space.
Our systems achieve this by using a tracking volume-independent representation of real-walking experiences — a graph structure that expresses the spatial and logical relationships between virtual locations, virtual elements contained within those locations, and user interactions with those elements. When run in a specific physical space, this graph representation is used to define a custom mapping of the elements of the virtual reality application and the physical space by parsing the graph using a constraint solver. To re-use space, our system splits virtual scenes and overlap virtual geometry. The system derives this split by means of hierarchically clustering of our virtual objects as nodes of our bi-partite directed graph that represents the logical ordering of events of the experience. We let applications express their demands for physical space and use pre-emptive scheduling between applications to have them share space. We present several application examples enabled by our system. They all enable real-walking, despite being mapped to physical spaces of different size and shape, containing different physical objects or other users.
We see substantial real-world impact in our systems. Today’s commercial virtual reality applications are generally designing to be navigated using less immersive solutions, as this allows them to be operated on any tracking volume. While this is a commercial necessity for the developers, it misses out on the higher immersion offered by real-walking. We let developers overcome this hurdle by allowing experiences to bring real-walking to any tracking volume, thus potentially bringing real-walking to consumers.
Die eigentlichen Kosten für Virtual Reality Anwendungen entstehen nicht primär durch die erforderliche Hardware, sondern durch die Nutzung von physischem Raum, da die eins-zu-eins Abbildung von physischem auf virtuellem Raum die immersivste Art von Navigation ermöglicht. Dieses als „Real-Walking“ bezeichnete Erlebnis erfordert hinsichtlich Größe und Form eine Entsprechung von physischem Raum und virtueller Welt. Resultierend daraus können Real-Walking-Anwendungen nicht an Orten angewandt werden, für die sie nicht entwickelt wurden.
Um den Bedarf an physischem Raum zu reduzieren, lassen Entwickler von Virtual Reality-Anwendungen ihre Nutzer auf verschiedene Arten navigieren, etwa mit Hilfe eines Laufbandes, verfälschten Abbildungen von physischem zu virtuellem Raum, Handheld-Controllern oder gestenbasierten Techniken. All diese Lösungen reduzieren zwar den Bedarf an physischem Raum, erreichen jedoch nicht denselben Grad an Immersion, den Real-Walking bietet.
Unser Ansatz zielt darauf, physischen Raum zu virtualisieren: Anstatt auf den physischen Raum direkt zuzugreifen, lassen wir Anwendungen ihren Raumbedarf auf abstrakte Weise formulieren, den unsere Softwaresysteme anschließend auf den verfügbaren physischen Raum abbilden. Dadurch ermöglichen wir Real-Walking-Anwendungen Räume mit unterschiedlichen Größen und Formen und Räume, die unterschiedliche physische Objekte enthalten, zu nutzen. Wir ermöglichen auch die zeitgleiche Nutzung desselben Raums durch mehrere Nutzer verschiedener Real-Walking-Anwendungen.
Unsere Systeme erreichen dieses Resultat durch eine Repräsentation von Real-Walking-Erfahrungen, die unabhängig sind vom gegebenen Trackingvolumen – eine Graphenstruktur, die die räumlichen und logischen Beziehungen zwischen virtuellen Orten, den virtuellen Elementen innerhalb dieser Orte, und Benutzerinteraktionen mit diesen Elementen, ausdrückt. Bei der Instanziierung der Anwendung in einem bestimmten physischen Raum wird diese Graphenstruktur und ein Constraint Solver verwendet, um eine individuelle Abbildung der virtuellen Elemente auf den physischen Raum zu erreichen. Zur mehrmaligen Verwendung des Raumes teilt unser System virtuelle Szenen und überlagert virtuelle Geometrie. Das System leitet diese Aufteilung anhand eines hierarchischen Clusterings unserer virtuellen Objekte ab, die als Knoten unseres bi-partiten, gerichteten Graphen die logische Reihenfolge aller Ereignisse repräsentieren. Wir verwenden präemptives Scheduling zwischen den Anwendungen für die zeitgleiche Nutzung von physischem Raum. Wir stellen mehrere Anwendungsbeispiele vor, die Real-Walking ermöglichen – in physischen Räumen mit unterschiedlicher Größe und Form, die verschiedene physische Objekte oder weitere Nutzer enthalten.
Wir sehen in unseren Systemen substantielles Potential. Heutige Virtual Reality-Anwendungen sind bisher zwar so konzipiert, dass sie auf einem beliebigen Trackingvolumen betrieben werden können, aber aus kommerzieller Notwendigkeit kein Real-Walking beinhalten. Damit entgeht Entwicklern die Gelegenheit eine höhere Immersion herzustellen. Indem wir es ermöglichen, Real-Walking auf jedes Trackingvolumen zu bringen, geben wir Entwicklern die Möglichkeit Real-Walking zu ihren Nutzern zu bringen.
Rheology describes the flow of matter under the influence of stress, and - related to solids- it investigates how solids subjected to stresses deform. As the deformation of the Earth’s outer layers, the lithosphere and the crust, is a major focus of rheological studies, rheology in the geosciences describes how strain evolves in rocks of variable composition and temperature under tectonic stresses. It is here where deformation processes shape the form of ocean basins and mountain belts that ultimately result from the complex interplay between lithospheric plate motion and the susceptibility of rocks to the influence of plate-tectonic forces. A rigorous study of the strength of the lithosphere and deformation phenomena thus requires in-depth studies of the rheological characteristics of the involved materials and the temporal framework of deformation processes.
This dissertation aims at analyzing the influence of the physical configuration of the lithosphere on the present-day thermal field and the overall rheological characteristics of the lithosphere to better understand variable expressions in the formation of passive continental margins and the behavior of strike-slip fault zones. The main methodological approach chosen is to estimate the present-day thermal field and the strength of the lithosphere by 3-D numerical modeling. The distribution of rock properties is provided by 3-D structural models, which are used as the basis for the thermal and rheological modeling. The structural models are based on geophysical and geological data integration, additionally constrained by 3-D density modeling. More specifically, to decipher the thermal and rheological characteristics of the lithosphere in both oceanic and continental domains, sedimentary basins in the Sea of Marmara (continental transform setting), the SW African passive margin (old oceanic crust), and the Norwegian passive margin (young oceanic crust) were selected for this study.
The Sea of Marmara, in northwestern Turkey, is located where the dextral North Anatolian Fault zone (NAFZ) accommodates the westward escape of the Anatolian Plate toward the Aegean. Geophysical observations indicate that the crust is heterogeneous beneath the Marmara basin, but a detailed characterization of the lateral crustal heterogeneities is presented for the first time in this study. Here, I use different gravity datasets and the general non-uniqueness in potential field modeling, to propose three possible end-member scenarios of crustal configuration. The models suggest that pronounced gravitational anomalies in the basin originate from significant density heterogeneities within the crust. The rheological modeling reveals that associated variations in lithospheric strength control the mechanical segmentation of the NAFZ. Importantly, a strong crust that is mechanically coupled to the upper mantle spatially correlates with aseismic patches where the fault bends and changes its strike in response to the presence of high-density lower crustal bodies. Between the bends, mechanically weaker crustal domains that are decoupled from the mantle are characterized by creep.
For the passive margins of SW Africa and Norway, two previously published 3-D conductive and lithospheric-scale thermal models were analyzed. These 3-D models differentiate various sedimentary, crustal, and mantle units and integrate different geophysical data, such as seismic observations and the gravity field. Here, the rheological modeling suggests that the present-day lithospheric strength across the oceanic domain is ultimately affected by the age and past thermal and tectonic processes as well as the depth of the thermal lithosphere-asthenosphere boundary, while the configuration of the crystalline crust dominantly controls the rheological behavior of the lithosphere beneath the continental domains of both passive margins.
The thermal and rheological models show that the variations of lithospheric strength are fundamentally influenced by the temperature distribution within the lithosphere. Moreover, as the composition of the lithosphere significantly influences the present-day thermal field, it therefore also affects the rheological characteristics of the lithosphere. Overall my studies add to our understanding of regional tectonic deformation processes and the long-term behavior of sedimentary basins; they confirm other analyses that have pointed out that crustal heterogeneities in the continents result in diverse lithospheric thermal characteristics, which in turn results in higher complexity and variations of rheological behavior compared to oceanic domains with a thinner, more homogeneous crust.
Die vorliegende Dissertation behandelt drei thematische Schwerpunkte. Im Ergebnisteil steht die chemische Synthese von sogenannten (1,7)-Naphthalenophanen im Vordergrund, die zur Substanzklasse von Cyclophanen gehören. Während zahlreiche Synthesemethoden Strategien zum Aufbau von Ringsystemen (wie z. B. von Naphthalenophanen) verfolgen, die Teil einer bereits existierenden aromatischen Struktur der Ausgangsverbindung sind, nutzen nur wenige Ansätze Reaktionen, die einen Ringschluss zum gewünschten Produkt erst im Zuge der Synthese etablieren. Eine Benzanellierung, die eine besondere Aufmerksamkeit im Arbeitskreis erfahren hat, ist die Dehydro-DIELS-ALDER-Reaktion (DDA-Reaktion). Im Rahmen dieser Arbeit konnte gezeigt werden, dass zwölf ausgewählte (1,7)-Naphthalenophane, die teilweise ringgespannt und makrozyklisch aufgebaut waren, mithilfe einer photochemischen Variante der DDA-Reaktion (PDDA-Reaktion) zugänglich gemacht werden können. Die Versuche, auf thermischem Wege (TDDA-Reaktion) (1,7)-Naphthalenophane herzustellen, misslangen. Die außergewöhnliche Reaktivität der Photoreaktanten konnte mithilfe quantenchemischer Berechnungen durch eine gefaltete Grundzustandsgeometrie erklärt werden. Darüber hinaus wurden Ringspannungen und strukturelle Spannungsindikatoren der relevanten Photoprodukte ermittelt und Trends in Abhängigkeit der Linkerlänge in den NMR-Spektren der Zielverbindungen ermittelt sowie diskutiert. Zudem zeigte eine Variation am Chromophor (Acyl-, Carbonsäure- und Carbonsäureester) der Photoreaktanten bei der Bestrahlung in Dichlormethan eine vergleichbare Photokinetik und -reaktivität. Der zweite Abschnitt dieser Dissertation ist dem Design und der Entwicklung zweier Photoreaktoren für UV-Anwendungen im kontinuierlichen Durchfluss gewidmet, da photochemische Transformationen bekanntermaßen in ihrer Skalierbarkeit limitiert sind. Im ersten Prototyp konnten mittels effizienter Parallelschaltung mit bis zu drei UV-Lampen (𝜆𝜆 = 254, 310 und 355 nm) Produktmaterialmengen von bis zu n = 188 mmol anhand eines ausgewählten Fallbeispiels erreicht werden. Im konstruktionstechnisch stark vereinfachten zweiten Photoreaktor wurden alle quarzhaltigen Elemente gegen günstigeres PLEXIGLAS® ersetzt. Das Resultat waren identische Raum-Zeit-Ausbeuten in Bezug auf das zuvor gewählte Synthesebeispiel. Demnach bietet die UV-Photochemie im kontinuierlichen Durchfluss Vorteile gegenüber der traditionellen Bestrahlung im Tauchreaktor. Hinsichtlich Reaktionszeit, Produktausbeuten und Lösemittelverbrauch ist sie synthetisch weit überlegen. Im letzten Abschnitt der Arbeit wurden diese Erkenntnisse genutzt, um biomedizinisch und pharmakologisch vielversprechende 1-Arylnaphthalen-Lignane mittels einer intramolekularen PDDA-Reaktion (IMPDDA-Reaktion) als Schlüsselschritt herzustellen. Hierzu wurden drei Konzepte erarbeitet und in der Totalsynthese von drei ausgewählten Zielstrukturen auf Basis des 1-Arylnaphthalengrundgerüsts realisiert.
The Earth's electron radiation belts exhibit a two-zone structure, with the outer belt being highly dynamic due to the constant competition between a number of physical processes, including acceleration, loss, and transport. The flux of electrons in the outer belt can vary over several orders of magnitude, reaching levels that may disrupt satellite operations. Therefore, understanding the mechanisms that drive these variations is of high interest to the scientific community.
In particular, the important role played by loss mechanisms in controlling relativistic electron dynamics has become increasingly clear in recent years. It is now widely accepted that radiation belt electrons can be lost either by precipitation into the atmosphere or by transport across the magnetopause, called magnetopause shadowing. Precipitation of electrons occurs due to pitch-angle scattering by resonant interaction with various types of waves, including whistler mode chorus, plasmaspheric hiss, and electromagnetic ion cyclotron waves. In addition, the compression of the magnetopause due to increases in solar wind dynamic pressure can substantially deplete electrons at high L shells where they find themselves in open drift paths, whereas electrons at low L shells can be lost through outward radial diffusion. Nevertheless, the role played by each physical process during electron flux dropouts still remains a fundamental puzzle.
Differentiation between these processes and quantification of their relative contributions to the evolution of radiation belt electrons requires high-resolution profiles of phase space density (PSD). However, such profiles of PSD are difficult to obtain due to restrictions of spacecraft observations to a single measurement in space and time, which is also compounded by the inaccuracy of instruments. Data assimilation techniques aim to blend incomplete and inaccurate spaceborne data with physics-based models in an optimal way. In the Earth's radiation belts, it is used to reconstruct the entire radial profile of electron PSD, and it has become an increasingly important tool in validating our current understanding of radiation belt dynamics, identifying new physical processes, and predicting the near-Earth hazardous radiation environment.
In this study, sparse measurements from Van Allen Probes A and B and Geostationary Operational Environmental Satellites (GOES) 13 and 15 are assimilated into the three-dimensional Versatile Electron Radiation Belt (VERB-3D) diffusion model, by means of a split-operator Kalman filter over a four-year period from 01 October 2012 to 01 October 2016. In comparison to previous works, the 3D model accounts for more physical processes, namely mixed pitch angle-energy diffusion, scattering by EMIC waves, and magnetopause shadowing. It is shown how data assimilation, by means of the innovation vector (the residual between observations and model forecast), can be used to account for missing physics in the model. This method is used to identify the radial distances from the Earth and the geomagnetic conditions where the model is inconsistent with the measured PSD for different values of the adiabatic invariants mu and K. As a result, the Kalman filter adjusts the predictions in order to match the observations, and this is interpreted as evidence of where and when additional source or loss processes are active.
Furthermore, two distinct loss mechanisms responsible for the rapid dropouts of radiation belt electrons are investigated: EMIC wave-induced scattering and magnetopause shadowing. The innovation vector is inspected for values of the invariant mu ranging from 300 to 3000 MeV/G, and a statistical analysis is performed to quantitatively assess the effect of both processes as a function of various geomagnetic indices, solar wind parameters, and radial distance from the Earth. The results of this work are in agreement with previous studies that demonstrated the energy dependence of these two mechanisms. EMIC wave scattering dominates loss at lower L shells and it may amount to between 10%/hr to 30%/hr of the maximum value of PSD over all L shells for fixed first and second adiabatic invariants. On the other hand, magnetopause shadowing is found to deplete electrons across all energies, mostly at higher L shells, resulting in loss from 50%/hr to 70%/hr of the maximum PSD. Nevertheless, during times of enhanced geomagnetic activity, both processes can operate beyond such location and encompass the entire outer radiation belt.
The results of this study are two-fold. Firstly, it demonstrates that the 3D data assimilative code provides a comprehensive picture of the radiation belts and is an important step toward performing reanalysis using observations from current and future missions. Secondly, it achieves a better understanding and provides critical clues of the dominant loss mechanisms responsible for the rapid dropouts of electrons at different locations over the outer radiation belt.
In the frame of a world fighting a dramatic global warming caused by human-related activities, research towards the development of renewable energies plays a crucial role. Solar energy is one of the most important clean energy sources and its role in the satisfaction of the global energy demand is set to increase. In this context, a particular class of materials captured the attention of the scientific community for its attractive properties: halide perovskites. Devices with perovskite as light-absorber saw an impressive development within the last decade, reaching nowadays efficiencies comparable to mature photovoltaic technologies like silicon solar cells. Yet, there are still several roadblocks to overcome before a wide-spread commercialization of this kind of devices is enabled. One of the critical points lies at the interfaces: perovskite solar cells (PSCs) are made of several layers with different chemical and physical features. In order for the device to function properly, these properties have to be well-matched.
This dissertation deals with some of the challenges related to interfaces in PSCs, with a focus on the interface between the perovskite material itself and the subsequent charge transport layer. In particular, molecular assemblies with specific properties are deposited on the perovskite surface to functionalize it. The functionalization results in energy level alignment adjustment, interfacial losses reduction, and stability improvement.
First, a strategy to tune the perovskite’s energy levels is introduced: self-assembled monolayers of dipolar molecules are used to functionalize the surface, obtaining simultaneously a shift in the vacuum level position and a saturation of the dangling bonds at the surface. A shift in the vacuum level corresponds to an equal change in work function, ionization energy, and electron affinity. The direction of the shift depends on the direction of the collective interfacial dipole. The magnitude of the shift can be tailored by controlling the deposition parameters, such as the concentration of the solution used for the deposition. The shift for different molecules is characterized by several non-invasive techniques, including in particular Kelvin probe. Overall, it is shown that it is possible to shift the perovskite energy levels in both directions by several hundreds of meV. Moreover, interesting insights on the molecules deposition dynamics are revealed.
Secondly, the application of this strategy in perovskite solar cells is explored. Devices with different perovskite compositions (“triple cation perovskite” and MAPbBr3) are prepared. The two resulting model systems present different energetic offsets at the perovskite/hole-transport layer interface. Upon tailored perovskite surface functionalization, the devices show a stabilized open circuit voltage (Voc) enhancement of approximately 60 meV on average for devices with MAPbBr3, while the impact is limited on triple-cation solar cells. This suggests that the proposed energy level tuning method is valid, but its effectiveness depends on factors such as the significance of the energetic offset compared to the other losses in the devices.
Finally, the above presented method is further developed by incorporating the ability to interact with the perovskite surface directly into a novel hole-transport material (HTM), named PFI. The HTM can anchor to the perovskite halide ions via halogen bonding (XB). Its behaviour is compared to that of another HTM (PF) with same chemical structure and properties, except for the ability of forming XB. The interaction of perovskite with PFI and PF is characterized through UV-Vis, atomic force microscopy and Kelvin probe measurements combined with simulations. Compared to PF, PFI exhibits enhanced resilience against solvent exposure and improved energy level alignment with the perovskite layer. As a consequence, devices comprising PFI show enhanced Voc and operational stability during maximum-power-point tracking, in addition to hysteresis reduction. XB promotes the formation of a high-quality interface by anchoring to the halide ions and forming a stable and ordered interfacial layer, showing to be a particularly interesting candidate for the development of tailored charge transport materials in PSCs.
Overall, the results exposed in this dissertation introduce and discuss a versatile tool to functionalize the perovskite surface and tune its energy levels. The application of this method in devices is explored and insights on its challenges and advantages are given. Within this frame, the results shed light on XB as ideal interaction for enhancing stability and efficiency in perovskite-based devices.
Transient permeability in porous and fractured sandstones mediated by fluid-rock interactions
(2021)
Understanding the fluid transport properties of subsurface rocks is essential for a large number of geotechnical applications, such as hydrocarbon (oil/gas) exploitation, geological storage (CO2/fluids), and geothermal reservoir utilization. To date, the hydromechanically-dependent fluid flow patterns in porous media and single macroscopic rock fractures have received numerous investigations and are relatively well understood. In contrast, fluid-rock interactions, which may permanently affect rock permeability by reshaping the structure and changing connectivity of pore throats or fracture apertures, need to be further elaborated. This is of significant importance for improving the knowledge of the long-term evolution of rock transport properties and evaluating a reservoir’ sustainability. The thesis focuses on geothermal energy utilization, e.g., seasonal heat storage in aquifers and enhanced geothermal systems, where single fluid flow in porous rocks and rock fracture networks under various pressure and temperature conditions dominates.
In this experimental study, outcrop samples (i.e., Flechtinger sandstone, an illite-bearing Lower Permian rock, and Fontainebleau sandstone, consisting of pure quartz) were used for flow-through experiments under simulated hydrothermal conditions. The themes of the thesis are (1) the investigation of clay particle migration in intact Flechtinger sandstone and the coincident permeability damage upon cyclic temperature and fluid salinity variations; (2) the determination of hydro-mechanical properties of self-propping fractures in Flechtinger and Fontainebleau sandstones with different fracture features and contrasting mechanical properties; and (3) the investigation of the time-dependent fracture aperture evolution of Fontainebleau sandstone induced by fluid-rock interactions (i.e., predominantly pressure solution). Overall, the thesis aims to unravel the mechanisms of the instantaneous reduction (i.e., direct responses to thermo-hydro-mechanical-chemical (THMC) conditions) and progressively-cumulative changes (i.e., time-dependence) of rock transport properties.
Permeability of intact Flechtinger sandstone samples was measured under each constant condition, where temperature (room temperature up to 145 °C) and fluid salinity (NaCl: 0 ~ 2 mol/l) were stepwise changed. Mercury intrusion porosimetry (MIP), electron microprobe analysis (EMPA), and scanning electron microscopy (SEM) were performed to investigate the changes of local porosity, microstructures, and clay element contents before and after the experiments. The results indicate that the permeability of illite-bearing Flechtinger sandstones will be impaired by heating and exposure to low salinity pore fluids. The chemically induced permeability variations prove to be path-dependent concerning the applied succession of fluid salinity changes. The permeability decay induced by a temperature increase and a fluid salinity reduction operates by relatively independent mechanisms, i.e., thermo-mechanical and thermo-chemical effects.
Further, the hydro-mechanical investigations of single macroscopic fractures (aligned, mismatched tensile fractures, and smooth saw-cut fractures) illustrate that a relative fracture wall offset could significantly increase fracture aperture and permeability, but the degree of increase depends on fracture surface roughness. X-ray computed tomography (CT) demonstrates that the contact area ratio after the pressure cycles is inversely correlated to the fracture offset. Moreover, rock mechanical properties, determining the strength of contact asperities, are crucial so that relatively harder rock (i.e., Fontainebleau sandstone) would have a higher self-propping potential for sustainable permeability during pressurization. This implies that self-propping rough fractures with a sufficient displacement are efficient pathways for fluid flow if the rock matrix is mechanically strong.
Finally, two long-term flow-through experiments with Fontainebleau sandstone samples containing single fractures were conducted with an intermittent flow (~140 days) and continuous flow (~120 days), respectively. Permeability and fluid element concentrations were measured throughout the experiments. Permeability reduction occurred at the beginning stage when the stress was applied, while it converged at later stages, even under stressed conditions. Fluid chemistry and microstructure observations demonstrate that pressure solution governs the long-term fracture aperture deformation, with remarkable effects of the pore fluid (Si) concentration and the structure of contact grain boundaries. The retardation and the cessation of rock fracture deformation are mainly induced by the contact stress decrease due to contact area enlargement and a dissolved mass accumulation within the contact boundaries. This work implies that fracture closure under constant (pressure/stress and temperature) conditions is likely a spontaneous process, especially at the beginning stage after pressurization when the contact area is relatively small. In contrast, a contact area growth yields changes of fracture closure behavior due to the evolution of contact boundaries and concurrent changes in their diffusive properties. Fracture aperture and thus permeability will likely be sustainable in the long term if no other processes (e.g., mineral precipitations in the open void space) occur.
River flooding poses a threat to numerous cities and communities all over the world. The detection, quantification and attribution of changes in flood characteristics is key to assess changes in flood hazard and help affected societies to timely mitigate and adapt to emerging risks. The Rhine River is one of the major European rivers and numerous large cities reside at its shores. Runoff from several large tributaries superimposes in the main channel shaping the complex from regime. Rainfall, snowmelt as well as ice-melt are important runoff components. The main objective of this thesis is the investigation of a possible transient merging of nival and pluvial Rhine flood regimes under global warming. Rising temperatures cause snowmelt to occur earlier in the year and rainfall to be more intense. The superposition of snowmelt-induced floods originating from the Alps with more intense rainfall-induced runoff from pluvial-type tributaries might create a new flood type with potentially disastrous consequences.
To introduce the topic of changing hydrological flow regimes, an interactive web application that enables the investigation of runoff timing and runoff season- ality observed at river gauges all over the world is presented. The exploration and comparison of a great diversity of river gauges in the Rhine River Basin and beyond indicates that river systems around the world undergo fundamental changes. In hazard and risk research, the provision of background as well as real-time information to residents and decision-makers in an easy accessible way is of great importance. Future studies need to further harness the potential of scientifically engineered online tools to improve the communication of information related to hazards and risks.
A next step is the development of a cascading sequence of analytical tools to investigate long-term changes in hydro-climatic time series. The combination of quantile sampling with moving average trend statistics and empirical mode decomposition allows for the extraction of high resolution signals and the identification of mechanisms driving changes in river runoff. Results point out that the construction and operation of large reservoirs in the Alps is an important factor redistributing runoff from summer to winter and hint at more (intense) rainfall in recent decades, particularly during winter, in turn increasing high runoff quantiles. The development and application of the analytical sequence represents a further step in the scientific quest to disentangling natural variability, climate change signals and direct human impacts.
The in-depth analysis of in situ snow measurements and the simulations of the Alpine snow cover using a physically-based snow model enable the quantification of changes in snowmelt in the sub-basin upstream gauge Basel. Results confirm previous investigations indicating that rising temperatures result in a decrease in maximum melt rates. Extending these findings to a catchment perspective, a threefold effect of rising temperatures can be identified: snowmelt becomes weaker, occurs earlier and forms at higher elevations. Furthermore, results indicate that due to the wide range of elevations in the basin, snowmelt does not occur simultaneously at all elevation, but elevation bands melt together in blocks. The beginning and end of the release of meltwater seem to be determined by the passage of warm air masses, and the respective elevation range affected by accompanying temperatures and snow availability. Following those findings, a hypothesis describing elevation-dependent compensation effects in snowmelt is introduced: In a warmer world with similar sequences of weather conditions, snowmelt is moved upward to higher elevations, i.e., the block of elevation bands providing most water to the snowmelt-induced runoff is located at higher elevations. The movement upward the elevation range makes snowmelt in individual elevation bands occur earlier. The timing of the snowmelt-induced runoff, however, stays the same. Meltwater from higher elevations, at least partly, replaces meltwater from elevations below.
The insights on past and present changes in river runoff, snow covers and underlying mechanisms form the basis of investigations of potential future changes in Rhine River runoff. The mesoscale Hydrological Model (mHM) forced with an ensemble of climate projection scenarios is used to analyse future changes in streamflow, snowmelt, precipitation and evapotranspiration at 1.5, 2.0 and
3.0 ◦ C global warming. Simulation results suggest that future changes in flood characteristics in the Rhine River Basin are controlled by increased precipitation amounts on the one hand, and reduced snowmelt on the other hand. Rising temperatures deplete seasonal snowpacks. At no time during the year, a warming climate results in an increase in the risk of snowmelt-driven flooding. Counterbalancing effects between snowmelt and precipitation often result in only little and transient changes in streamflow peaks. Although, investigations point at changes in both rainfall and snowmelt-driven runoff, there are no indications of a transient merging of nival and pluvial Rhine flood regimes due to climate warming. Flooding in the main tributaries of the Rhine, such as the Moselle River, as well as the High Rhine is controlled by both precipitation and snowmelt. Caution has to be exercised labelling sub-basins such as the Moselle catchment as purely pluvial-type or the Rhine River Basin at Basel as purely nival-type. Results indicate that this (over-) simplifications can entail misleading assumptions with regard to flood-generating mechanisms and changes in flood hazard. In the framework of this thesis, some progress has been made in detecting, quantifying and attributing past, present and future changes in Rhine flow/flood characteristics. However, further studies are necessary to pin down future changes in the flood genesis of Rhine floods, particularly very rare events.
The optical properties of chromophores, especially organic dyes and optically active inorganic molecules, are determined by their chemical structures, surrounding media, and excited state behaviors. The classical optical go-to techniques for spectroscopic investigations are absorption and luminescence spectroscopy. While both techniques are powerful and easy to apply spectroscopic methods, the limited time resolution of luminescence spectroscopy and its reliance on luminescent properties can make its application, in certain cases, complex, or even impossible. This can be the case when the investigated molecules do not luminesce anymore due to quenching effects, or when they were never luminescent in the first place. In those cases, transient absorption spectroscopy is an excellent and much more sophisticated technique to investigate such systems. This pump-probe laser-spectroscopic method is excellent for mechanistic investigations of luminescence quenching phenomena and photoreactions. This is due to its extremely high time resolution in the femto- and picosecond ranges, where many intermediate or transient species of a reaction can be identified and their kinetic evolution can be observed. Furthermore, it does not rely on the samples being luminescent, due to the active sample probing after excitation. In this work it is shown, that with transient absorption spectroscopy it was possible to identify the luminescence quenching mechanisms and thus luminescence quantum yield losses of the organic dye classes O4-DBD, S4-DBD, and pyridylanthracenes. Hence, the population of their triplet states could be identified as the competitive mechanism to their luminescence. While the good luminophores O4-DBD showed minor losses, the S4-DBD dye luminescence was almost entirely quenched by this process. However, for pyridylanthracenes, this phenomenon is present in both the protonated and unprotonated forms and moderately effects the luminescence quantum yield. Also, the majority of the quenching losses in the protonated forms are caused by additional non-radiative processes introduced by the protonation of the pyridyl rings. Furthermore, transient absorption spectroscopy can be applied to investigate the quenching mechanisms of uranyl(VI) luminescence by chloride and bromide. The reduction of the halides by excited uranyl(VI) leads to the formation of dihalide radicals X^(·−2). This excited state redox process is thus identified as the quenching mechanism for both halides, and this process, being diffusion-limited, can be suppressed by cryogenically freezing the samples or by observing these interactions in media with a lower dielectric constant, such as ACN and acetone.
In our daily life, recurrence plays an important role on many spatial and temporal scales and in different contexts. It is the foundation of learning, be it in an evolutionary or in a neural context. It therefore seems natural that recurrence is also a fundamental concept in theoretical dynamical systems science. The way in which states of a system recur or develop in a similar way from similar initial states makes it possible to infer information about the underlying dynamics of the system. The mathematical space in which we define the state of a system (state space) is often high dimensional, especially in complex systems that can also exhibit chaotic dynamics. The recurrence plot (RP) enables us to visualize the recurrences of any high-dimensional systems in a two-dimensional, binary representation. Certain patterns in RPs can be related to physical properties of the underlying system, making the qualitative and quantitative analysis of RPs an integral part of nonlinear systems science. The presented work has a methodological focus and further develops recurrence analysis (RA) by addressing current research questions related to an increasing amount of available data and advances in machine learning techniques. By automatizing a central step in RA, namely the reconstruction of the state space from measured experimental time series, and by investigating the impact of important free parameters this thesis aims to make RA more accessible to researchers outside of physics.
The first part of this dissertation is concerned with the reconstruction of the state space from time series. To this end, a novel idea is proposed which automates the reconstruction problem in the sense that there is no need to preprocesse the data or estimate parameters a priori. The key idea is that the goodness of a reconstruction can be evaluated by a suitable objective function and that this function is minimized in the embedding process. In addition, the new method can process multivariate time series input data. This is particularly important because multi-channel sensor-based observations are ubiquitous in many research areas and continue to increase. Building on this, the described minimization problem of the objective function is then processed using a machine learning approach.
In the second part technical and methodological aspects of RA are discussed. First, we mathematically justify the idea of setting the most influential free parameter in RA, the recurrence threshold ε, in relation to the distribution of all pairwise distances in the data. This is especially important when comparing different RPs and their quantification statistics and is fundamental to any comparative study. Second, some aspects of recurrence quantification analysis (RQA) are examined. As correction schemes for biased RQA statistics, which are based on diagonal lines, we propose a simple method for dealing with border effects of an RP in RQA and a skeletonization algorithm for RPs. This results in less biased (diagonal line based) RQA statistics for flow-like data. Third, a novel type of RQA characteristic is developed, which can be viewed as a generalized non-linear powerspectrum of high dimensional systems. The spike powerspectrum transforms a spike-train like signal into its frequency domain. When transforming the diagonal line-dependent recurrence rate (τ-RR) of a RP in this way, characteristic periods, which can be seen in the state space representation of the system can be unraveled. This is not the case, when Fourier transforming τ-RR.
Finally, RA and RQA are applied to climate science in the third part and neuroscience in the fourth part. To the best of our knowledge, this is the first time RPs and RQA have been used to analyze lake sediment data in a paleoclimate context. Therefore, we first elaborate on the basic formalism and the interpretation of visually visible patterns in RPs in relation to the underlying proxy data. We show that these patterns can be used to classify certain types of variability and transitions in the Potassium record from six short (< 17m) sediment cores collected during the Chew Bahir Drilling Project. Building on this, the long core (∼ m composite) from the same site is analyzed and two types of variability and transitions are
identified and compared with ODP Site wetness index from the eastern Mediterranean. Type variability likely reflects the influence of precessional forcing in the lower latitudes at times of maximum values of the long eccentricity cycle ( kyr) of the earth’s orbit around the sun, with a tendency towards extreme events. Type variability appears to be related to the minimum values of this cycle and corresponds to fairly rapid transitions between relatively dry and relatively wet conditions.
In contrast, RQA has been applied in the neuroscientific context for almost two decades. In the final part, RQA statistics are used to quantify the complexity in a specific frequency band of multivariate EEG (electroencephalography) data. By analyzing experimental data, it can be shown that the complexity of the signal measured in this way across the sensorimotor cortex decreases as motor tasks are performed. The results are consistent with and comple- ment the well known concepts of motor-related brain processes. We assume that the thus discovered features of neuronal dynamics in the sensorimotor cortex together with the robust RQA methods for identifying and classifying these contribute to the non-invasive EEG-based development of brain-computer interfaces (BCI) for motor control and rehabilitation.
The present work is an important step towards a robust analysis of complex systems based on recurrence.
The Central Andes region in South America is characterized by a complex and heterogeneous deformation system. Recorded seismic activity and mapped neotectonic structures indicate that most of the intraplate deformation is located along the margins of the orogen, in the transitions to the foreland and the forearc. Furthermore, the actively deforming provinces of the foreland exhibit distinct deformation styles that vary along strike, as well as characteristic distributions of seismicity with depth. The style of deformation transitions from thin-skinned in the north to thick-skinned in the south, and the thickness of the seismogenic layer increases to the south. Based on geological/geophysical observations and numerical modelling, the most commonly invoked causes for the observed heterogeneity are the variations in sediment thickness and composition, the presence of inherited structures, and changes in the dip of the subducting Nazca plate. However, there are still no comprehensive investigations on the relationship between the lithospheric composition of the Central Andes, its rheological state and the observed deformation processes. The central aim of this dissertation is therefore to explore the link between the nature of the lithosphere in the region and the location of active deformation. The study of the lithospheric composition by means of independent-data integration establishes a strong base to assess the thermal and rheological state of the Central Andes and its adjacent lowlands, which alternatively provide new foundations to understand the complex deformation of the region. In this line, the general workflow of the dissertation consists in the construction of a 3D data-derived and gravity-constrained density model of the Central Andean lithosphere, followed by the simulation of the steady-state conductive thermal field and the calculation of strength distribution. Additionally, the dynamic response of the orogen-foreland system to intraplate compression is evaluated by means of 3D geodynamic modelling.
The results of the modelling approach suggest that the inherited heterogeneous composition of the lithosphere controls the present-day thermal and rheological state of the Central Andes, which in turn influence the location and depth of active deformation processes. Most of the seismic activity and neo--tectonic structures are spatially correlated to regions of modelled high strength gradients, in the transition from the felsic, hot and weak orogenic lithosphere to the more mafic, cooler and stronger lithosphere beneath the forearc and the foreland. Moreover, the results of the dynamic simulation show a strong localization of deviatoric strain rate second invariants in the same region suggesting that shortening is accommodated at the transition zones between weak and strong domains. The vertical distribution of seismic activity appears to be influenced by the rheological state of the lithosphere as well. The depth at which the frequency distribution of hypocenters starts to decrease in the different morphotectonic units correlates with the position of the modelled brittle-ductile transitions; accordingly, a fraction of the seismic activity is located within the ductile part of the crust. An exhaustive analysis shows that practically all the seismicity in the region is restricted above the 600°C isotherm, in coincidence with the upper temperature limit for brittle behavior of olivine. Therefore, the occurrence of earthquakes below the modelled brittle-ductile could be explained by the presence of strong residual mafic rocks from past tectonic events. Another potential cause of deep earthquakes is the existence of inherited shear zones in which brittle behavior is favored through a decrease in the friction coefficient. This hypothesis is particularly suitable for the broken foreland provinces of the Santa Barbara System and the Pampean Ranges, where geological studies indicate successive reactivation of structures through time. Particularly in the Santa Barbara System, the results indicate that both mafic rocks and a reduction in friction are required to account for the observed deep seismic events.
The survey of the prevalence of chronic ankle instability in elite Taiwanese basketball athletes
(2021)
BACKGROUND: Ankle sprains are common in basketball. It could develop into Chronic Ankle Instability (CAI) causing decreased quality of life, functional performance, early osteoarthritis, and increased risk of other injuries. To develop a strategy of CAI prevention, localized epidemiology data and a valid/reliable tool are essential. However, the epidemiological data of CAI is not conclusive from previous studies and the prevalence of CAI in Taiwanese basketball athletes are not clear. In addition, a valid and reliable tool among the Taiwan-Chinese version to evaluate ankle instability is missing.
PURPOSE: The aims were to have an overview of the prevalence of CAI in sports population using a systematic review, to develop a valid and reliable cross-cultural adapted Cumberland Ankle Instability Tool Questionnaire (CAIT) in Taiwan-Chinese (CAIT-TW), and to survey the prevalence of CAI in elite basketball athletes in Taiwan using CAIT-TW.
METHODS: Firstly, a systematic search was conducted. Research articles applying CAI related questionnaires in order to survey the prevalence of CAI were included in the review. Second, the English version of CAIT was translated and cross-culturally adapted into the CAIT-TW. The construct validity, test-retest reliability, internal consistency, and cutoff score of CAIT-TW were evaluated in an athletic population (N=135). Finally, the cross-sectional data of CAI prevalence in 388 elite Taiwanese basketball athletes were presented. Demographics, presence of CAI, and difference of prevalence between gender, different competitive levels and play positions were evaluated.
RESULTS: The prevalence of CAI was 25%, ranging between 7% and 53%. The prevalence of CAI among participants with a history of ankle sprains was 46%, ranging between 9% and 76%. In addition, the cross-cultural adapted CAIT-TW showed a moderate to strong construct validity, an excellent test-retest reliability, a good internal consistency, and a cutoff score of 21.5 for the Taiwanese athletic population. Finally, 26% of Taiwanese basketball athletes had unilateral CAI while 50% of them had bilateral CAI. In addition, women athletes in the investigated cohort had a higher prevalence of CAI than men. There was no difference in prevalence between competitive levels and among play positions.
CONCLUSION: The systematic review shows that the prevalence of CAI has a wide range among included studies. This could be due to the different exclusion criteria, age, sports discipline, or other factors among the included studies. For future studies, standardized criteria to investigate the epidemiology of CAI are required. The CAI epidemiological study should be prospective. Factors affecting the prevalence of CAI ability should be investigated and described. The translated CAIT-TW is a valid and reliable tool to differentiate between stable and unstable ankles in athletes and may further apply for research or daily practice in Taiwan. In the Taiwanese basketball population, CAI is highly prevalent. This might relate to the research method, preexisting ankle instability, and training-related issues. Women showed a higher prevalence of CAI than men. When applying the preventive measure, gender should be taken into consideration.
Flooding is a vast problem in many parts of the world, including Europe. It occurs mainly due to extreme weather conditions (e.g. heavy rainfall and snowmelt) and the consequences of flood events can be devastating. Flood risk is mainly defined as a combination of the probability of an event and its potential adverse impacts. Therefore, it covers three major dynamic components: hazard (physical characteristics of a flood event), exposure (people and their physical environment that being exposed to flood), and vulnerability (the elements at risk). Floods are natural phenomena and cannot be fully prevented. However, their risk can be managed and mitigated. For a sound flood risk management and mitigation, a proper risk assessment is needed. First of all, this is attained by a clear understanding of the flood risk dynamics. For instance, human activity may contribute to an increase in flood risk. Anthropogenic climate change causes higher intensity of rainfall and sea level rise and therefore an increase in scale and frequency of the flood events. On the other hand, inappropriate management of risk and structural protection measures may not be very effective for risk reduction. Additionally, due to the growth of number of assets and people within the flood-prone areas, risk increases. To address these issues, the first objective of this thesis is to perform a sensitivity analysis to understand the impacts of changes in each flood risk component on overall risk and further their mutual interactions. A multitude of changes along the risk chain are simulated by regional flood model (RFM) where all processes from atmosphere through catchment and river system to damage mechanisms are taken into consideration. The impacts of changes in risk components are explored by plausible change scenarios for the mesoscale Mulde catchment (sub-basin of the Elbe) in Germany.
A proper risk assessment is ensured by the reasonable representation of the real-world flood event. Traditionally, flood risk is assessed by assuming homogeneous return periods of flood peaks throughout the considered catchment. However, in reality, flood events are spatially heterogeneous and therefore traditional assumption misestimates flood risk especially for large regions. In this thesis, two different studies investigate the importance of spatial dependence in large scale flood risk assessment for different spatial scales. In the first one, the “real” spatial dependence of return period of flood damages is represented by continuous risk modelling approach where spatially coherent patterns of hydrological and meteorological controls (i.e. soil moisture and weather patterns) are included. Further the risk estimations under this modelled dependence assumption are compared with two other assumptions on the spatial dependence of return periods of flood damages: complete dependence (homogeneous return periods) and independence (randomly generated heterogeneous return periods) for the Elbe catchment in Germany. The second study represents the “real” spatial dependence by multivariate dependence models. Similar to the first study, the three different assumptions on the spatial dependence of return periods of flood damages are compared, but at national (United Kingdom and Germany) and continental (Europe) scales. Furthermore, the impacts of the different models, tail dependence, and the structural flood protection level on the flood risk under different spatial dependence assumptions are investigated.
The outcomes of the sensitivity analysis framework suggest that flood risk can vary dramatically as a result of possible change scenarios. The risk components that have not received much attention (e.g. changes in dike systems and in vulnerability) may mask the influence of climate change that is often investigated component.
The results of the spatial dependence research in this thesis further show that the damage under the false assumption of complete dependence is 100 % larger than the damage under the modelled dependence assumption, for the events with return periods greater than approximately 200 years in the Elbe catchment. The complete dependence assumption overestimates the 200-year flood damage, a benchmark indicator for the insurance industry, by 139 %, 188 % and 246 % for the UK, Germany and Europe, respectively. The misestimation of risk under different assumptions can vary from upstream to downstream of the catchment. Besides, tail dependence in the model and flood protection level in the catchments can affect the risk estimation and the differences between different spatial dependence assumptions.
In conclusion, the broader consideration of the risk components, which possibly affect the flood risk in a comprehensive way, and the consideration of the spatial dependence of flood return periods are strongly recommended for a better understanding of flood risk and consequently for a sound flood risk management and mitigation.
Proteins of halophilic organisms that accumulate molar concentrations of KCl in their cytoplasm have much higher content in acidic amino acids than proteins of mesophilic organisms. It has been proposed that this excess is necessary to maintain proteins hydrated in an environment with low water activity: either via direct interactions between water and the carboxylate groups of acidic amino acids or via cooperative interactions between acidic amino acids and hydrated cations, which would stabilize the folded protein. In the course of this Ph.D. study, we investigated these possibilities using atomistic molecular dynamics simulations and classical force fields. High quality parameters describing the interaction between K+ and carboxylate groups present in acidic amino acids are indispensable for this study. We first evaluated the quality of the default parameters for these ions within the widely used AMBER ff14SB force field for proteins and found that they perform poorly. We propose new parameters, which reproduce solution activity derivatives of potassium acetate solutions up to 2 mol/kg and the distances between potassium ions and carboxylate groups observed in x-ray structures of proteins. To understand the role of acidic amino acids in protein hydration, we investigated this aspect for 5 halophilic proteins in comparison with 5 mesophilic ones. Our results do not support the necessity of acidic amino acids to keep folded proteins hydrated. Proteins with a larger fraction of acidic amino acids indeed have higher hydration levels. However, the hydration level of each protein is identical at low (b_KCl = 0.15 mol/kg) and high (b_KCl = 2 mol/kg) KCl concentration. It has also been proposed that cooperative interactions between acidic amino acids with nearby hydrated cations stabilize the folded protein and slow down its solvation shell; according to this theory, the cations would be preferentially excluded from the unfolded structure. We investigate this possibility through extensive free energy calculation simulations. We find that cooperative interactions between neighboring acidic amino acids exist and are mediated by the ions in solution but are present in both folded and unfolded structures of halophilic proteins. The translational dynamics of the solvation shell is barely distinguishable between halophilic and mesophilic proteins; therefore, such a cooperative effect does not result in unusually slow solvent dynamics as has been suggested.
The spread of antibiotic-resistant bacteria poses a globally increasing threat to public health care. The excessive use of antibiotics in animal husbandry can develop resistances in the stables. Transmission through direct contact with animals and contamination of food has already been proven. The excrements of the animals combined with a binding material enable a further potential path of spread into the environment, if they are used as organic manure in agricultural landscapes. As most of the airborne bacteria are attached to particulate matter, the focus of the work will be the atmospheric dispersal via the dust fraction.
Field measurements on arable lands in Brandenburg, Germany and wind erosion studies in a wind tunnel were conducted to investigate the risk of a potential atmospheric dust-associated spread of antibiotic-resistant bacteria from poultry manure fertilized agricultural soils. The focus was to (i) characterize the conditions for aerosolization and (ii) qualify and quantify dust emissions during agricultural operations and wind erosion.
PM10 (PM, particulate matter with an aerodynamic diameter smaller than 10 µm) emission factors and bacterial fluxes for poultry manure application and incorporation have not been previously reported before. The contribution to dust emissions depends on the water content of the manure, which is affected by the manure pretreatment (fresh, composted, stored, dried), as well as by the intensity of manure spreading from the manure spreader. During poultry manure application, PM10 emission ranged between 0.05 kg ha-1 and 8.37 kg ha-1. For comparison, the subsequent land preparation contributes to 0.35 – 1.15 kg ha-1 of PM10 emissions. Manure particles were still part of dust emissions but they were accounted to be less than 1% of total PM10 emissions due to the dilution of poultry manure in the soil after manure incorporation. Bacterial emissions of fecal origin were more relevant during manure application than during the subsequent manure incorporation, although PM10 emissions of manure incorporation were larger than PM10 emissions of manure application for the non-dried manure variants.
Wind erosion leads to preferred detachment of manure particles from sandy soils, when poultry manure has been recently incorporated. Sorting effects were determined between the low-density organic particles of manure origin and the soil particles of mineral origin close above the threshold of 7 m s-1. In dependence to the wind speed, potential erosion rates between 101 and 854 kg ha-1 were identified, if 6 t ha-1 of poultry manure were applied. Microbial investigation showed that manure bacteria got detached more easily from the soil surface during wind erosion, due to their attachment on manure particles.
Although antibiotic-resistant bacteria (ESBL-producing E. coli) were still found in the poultry barns, no further contamination could be detected with them in the manure, fertilized soils or in the dust generated by manure application, land preparation or wind erosion. Parallel studies of this project showed that storage of poultry manure for a few days (36 – 72 h) is sufficient to inactivate ESBL-producing E. coli. Further antibiotic-resistant bacteria, i.e. MRSA and VRE, were only found sporadically in the stables and not at all in the dust. Therefore, based on the results of this work, the risk of a potential infection by dust-associated antibiotic-resistant bacteria can be considered as low.
Conceptual knowledge about objects, people and events in the world is central to human cognition, underlying core cognitive abilities such as object recognition and use, and word comprehension. Previous research indicates that concepts consist of perceptual and motor features represented in modality-specific perceptual-motor brain regions. In addition, cross-modal convergence zones integrate modality-specific features into more abstract conceptual representations.
However, several questions remain open: First, to what extent does the retrieval of perceptual-motor features depend on the concurrent task? Second, how do modality-specific and cross-modal regions interact during conceptual knowledge retrieval? Third, which brain regions are causally relevant for conceptually-guided behavior? This thesis addresses these three key issues using functional magnetic resonance imaging (fMRI) and transcranial magnetic stimulation (TMS) in the healthy human brain.
Study 1 - an fMRI activation study - tested to what extent the retrieval of sound and action features of concepts, and the resulting engagement of auditory and somatomotor brain regions depend on the concurrent task. 40 healthy human participants performed three different tasks - lexical decision, sound judgment, and action judgment - on words with a high or low association to sounds and actions. We found that modality-specific regions selectively respond to task-relevant features: Auditory regions selectively responded to sound features during sound judgments, and somatomotor regions selectively responded to action features during action judgments. Unexpectedly, several regions (e.g. the left posterior parietal cortex; PPC) exhibited a task-dependent response to both sound and action features. We propose these regions to be "multimodal", and not "amodal", convergence zones which retain modality-specific information.
Study 2 - an fMRI connectivity study - investigated the functional interaction between modality-specific and multimodal areas during conceptual knowledge retrieval. Using the above fMRI data, we asked (1) whether modality-specific and multimodal regions are functionally coupled during sound and action feature retrieval, (2) whether their coupling depends on the task, (3) whether information flows bottom-up, top-down, or bidirectionally, and (4) whether their coupling is behaviorally relevant. We found that functional coupling between multimodal and modality-specific areas is task-dependent, bidirectional, and relevant for conceptually-guided behavior. Left PPC acted as a connectivity "switchboard" that flexibly adapted its coupling to task-relevant modality-specific nodes.
Hence, neuroimaging studies 1 and 2 suggested a key role of left PPC as a multimodal convergence zone for conceptual knowledge. However, as neuroimaging is correlational, it remained unknown whether left PPC plays a causal role as a multimodal conceptual hub. Therefore, study 3 - a TMS study - tested the causal relevance of left PPC for sound and action feature retrieval. We found that TMS over left PPC selectively impaired action judgments on low sound-low action words, as compared to sham stimulation. Computational simulations of the TMS-induced electrical field revealed that stronger stimulation of left PPC was associated with worse performance on action, but not sound, judgments. These results indicate that left PPC causally supports conceptual processing when action knowledge is task-relevant and cannot be compensated by sound knowledge. Our findings suggest that left PPC is specialized for action knowledge, challenging the view of left PPC as a multimodal conceptual hub.
Overall, our studies support "hybrid theories" which posit that conceptual processing involves both modality-specific perceptual-motor regions and cross-modal convergence zones. In our new model of the conceptual system, we propose conceptual processing to rely on a representational hierarchy from modality-specific to multimodal up to amodal brain regions. Crucially, this hierarchical system is flexible, with different regions and connections being engaged in a task-dependent fashion. Our model not only reconciles the seemingly opposing grounded cognition and amodal theories, it also incorporates task dependency of conceptually-related brain activity and connectivity, thereby resolving several current issues on the neural basis of conceptual knowledge retrieval.
The High Energy Stereoscopic System (H.E.S.S.) is an array of five imaging atmospheric Cherenkov telescopes located in the Khomas Highland of Namibia. H.E.S.S. operates in a wide energy range from several tens of GeV to several tens of TeV, reaching the best sensitivity around 1 TeV or at lower energies. However, there are many important topics – such as the search for Galactic PeVatrons, the study of gamma-ray production scenarios for sources (hadronic vs. leptonic), EBL absorption studies – which require good sensitivity at energies above 10 TeV. This work aims at improving the sensitivity of H.E.S.S. and increasing the gamma-ray statistics at high energies. The study investigates an enlargement of the H.E.S.S. effective field of view using events with larger offset angles in the analysis. The greatest challenges in the analysis of large-offset events are a degradation of the reconstruction accuracy and a rise of the background rate as the offset angle increases. The more sophisticated direction reconstruction method (DISP) and improvements to the standard background rejection technique, which by themselves are effective ways to increase the gamma-ray statistics and improve the sensitivity of the analysis, are implemented to overcome the above-mentioned issues. As a result, the angular resolution at the preselection level is improved by 5 - 10% for events at 0.5◦ offset angle and by 20 - 30% for events at 2◦ offset angle. The background rate at large offset angles is decreased nearly to a level typical for offset angles below 2.5◦. Thereby, sensitivity improvements of 10 - 20% are achieved for the proposed analysis compared to the standard analysis at small offset angles. Developed analysis also allows for the usage of events at large offset angles up to approximately 4◦, which was not possible before. This analysis method is applied to the analysis of the Galactic plane data above 10 TeV. As a result, 40 sources out of the 78 presented in the H.E.S.S. Galactic plane survey (HGPS) are detected above 10 TeV. Among them are representatives of all source classes that are present in the HGPS catalogue; namely, binary systems, supernova remnants, pulsar wind nebulae and composite objects. The potential of the improved analysis method is demonstrated by investigating the more than 10 TeV emission for two objects: the region associated with the shell-type SNR HESS J1731−347 and the PWN candidate associated with PSR J0855−4644 that is coincident with Vela Junior (HESS J0852−463).
The aim of the doctoral project was to answer the question of whether the structural word-initial noun capitalization, as it can otherwise only be found in Luxembourgish alongside German, has a function that is advantageous for the reader. The overriding hypothesis was that an advantage is achieved by activating a syntactic category, namely the core of a noun phrase, through the parafoveal perception of the capital letters. This perception from the corner of the eye should make it possible to preprocess the following noun. As a result, sentence processing should be facilitated, which should ultimately be reflected in overall faster reading times and fixation durations.
The structure of the project includes three studies, some of which included different participant groups:
Study 1:
Study design: Semantic priming using garden-path sentences should bring out the functionality of noun capitalization for the reader
Participant groups: German natives reading German
Study 2:
Study design: same design as study 1, but in English
Participant groups:
English natives without any knowledge of German reading English
English natives who regularly read German reading English
German with high proficiency in English reading English
Study 3:
Study design:
Influence of the noun frequency on a potential preprocessing using the boundary paradigm; Study languages: German and English
Participant groups:
German natives reading German
English natives without any knowledge of German reading English
German with high proficiency in English reading English
Brief summary: The noun capitalization clearly has an impact on sentence processing in both German and English. It cannot be confirmed that this has a substantial, decisive advantage.
Membrane contact sites are of particular interest in the field of synthetic biology and biophysics. They are involved in a great variety of cellular functions. They form in between two cellular organelles or an organelle and the plasma membrane in order to establish a communication path for molecule transport or signal transmission.
The development of an artificial membrane system which can mimic membrane contact sites using bottom up synthetic biology was the goal of this research study. For this, a multi - compartmentalised giant unilamellar vesicle (GUV) system was created with the membrane of the outer vesicle mimicking the plasma membrane and the inner GUVs posing as cellular organelles.
In the following steps, three different strategies were used to achieve an internal membrane - membrane adhesion.
The majority of baryons in the Universe is believed to reside in the intergalactic medium (IGM). This makes the IGM an important component in understanding cosmological structure formation. It is expected to trace the same dark matter distribution as galaxies, forming structures like filaments and clusters. However, whereas galaxies can be observed to be arranged along these large-scale structures, the spatial distribution of the diffuse IGM is not as easily unveiled. Absorption line studies of quasar (QSO) spectra can help with mapping the IGM, as well as the boundary layer between IGM and galaxies: the circumgalactic medium (CGM). By studying gas in the Local Group, as well as in the IGM, this study aims to get a better understanding of how the gas is linked to the large-scale structure of the local Universe and the galaxies residing in that structure.
Chapter 1 gives an introduction to the CGM and IGM, while the methods used in this study are explained in Chapter 2. Chapter 3 starts on a relatively small cosmological scale, namely that of our Local Group, which includes i.a. the Milky Way (MW) and the M31. Within the CGM of the MW, there exist denser clouds, some of which are infalling while others are moving away from the Galactic disc. To study these clouds, 29 QSO spectra obtained with the Cosmic Origins Spectrograph (COS) aboard the Hubble Space Telescope (HST) were analysed. Abundances of Si II, Si III, Si IV, C II, and C IV were measured for 69 HVCs belonging to two samples: one in the direction of the LG’s barycentre and the other in the anti-barycentre direction. Their velocities range from -100 ≥ vLSR ≥ -400 km/s for the barycentre sample and between +100 ≤ vLSR ≤ +300 km/s for the anti-barycentre sample. By using Cloudy models, these data could then be used to derive gas volume densities for the HVCs. Because of the relationship between density and pressure of the ambient medium, which is in turn determined by the Galactic radiation field, the distances of the HVCs could be estimated. From this, a subsample of absorbers located in the direction of M31 was found to exist outside of the MW’s virial radius, their low densities (log nH ≤ -3.54) making it likely for them to be part of the gas in between the MW and M31. No such low-density absorbers were found in the anti-barycentre sample. Our results thus hint at gas following the dark matter potential, which would be deeper between the MW and M31 as they are by far the most massive members of the LG.
From this bridge of gas in the LG, this study zooms out to the large-scale structure of the local Universe (z ~ 0) in Chapter 4. Galaxy data from the V8k catalogue and QSO spectra from COS were used to study the relation between the galaxies tracing large-scale filaments and the gas existing outside of those galaxies. This study used the filaments defined in Courtois et al. (2013). A total of 587 Lyman α (Lyα) absorbers were found in the 302 QSO spectra in the velocity range 1070 - 6700 km/s. After selecting sightlines passing through or close to these filaments, model spectra were made for 91 sightlines and 215 (227) Lyα absorbers (components) were measured in this sample. The velocity gradient along each filament was calculated and 74 absorbers were found within 1000 km/s of the nearest filament segment.
In order to find whether the absorbers are more tied to galaxies or to the large-scale structure, equivalent widths of the Lyα absorbers were plotted against both galaxy and filament impact parameters. While stronger absorbers do tend to be closer to either galaxies or filaments, there is a large scatter in this relation. Despite this large scatter, this study found that the absorbers do not follow a random distribution either. They cluster less strongly around filaments than galaxies, but stronger than random distributions, as confirmed by a Kolmogorov-Smirnov test.
Furthermore, the column density distribution function found in this study has a slope of -β = 1.63±0.12 for the total sample and -β =1.47±0.24 for the absorbers within 1000 km/s of a filament. The shallower slope for the latter subsample could indicate an excess of denser absorbers within the filament, but they are consistent within errors. These values are in agreement with values found in e.g. Lehner et al. (2007); Danforth et al. (2016).
The picture that emerges from this study regarding the relation between the IGM and the large-scale structure in the local Universe fits with what is found in other studies: while at least part of the gas traces the same filamentary structure as galaxies, the relation is complex. This study has shown that by taking a large sample of sightlines and comparing the data gathered from those with galaxy data, it is possible to study the gaseous large-scale structure. This approach can be used in the future together with simulations to get a better understanding of structure formation and evolution in the Universe.
Mental health problems are highly prevalent worldwide. Fortunately, psychotherapy has proven highly effective in the treatment of a number of mental health issues, such as depression and anxiety disorders. In contrast, psychotherapy training as is practised currently cannot be considered evidence-based. Thus, there is much room for improvement. The integration of simulated patients (SPs) into psychotherapy training and research is on the rise. SPs originate from the medical education and have, in a number of studies, been demonstrated to contribute to effective learning environments. Nevertheless, there has been voiced criticism regarding the authenticity of SP portrayals, but few studies have examined this to date.
Based on these considerations, this dissertation explores SPs’ authenticity while portraying a mental disorder, depression. Altogether, the present cumulative dissertation consists of three empirical papers. At the time of printing, Paper I and Paper III have been accepted for publication, and Paper II is under review after a minor revision.
First, Paper I develops and validates an observer-based rating-scale to assess SP authenticity in psychotherapeutic contexts. Based on the preliminary findings, it can be concluded that the Authenticity of Patient Demonstrations scale is a reliable and valid tool that can be used for recruiting, training, and evaluating the authenticity of SPs.
Second, Paper II tests whether student SPs are perceived as more authentic after they receive an in-depth role-script compared to those SPs who only receive basic information on the patient case. To test this assumption, a randomised controlled study design was implemented and the hypothesis could be confirmed. As a consequence, when engaging SPs, an in-depth role-script with details, e.g. on nonverbal behaviour and feelings of the patient, should be provided.
Third, Paper III demonstrates that psychotherapy trainees cannot distinguish between trained SPs and real patients and therefore suggests that, with proper training, SPs are a promising training method for psychotherapy.
Altogether, the dissertation shows that SPs can be trained to portray a depressive patient authentically and thus delivers promising evidence for the further dissemination of SPs.
Zentrales Element dieser Arbeit ist die Synthese und Charakterisierung praktisch nutzbarer Ionogele. Die Basis der Polymerionogele bildet das Modellpolymer Polymethylmethacrylat. Als Additive kommen ionische Flüssigkeiten zum Einsatz, deren Grundlage Derivate des vielfach verwendeten Imidazoliumkations sind. Die Eigenschaften der eingebetteten ionischen Flüssigkeiten sind für die Ionogele funktionsgebend. Die Funktionalität der jeweiligen Gele und damit der Transfer der Eigenschaften von ionischen Flüssigkeiten auf die Ionogele wurde in der vorliegenden Arbeit mittels zahlreicher Charakterisierungstechniken überprüft und bestätigt. In dieser Arbeit wurden durch Ionogelbildung makroskopische Ionogelobjekte in Form von Folien und Vliesen erzeugt. Dabei kamen das Filmgießen und das Elektrospinnen als Methoden zur Erzeugung dieser Folien und Vliese zum Einsatz, woraus jeweils ein Modellsystem resultiert. Dadurch wird die vorliegende Arbeit in die Themenkomplexe „elektrisch halbleitende Ionogelfolien“ und „antimikrobiell aktive Ionogelvliese“ gegliedert. Der Einsatz von triiodidhaltigen ionischen Flüssigkeiten und einer Polymermatrix in einem diskontinuierlichen Gießprozess resultiert in elektrisch halbleitenden Ionogelfolien. Die flexiblen und transparenten Folien können Mittelpunkt zahlreicher neuer Anwendungsfelder im Bereich flexibler Elektronik sein. Das Elektrospinnen von Polymethylmethacrylat mit einer ionischen Flüssigkeit führte zu einem homogen Ionogelvlies, welches ein Modell für die Übertragung antimikrobiell aktiver Eigenschaften ionischer Flüssigkeiten auf poröse Strukturen zur Filtration darstellt. Gleichzeitig ist es das erste Beispiel für ein kupferchloridhaltiges Ionogel. Ionogele sind attraktive Materialien mit zahlreichen Anwendungsmöglichkeiten. Mit der vorliegenden Arbeit wird das Spektrum der Ionogele um ein elektrisch halbleitendes und ein antimikrobiell aktives Ionogel erweitert. Gleichzeitig wurden durch diese Arbeit der Gruppe der ionischen Flüssigkeiten drei Beispiele für elektrisch halbleitende ionische Flüssigkeiten sowie zahlreiche kupfer(II)chloridbasierte ionische Flüssigkeiten hinzugefügt.
Supernova remnants (SNRs) are discussed as the most promising sources of galactic cosmic rays (CR). The diffusive shock acceleration (DSA) theory predicts particle spectra in a rough agreement with observations. Upon closer inspection, however, the photon spectra of observed SNRs indicate that the particle spectra produced at SNRs shocks deviate from the standard expectation. This work suggests a viable explanation for a softening of the particle spectra in SNRs. The basic idea is the re-acceleration of particles in the turbulent region immediately downstream of the shock. This thesis shows that at the re-acceleration of particles by the fast-mode waves in the downstream region can be efficient enough to impact particle spectra over several decades in energy. To demonstrate this, a generic SNR model is presented, where the evolution of particles is described by the reduced transport equation for CR. It is shown that the resulting particle and the corresponding synchrotron spectra are significantly softer compared to the standard case. Next, this work outlines RATPaC, a code developed to model particle acceleration and corresponding photon emissions in SNRs. RATPaC solves the particle transport equation in test-particle mode using hydrodynamic simulations of the SNR plasma flow. The background magnetic field can be either computed from the induction equation or follows analytic profiles. This work presents an extended version of RATPaC that accounts for stochastic re-acceleration by fast-mode waves that provide diffusion of particles in momentum space. This version is then applied to model the young historical SNR Tycho. According to radio observations, Tycho’s SNR features the radio spectral index of approximately −0.65. In previous modeling approaches, this fact has been attributed to the strongly distinctive Alfvénic drift, which is assumed to operate in the shock vicinity. In this work, the problems and inconsistencies of this scenario are discussed. Instead, stochastic re-acceleration of electrons in the immediate downstream region of Tycho’s SNR is suggested as a cause for the soft radio spectrum. Furthermore, this work investigates two different scenarios for magnetic-field distributions inside Tycho’s SNR. It is concluded that magnetic-field damping is needed to account for the observed filaments in the radio range. Two models are presented for Tycho’s SNR, both of them feature strong hadronic contribution. Thus, a purely leptonic model is considered as very unlikely. Additionally, to the detailed modeling of Tycho’s SNR, this dissertation presents a relatively simple one-zone model for the young SNR Cassiopeia A and an interpretation for the recently analyzed VERITAS and Fermi-LAT data. It shows that the γ-ray emission of Cassiopeia A cannot be explained without a hadronic contribution and that the remnant accelerates protons up to TeV energies. Thus, Cassiopeia A is found to be unlikely a PeVatron.
Natural products have proved to be a major resource in the discovery and development of many pharmaceuticals that are in use today. There is a wide variety of biologically active natural products that contain conjugated polyenes or benzofuran structures. Therefore, new synthetic methods for the construction of such building blocks are of great interest to synthetic chemists. The recently developed one-pot tethered ring-closing metathesis approach allows for the formation of Z,E-dienoates in high stereoselectivity. The extension of this method with a Julia-Kocienski olefination protocol would allow for the formation of conjugated trienes in a stereoselective manner. This strategy was applied in the total synthesis of conjugated triene containing (+)-bretonin B. Additionally, investigations of cross metathesis using methyl substituted olefins were pursued. This methodology was applied, as a one-pot cross metathesis/ring-closing metathesis sequence, in the total synthesis of benzofuran containing 7-methoxywutaifuranal. Finally, the design and synthesis of a catalyst for stereoretentive metathesis in aqueous media was investigated.
An ever-increasing number of prediction models is published every year in different medical specialties. Prognostic or diagnostic in nature, these models support medical decision making by utilizing one or more items of patient data to predict outcomes of interest, such as mortality or disease progression. While different computer tools exist that support clinical predictive modeling, I observed that the state of the art is lacking in the extent to which the needs of research clinicians are addressed. When it comes to model development, current support tools either 1) target specialist data engineers, requiring advanced coding skills, or 2) cater to a general-purpose audience, therefore not addressing the specific needs of clinical researchers. Furthermore, barriers to data access across institutional silos, cumbersome model reproducibility and extended experiment-to-result times significantly hampers validation of existing models. Similarly, without access to interpretable explanations, which allow a given model to be fully scrutinized, acceptance of machine learning approaches will remain limited. Adequate tool support, i.e., a software artifact more targeted at the needs of clinical modeling, can help mitigate the challenges identified with respect to model development, validation and interpretation. To this end, I conducted interviews with modeling practitioners in health care to better understand the modeling process itself and ascertain in what aspects adequate tool support could advance the state of the art. The functional and non-functional requirements identified served as the foundation for a software artifact that can be used for modeling outcome and risk prediction in health research. To establish the appropriateness of this approach, I implemented a use case study in the Nephrology domain for acute kidney injury, which was validated in two different hospitals. Furthermore, I conducted user evaluation to ascertain whether such an approach provides benefits compared to the state of the art and the extent to which clinical practitioners could benefit from it. Finally, when updating models for external validation, practitioners need to apply feature selection approaches to pinpoint the most relevant features, since electronic health records tend to contain several candidate predictors. Building upon interpretability methods, I developed an explanation-driven recursive feature elimination approach. This method was comprehensively evaluated against state-of-the art feature selection methods. Therefore, this thesis' main contributions are three-fold, namely, 1) designing and developing a software artifact tailored to the specific needs of the clinical modeling domain, 2) demonstrating its application in a concrete case in the Nephrology context and 3) development and evaluation of a new feature selection approach applicable in a validation context that builds upon interpretability methods. In conclusion, I argue that appropriate tooling, which relies on standardization and parametrization, can support rapid model prototyping and collaboration between clinicians and data scientists in clinical predictive modeling.
In the light of climate change, rising demands for agricultural products and the intensification and specialization of agricultural systems, ensuring an adequate and reliable supply of food is fundamental for food security. Maintaining diversity and redundancy has been postulated as one generic principle to increase the resilience of agricultural production and other ecosystem services. For example, if one crop fails due to climate instability and extreme events, others can compensate the losses. Crop diversity might be particularly important if different crops show asynchronous production trends. Furthermore, spatial heterogeneity has been suggested to increase stability at larger scales as production losses in some areas can be buffered by surpluses in undisturbed ones. Besides systematically investigating the mechanisms underlying stability, identifying transformative pathways that foster them is important.
In my thesis, I aim at answering the following questions: (i) How does yield stability differ between nations, regions and farms, and what is the effect of crop diversity on yield stability in relation to agricultural inputs, climate heterogeneity, climate instability and time at the national, regional or farm level? (ii) Is asynchrony between crops a better predictor of production stability than crop diversity? (iii) What is the effect of asynchrony between and within crops on stability and how is it related to crop diversity and space, respectively? (iv) What is the state of the art and what are knowledge gaps in exploring resilience and its multidimensionality in ecological and social-ecological systems with agent-based models and what are potential ways forward?
In the first chapter, I provide the theoretical background for the subsequent analyses. I stress the need to better understand the resilience of social-ecological systems and particularly the stability of agricultural production. Moreover, I introduce diversity and spatial heterogeneity as two prominently discussed resilience mechanisms and describe approaches to assess resilience.
In the second chapter, I combined agriculture and climate data at three levels of organization and spatial extents to investigate yield stability patterns and their relation to crop diversity, fertilizer, irrigation, climate heterogeneity and instability and time of nations globally, regions in Europe and farms in Germany using statistical analyses. Yield stability decreased from the national to the farm level. Several nations and regions substantially contributed to larger-scale stability. Crop diversity was positively associated with yield stability across all three levels of organization. This effect was typically more profound at smaller scales and in variable climates. In addition to crop diversity, climate heterogeneity was an important stabilizing mechanism especially at larger scales. These results confirm the stabilizing effect of crop diversity and spatial heterogeneity, yet their importance depends on the scale and agricultural management.
Building on the findings of the second chapter, I deepened in the third chapter my research on the effect of crop diversity at the national level. In particular, I tested if asynchrony between crops, i.e. between the temporal production patterns of different crops, better predicts agricultural production stability than crop diversity. The stabilizing effect of asynchrony was multiple times higher than the effect of crop diversity, i.e. asynchrony is one important property that can explain why a higher diversity supports the stability of national food production. Therefore, strategies to stabilize agricultural production through crop diversification also need to account for the asynchrony of the crops considered.
The previous chapters suggest that both asynchrony between crops and spatial heterogeneity are important stabilizing mechanisms. In the fourth chapter, I therefore aimed at better understanding the relative importance of asynchrony between and within crops, i.e. between the temporal production patterns of different crops and between the temporal production patterns of different cultivation areas of the same crop. Better understanding their relative importance is important to inform agricultural management decisions, but so far this has been hardly assessed. To address this, I used crop production data to study the effect of asynchrony between and within crops on the stability of agricultural production in regions in Germany and nations in Europe. Both asynchrony between and within crops consistently stabilized agricultural production. Adding crops increased asynchrony between crops, yet this effect levelled off after eight crops in regions in Germany and after four crops in nations in Europe. Combining already ten farms within a region led to high asynchrony within crops, indicating distinct production patters, while this effect was weaker when combining multiple regions within a nation. The results suggest, that both mechanisms need to be considered in agricultural management strategies that strive for more resilient farming systems.
The analyses in the foregoing chapters focused at different levels of organization, scales and factors potentially influencing agricultural stability. However, these statistical analyses are restricted by data availability and investigate correlative relationships, thus they cannot provide a mechanistic understanding of the actual processes underlying resilience. In this regard, agent-based models (ABM) are a promising tool. Besides their ability to measure different properties and to integrate multiple situations through extensive manipulation in a fully controlled system, they can capture the emergence of system resilience from individual interactions and feedbacks across different levels of organization. In the fifth chapter, I therefore reviewed the state of the art and potential knowledge gaps in exploring resilience and its multidimensionality in ecological and social-ecological systems with ABMs. Next, I derived recommendations for a more effective use of ABMs in resilience research. The review suggests that the potential of ABMs is not utilized in most models as they typically focus on a single dimension of resilience and are mostly limited to one reference state, disturbance type and scale. Moreover, only few studies explicitly test the ability of different mechanisms to support resilience. To solve real-world problems related to the resilience of complex systems, ABMs need to assess multiple stability properties for different situations and under consideration of the mechanisms that are hypothesized to render a system resilient.
In the sixth chapter, I discuss the major conclusions that can be drawn from the previous chapters. Moreover, I showcase the use of simulation models to identify management strategies to enhance asynchrony and thus stability, and the potential of ABMs to identify pathways to implement such strategies.
The results of my thesis confirm the stabilizing effect of crop diversity, yet its importance depends on the scale, agricultural management and climate. Moreover, strategies to stabilize agricultural production through crop diversification also need to account for the asynchrony of the crops considered. As spatial heterogeneity and particularly asynchrony within crops strongly enhances stability, integrated management approaches are needed that simultaneously address multiple resilience mechanisms at different levels of organization, scales and time horizons. For example, the simulation suggests that only increasing the number of crops at both the pixel and landscape level avoids trade-offs between asynchrony between and within crops. If their potential is better exploited, agent-based models have the capacity to systematically assess resilience and to identify comprehensive pathways towards resilient farming systems.
The propagation of test fields, such as electromagnetic, Dirac or linearized gravity, on a fixed spacetime manifold is often studied by using the geometrical optics approximation. In the limit of infinitely high frequencies, the geometrical optics approximation provides a conceptual transition between the test field and an effective point-particle description. The corresponding point-particles, or wave rays, coincide with the geodesics of the underlying spacetime. For most astrophysical applications of interest, such as the observation of celestial bodies, gravitational lensing, or the observation of cosmic rays, the geometrical optics approximation and the effective point-particle description represent a satisfactory theoretical model. However, the geometrical optics approximation gradually breaks down as test fields of finite frequency are considered.
In this thesis, we consider the propagation of test fields on spacetime, beyond the leading-order geometrical optics approximation. By performing a covariant Wentzel-Kramers-Brillouin analysis for test fields, we show how higher-order corrections to the geometrical optics approximation can be considered. The higher-order corrections are related to the dynamics of the spin internal degree of freedom of the considered test field. We obtain an effective point-particle description, which contains spin-dependent corrections to the geodesic motion obtained using geometrical optics. This represents a covariant generalization of the well-known spin Hall effect, usually encountered in condensed matter physics and in optics. Our analysis is applied to electromagnetic and massive Dirac test fields, but it can easily be extended to other fields, such as linearized gravity. In the electromagnetic case, we present several examples where the gravitational spin Hall effect of light plays an important role. These include the propagation of polarized light rays on black hole spacetimes and cosmological spacetimes, as well as polarization-dependent effects on the shape of black hole shadows. Furthermore, we show that our effective point-particle equations for polarized light rays reproduce well-known results, such as the spin Hall effect of light in an inhomogeneous medium, and the relativistic Hall effect of polarized electromagnetic wave packets encountered in Minkowski spacetime.
Spatiotemporal variations of key air pollutants and greenhouse gases in the Himalayan foothills
(2021)
South Asia is a rapidly developing, densely populated and highly polluted region that is facing the impacts of increasing air pollution and climate change, and yet it remains one of the least studied regions of the world scientifically. In recognition of this situation, this thesis focuses on studying (i) the spatial and temporal variation of key greenhouse gases (CO2 and CH4) and air pollutants (CO and O3) and (ii) the vertical distribution of air pollutants (PM, BC) in the foothills of the Himalaya. Five sites were selected in the Kathmandu Valley, the capital region of Nepal, along with two sites outside of the valley in the Makawanpur and Kaski districts, and conducted measurements during the period of 2013-2014 and 2016. These measurements are analyzed in this thesis.
The CO measurements at multiple sites in the Kathmandu Valley showed a clear diurnal cycle: morning and evening levels were high, with an afternoon dip. There are slight differences in the diurnal cycles of CO2 and CH4, with the CO2 and CH4 mixing ratios increasing after the afternoon dip, until the morning peak the next day. The mixing layer height (MLH) of the nocturnal stable layer is relatively constant (~ 200 m) during the night, after which it transitions to a convective mixing layer during the day and the MLH increases up to 1200 m in the afternoon. Pollutants are thus largely trapped in the valley from the evening until sunrise the following day, and the concentration of pollutants increases due to emissions during the night. During afternoon, the pollutants are diluted due to the circulation by the valley winds after the break-up of the mixing layer. The major emission sources of GHGs and air pollutants in the valley are transport sector, residential cooking, brick kilns, trash burning, and agro-residue burning. Brick industries are influential in the winter and pre-monsoon season. The contribution of regional forest fires and agro-residue burning are seen during the pre-monsoon season. In addition, relatively higher CO values were also observed at the valley outskirts (Bhimdhunga and Naikhandi), which indicates the contribution of regional emission sources. This was also supported by the presence of higher concentrations of O3 during the pre-monsoon season.
The mixing ratios of CO2 (419.3 ±6.0 ppm) and CH4 (2.192 ±0.066 ppm) in the valley were much higher than at background sites, including the Mauna Loa observatory (CO2: 396.8 ± 2.0 ppm, CH4:1.831 ± 0.110 ppm) and Waligaun (CO2: 397.7 ± 3.6 ppm, CH4: 1.879 ± 0.009 ppm), China, as well as at an urban site Shadnagar (CH4: 1.92 ± 0.07 ppm) in India.
The daily 8 hour maximum O3 average in the Kathmandu Valley exceeds the WHO recommended value during more than 80% of the days during the pre-monsoon period, which represents a significant risk for human health and ecosystems in the region. Moreover, in the measurements of the vertical distribution of particulate matter, which were made using an ultralight aircraft, and are the first of their kind in the region, an elevated polluted layer at around ca. 3000 m asl. was detected over the Pokhara Valley. The layer could be associated with the large-scale regional transport of pollution. These contributions towards understanding the distributions of key air pollutants and their main sources will provide helpful information for developing management plans and policies to help reduce the risks for the millions of people living in the region.
Centroid moment tensor inversion can provide insight into ongoing tectonic processes and active faults. In the Alpine mountains (central Europe), challenges result from low signal-to-noise ratios of earthquakes with small to moderate magnitudes and complex wave propagation effects through the heterogeneous crustal structure of the mountain belt. In this thesis, I make use of the temporary installation of the dense AlpArray seismic network (AASN) to establish a work flow to study seismic source processes and enhance the knowledge of the Alpine seismicity. The cumulative thesis comprises four publications on the topics of large seismic networks, seismic source processes in the Alps, their link to tectonics and stress field, and the inclusion of small magnitude earthquakes into studies of active faults.
Dealing with hundreds of stations of the dense AASN requires the automated assessment of data and metadata quality. I developed the open source toolbox AutoStatsQ to perform an automated data quality control. Its first application to the AlpArray seismic network has revealed significant errors of amplitude gains and sensor orientations. A second application of the orientation test to the Turkish KOERI network, based on Rayleigh wave polarization, further illustrated the potential in comparison to a P wave polarization method. Taking advantage of the gain and orientation results of the AASN, I tested different inversion settings and input data types to approach the specific challenges of centroid moment tensor (CMT) inversions in the Alps. A comparative study was carried out to define the best fitting procedures.
The application to 4 years of seismicity in the Alps (2016-2019) substantially enhanced the amount of moment tensor solutions in the region. We provide a list of moment tensors solutions down to magnitude Mw 3.1. Spatial patterns of typical focal mechanisms were analyzed in the seismotectonic context, by comparing them to long-term seismicity, historical earthquakes and observations of strain rates. Additionally, we use our MT solutions to investigate stress regimes and orientations along the Alpine chain. Finally, I addressed the challenge of including smaller magnitude events into the study of active faults and source processes. The open-source toolbox Clusty was developed for the clustering of earthquakes based on waveforms recorded across a network of seismic stations. The similarity of waveforms reflects both, the location and the similarity of source mechanisms. Therefore the clustering bears the opportunity to identify earthquakes of similar faulting styles, even when centroid moment tensor inversion is not possible due to low signal-to-noise ratios of surface waves or oversimplified velocity models. The toolbox is described through an application to the Zakynthos 2018 aftershock sequence and I subsequently discuss its potential application to weak earthquakes (Mw<3.1) in the Alps.
Lie group method in combination with Magnus expansion is utilized to develop a universal method applicable to solving a Sturm–Liouville Problem (SLP) of any order with arbitrary boundary conditions. It is shown that the method has ability to solve direct regular and some singular SLPs of even orders (tested up to order eight), with a mix of boundary conditions (including non-separable and finite singular endpoints), accurately and efficiently.
The present technique is successfully applied to overcome the difficulties in finding suitable sets of eigenvalues so that the inverse SLP problem can be effectively solved.
Next, a concrete implementation to the inverse Sturm–Liouville problem
algorithm proposed by Barcilon (1974) is provided. Furthermore, computational feasibility and applicability of this algorithm to solve inverse Sturm–Liouville problems of order n=2,4 is verified successfully. It is observed that the method is successful even in the presence of significant noise, provided that the assumptions of the algorithm are satisfied.
In conclusion, this work provides methods that can be adapted successfully for solving a direct (regular/singular) or inverse SLP of an arbitrary order with arbitrary boundary conditions.
Major challenges during geothermal exploration and exploitation include the structural-geological characterization of the geothermal system and the application of sustainable monitoring concepts to explain changes in a geothermal reservoir during production and/or reinjection of fluids. In the absence of sufficiently permeable reservoir rocks, faults and fracture networks are preferred drilling targets because they can facilitate the migration of hot and/or cold fluids. In volcanic-geothermal systems considerable amounts of gas emissions can be released at the earth surface, often related to these fluid-releasing structures.
In this thesis, I developed and evaluated different methodological approaches and measurement concepts to determine the spatial and temporal variation of several soil gas parameters to understand the structural control on fluid flow. In order to validate their potential as innovative geothermal exploration and monitoring tools, these methodological approaches were applied to three different volcanic-geothermal systems. At each site an individual survey design was developed regarding the site-specific questions.
The first study presents results of the combined measurement of CO2 flux, ground temperatures, and the analysis of isotope ratios (δ13CCO2, 3He/4He) across the main production area of the Los Humeros geothermal field, to identify locations with a connection to its supercritical (T > 374◦C and P > 221 bar) geothermal reservoir. The results of the systematic and large-scale (25 x 200 m) CO2 flux scouting survey proved to be a fast and flexible way to identify areas of anomalous degassing. Subsequent sampling with high resolution surveys revealed the actual extent and heterogenous pattern of anomalous degassing areas. They have been related to the internal fault hydraulic architecture and allowed to assess favourable structural settings for fluid flow such as fault intersections. Finally, areas of unknown structurally controlled permeability with a connection to the superhot geothermal reservoir have been determined, which represent promising targets for future geothermal exploration and development.
In the second study, I introduce a novel monitoring approach by examining the variation of CO2 flux to monitor changes in the reservoir induced by fluid reinjection. For that reason, an automated, multi-chamber CO2 flux system was deployed across the damage zone of a major normal fault crossing the Los Humeros geothermal field. Based on the results of the CO2 flux scouting survey, a suitable site was selected that had a connection to the geothermal reservoir, as identified by hydrothermal CO2 degassing and hot ground temperatures (> 50 °C). The results revealed a response of gas emissions to changes in reinjection rates within 24 h, proving an active hydraulic communication between the geothermal reservoir and the earth surface. This is a promising monitoring strategy that provides nearly real-time and in-situ data about changes in the reservoir and allows to timely react to unwanted changes (e.g., pressure decline, seismicity).
The third study presents results from the Aluto geothermal field in Ethiopia where an area-wide and multi-parameter analysis, consisting of measurements of CO2 flux, 222Rn, and 220Rn activity concentrations and ground temperatures was conducted to detect hidden permeable structures. 222Rn and 220Rn activity concentrations are evaluated as a complementary soil gas parameter to CO2 flux, to investigate their potential to understand tectono-volcanic degassing. The combined measurement of all parameters enabled to develop soil gas fingerprints, a novel visualization approach. Depending on the magnitude of gas emissions and their migration velocities the study area was divided in volcanic (heat), tectonic (structures), and volcano-tectonic dominated areas. Based on these concepts, volcano-tectonic dominated areas, where hot hydrothermal fluids migrate along permeable faults, present the most promising targets for future geothermal exploration and development in this geothermal field. Two of these areas have been identified in the south and south-east which have not yet been targeted for geothermal exploitation. Furthermore, two unknown areas of structural related permeability could be identified by 222Rn and 220Rn activity concentrations.
Eventually, the fourth study presents a novel measurement approach to detect structural controlled CO2 degassing, in Ngapouri geothermal area, New Zealand. For the first time, the tunable diode laser (TDL) method was applied in a low-degassing geothermal area, to evaluate its potential as a geothermal exploration method. Although the sampling approach is based on profile measurements, which leads to low spatial resolution, the results showed a link between known/inferred faults and increased CO2 concentrations. Thus, the TDL method proved to be a successful in the determination of structural related permeability, also in areas where no obvious geothermal activity is present. Once an area of anomalous CO2 concentrations has been identified, it can be easily complemented by CO2 flux grid measurements to determine the extent and orientation of the degassing segment.
With the results of this work, I was able to demonstrate the applicability of systematic and area-wide soil gas measurements for geothermal exploration and monitoring purposes. In particular, the combination of different soil gases using different measurement networks enables the identification and characterization of fluid-bearing structures and has not yet been used and/or tested as standard practice. The different studies present efficient and cost-effective workflows and demonstrate a hands-on approach to a successful and sustainable exploration and monitoring of geothermal resources. This minimizes the resource risk during geothermal project development. Finally, to advance the understanding of the complex structure and dynamics of geothermal systems, a combination of comprehensive and cutting-edge geological, geochemical, and geophysical exploration methods is essential.
Massive Open Online Courses (MOOCs) open up new opportunities to learn a wide variety of skills online and are thus well suited for individual education, especially where proffcient teachers are not available locally. At the same time, modern society is undergoing a digital transformation, requiring the training of large numbers of current and future employees. Abstract thinking, logical reasoning, and the need to formulate instructions for computers are becoming increasingly relevant. A holistic way to train these skills is to learn how to program. Programming, in addition to being a mental discipline, is also considered a craft, and practical training is required to achieve mastery. In order to effectively convey programming skills in MOOCs, practical exercises are incorporated into the course curriculum to offer students the necessary hands-on experience to reach an in-depth understanding of the programming concepts presented. Our preliminary analysis showed that while being an integral and rewarding part of courses, practical exercises bear the risk of overburdening students who are struggling with conceptual misunderstandings and unknown syntax. In this thesis, we develop, implement, and evaluate different interventions with the aim to improve the learning experience, sustainability, and success of online programming courses. Data from four programming MOOCs, with a total of over 60,000 participants, are employed to determine criteria for practical programming exercises best suited for a given audience.
Based on over five million executions and scoring runs from students' task submissions, we deduce exercise difficulties, students' patterns in approaching the exercises, and potential flaws in exercise descriptions as well as preparatory videos. The primary issue in online learning is that students face a social gap caused by their isolated physical situation. Each individual student usually learns alone in front of a computer and suffers from the absence of a pre-determined time structure as provided in traditional school classes. Furthermore, online learning usually presses students into a one-size-fits-all curriculum, which presents the same content to all students, regardless of their individual needs and learning styles. Any means of a personalization of content or individual feedback regarding problems they encounter are mostly ruled out by the discrepancy between the number of learners and the number of instructors. This results in a high demand for self-motivation and determination of MOOC participants. Social distance exists between individual students as well as between students and course instructors. It decreases engagement and poses a threat to learning success. Within this research, we approach the identified issues within MOOCs and suggest scalable technical solutions, improving social interaction and balancing content difficulty.
Our contributions include situational interventions, approaches for personalizing educational content as well as concepts for fostering collaborative problem-solving. With these approaches, we reduce counterproductive struggles and create a universal improvement for future programming MOOCs. We evaluate our approaches and methods in detail to improve programming courses for students as well as instructors and to advance the state of knowledge in online education.
Data gathered from our experiments show that receiving peer feedback on one's programming problems improves overall course scores by up to 17%. Merely the act of phrasing a question about one's problem improved overall scores by about 14%. The rate of students reaching out for help was significantly improved by situational just-in-time interventions. Request for Comment interventions increased the share of students asking for help by up to 158%. Data from our four MOOCs further provide detailed insight into the learning behavior of students. We outline additional significant findings with regard to student behavior and demographic factors. Our approaches, the technical infrastructure, the numerous educational resources developed, and the data collected provide a solid foundation for future research.
The goal of this dissertation is to empirically evaluate the predictions of two classes of models applied to language processing: the similarity-based interference models (Lewis & Vasishth, 2005; McElree, 2000) and the group of smaller-scale accounts that we will refer to as faulty encoding accounts (Eberhard, Cutting, & Bock, 2005; Bock & Eberhard, 1993). Both types of accounts make predictions with regard to processing the same class of structures: sentences containing a non-subject (interfering) noun in addition to a subject noun and a verb. Both accounts make the same predictions for processing ungrammatical sentences with a number-mismatching interfering noun, and this prediction finds consistent support in the data. However, the similarity-based interference accounts predict similar effects not only for morphosyntactic, but also for the semantic level of language organization. We verified this prediction in three single-trial online experiments, where we found consistent support for the predictions of the similarity-based interference account. In addition, we report computational simulations further supporting the similarity-based interference accounts. The combined evidence suggests that the faulty encoding accounts are not required to explain comprehension of ill-formed sentences.
For the processing of grammatical sentences, the accounts make conflicting predictions, and neither the slowdown predicted by the similarity-based interference account, nor the complementary slowdown predicted by the faulty encoding accounts were systematically observed. The majority of studies found no difference between the compared configurations. We tested one possible explanation for the lack of predicted difference, namely, that both slowdowns are present simultaneously and thus conceal each other. We decreased the amount of similarity-based interference: if the effects were concealing each other, decreasing one of them should allow the other to surface. Surprisingly, throughout three larger-sample single-trial online experiments, we consistently found the slowdown predicted by the faulty encoding accounts, but no effects consistent with the presence of inhibitory interference.
The overall pattern of the results observed across all the experiments reported in this dissertation is consistent with previous findings: predictions of the interference accounts for the processing of ungrammatical sentences receive consistent support, but the predictions for the processing of grammatical sentences are not always met. Recent proposals by Nicenboim et al. (2016) and Mertzen et al. (2020) suggest that interference might arise only in people with high working memory capacity or under deep processing mode. Following these proposals, we tested whether interference effects might depend on the depth of processing: we manipulated the complexity of the training materials preceding the grammatical experimental sentences while making no changes to the experimental materials themselves. We found that the slowdown predicted by the faulty encoding accounts disappears in the deep processing mode, but the effects consistent with the predictions of the similarity-based interference account do not arise.
Independently of whether similarity-based interference arises under deep processing mode or not, our results suggest that the faulty encoding accounts cannot be dismissed since they make unique predictions with regard to processing grammatical sentences, which are supported by data. At the same time, the support is not unequivocal: the slowdowns are present only in the superficial processing mode, which is not predicted by the faulty encoding accounts. Our results might therefore favor a much simpler system that superficially tracks number features and is distracted by every plural feature.
While the last few decades have seen impressive improvements in several areas in Natural Language Processing, asking a computer to make sense of the discourse of utterances in a text remains challenging. There are several different theories that aim to describe and analyse the coherent structure that a well-written text inhibits. These theories have varying degrees of applicability and feasibility for practical use. Presumably the most data-driven of these theories is the paradigm that comes with the Penn Discourse TreeBank, a corpus annotated for discourse relations containing over 1 million words. Any language other than English however, can be considered a low-resource language when it comes to discourse processing.
This dissertation is about shallow discourse parsing (discourse parsing following the paradigm of the Penn Discourse TreeBank) for German. The limited availability of annotated data for German means the potential of modern, deep-learning based methods relying on such data is also limited. This dissertation explores to what extent machine-learning and more recent deep-learning based methods can be combined with traditional, linguistic feature engineering to improve performance for the discourse parsing task. A pivotal role is played by connective lexicons that exhaustively list the discourse connectives of a particular language along with some of their core properties.
To facilitate training and evaluation of the methods proposed in this dissertation, an existing corpus (the Potsdam Commentary Corpus) has been extended and additional data has been annotated from scratch. The approach to end-to-end shallow discourse parsing for German adopts a pipeline architecture and either presents the first results or improves over state-of-the-art for German for the individual sub-tasks of the discourse parsing task, which are, in processing order, connective identification, argument extraction and sense classification. The end-to-end shallow discourse parser for German that has been developed for the purpose of this dissertation is open-source and available online.
In the course of writing this dissertation, work has been carried out on several connective lexicons in different languages. Due to their central role and demonstrated usefulness for the methods proposed in this dissertation, strategies are discussed for creating or further developing such lexicons for a particular language, as well as suggestions on how to further increase their usefulness for shallow discourse parsing.
Background: A growing body of research has documented negative effects of sexualization in the media on individuals’ self-objectification. This research is predominantly built on studies examining traditional media, such as magazines and television, and young female samples. Furthermore, longitudinal studies are scarce, and research is missing studying mediators of the relationship. The first aim of the present PhD thesis was to investigate the relations between the use of sexualized interactive media and social media and self-objectification. The second aim of this work was to examine the presumed processes within understudied samples, such as males and females beyond college age, thus investigating the moderating roles of age and gender. The third aim was to shed light on possible mediators of the relation between sexualized media and self-objectification.
Method: The research aims were addressed within the scope of four studies. In an experiment, women’s self-objectification and body satisfaction was measured after playing a video game with a sexualized vs. a nonsexualized character that was either personalized or generic. The second study investigated the cross-sectional link between sexualized television use and self-objectification and consideration of cosmetic surgery in a sample of women across a broad age spectrum, examining the role of age in the relations. The third study looked at the cross-sectional link between male and female sexualized images on Instagram and their associations with self-objectification among a sample of male and female adolescents. Using a two-wave longitudinal design, the fourth study examined sexualized video game and Instagram use as predictors of adolescents’ self-objectification. Path models were conceptualized for the second, third and fourth study, in which media use predicted body surveillance via appearance comparisons (Study 4), thin-ideal internalization (Study 2, 3, 4), muscular-ideal internalization (Study 3, 4), and valuing appearance (all studies).
Results: The results of the experimental study revealed no effect of sexualized video game characters on women’s self-objectification and body satisfaction. No moderating effect of personalization emerged. Sexualized television use was associated to consideration of cosmetic surgery via body surveillance and valuing appearance for women of all ages in Study 2, while no moderating effect of age was found. Study 3 revealed that seeing sexualized male images on Instagram was indirectly associated with higher body surveillance via muscular-ideal internalization for boys and girls. Sexualized female images were indirectly linked to higher body surveillance via thin-ideal internalization and valuing appearance over competence only for girls. The longitudinal analysis of Study 4 showed no moderating effect of gender: For boys and girls, sexualized video game use at T1 predicted body surveillance at T2 via appearance comparisons, thin-ideal internalization and valuing appearance over competence. Furthermore, the use of sexualized Instagram images at T1 predicted body surveillance at T2 via valuing appearance.
Conclusion: The findings show that sexualization in the media is linked to self-objectification among a variety of media formats and within diverse groups of people. While the longitudinal study indicates that sexualized media predict self-objectification over time, the experimental null findings warrant caution regarding this temporal order. The results demonstrate that several mediating variables might be involved in this link. Possible implications for research and practice, such as intervention programs and policy-making, are discussed.
Role of dietary sulfonates in the stimulation of gut bacteria promoting intestinal inflammation
(2021)
The interplay between intestinal microbiota and host has increasingly been recognized as a major factor impacting health. Studies indicate that diet is the most influential determinant affecting the gut microbiota. A diet rich in saturated fat was shown to stimulate the growth of the colitogenic bacterium Bilophila wadsworthia by enhancing the secretion of the bile acid taurocholate (TC). The sulfonated taurine moiety of TC is utilized as a substrate by B. wadsworthia. The resulting overgrowth of B. wadsworthia was accompanied by an increased incidence and severity of colitis in interleukin (IL)-10-deficient mice, which are genetically prone to develop inflammation.
Based on these findings, the question arose whether the intake of dietary sulfonates also stimulates the growth of B. wadsworthia and thereby promotes intestinal inflammation in genetically susceptible mice. Dietary sources of sulfonates include green vegetables and cyanobacteria, which contain the sulfolipids sulfoquinovosyl diacylglycerols (SQDG) in considerable amounts. Based on literature reports, the gut commensal Escherichia coli is able to release sulfoquinovose (SQ) from SQDG and in further steps, convert SQ to 2,3-dihydroxypropane-1-sulfonate (DHPS) and dihydroxyacetone phosphate. DHPS may then be utilized as a growth substrate by B. wadsworthia, which results in the formation of sulfide. Both, sulfide formation and a high abundance of B. wadsworthia have been associated with intestinal inflammation.
In the present study, conventional IL-10-deficient mice were fed either a diet supplemented with the SQDG-rich cyanobacterium Spirulina (20%, SD) or a control diet. In addition SQ, TC, or water were orally applied to conventional or gnotobiotic IL-10-deficient mice. The gnotobiotic mice harbored a simplified human intestinal microbiota (SIHUMI) either with or without B. wadsworthia. During the intervention period, the body weight of the mice was monitored, the colon permeability was assessed and fecal samples were collected. After the three-week intervention, the animals were examined with regard to inflammatory parameters, microbiota composition and sulfonate concentrations in different intestinal sites.
None of the mice treated with the above-mentioned sulfonates showed weight loss or intestinal inflammation. Solely mice fed SD or gavaged with TC displayed a slight immune response. These mice also displayed an altered microbiota composition, which was not observed in mice gavaged with SQ. The abundance of B. wadsworthia was strongly reduced in mice fed SD, while that of mice treated with SQ or TC was in part slightly increased. The intestinal SQ-concentration was elevated in mice orally treated with SD or SQ, whereas neither TC nor taurine concentrations were consistently elevated in mice gavaged with TC. Additional colonization of SIHUMI mice with B. wadsworthia resulted in a mild inflammatory response, but only in mice treated with TC. In general, TC-mediated effects on the immune system and abundance of B. wadsworthia were not as strong as described in the literature.
In summary, neither the tested dietary sulfonates nor TC led to bacteria-induced intestinal inflammation in the IL-10-deficient mouse model, which was consistently observed in both conventional and gnotobiotic mice. For humans, this means that foods containing SQDG, such as spinach or Spirulina, do not increase the risk of intestinal inflammation.
As part of our everyday life we consume breaking news and interpret it based on our own viewpoints and beliefs. We have easy access to online social networking platforms and news media websites, where we inform ourselves about current affairs and often post about our own views, such as in news comments or social media posts. The media ecosystem enables opinions and facts to travel from news sources to news readers, from news article commenters to other readers, from social network users to their followers, etc. The views of the world many of us have depend on the information we receive via online news and social media. Hence, it is essential to maintain accurate, reliable and objective online content to ensure democracy and verity on the Web. To this end, we contribute to a trustworthy media ecosystem by analyzing news and social media in the context of politics to ensure that media serves the public interest. In this thesis, we use text mining, natural language processing and machine learning techniques to reveal underlying patterns in political news articles and political discourse in social networks.
Mainstream news sources typically cover a great amount of the same news stories every day, but they often place them in a different context or report them from different perspectives. In this thesis, we are interested in how distinct and predictable newspaper journalists are, in the way they report the news, as a means to understand and identify their different political beliefs. To this end, we propose two models that classify text from news articles to their respective original news source, i.e., reported speech and also news comments. Our goal is to capture systematic quoting and commenting patterns by journalists and news commenters respectively, which can lead us to the newspaper where the quotes and comments are originally published. Predicting news sources can help us understand the potential subjective nature behind news storytelling and the magnitude of this phenomenon. Revealing this hidden knowledge can restore our trust in media by advancing transparency and diversity in the news.
Media bias can be expressed in various subtle ways in the text and it is often challenging to identify these bias manifestations correctly, even for humans. However, media experts, e.g., journalists, are a powerful resource that can help us overcome the vague definition of political media bias and they can also assist automatic learners to find the hidden bias in the text. Due to the enormous technological advances in artificial intelligence, we hypothesize that identifying political bias in the news could be achieved through the combination of sophisticated deep learning modelsxi and domain expertise. Therefore, our second contribution is a high-quality and reliable news dataset annotated by journalists for political bias and a state-of-the-art solution for this task based on curriculum learning. Our aim is to discover whether domain expertise is necessary for this task and to provide an automatic solution for this traditionally manually-solved problem. User generated content is fundamentally different from news articles, e.g., messages are shorter, they are often personal and opinionated, they refer to specific topics and persons, etc. Regarding political and socio-economic news, individuals in online communities make use of social networks to keep their peers up-to-date and to share their own views on ongoing affairs. We believe that social media is also an as powerful instrument for information flow as the news sources are, and we use its unique characteristic of rapid news coverage for two applications. We analyze Twitter messages and debate transcripts during live political presidential debates to automatically predict the topics that Twitter users discuss. Our goal is to discover the favoured topics in online communities on the dates of political events as a way to understand the political subjects of public interest. With the up-to-dateness of microblogs, an additional opportunity emerges, namely to use social media posts and leverage the real-time verity about discussed individuals to find their locations.
That is, given a person of interest that is mentioned in online discussions, we use the wisdom of the crowd to automatically track her physical locations over time. We evaluate our approach in the context of politics, i.e., we predict the locations of US politicians as a proof of concept for important use cases, such as to track people that
are national risks, e.g., warlords and wanted criminals.
Soft actuators have drawn significant attention due to their relevance for applications, such as artificial muscles in devices developed for medicine and robotics. Tuning their performance and expanding their functionality are frequently done by means of chemical modification. The introduction of structural elements rendering non-synthetic modification of the performance possible, as well as control over physical appearance and facilitating their recycling is a subject of a great interest in the field of smart materials. The primary aim of this thesis was to create a shape-memory polymeric actuator, where the capability for non-synthetic tuning of the actuation performance is combined with reprocessability. Physically cross-linked polymeric matrices provide a solid material platform, where the in situ processing methods can be employed for modification of the composition and morphology, resulting in the fine tuning of the related mechanical properties and shape-memory actuation capability.
The morphological features, required for shape-memory polymeric actuators, namely two crystallisable domains and anchoring points for physical cross-links, were embedded into a multiblock copolymer with poly(ε-caprolactone) and poly(L-lactide) segments (PLLA-PCL). Here, the melting transition of PCL was bisected into the actuating and skeleton-forming units, while the cross-linking was introduced via PLA stereocomplexation in blends with oligomeric poly(D-lactide) (ODLA). PLLA segment number average length of 12-15 repeating units was experimentally defined to be capable of the PLA stereocomplexes formation, but not sufficient for the isotactic crystallisation. Multiblock structure and phase dilution broaden the PCL melting transition, facilitating its separation into two conditionally independent crystalline domains. Low molar mass of the PLA stereocomplex components and a multiblock structure enables processing and reprocessing of the PLLA-PCL / ODLA blends with common non-destructive techniques. The modularity of the PLLA-PCL structure and synthetic approach allows for independent tuning of the properties of its components. The designed material establishes a solid platform for non-synthetic tuning of thermomechanical and structural properties of thermoplastic elastomers.
To evaluate the thermomechanical stability of the formed physical network, three criteria were appraised. As physical cross-links, PLA stereocomplexes have to be evenly distributed within the material matrix, their melting temperature shall not overlap with the thermal transitions of the PCL domains and they have to maintain the structural integrity within the strain ε ranges further applied in the shape-memory actuation experiments. Assigning PCL the function of the skeleton-forming and actuating units, and PLA stereocomplexes the role of physical netpoints, shape-memory actuation was realised in the PLLA-PCL / ODLA blends. Reversible strain of shape-memory actuation was found to be a function of PLA stereocomplex crystallinity, i.e. physical cross-linking density, with a maximum of 13.4 ± 1.5% at PLA stereocomplex content of 3.1 ± 0.3 wt%. In this way, shape-memory actuation can be tuned via adjusting the composition of the PLLA-PCL / ODLA blend. This makes the developed material a valuable asset in the production of cost-effective tunable soft polymeric actuators for the applications in medicine and soft robotics.
Rehabilitationspädagogik
(2021)
Die Rehabilitationspädagogik ist eine jüngere eigenständige Hybridwissenschaft im Feld der Humanwissenschaften. Sie setzt theoriebildend im Sinne des Neunten Buchs Sozialgesetzbuch (SGB IX) an den längerfristigen Folgen einer Krankheit oder eines biologischen Mangels an. Dabei orientiert sie sich konzeptionell zum Beispiel an der UN-Behindertenrechtskonvention (UN-BRK) und an der International Classification of Functioning, Disability and Health (ICF). Des Weiteren an den Konzepten der Humanontogenetik von K.-F. Wessel, insbesondere: dem ganzen Menschen, der Hierarchie der Kompetenzen, den sensiblen Phasen und der Souveränität.
Die Rehabilitationspädagogik ist Bestandteil der komplexen gesundheitlichen Rehabilitation und eine Tochterdisziplin der allgemeinen Pädagogik. Bei ihrem rehabilitationspädagogischen Prozess gilt das Richtziel, die umfassende Teilhabe des Menschen an individuellen Lebensbereichen durch rehabilitationspädagogische Mittel, Methoden und Organisationsformen zu unterstützen.
Die Dissertation setzt sich mittels Methoden der Hermeneutik mit der DDR-Rehabilitationspädagogik von K.- P. Becker und Autorenkollektiv kritisch-konstruktiv auseinander. Sie legt eine aktuelle fortführende Theorie der Rehabilitationspädagogik unter der Berücksichtigung der UN-BRK, der ICF und des SGB IX vor und liefert eine neue Sichtweise auf die Rehabilitationspädagogik aus historischer und aktueller Perspektive.
Polymeric semiconductors are strong contenders for replacing traditional inorganic semiconductors in electronic applications requiring low power, low cost and flexibility, such as biosensors, flexible solar cells and electronic displays. Molecular doping has the potential to enable this revolution by improving the conductivity and charge transport properties of this class of materials. Despite decades of research in this field, gaps in our understanding of the nature of dopant–polymer interactions has resulted in limited commercialization of this technology. This work aims at providing a deeper insight into the underlying mechanisms of molecular p-doping of semiconducting polymers in the solution and solid-state, and thereby bring the scientific community closer to realizing the dream of making organic semiconductors commonplace in the electronics industry. The role of 1) dopant size/shape, 2) polymer chain aggregation and 3) charge delocalization on the doping mechanism and efficiency is addressed using optical (UV-Vis-NIR) and electron paramagnetic resonance (EPR) spectroscopies. By conducting a comprehensive study of the nature and concentration of the doping-induced species in solutions of the polymer poly(3-hexylthiophene) (P3HT) with 3 different dopants, we identify the unique optical signatures of the delocalized polaron, localized polaron and charge-transfer complex, and report their extinction coefficient values. Furthermore, with X-ray diffraction, atomic force microscopy and electrical conductivity measurements, we study the impact of processing technique and doping mechanism on the morphology and thereby, charge transport through the doped films.
This work demonstrates that the doping mechanism and type of doping-induced species formed are strongly influenced by the polymer backbone arrangement rather than dopant shape/size. The ability of the polymer chain to aggregate is found to be crucial for efficient charge transfer (ionization) and polaron delocalization. At the same time, our results suggest that the high ionization efficiency of a dopant–polymer system in solution may subsequently hinder efficient charge transport in the solid-state due to the reduction in the fraction of tie chains, which enable charges to move efficiently between aggregated domains in the films. This study demonstrates the complex multifaceted nature of polymer doping while providing important hints for the future design of dopant-host systems and film fabrication techniques.
Bottom-up synthetic biology is used for the understanding of how a cell works. It is achieved through developing techniques to produce lipid-based vesicular structures as cellular mimics. The most common techniques used to produce cellular mimics or synthetic cells is through electroformation and swelling method. However, the abovementioned techniques cannot efficiently encapsulate macromolecules such as proteins, enzymes, DNA and even liposomes as synthetic organelles. This urges the need to develop new techniques that can circumvent this issue and make the artificial cell a reality where it is possible to imitate a eukaryotic cell through encapsulating macromolecules. In this thesis, the aim to construct a cell system using giant unilamellar vesicles (GUVs) to reconstitute the mitochondrial molybdenum cofactor biosynthetic pathway. This pathway is highly conserved among all life forms, and therefore is known for its biological significance in disorders induced through its malfunctioning. Furthermore, the pathway itself is a multi-step enzymatic reaction that takes place in different compartments. Initially, GTP in the mitochondrial matrix is converted to cPMP in the presence of cPMP synthase. Further, produced cPMP is transported across the membrane to the cytosol, to be converted by MPT synthase into MPT. This pathway provides a possibility to address the general challenges faced in the development of a synthetic cell, to encapsulate large biomolecules with good efficiency and greater control and to evaluate the enzymatic reactions involved in the process.
For this purpose, the emulsion-based technique was developed and optimised to allow rapid production of GUVs (~18 min) with high encapsulation efficiency (80%). This was made possible by optimizing various parameters such as density, type of oil, the impact of centrifugation speed/time, lipid concentration, pH, temperature, and emulsion droplet volume. Furthermore, the method was optimised in microtiter plates for direct experimentation and visualization after the GUV formation. Using this technique, the two steps - formation of cPMP from GTP and the formation of MPT from cPMP were encapsulated in different sets of GUVs to mimic the two compartments. Two independent fluorescence-based detection systems were established to confirm the successful encapsulation and conversion of the reactants. Alternatively, the enzymes produced using bacterial expression and measured. Following the successful encapsulation and evaluation of enzymatic reactions, cPMP transport across mitochondrial membrane has been mimicked using GUVs using a complex mitochondrial lipid composition. It was found that the cPMP interaction with the lipid bilayer results in transient pore-formation and leakage of internal contents.
Overall, it can be concluded that in this thesis a novel technique has been optimised for fast production of functional synthetic cells. The individual enzymatic steps of the Moco biosynthetic pathway have successfully implemented and quantified within these cellular mimics.
Ionizing radiation is used in cancer radiation therapy to effectively damage the DNA of tumors leading to cell death and reduction of the tumor tissue. The main damage is due to generation of highly reactive secondary species such as low-energy electrons (LEE) with the most probable energy around 10 eV through ionization of water molecules in the cells. A simulation of the dose distribution in the patient is required to optimize the irradiation modality in cancer radiation therapy, which must be based on the fundamental physical processes of high-energy radiation with the tissue. In the present work the accurate quantification of DNA radiation damage in the form of absolute cross sections for LEE-induced DNA strand breaks (SBs) between 5 and 20 eV is done by using the DNA origami technique. This method is based on the analysis of well-defined DNA target sequences attached to DNA origami triangles with atomic force microscopy (AFM) on the single molecule level. The present work focuses on poly-adenine sequences (5'-d(A4), 5'-d(A8), 5'-d(A12), 5'-d(A16), and 5'- d(A20)) irradiated with 5.0, 7.0, 8.4, and 10 eV electrons. Independent of the DNA length, the strand break cross section shows a maximum around 7.0 eV electron energy for all investigated oligonucleotides confirming that strand breakage occurs through the initial formation of negative ion resonances. Additionally, DNA double strand breaks from a DNA hairpin 5'-d(CAC)4T(Bt-dT)T2(GTG)4 are examined for the first time and are compared with those of DNA single strands 5'-d(CAC)4 and 5'- d(GTG)4. The irradiation is made in the most likely energy range of 5 to 20 eV with an anionic resonance maximum around 10 eV independently of the DNA sequence. There is a clear difference between σSSB and σDSB of DNA single and double strands, where the strand break for ssDNA are always higher in all electron energies compared to dsDNA by the factor 3. A further part of this work deals with the characterization and analysis of new types of radiosensitizers used in chemoradiotherapy, which selectively increases the DNA damage upon radiation. Fluorinated DNA sequences with 2'-fluoro-2'-deoxycytidine (dFC) show an increased sensitivity at 7 and 10 eV compared to the unmodified DNA sequences by an enhancement factor between 2.1 and 2.5. In addition, light-induced oxidative damage of 5'-d(GTG)4 and 5'-d((CAC)4T(Bt-dT)T2(GTG)4) modified DNA origami triangles by singlet oxygen 1O2 generated from three photoexcited DNA groove binders [ANT994], [ANT1083] and [Cr(ddpd)2][BF4]3 illuminated in different experiments with UV-Vis light at 430, 435 and 530 nm wavelength is demonstrated. The singlet oxygen induced generation of DNA damage could be detected in both aqueous and dry environments for [ANT1083] and [Cr(ddpd)2][BF4]3.
Der Bildungshausbau ist Thema aktueller Debatten in der Stadtentwicklung und Stadtplanung sowie in der Pädagogik. Viele Expert*innen beschäftigen sich in Studien mit Fragen zu gutem und gelingendem Schulbau. Die Anforderungen der Gesellschaft an Bildungshäuser verändern sich, wenn in ganztägigen Schulformen nicht nur Unterricht, sondern auch Freizeitbetreuung für die Schülerinnen und Schüler stattfinden soll. Gleichzeitig soll Schule ein Ort der Begegnung und Kommunikation, des sozialen Lernens und der Kooperation sein. Schule ist in vielfacher Hinsicht in Bewegung. Um mit den Veränderungen und Ansprüchen Schritt zu halten, steht der Bildungshausbau immer wieder vor Herausforderungen. Einerseits werden Leuchtturmprojekte geschaffen, andererseits entstehen nach wie vor Bildungsbauten, die den gegenwärtigen Anforderungen und zukünftigen Entwicklungen nicht gerecht werden.
An dieser Stelle setzt die vorliegende Arbeit an, die nicht neue Normen zu gutem Schulbau vorlegt, sondern in einer qualitativen empirischen Studie nach den pädagogischen Vorstellungen von Beteiligten im Bildungshausbau und den typischen Entwicklungen im Planungsprozess fragt. Der vorliegenden Fallstudie wurde die dokumentarische Methode als Auswertungsverfahren zugrunde gelegt. Gegenstand der Untersuchung waren zwei Bildungsbauten eines Großbauprojektes. Im Zuge der Auswertung erfolgten eine Analyse der Projektstrukturen und eine Analyse der Deutungsmuster der befragten Akteur*innen, die in einer zusammen¬führenden Ergebnisdarstellung in Form eines Handlungs-Struktur-Gefüges mündeten.
Es werden Einblicke in Zusammenhänge von Handlungen der Beteiligten und Projektstrukturen gegeben, wie sie sich gegenseitig beeinflussen oder im Prozessverlauf verändern. Die Auswertung zeigt, dass Transferproblematiken zwischen Wissenschaft und Praxis nach wie vor bestehen. Besonderes Gewicht bei Planungsentscheidungen haben finanzielle, zeitliche und architektonische Strukturen. Nur wenige pädagogische Vorstellungen bzw. Deutungsmuster können in Erscheinung treten.
The ubiquitin-proteasome-system (UPS) is a cellular cascade involving three enzymatic steps for protein ubiquitination to target them to the 26S proteasome for proteolytic degradation. Several components of the UPS have been shown to be central for regulation of defense responses during infections with phytopathogenic bacteria. Upon recognition of the pathogen, local defense is induced which also primes the plant to acquire systemic resistance (SAR) for enhanced immune responses upon challenging infections. Here, ubiquitinated proteins were shown to accumulate locally and systemically during infections with Psm and after treatment with the SAR-inducing metabolites salicylic acid (SA) and pipecolic acid (Pip). The role of the 26S proteasome in local defense has been described in several studies, but the potential role during SAR remains elusive and was therefore investigated in this project by characterizing the Arabidopsis proteasome mutants rpt2a-2 and rpn12a-1 during priming and infections with Pseudomonas. Bacterial replication assays reveal decreased basal and systemic immunity in both mutants which was verified on molecular level showing impaired activation of defense- and SAR-genes. rpt2a-2 and rpn12a-1 accumulate wild type like levels of camalexin but less SA. Endogenous SA treatment restores local PR gene expression but does not rescue the SAR-phenotype. An RNAseq experiment of Col-0 and rpt2a-2 reveal weak or absent induction of defense genes in the proteasome mutant during priming. Thus, a functional 26S proteasome was found to be required for induction of SAR while compensatory mechanisms can still be initiated.
E3-ubiquitin ligases conduct the last step of substrate ubiquitination and thereby convey specificity to proteasomal protein turnover. Using RNAseq, 11 E3-ligases were found to be differentially expressed during priming in Col-0 of which plant U-box 54 (PUB54) and ariadne 12 (ARI12) were further investigated to gain deeper understanding of their potential role during priming.
PUB54 was shown to be expressed during priming and /or triggering with virulent Pseudomonas. pub54 I and pub54-II mutants display local and systemic defense comparable to Col-0. The heavy-metal associated protein 35 (HMP35) was identified as potential substrate of PUB54 in yeast which was verified in vitro and in vivo. PUB54 was shown to be an active E3-ligase exhibiting auto-ubiquitination activity and performing ubiquitination of HMP35. Proteasomal turnover of HMP35 was observed indicating that PUB54 targets HMP35 for ubiquitination and subsequent proteasomal degradation. Furthermore, hmp35-I benefits from increased resistance in bacterial replication assays. Thus, HMP35 is potentially a negative regulator of defense which is targeted and ubiquitinated by PUB54 to regulate downstream defense signaling. ARI12 is transcriptionally activated during priming or triggering and hyperinduced during priming and triggering. Gene expression is not inducible by the defense related hormone salicylic acid (SA) and is dampened in npr1 and fmo1 mutants consequently depending on functional SA- and Pip-pathways, respectively. ARI12 accumulates systemically after priming with SA, Pip or Pseudomonas. ari12 mutants are not altered in resistance but stable overexpression leads to increased resistance in local and systemic tissue. During priming and triggering, unbalanced ARI12 levels (i.e. knock out or overexpression) leads to enhanced FMO1 activation indicating a role of ARI12 in Pip-mediated SAR. ARI12 was shown to be an active E3-ligase with auto-ubiquitination activity likely required for activation with an identified ubiquitination site at K474. Mass spectrometrically identified potential substrates were not verified by additional experiments yet but suggest involvement of ARI12 in regulation of ROS in turn regulating Pip-dependent SAR pathways.
Thus, data from this project provide strong indications about the involvement of the 26S proteasome in SAR and identified a central role of the two so far barely described E3-ubiquitin ligases PUB54 and ARI12 as novel components of plant defense.